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STRICTLY ACCORDING TO THE NEW SYLLABUS ay i

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INDIA'S FIRST SMART BOOK Dr. S.P Ja
According to new syllabus prescribed by Central Board of Secondary Education (CBSE), New Delhi and State
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For Class Xll

strictly -
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Department of Chemistry
Panjab University, Chandigarh

yr. ce ove REVISED AND UPDATED EDITION 2019-2020

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 Preface & Acknowledgement
I feel pleasure in presenting the revised edition of the book “‘Modern’s abc + of Chemistry” for Class XII students.
The book has been prepared strictly according to the new syllabus proposed by C.B.S.E. New Delhi and
Education Boards of Indian States.
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@ ‘Text matter has been planned giving emphasis on fundamental concepts in a simple, clear and
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Reason Type Questions, Matrix Match Type Questions and Integer Type questions in the light of new
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@ The book provides complete coverage of previous years’ Board examinations of different States and All
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I am extremely thankful to Mrs. Sheenu Jauhar for her sincere efforts and unmatched contribution in crictical
and thorough revision of the whole book and revising Objective Questions. I am also thankful to many teachers
and students who have been sending their valuable suggestions and comments for the improvement of the
book. I am greatly indebted to them. I wish to acknowledge my sincere thanks to Mr. Arun Kambgj (G.5.5.
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I am thankful to Mr. Vinod Jangra (G.5.S.S., Akbarpur Baroto, Sonepat) and Dr. Anjul Rajput (Dhampur) their
valuable suggestions/corrections. I am also thankful to Ms. Arshdeep for her sincere editorial work. Finally, I
am happy to express my sincerest thanks and indebtness to our dynamic and versatile publisher and his
efficient staff for making the project successful. I am also thankful to Mr. Manik Juneja, National Head —
Content Operations, Mr. S.K. Sikka, Mr. B.S. Rawat, Ravinder Pathania and L.B. Mishra who have taken great
pains in bringing up the book.
I would also like to gratefully appreciate the tremendous efforts of Mr. Manu Jauhar for excellent thoughtful
editing of the book. -
I hope that the present book will be warmly received by the students and the teachers. fate ie
Me,

_ Dr. S.P. Jauhar

 PERIODIC TA
Modern group ,
si 1 2 3 4 | 5 6 7 | 8 : 9
Old group VIII
No. >
Period | ‘%
s-BLOCK (ns °)

i Alkali metals
* Alkaline eartt

2 Manganese — Namie | | Transition me

4 3542 Electronic _ | Lanthanides

© | Configuration

3 d-BLOCK [(n—1) d*“ns *]

N TRANSITION ELEMENTS
é

Ar

Kr

6
Hainium

Xe ' | 4f'45076s?|
89 to 103} 104 711) 41
Francium Rutherfordium | Dubnium | Seaborgium Bohrium

Rn | | 5f'6d?7s*| 5f'46d°7s*| 5f'46d*7s?| 5f!46d°7s*

,__REPRESENTATIVE __,
ELEMENTS

57 -138.91|
5g 140.12 59 140.91 | EQ 144.24 61 146.92] 69 1

C sod LANTHANDES =~ (La.

(4f 5d” '6s*) Lanthanum
=6|Ce
Cerium
|Pr_
Praseodymium
|Nd
| Neodymium
|Pm
Promethium
|Sm
Samarium

Br Liquid Sd'és?7| 46s? 4f6s2 4i6s2 4f>6s2 af

|H |Gas ACTIMIDES "eq. 227.03! qn “232.04 | q 4 | 03) QQ *237.05 |

Tc Synthetic (5f 6d" '7s°)

Actinium Thorium Protactinium Uranium Neptunium Plutonium

* Most stable isotope (discovery claimed) | 6d'7s* 6d°7s*| 5f*6d'7s* | 5f6d'7s° 5f*6d'7s* Bf
 BLE OF THE ELEMENTS
=o] oF —_

p — BLOCK (ns‘np'_)

Actinides

h metals Other metals

atals * Non-metals

. Noble gases

13 26

Al
58.933 28 58.693 29 63.546 | 30 65.39

Ni
Nickel
|Cu
Copper
{Zn Zinc Gallium Germanium

174s° 3d°4s* 3d'°4s' 3d'104s? | 3d'04s74p! |3d'04s74p?

102.91
46 106.42
47 107.87 |
48 112.41 £ :
51* 121.76

Palladium Siiver | Cadmium | Antimony

85s! 4d'0 4d'°5s' 4d'95s° 5p! | 4d'°Ss75p2 | 4d!95s75p

192.22 78 195.08 79 196.97 | 80 200.59

Pt
Platinum
Au
Gold |
(|Hg
Mercury

76s2) 4f145q%6s1 |4f145q1%Gs1 |4f145q19Gs2

110 2 1444 2721442 114 289
m
Ds (Rg |Cn
Darmstadtium | Rontgenium | Copernicium ve
FI
_ Teiwwessins Bigsiesson
"752 5f! 468752 Bf! 46d 1 7s | 5f! 46q! OF 62 Bf! 46q | "7577p! Bf!4eq' °75"7p° Bf"46q' 07s *76

f-BLOCK [(n—2)f 1-14

14 (n— td ° ns]
INNER TRANSITION ELEMENTS

Gadolinium iui | , | iun Lutetium

Af’5d'6s* Gs? . | if! 1652 fl : 2 | 4f'45d'6s*

| 100 957.18 ie

1 Americium Curium Berkelium Californium Einsteinium Fermium Lawrencium

fo7s5* 5f’7s*| 5f’6d'7s? 5197s? 5f1975? Bi 7s 5f'°752 5f'46d'7s2

 Atomic Masses (C'? = 12.00) and Electronic Configurations of Elements
Element Symbol Atomic Atomic Electronic Configuration
Number Mass
Actinium 89 227 [Rn]* 6d! 7s?
Aluminium 13 26.9 [Ne]!° 3s? 3p!
Americium 95 243 [Rn]® 5f7 7s?
[Kr}°6 4d19 5s? 5p?
Antimony 51 121.75
[Ne] 10 3s? 3p®
Argon 18 39.94
[Ar] 18 3q10 As? 4p3
Arsenic 74.92
Astatine 210 [Xe] 54 4fi4 5d 10 6s? 6p°

Barium 137.3 [Xe]®4 6s”

Berkelium 247 lin eee
Beryllium 9.01 [He]* 2s?
Bismuth 208.98 [Xe]54 Afit 5d!° 6s? 6p?

Boron 10.81 [He]°* 2s? 2p"

Bromine 79.90 [Ar]}8 3q10 4s? 4p®

Cadmium 112.40 [Kr}%6 4d} 5s?

[Ar] 15 As?
Calcium 40.02
Californium [Rn]°° 5f*° 7s?
Carbon [He]? 2s 2p?
[Xe] 4 4f! 5d} 6s2
Cerium
Cesium [Xe] 4 6s!
[Ne] 10 3s? 3p°
Chlorine
[Ar]! 3d5 Ag!
Chromium
[Ayr] 18 3d! As?
Cobalt
[Rn]8 5/14 6d?° 752
[Ar]}8 3q10 4g!
Copper
Curium lial a oo ee
[Xe]°4 4fi0 6s?
Dysprosium
Einsteinium [Rn]® 5/"? 75?
Erbium [Xe]®*f?6s?
Europium [Xe]®* 4/7 6s”
Fermium 1° 5f'? 79?
Flerovium Le
gts atl7 ealfaeae
Fluorine [He]? 2s? 2p°
Francium [Rn]* 7s!
Gadolinium [Xe]°4 4f" 5d! 6s?
SHR
OR“
RISK
SPPSRRBENVVGAS
SRR [Ar]}8 3q1° 4s? 4p!
[Ar]!® 3q10 As? 4p?
Germanium
Gold [Xe]54 4fi4 5d) 6s!

[Xe]°4 4/14 5d? 6s”

Hanium [Rn]™ a is
Helium ls
Holmium [Xe]>4 4fil 6s2

Hydrogen 1s!

Indium [Kr]26 441° 5s? 5p!

Iodine [Kr]26 41° 5s2 5p®
Iridium [Xe]54 4f14 5d? 6s?
Iron [Ar]!® 3d® 4s?
Krypton [Ar]}8 3q10 4s? 4p®

Lanthanum [Xe]°* 5d! 6s?

Lawrencium [Rn]*° 5f"* 6d* 7s?
Lead [Xe]54 4/14 5d10 Gs2 6p?
Lithium “BSASRISE-S°Ssuae
[He]? 1s?
[Rn] 86 5f'46d!7s27p4
Livermorium 116
Lutetium [Xe] 4 4fi4 5d! 6s2
[Ne]?° 352
EERE
BEES
RPORPRPRER
UP
ASR
GRR
SSEPE
EPPS
TE
PTA
PRR
PCRP
OPER
OSS [Ar]!® 3d° As?
 Element Symbol Atomic Electronic Configuration
Number
Mendelevium 101 [nl Sf is
Mercury [Xe] 54 4fi4 5d19 Gs?

Molybdenum [Kr]6 Ad® 5s!

Moscovium llo [Rn]®6 5/14 6d!° 7s? 7p3

Neodymium [Xe]°* 4f* 6s?
Neon 10 [He]? 2s? 2p®
Neptunium [Rn] 5* 6d" Ts*
Nickel ES
SASSER
AG [Ar] 18 3d8 As?

Nihonium 113 [Rn]® 5/14 6d!° 7s? 7p}

Niobium [Kr]*6 4d‘ 5s1

Nitrogen [He]? 2s? 2p*

Nobelium [Rn]°° 5f** 7s*
Oganesson [Rn]*° 5f14 6d?° 7s? 7p®
Osmium [Xe] 54 4fi4 5d® 6s?

Oxygen [He]? 2s? 2p*

Palladium [Kr]*° 4d"
Phosphorus [Ne]*° 3s* 3p°
Platinum [Xe]°* 4f14 5d? 6s!
Plutonium ln” 6" 73"
Polonium [Xe] 4 4fi4 5d)° Gs? 6p*

Potassium [Ar] 18 Agl

Praseodymium [Xe]°* 4f° 6s?

Promethium [Xe]°* 4° 6s?
Protactinium [Rn]® 5/2 6d! 7s?
Radium [Rn]® 7s?
Radon [Xe]>4 4fi4 5d! 6s? 6p®

Rhenium [Xe] 4 4fi4 5d® 6s2

[Kr]36 4d? 5s1
Rhodium
Rubidium [Kr]*° 5s?
Ruthenium [Kr]? Ad’ 5sl

Rutherfordium [Rn]*° 5f"* 6d* 7s*

Samarium [Xe]°* 4° 6s?
[Ar]!® 3d! As?
Scandium
[Ar]!® 3d19 4s? 4p4
Selenium
Silicon [Ne]*° 3s* 3p?
ZAZA
ZAC
BODO
eV
DUPE
BER
ERR
OOM
Z
[Kr]? 4d'° 5s!
Silver
[Ne]?° 351
Sodium
Strontium [Kr]*° 5s?
Sulphur [Ne]*° 3s* 3p*
Tantalum [Xe] 4 4fi4 5d 3 6s?
[Kr]36 4d ® 5s?
Technetium
[Kr]? 4d) 5s2 5p*
Tellurium
[Rn]® 5fi4 6d1° Ts? Tp°
Tennessine 117
Terbium [Xe]°* 4f° 6s?
[Xe] 4 Afi4 5d!9 6s? 6 p}

Thorium [Rn]°° 6d? 7s?

Thulium [Xe]>4 4fis 6s2

Tin [Kr]? 4d) 5s2 5p?

[Ar]}8 3d? As?
Titanium
Tungsten [Xe]°* 4/14 5d* 6s”
Uranium [Rn]® 5/2 6d! 7s?
[Ar]}8 3d3 As?
Vanadium
Xenon [Kr]? 4q10 5s2 5p®

Ytterbium [Xe]>4 4fi4 6s?

Yttrium [Kr]? 4d} 5s?

Alnc poe
area
Pras
P<ee<Caen [Ar]}8 3q10 As?

Zirconium NON
4 SSSSRFSRENSSSZSE [Kr]? 4d? 5s?
 Modern’s abc+ of Chemistry (XI & XII) was awarded
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Useful Relations

Tt = 3.1416 InX = 2.303 log X 2.303 RT/F = 0.05916 V

e = 2.71828 2.303 RT = 5709 J mol (at 25°C)
(at 25°C)

Selected Greek letters Some Useful Conversion Factors

1000 gram
10 decigram
100 centigram
& 1000 milligram
1 dm? = 10? cm?
1.6022 x 107° J
4.184 J = 4.184 x 10’ erg
10’ erg
> 24.217 cal = 101.32 J

om
S3
fb
ze
YFP
Be
tT
a 10° cm = 10° m= 0.1 nm
760 mm Hg
1.013 < 10° pascals
10° pascals

Quantity

Speed of light 2.9979 x 108 ms”

Atomic mass unit 1.6606 x 107 kg

Avogadro constant 6.022 x 10” mol”

Planck constant 6.6262 x10“ Js
Faraday constant 9.64846 x 104C mol"
Boltzmann constant 1.3807 x 10°? JK"
Charge-to-mass ratio of electron 1.7588 x 10" C kg?
Electronic charge 1.60219 x 10°" C
Gas constant 8.314J mol K"
Molar volume (STP) 22.414 x 10° m? mol
22.414 dm? mol"
Mass of electron 9.10953 x 10°! kg
Mass of proton 1.67265 x 10°" kg
Mass of neutron 1.67495 x 10°" kg
Rydberg constant 1.096 x 107 m7
 SYLLABUS
(THEORY)
* ——— 1 ioe

Time :3 Hours 70 Marks

UNIT Title No. of Periods Marks
I. Solid State 10
II. Solutions 10
II. Electrochemistry 12 Zz
IV. Chemical Kinetics 10
V. Surface Chemistry 08
VI. General Principles and Processes of Isolation of Elements 08
VII. p-Block Elements 12 "
VII. d-andf-Block Elements 12 |
IX. Coordination Compounds 12
X. Haloalkanes and Haloarenes 10
XI. Alcohols, Phenols and Ethers 10
XII. Aldehydes, Ketones and Carboxylic Acids 10
XIII. OrganicCompounds Containing Nitrogen 10 28
XIV. Biomolecules 12
XV. Polymers 08
XVI. Chemistry in Everyday Life
Total 70
Unit I: Solid State (Periods 10)
e Classification of solids based on different binding forces: molecular, ionic, covalent and metallic solids,
amorphous and crystalline solids (elementary idea). Unit cell in two dimensional and three dimensional
lattices, calculation of density of unit cell, packing in solids, packing efficiency, voids, number of atoms
per unit cell ina cubic unit cell, point defects, electrical and magnetic properties.
Band theory of metals, conductors, semiconductors and insulators, and n-and p-type semiconductors
Unit II: Solutions (Periods 10)
e Types of solutions, expression of concentration of solutions of solids in liquids, solubility of gases in
liquids, solid solutions, colligative properties — relative lowering of vapour pressure, Raoult's law,
elevation of boiling point, depression of freezing point, osmotic pressure, determination of molecular
masses using colligative properties, abnormal molecular mass, Van't Hoff factor.
Unit III: Electrochemistry (Periods 12)
e Redox reactions; conductance in electrolytic solutions, specific and molar conductivity variations of
conductivity with concentration, Kohlrausch’s Law, electrolysis and laws of electrolysis (elementary
idea), dry cell—electrolytic cells and Galvanic cells; lead accumulator, EMF of a cell, standard electrode
potential, Nernst equation and its application to chemical cells, relation between Gibb's energy change
and emf of acell, fuel cells, corrosion.
Unit IV: Chemical Kinetics (Periods 10)
Rate of a reaction (average and instantaneous), factors affecting rates of reaction: concentration,
temperature, catalyst; order and molecularity of a reaction; rate law and specific rate constant,
integrated rate equations and half-life (only for zero and first order reactions); concept of collision
theory (elementary idea, no mathematical treatment) Activation energy, Arrhenius equation.
Unit V: Surface Chemistry (Periods 8)
Adsorption — physisorption and chemisorption; factors affecting adsorption of gases on solids;
catalysis, homogeneous and heterogeneous activity and selectivity, enzyme catalysis, colloidal state
distinction between true solutions, colloids and suspensions; lyophillic, lyophobic, multi-molecular
and macromolecular colloids; properties of colloids; Tyndall effect, Brownian movement,
electrophoresis, coagulation; emulsions — types of emulsions.
Unit VI: General Principles and Processes of Isolation of Elements (Periods 8)
Principles and methods of extraction—concentration, oxidation, reduction : electrolytic method and
refining; occurrence and principles of extraction of aluminium, copper, zinc and iron.
Unit VII: Some p-Block Elements
(Periods 12)
Group 15 elements : General introduction, electronic configuration, occurrence, oxidation states,
trends in physical and chemical properties; Nitrogen preparation properties and uses; compounds of
nitrogen, preparation and properties of Ammonia and Nitric Acid, Oxides of Nitrogen (Structure
only); Phosphorus—allotropic forms; compounds of Phosphorus: Preparation and Properties of
phosphine, halides and Oxoacids (elementary idea only).
Group 16 elements : General introduction, electronic configuration, oxidation states, occurrence,
trends in physical and chemical properties, Dioxygen: preparation, properties and uses; classification
of oxides; Ozone. Sulphur-dioxide, Sulphur — allotropic forms; compounds of sulphur: preparation,
properties and uses of sulphuric acid: industrial process of manufacture, properties and uses;
Oxoacids of Sulphur (Structures only).
Group 17 elements : General introduction, electronic configuration, oxidation states, occurrence,
trends in physical and chemical properties; compounds of halogens: Preparation, properties and uses
of Chlorine and hydrochloric acid, interhalogen compounds, Oxoacids of halogens (structures only).
Group 18 elements : General introduction, electronic configuration, occurrence, trends in physical
and chemical properties, uses.
Unit VIII: d and f-Block Elements (Periods 12)
® General introduction, electronic configuration, occurrence and characteristics of transition metals,
general trends in properties of the first row transition metals — metallic character, ionization enthalpy,
oxidation states, ionic radii, colour, catalytic property, magnetic properties, interstitial compounds,
alloy formation. Preparation and properties of K,Cr,O, and KMnQ,.
Lanthanoids - Electronic configuration, oxidation states, chemical reactivity and lanthanoid
contraction and its consequences.
Actinoids-— Electronic configuration, oxidation states and comparison with lanthanoids.
Unit IX: Coordination Compounds (Periods 12)
® Coordination compounds — Introduction, ligands, coordination number, colour, magnetic properties
and shapes, IUPAC nomenclature of mononuclear coordination compounds, bonding; Werner's
theory, VBT, CFT, structure and stereoisomerism, importance of coordination compounds (in
qualitative analysis, extraction of metals and biological systems).
Unit X: Haloalkanes and Haloarenes (Periods 10)
Haloalkanes: Nomenclature, nature of C-X bond, physical and chemical properties, mechanism of
substitution reactions, optical rotation.
Haloarenes: Nature of C-X bond, substitution reactions (Directive influence of halogen for
monosubstituted compounds only).
Uses and environmental effects of dichloromethane, trichloromethane, tetrachloromethane,
iodoform, freons, DDT.
Unit XI: Alcohols, Phenols and Ethers (Periods 10)
Alcohols : Nomenclature, methods of preparation, physical and chemical properties (of primary
alcohols only); identification of primary, secondary and tertiary alcohols; mechanism of dehydration,
uses, with special reference to methanol and ethanol.
Phenols : Nomenclature, methods of preparation, physical and chemical properties, acidic nature of
phenol, electrophillic substitution reactions, uses of phenols.
Ethers : Nomenclature, methods of preparation, physical and chemical properties, uses.
Unit XII: Aldehydes, Ketones, Carboxylic Acids (Periods 10)
@ Aldehydes and Ketones : Nomenclature, nature of carbonyl group, methods of preparation, physical
and chemical properties, mechanism of nucleophilic addition, reactivity of alpha hydrogen in
aldehydes, uses.
Carboxylic acids : Nomenclature, acidic nature, methods of preparation, physical and chemical
properties; uses.
Unit XIII: Organic Compounds Containing Nitrogen (Periods 10)
Amines : Nomenclature, classification, structure, methods of preparation, physical and chemical
properties, uses, identification of primary, secondary and tertiary amines.
Cyanides and Isocyanides-will be mentioned at relevant places in text.
Diazonium salts : Preparation, chemical reactions and importance in synthetic organic chemistry.
Biomolecules (Periods 12)
Carbohydrates — Classification (aldoses and ketoses), monosaccharides (glucose and fructose), D - L
configuration oligosaccharides (sucrose, lactose, maltose), polysaccharides (starch, cellulose,
glycogen) importance of carbohydrates.
Proteins — Elementary idea of - amino acids, peptide bond, polypeptides, proteins, structure of
proteins - primary, secondary, tertiary structure and quaternary structure (qualitative idea only),
denaturation of proteins, enzymes, Hormones - Elementary idea excluding structure.
Vitamins — Classification and functions.
Nucleic Acids: DNAand RNA.
Unit X : Polymers (Periods 8)
Classification — Natural and synthetic, methods of polymerization (addition and condensation),
copolymerization. Some important polymers: natural and synthetic like polythene, nylon, polyesters,
bakelite, rubber; Biodegradable and non-biodegradable polymers.
Unit XVI: Chemistry in Everyday Life (Periods 6)
a Chemicals in medicines — analgesics, tranquilizers, antiseptics, disinfectants, antimicrobials,
antifertility drugs, antibiotics, antacids, antihistamines.
Chemicals in food—preservatives, artificial sweetening agents, elementary idea of anti - oxidants.
Cleansing agents —soaps and detergents, cleansing action.
 CONTENTS/
PART-I

o'
1

ni Solid State* 1/1 — 1/104

2. Solutions 2/1 — 2/131

3. Electrochemistry 3/1 — 3/130

4. Chemical Kinetics 4/1 — 4/129

5. Surface Chemistry 5/1 — 5/80

6. General Principles and Processes of Isolation of Elements 6/1 — 6/61

1 p-Block Elements* 7/162

8. d- and f-Block Elements 8/1 — 8/86

9. Coordination Compounds 9/1 — 9/105

e Hints and Solutions to Unit Practice Tests S-1 -S-8

e Log Tables 1—Vvi

* This chapter has been moved to Class XI by CBSE

* Topic Group 15 in this chapter has been moved to Class XI by CBSE
 SOLID STATE

Building on..... Assessing..... Preparing for Competition.....

@ Understanding Text 1 @ Quick Memory Test with @ Additional Useful Information 79
Conceptual Questions 30, 65 Answers 69 #@ Topicwise MCQs 81
¢@ Advanced Level Problems 32 @¢ HOTS & Advance Level Competitive Examination Qs
41,48 Question with Answer. 71 =» AIPMT & Other State Boards’
SOLUTION FILE REVISION EXERCISES Medical Entrance 83
@ Hints & Solutions for Practice (with Previous Years’ CBSE Qs > JEE (Main) & Other State
Problems 57 & Other State Boards Qs) 72 Boards’ Engineering Entrance 84.
CHAPTER SUMMARY & QUICK ¢ Hints & Answers for Revision » JEE (Advance) for ITT Entrance
CHAPTER ROUND UP 61 Exercises 77 86
NCERT FILE @ NCERT Exemplar Problems
@ In-text Qs & Exercises with (Objective Questions) 92
Solutions 64 a | | Hints & Explanations for
@ NCERT Exemplar Problems with UNE te ane Difficult Questions 97
Answers & Solutions (Subjective) 68

The solids are the substances which have definite volume and definite
shape. |n terms of kinetic molecular model, solids have regular order of
their constituent particles (atoms, molecules or ions). These particles
are held together by fairly strong forces, therefore, they are present at
fixed positions. The properties of the solids not only depend upon
the nature of the constituents but also on their arrangements and
the types of forces which hold the constituent particles together
in a tightly packed arrangement.
The solids are rigid and maintain their own shape when subjected
to outside force. On the other hand, liquids and gases change their
shapes in response to outside forces. Therefore, liquids and gases
are called fluids because of their ability to flow. The fluidity of
liquids and gases is due to the fact that their constituent particles
are free to move about. On the other hand, the rigidity of the solids
is because their constituent particles have fixed positions and can
only oscillate about their mean positions.
GENERAL CHARACTERISTICS OF SOLID STATE
As we have learnt that matter can exist in three different physical
states namely solid, liquid, and gas. Under a given set of conditions of
temperature and pressure, the most stable state of a substance depends upon
the net effect of two opposing forces; intermolecular forces and thermal energy.
Intermolecular forces tend to keep the constituent particles (atoms, ions or molecules) closer whereas thermal energy
tends to keep them apart by making them move faster. The competition between molecular interaction energy due
to intermolecular forces and thermal energy determines whether a given substance under given set of conditions
is a gas, a liquid or a solid. At sufficiently low temperature, the thermal energy is low and molecular forces are
very strong. As a result, the intermolecular forces keep the constituents so close that they cling to one another and
occupy fixed positions and the substance exists in solid state.
 MODERN'’S abc + OF CHEMISTRY
-XII

Three states of matter arise due to Some of the important characteristic properties of solids are :
competition between (4) Solids have definite mass, volume and shape.
@ Intermolecular forces: The forces (11) The intermolecular distances in solids are short and intermolecular
of attraction and repulsion between forces are strong.
particles (atoms or molecules). (iit) The constituent particles (atoms, ions or molecules) of solids have
e Thermal energy: Energy possessed fixed positions and can only oscillate about their mean positions.
by the particles due to temperature (tv) Solids are almost incompressible and rigid.
which tend to make them move. (v) The density of solids is greater than that of liquids and gases.
Predominance of intermolecular (vi) Solids diffuse very slowly as compared to liquids and gases.
forces results into change of gaseous (vit) Most solids become liquids when heated. This process is known as
to liquid to solid state melting and the temperature at which a solid changes into a liquid
Gas = Liquid = Solid is called the melting point. The melting point of a solid depends
Predominance of thermal energy upon the nature of the solid and melting points of solids vary widely.
results into change of solid to liquid
to gas CLASSIFICATION OF SOLIDS
Solid = Liquid =» Gas Solids can be classified on the basis of nature of order present in the
arrangement of constituent particles (atoms,ions or molecules) intotwo types as:
The constituent particles in 1. Crystalline solids
the solid state have no translatory 2. Amorphous solids
motion and can only oscillate 1. Crystalline solids
about their mean positions. The substances whose constituent particles (atoms, ions or molecules)
Therefore, the solids can have are arranged in a definite geometric pattern in three dimensional
only vibratory motion. space are called erystalline solids.
X-ray diffraction studies of crystalline solids reveal that in these solids,
the constituents (atoms, ions or molecules) are arranged in a definite orderly
arrangement. The regular arrangement of the constituents extends throughout
the three dimensional network of crystals. In other words, the crystalline
substances are said to have long range order. This means that in crystalline
solids, there is a regular pattern or arrangement of particles which repeats
itself periodically over the entire crystal. In fact, a crystalline solid consists of
a large number of small crystals, each of them having a definite characteristic
geometrical shape.
Most of the substances (elements and compounds) form crystalline solids.
For example, the elements like copper, silver, iron, sulphur, phosphorus and
iodine and common compounds such as sodium chloride, potassium nitrate,
zine sulphide, quartz, etc. all form crystalline solids.
2. Amorphous solids
The substances whose constituent particles are not arranged in any
regular arrangement are called amorphous solids (Greek amorphos
meaning no form).
The amorphous solids have a random, disordered arrangement of
constituents. Therefore, they do not have definite shape or form like crystalline
solids. Itis observed that some amorphous solids have some orderly arrangement
but it is not extended to more than a few Angstrom units. Thus, the amorphous
solids are said to have short range order. This means that in amorphous
solids, a regular and periodically repeating pattern is observed over short
distances only. These regular patterns are scattered and in between, the
arrangement is disordered.
The common examples of amorphous solids are glass, rubber, plastic, coal etc.
Differences between Crystalline and Amorphous solids
The important differences between crystalline and amorphous solids are :
1. Characteristic geometry. The crystalline solids have definite regular
geometry because of orderly arrangement of constituents (atoms, molecules or
ions) in three dimensional space. On the other hand, amorphous solids do not
possess any regular arrangement of constituent particles and therefore, do
not have any definite geometric shape.
SOLID STATE

Structure of quartz (crystalline) and quartz glass (amorphous)

Quartz is a form of SiO, (silica). It has tetrahedral S10, units which are orderly
arranged in crystalline quartz as shown in Fig. 1 (a). In this arrangement, Pseudo solids or Super cooled
S10, tetrahedra are connected to one another such that oxygen atom of each liquids
S10, tetrahedral is shared with another atom. When S10, is melted and Like liquids, amorphous solids have a
the melt is cooled, it forms quartz glass which is amorphous. In this state, tendency to flow. Therefore, sometimes
the Si0, units are randomly joined [Fig 1 (6)]. Thus, in quartz (crystalline), these are also called pseudo solids
S10, units are orderly arranged while in quartz glass (amorphous), the Si0, or super cooled liquids. Glass is
units are randomly arranged. While the two structures are almost identical, a common example of pseudo solid.
yet in case of amorphous quartz glass, there is no long range order. The It softens on heating to a certain
structure of amorphous solids is similar to that of liquids. temperature. It behaves more or less
like a fluid. Pitch is another example
of pseudo solid.
Thus, the pseudo solids possess the
following characteristics :
(z) They do not have sharp melting
point but soften over a range of
temperature.
(11) They can be easily distorted by
applying force.
(11) They can flow slowly under their
own weight and lose shape.

(a) Crystalline quartz

Fig.1. Two dimensional structure of (a) crystalline quartz and (}) quartz glass.

2. Melting points. The crystalline solids have sharp melting points. On

R U Curious...%
the other hand, amorphous solids do not have sharp melting points. Therefore,
crystalline solids have definite enthalpies of fusion whereas amorphous solids 0 Glass window panes of very
do not have definite enthalpies of fusion. The amorphous solids, in fact, on old buildings are found to
heating first soften and then melt over a range of temperature. Therefore, be slightly thicker at the
amorphous solids can be moulded and blown into various shapes. For example, bottom than at the top.
when glass is heated gradually, it softens and starts to flow without undergoing >» Glass is an amorphous solid which
a definite and abrupt change into liquid state. Therefore, glass can be moulded is super cooled liquid of very high
and given any desired shape. viscosity and behaves more or less
like a liquid. The glass flows down
It has been observed that on heating and then cooling slowly (i.e., annealing) very slowly and hence makes the
some amorphous solids become crystalline at some temperature. It is for this bottom portion slightly thicker.
reason that some glass objects from ancient civilizations are found to
become milky in appearance. Milkiness of glass is due to the fact that it
undergoes heating during the day and cooling at night (1.e., annealing) over
a number of years. As a result, it acquires some crystalline character.
3. Isotropy and anisotropy. In crystalline substances, some of the
physical properties such as electrical conductivity or refractive index have
different values when measured along different directions in the same
crystals. Such substances which have physical properties different in
different directions are called anisotropic. Thus, crystalline substances
are anisotropic.
On the other hand, amorphous substances have physical properties
same in all directions and are called isotropic. For example, the velocity
of light passing through a crystal varies with the direction in which it is
measured. Thus, anisotropy is a strong evidence for the existence of orderly
arrangement in crystalline solids. This is shown in Fig 2. In this figure,
a simple two dimensional arrangement of two different kinds of atoms is
shown. It is clear from the figure that if the properties are measured along
two different directions AA’ and BB’, different types of particles come on the Fig. 2. Anistropy in crystalline
way. Along AA’ direction only one type of particles come on the way while substances.
 MODERN'’S abc + OF CHEMISTRY
-XII

REMEMBER along BB’ direction, alternate types of particles come on the way. Hence, the
crystalline solids have different physical properties in different directions. In
The substances which show same amorphous solids, the constituent particles are arranged at random and in
physical properties (electrical
disorderly manner and therefore, all directions are identical and all properties
conductivity, thermal conductivity,
are same in all directions.
refractive index, etc.) in all
directions are called isotropic
4, Cleavage. Crystalline solids can be cleaved along definite planes.When
substances. cut with a sharp edged tool (e.g. knife) they split into two pieces and the newly
The substances which show generated surfaces are plain and smooth. On the other hand, amorphous solids
different physical properties cannot be cleaved along definite planes. When cut with a sharp edged tool
(electrical conductivity, thermal (e.g., knife) they undergo irregular breakage and split into two pieces with
conductivity, refractive index, etc.) irregular surfaces. This is shown in Fig 3.
in different directions are called
anisotropic substances.
Crystalline substances exhibit
anisotropy while amorphous
substances exhibit isotropy.
Liquids and gases are also
isotropic.

(a) Crystalline solid undergoes (b) Amorphous solid undergoes irregular

a clean cleavage cleavage

Fig. 3. Cleavage of (a) crystalline and (5) amorphous solid

The important differences between crystalline solids and amorphous solids

are summed up below :
Table 1. Distinction between crystalline and amorphous solids.

Crystalline solids Amorphous solids

The crystalline solids have definite characteristic shape. | The amorphous solids have irregular shapes.
2. Order in They have regular arrangement of the constituent | They donot have any regular arrangement of
arrangement of | particles. They are said to exhibit long range order. the constituent particles. They may have short
constituent range order.
particles.
3. Melting point They have sharp and characteristic melting point. They donot have sharp melting point. They
gradually soften over a range of temperature.
4. Enthalpy of They have a definite and characteristic enthalpy of fusion. They donot have definite enthalpy of fusion.
fusion
5. Cleavage When cut with a sharp edged tool, they split into two pieces When cut with a sharp edged tool they cut
property and the newly generated surfaces are plain and smooth. into two pieces with irregular surfaces.
6. Anisotropy They are anisotropic and have different physical properties They are isotropic and have same physical
in different directions. properties in all directions.
7. Nature They are true solids They are pseudo solids and supercooled liquids.
Common Copper, silver, iron, common salt, zinc suphide, potassium Glass, rubber, plastics, etc.
examples nitrate, etc.

Uses of Amorphous Solids

Amorphous solids such as glass, rubber, plastic, etc. find many uses in
our daily lives because of their unique characteristics. For example,
(4) The most widely used amorphous solids are inorganic glasses which
are used in construction, houseware, laboratoryware, etc.
(it) Amorphous silicon is the best photovoltaic material for converting
the sunlight into electricity (in photovoltaic cells).
(iit) Rubber is also an amorphous solid which is used in making tyres,
shoe soles, etc.
(iv) A large number of plastics which are amorphous solids are used in
making articles of daily use.
SOLID STATE

CLASSIFICATION OF CRYSTALLINE SOLIDS

The crystalline solids can be classified into following four types depending
upon the nature of intermolecular forces operating in them.
e It may be noted that some
1. Molecular solids 2. Ionic solids
substances adopt different structural
3. Metallic solids 4, Covalent or network solids arrangements under different
1. Molecular solids conditions. Such arrangements
These are crystalline substances in which the constituent particles are called polymorphs (meaning
are molecules. The molecules are held together by dispersion forces or London many forms). For example, diamond
forces, dipole-dipole forces or hydrogen bonds. These are further subdivided and graphite are two different
into the following categories : polymorphic forms of carbon.
(a) Non-polar molecular solids. These are those crystalline substances in Polymorphic forms are also called
which the constituent particles are either atoms like those of noble gases (helium, allotropes. These different
neon, argon, etc.) or non-polar molecules. For example, solid helium, solid argon, structures have different properties
solid hydrogen, solid carbon dioxide, iodine, etc. In these solids, the atoms or such as melting point, density, etc.
molecules are held by weak dispersion forces or London forces. These solids have For example, as we know, graphite
the following characteristics: is soft and a good conductor of
(1) They are generally soft. electricity while diamond is hard
(it) They have low melting points. and a poor conductor of electricity.
(iit) They are usually in liquid or gaseous state at room temperature and Isomorphism and Polymorphism
pressure. e The existence of two or more
(iv) They are non-conductors of electricity because they consist of neutral crystalline solids having similar
molecules in solid as well as in dissolved state. chemical composition in the same
(6) Polar molecular solids. These comprise of molecules of substances erystalline form or structure
formed by polar covalent bonds. For example, solid HCl, solid SO,, solid NH,, is called isomorphism (iso—
etc. The molecules in such solids are held together by relatively stronger same, morphous—form). For
dipole- dipole forces. They have characteristics similar to non-polar covalent example, Na,PO, and Na,AsO,
molecules as given below : are isomorphs.
(4) These solids are also soft. The existence of a particular
(ii) They are non-conductors of electricity. substance in more than one
erystalline forms is called
(iit) They have low melting and boiling points. But their melting and
polymorphism. For example,
boiling points are higher than those of non-polar molecular solids.
calcium carbonate exists in two
(iv) Because their melting and boiling points are not very high, most crystalline forms known as calcite
of these are gases or liquids under room temperature and pressure and aragonite.
conditions.
Q In case of elements, polymorphism
(ec) Hydrogen bonded molecular solids. The molecules of such solids
is also called allotropy.
contain hydrogen bonds between them. For example, in case of solid water (ice),
the negative end of one molecule (O°) attracts the positive end of a neighbouring
molecule (H**) forming hydrogen bond between O and H. These solids contain
Force of attraction
hydrogen bonds between H and highly electronegative elements; F, O or N.
= ==
=a
These solids have the following characteristics :
*)
|

(4) They are generally volatile liquids or soft solids under room ™

temperature and normal pressure conditions.

tae
= = = a
sl ™ =
fr > $5§ we
/ -=
a
(ii) They are non-conductors of electricity. Momentary dipole
(iit) Their melting and boiling points are generally higher than those of in He atom in He atom

non polar molecular solids and polar molecular solids. Weak dispersion or London forces
2. Ionic Solids in solid He
fonic solids consist of positively and negatively charged ions arranged in a
regular manner throughout the solid. The ions are held together by strong
coulombic (or electrostatic) forces. Thus, in ionic solids, the constituent particles
are 10ns.
The regular arrangement of ions extends continuously throughout the
crystal. For example, in sodium chloride, Na* and Cl ions have a definite
regular arrangement as shown in Fig. 4. In this arrangement, each Na’* is
surrounded by six Cl ions and each Cl is surrounded by six Nat ions. Similar
regular arrangements are also observed in other ionic solids. The main
characteristics of ionic crystals are :
Dipole — dipole forces in solid HCl
(4) Ionic solids are very hard and brittle.
(it) They have very high melting and boiling points.
 MODERN'’S abc + OF CHEMISTRY
-XII

(iit) They are poor conductors of electricity and, therefore, are insulators
in solid state. This is because in the solid state, the ions are not free
to move about. However, in the molten state or when dissolved in
water (aqueous solution), the ions become free to move about and
they conduct electricity.
(iv) They have high enthalpies of vaporisation.
(v) Ionic crystals are soluble in water and also in other polar solvents.
They are insoluble or very slightly soluble in non-polar solvents such
as benzene, carbon tetrachloride, carbon disulphide.
The common examples of ionic crystals are : salts like NaCl, KNO,, LiF,
Na,SO,, ete.
3. Metallic solids or crystals
In metallic crystals, the constituent particles are positive tons (called kernels)
Fig. 4. Structure of sodium chloride. immersed in a sea of mobile electrons. This is shown in Fig. 5. The electrons
in metallic crystals are mobile and are evenly spread throughout the crystal.
Sea of electrons Each metal atom contributes one or more electrons towards this sea of mobile
electrons. These free mobile electrons are responsible for high electrical and
Kernel thermal conductivities of metals. When electric field is applied, these electrons
flow through the network of positive ions (called kernels). Similarly, when
heat is supplied to one portion of a metal, the thermal energy is uniformly
HOU0NNO
IDIPTTE Lt
Il
IVUDNNOTONM DIVTENTT
HindeENat
FEM spread throughout the crystal by free electrons. The forces present between
the metal ions are metallic bonds. The main characteristics of metallic
crystals are:
(4) Metallic crystals may be hard as well as soft.
(ii) They are good conductors of heat and electricity.
(iit) They have metallic lustre and colour in certain cases.
(iv) They are malleable and ductile. Due to malleable nature, they can
be beaten into sheets and drawn into wires.
(v) They have moderate enthalpies of fusion.
The examples of metallic crystals are common metals such as nickel,
copper and alloys.
Fig. 5. Electron sea model for a metal. 4. Covalent or network solids or crystals
In covalent crystals, the constituent particles are non-metal atoms which are
linked to the adjacent atoms by covalent bonds throughout the erystal. In
other words, there is a continuous network of covalent bonds forming a giant
three dimensional structure. They are also called giant molecules. Covalent
bonds are strong and directional in nature and therefore, atoms in these
solids are held very strongly at their positions. The important characteristics
of covalent crystals are :
(1) The covalent crystals are hard.
(it) They have extremely high melting points and may even decompose
before melting.
(iit) They are poor conductors of electricity and are insulators.
The common examples of covalent crystals are : diamond, carborundum
(silicon carbide), quartz (Si0,), boron nitride (BN), ete.
Diamond is atypical example of covalent crystal. It has a network structure
consisting of a very large number of carbon atoms bonded to each other. Each
carbon atom is bonded to four other carbon atoms by single covalent bonds. It
is clear from Fig. 6 (a), that each carbon atom lies at the centre of a regular
tetrahedron and the other four carbon atoms are present at the corners of the
tetrahedron. Therefore, there is a three dimensional network of strong covalent
bonds. This makes diamond an extremely hard crystal with very high melting
point (8843 K). Since all the valence electrons of carbon are strongly held in
carbon-carbon bonds, diamond ts a poor conductor of electricity.
Graphite is also a covalent solid but it is soft and a good conductor of
electricity. Its exceptional properties are due to its typical structure as
shown in Fig. 6 (b).
In graphite, carbon atoms are arranged in different layers consisting of
hexagonal rings. In these layers, each carbon atom is covalently bonded to three
SOLID STATE

other neighbouring carbon atoms by single covalent bonds in the same layer.
The fourth valence electron of each carbon atom is present between different R U Curious...%
layers and is free to move about. Because of the presence of free electrons,
graphite is a good conductor of electricity. Further, the different layers are > Graphite is a good conductor
separated by a large distance (340 pm), which is greater than carbon-carbon of electricity, though it is a
bond length. This suggests that only weak van der Waals forces are present non-metal.
between these layers and therefore, these layers can slide one over the other. 4) Graphite is a covalent solid but
This makes graphite a soft solid and a good solid lubricant. it ig soft and a good conductor
of electricity. Its exceptional
behaviour is because ofits typical
structure having 1-delocalised
electrons in hexagonal rings
which are free to move.

In diamond, each carbon atom

is sp® hybridised.
In graphite, each carbon atom
is sp* hybridised.

(a) Diamond (6) Graphite

Fig. 6. Structure of (a) diamond and (5) graphite

The main characteristics of various types of crystals are summed up in

Table 2.
Table 2. Summary of the characteristics of various types of solids
Physical properties
Constituent Bonding/ Physical] Melting | Approx Electrical conductivity
particles attractive
forces

1. Molecular Small covalent

molecules Less than 40] Insulators
(i) Non-polar Non polar mole- Dispersion or Solid CO,, argon,
cules or atoms London forces Boi Cok Ca,
of noble gases
(ti) Polar Polar molecules Dipole- dipole HCl, SO,
interactions
(iii) Hydrogen Molecules cont- Hydrogen Ice (HO)
bonded aining H bonded bonding
to F, O or N
2. Tonic solids Positive and trong electro- NaCl, MgO, BaO, Very high ~—400—4000 | Insulators in solid state
negative ions static or coulombic CaF, 2nS, KCl, (~ 1500K) but conductors in molten
forces BaSO,, LiF state and in aqueous
solution.
3. Metallic Positive ions in Metallic bonding Common metals Moderate to J 70-1000 Good conductors of heat
solids a sea of deloca- [electric attraction (Cu, Ag, Fe, Mg) and electricity
lized electrons between kernels and some alloys
(positive ions) and
electrons]
4, Covalent Covalent (electron Quartz (Si0,) 150-500 Insulators
or network sharing ) bonding niC, diamond (C) (except graphite which
solids AIN is conductor)
graphite (C)
 MODERN’S abc + OF CHEMISTRY
-XII

SOLVED EXAMPLES

Example 1 LJ EKxample 2
Classify the following as amorphous or crystalline Classify the following solids as tonic, metallic,
solids : molecular, network (covalent) or amorphous :
(1) Naphthalene (it) Teflon (111) Polyurethane (i) Tetraphosphorus decaoxide (P,O,,) (u) Graphite
(iv) Benzoic acid (v) Potassium nitrate (vi) Cellophane (tit) SiC (tv) Brass (v) Rubidium (vi) [, (vii) Ammonium
(vit) Polyvinyl chloride (viit) Fibre glass (ix) Copper phosphate, (NH,),PO, (vii) LiBr io Si (x) Plastics
(x) Zine sulphide N.C (xi) P, (xtt) Solid CO,.
Solution: Solution: The solids are classified as:
Amorphous solids: (ii) Teflon (iit) Polyurethane Ionic : (NH,),PO,, LiBr
(vt) Cellophane (viz) Polyvinyl chloride (viii) Fibre glass Metallic : Brass, Rubidium
Crystalline solids: (:) Naphthalene (iv) Benzoic acid Molecular : P,O,,,1,,
4 10?
P,, solid CO,
(v) Potassium nitrate (ix) Copper (x) Zinc sulphide. Network (covalent) :Graphite, SiC, Si
Amorphous : Plastics.

CRYSTAL LATTICE OR SPACE LATTICE AND UNIT CELL

The crystalline solids have definite orderly arrangement of their constituent
particles in three dimensions. The positions of these particles in a crystal,
relative to one another, are usually shown by points. The arrangement of
an infinite set of these points is called space lattice. The positions which
are occupied by the atoms, ions or molecules in the crystal lattice are called
lattice points or lattice sites.
To understand space lattice, let us first learn about two dimensional
lattices and then three dimensional lattices.
A. Two Dimensional Lattices
A two dimensional lattice is a regular arrangement of constituent
particles (atoms, ions or molecules) in a plane. A two dimensional pattern is
shown in Fig. 7 (a) and the lattice is shown by points in Fig. 7 (0)

There are five types of two dimensional lattices. These are, square,
rectangular, parallelogram, rhombic and hexagonal lattice as shown in Fig. 8.
These differ in symmetry of the arrangement of points. The hexagonal lattice
has the most symmetrical arrangement of points while parallelogram lattice
(b) Lattice points has the least symmetrical arrangement of points.
Fig. 7. Two dimensional pattern

(a) Square lattice (b) Rectangular (c) Parallelogram (d) Rhombic lattice, (e) Hexagonal
lattice lattice Rectangular with lattice
interior point

Fig. 8. Five different two dimensional lattices.

SOLID STATE

Because of the regular repeating arrangement of the points in a two

dimensional lattice, we need only to describe a small part of the lattice (called
motif) in order to specify it completely. For example, we select four points
in two dimensional lattice and connect them to give a parallelogram. This
smallest part is known as unit cell. We can generate the complete lattice
by repeatedly moving the unit cell in the direction of its edges by a distance
equal to the cell edge as shown in Fig. 9.

Lattice generated

Unit cell

Fig. 9. (a) A unit cell (6) The complete lattice generated by

repeatedly moving the unit cell in the direction of its cell
edges by distance equal to cell edge.

Thus, the unit cell gives the shape of the entire lattice. However, it
may be noted that for any given lattice, the unit cells may be chosen in many
different ways. This is because a lattice contains a very large number of atoms
and numerous identical points may be found. Naturally, a question arises.
“What are the characteristics of this unit cell?” The most convenient cell is the
smallest unit cell which has the full symmetry of the lattice. For the square,
rectangular and parallelogram lattices, the unit cells chosen are the square,
the rectangle and the parallelogram respectively. However, for the hexagonal
lattice the unit cell is a rhombus with an angle of 60°.
For the rhombic lattices, a rectangular unit cell with an interior point is
generally selected. A cell with an interior point is called a centered unit cell.
The unit cells which do not contain any interior point are called primitive
unit cells.
Thus, we see that for describing a two dimensional lattice, we must specify
the unit cell by the lengths of the edges and the angles between them.
Thus, the five two dimensional lattices and their unit cells are :

Two dimensional lattice | Unit cell

(a) Square lattice Square
(b) Rectangular lattice Rectangle
(c) Parallelogram lattice Parallelogram
(d) Rhombic lattice Rectangular with an interior point
(e) Hexagonal lattice Rhombus with an angle of 60°

B. Three Dimensional Crystal Lattice

The crystalline solids have definite three dimensional arrangement of
constituent particles (atoms, ions or molecules). If the three dimensional
arrangement of constituent particles in a crystal is represented diagrammatically
by depicting each particle by a point, the arrangement is called crystal lattice
or space lattice. Thus, a crystal lattice is a
regular arrangement of the constituent particles (atoms, ions or
molecules) of a crystalline solid in three dimensional space.
 MODERN'’S abc + OF CHEMISTRY
-XII

A three dimensional crystal lattice is shown in Fig. 10. Like two dimensional
lattice, if we carefully look a crystal lattice, it is observed that we can select a
group of lattice points (a smallest three dimensional portion) which is repeated
over and over again in the whole crystal lattice. This smallest repeating
pattern (motif) is called the unit cell. Thus, a unit cell may be defined as:
the smallest three dimensional repeating portion of a space lattice
which when repeated over and again in different directions produces
the complete crystal lattice.
This smallest repeating pattern (unit cell) represents the shape of the
entire crystal. We can generate the complete lattice by repeatedly moving
the unit cell in the direction of its edges by a distance equal to the cell edge.
In fact, the crystal may be considered to consist of an infinite number of unit
— =

Space Lattice Showing Unit Cell cells. The unit cell in the above crystal lattice is shown by solid lines.
Parameters of a Unit cell
Fig. 10. Three dimensional lattice.
A unit cell is characterized by
(4) its dimensions (lengths) along the three edges as a, b and c. These
edges may or may not be mutually perpendicular.
(ii) angles a, B and y between the pair of edges. The angle & is between
the edges b and c, angle f is between the edges c and a and angle
y is between the edges a and b. Thus, a unit cell is characterized
by six parameters, a, b, c, @, B and y. The parameters of a unit cell
are shown in Fig. 11. The complete crystal lattice can be obtained
by extending the unit cell in all the three directions.
Characteristics of a Crystal Lattice
Let us sum up the characteristics of a crystal lattice. The following are
the characteristics of a crystal lattice.
(4) Each point in a crystal lattice is called lattice point or lattice site.
Fig. 11. Parameters of a unit cell. (ii) Each point in a crystal lattice represents one constituent particle
which may be an atom, a molecule (group of atoms) or an ion.
(iii) The three dimensional arrangement of lattice points represents a
crystal lattice.
(tv) Lattice points are joined by straight lines to bring out the geometry
of the lattice.
Types of Unit Cells
There are basically two types of unit cells constituting different crystal
systems. These are :
(1) Primitive or stmple untt cells
(it) Non primitive or centred unit cells.
(i) Primitive unit cells. These are unit cells which have points (or
particles) only at the corners. These are also called simple unit cells.
(it) Non-primitive or centred unit cells. These are unit cells which
have points (or particles) at the corners as well as at some other positions.
The centred unit cells are of three types :
(a) Face centred unit cells in which the points are present at the
corners as well as at the centre of each face.
(6) Body centred unit cells in which the points are present at all the
corners as well as at the body centre of the unit cell.
(c) End centred unit cells in which the points are present at all the
corners and at the centre of two opposite faces.
Seven Crystal Systems
When a unit cell in a crystal lattice has lattice points only at its corners
it is called a simple or primitive unit cell. In all, there are seven types of
simple or primitive unit cells among crystals. These unit cells are characterised
SOLID STATE

by the axial lengths a, b and c and the angles a, B and y. These are called
seven crystal systems or crystal habits. These are shown in Fig. 12. All
crystals can be placed in one of these seven crystal systems. These are :
1. Cubic. All the three axes are of equal length and are at right angles
to each other (a = b =e, all angles = 90°).
2. Tetragonal. The three axes are at right angles to each other but only
the two axes are equal (a = b # ¢, all angles = 90°).
3. Orthorhombic. It has three unequal axes which are at right angles
to each other (a # b # ¢, all angles = 90°).
4. Monoclinic. The three axes are of unequal length and two angles are
of 90° (a + b # c, two angles = 90° and one angle # 90°).
5. Hexagonal. It has two edges of equal length (a = }) and two angles of
90° and one angle of 120° (a = b # c, two angles of 90° and one angle of 120°).
6. Rhombohedral or trigonal. The three axes are of equal length which REMEMBER
are inclined at the same angle but the angle is not equal to 90° (a = b =e, all
three angles equal but not equal to 90°). It may be noted that among the seven
crystal systems :
7. Triclinic. The three axes are of unequal length, and all angles are
= Cubic is the most symmetrical
different but none is perpendicular to any of the others (a + b #¢, all angles while
different and none equal to 90°). = Triclinic is the most
These seven crystal systems are shown in Fig. 12 and are summed up in unsymmetrical system
Table 3.

a eT 77
a=
CUBIC
a=b=¢g
6 =i re
TETRAGONAL

f=
a=bsc
boy= 3"
ORTHORHOMBIC

=
astb+c
fo7= 9
MONOCLINIC
azbpzc
e= y= 90", 690°

HEXAGONAL RHOMBOHEDRAL OR TRIGONAL TRICLINIC

a=b+#c a=b=c a#+b+#c
a@= 6 =90°, y= 120° a=B=y2#90° a#B2#y2490°

Fig. 12. The seven crystal systems.

 MODERN'’S abc + OF CHEMISTRY
-XII

The characteristics of the seven crystal systems are summed up in Table 8.

Table 3. The seven crystal systems.
Possible Variations Axial distances Axial angles
Primitive a=B=y=90° #£x™NaCl, KCl, Zinc blende, Cu, Ag
Body-centred
Face-centred
Tetragonal Primitive a&=B=y=90° White tin, SnO,, TiO,, CaSO,
Body-centred
Orthorhombic Primitive &=B=y=90° Rhombic sulphur, KNO,, PbCO,, BaSO,
Body-centred
Face-centred
Knd-centred
Primitive a = y= 90°, B 90° Monoclinic sulphur, PbCrO,, Na,SO,- 10H,O
Kind-centred
Hexagonal Primitive o = B = 90°, y= 120° Graphite, ZnO, BeO, Cd5,
Rhombohedral or Trigonal Primitive o—=F=v72-o0" Calcite (CaCO,), NaNO,, cinnabar (HgS), quartz, Sb
Trichinic Primitive atBPp+y 4 SP Spiesorg.O, K,Cr,0,, H,BO,.

It may be noted that all crystals do not have simple lattices i.e., having
lattice points only at the corners. In addition, there are some lattices which are
different from the simple lattice. For example, if we consider a cubic system,
which is simplest of all these seven systems, it is observed that a cube has three
types of lattices.
Types of Cubic Lattices
There are three types of cubic unit cells or lattices. These are :
1. Simple or Primitive. Jt has points at all the corners of the unit cell.
A primitive cubic unit cell is shown in Fig. 18 (a). It consists of one atom at
each of the eight corners.
2. Body centred cubic unit cell (bce). lt has points at all the corners
as well as at the body centre of the cube (Fig. 13 (6)]. It is labelled as bee. As
shown in the figure, in a body centred cubic unit cell, there are eight atoms
at the corners and one at the centre.
3. Face centred cubic unit cell (fcc). In this case, there are points at
all the corners as well as at the centre of each face. It is shown in Fig 18 (ce).
It is labelled as fee. As shown in the figure, it has eight atoms at the corners
and six atoms at the centre of faces.

(a) Simple or primitive cubic: (6) Body centred cubic: Atoms (c) Face centred cubic: Atoms at the
Atoms at eight corners only. at the corners and at the body corners and centre of each face. Atoms 1,
centre of the cube. Atom 1 is at 2,3, 4,5, and6 are present at the centres
the body centre of the cube. of six faces (atom 5 corresponds to atom
at the centre of back face and atom 6
corresponds to the centre of front face.)

Fig. 13. Three types of cubic lattices.

SOLID STATE

Similarly, if we consider the other lattices, in addition

to simple lattices for other systems, it is observed that
there are 14 different types of space lattices. These are It may be noted that there is another type of non-primitive
known as 14 Bravais lattices after the name of French unit cell known as end centred unit cell. In this case,
mathematician who first described them. These are given there are points (or atoms) at all the corners and at the
in Fig. 14. centres of any two opposite faces.
O There is no end centred cubic unit cell.
Q Only orthorhombic and monoclinic crystal systems have
end centred unit cells.

Pa
Ly
;
Mi: Sa
™s

.
aa .

* 7 =

an, |©
Primitive Body-centred Face-centred

Tetragonal

a=b#e
a=f=y=90°

Orthorhombic

azb#e
a= f=y=90°

Primitive

Monoclinic

a#zb#c
a = y= 90°
B # 90°

Primitive
Hexagonal
The full hexagonal prism is shown,
a=b#e although the unit cell is just the part
co = B = 90° shown in solid lines.
y= 120°

Rhombohedral REMEMBER
or trigonal
There are seven crystal systems and
a=b=c fourteen Bravais lattices
eae Primitive
Triclinic

azb#e
a#B+#y#90°

Fig. 14. Unit cells of 14 Bravais lattices.

 MODERN'’S abc + OF CHEMISTRY
-XII

TYPES OF CUBIC CRYSTALS AND NUMBER OF ATOMS

PER UNIT CELL
We know that a crystal lattice is made up of a very large number of unit cells
and every lattice point is occupied by one constituent particle (atom, molecule or
ion). In different types of unit cells, the particles may be at the corners, at the
body centre or, at the centre of faces. Since every unit cell in a crystalline solid
is adjacent to other unit cells, most of the atoms (or constituent particles) are
shared by neighbouring unit cells. As a result, only some portion of each atom
belongs to a particular unit cell. For example, in all types of cubic cells, each
corner atom belongs to eight adjacent unit cells as shown in Fig 15, four unit
cells in the same layer and four unit cells of the upper layer. Therefore, only
1/8th of an atom (or molecule or ion) actually belongs to a particular unit cell.
Similarly, each face centred atom is shared by two unit cells (shown in
Fig. 15. A corner atom in cubic unit Fig. 16) and only 1/2 of an atom (or molecule or ion) belongs to a particular
cell is shared by 8 unit cells. unit cell.
An atom at the body centre of a unit cell is not shared by other unit cells
and it completely belongs to the unit cell (Fig. 17).
Thus, the contribution of each atom to the unit cell is:
it
Si corner = 8° at the face = - ; within the body = 1

For simplicity assume that the constituent particle is an atom. The unit
cell may be represented in three different ways.
(a) Each small sphere in figure represents only the centre of the par-
ticle occupying that position and not its actual size. Such type of
structures are called open structures. It is easier to follow the
arrangement of particles in open structures [Fig. 18 (a)].
Fig. 16. A face centred atom in a cubic
(6) Space filling representation of the unit cell with actual particle
unit cell is shared by two unit cells.
size [Fig. 18 (b)]. This gives a more realistic picture showing how
the particles actually pack within the solid.
(c) Actual portion of different atoms present in a unit cell [Fig. 18 (c)].
Let us now calculate number of atoms in different types of cubic unit
cells.
(4) Simple or primitive cubic unit cell
In this unit cell, the points (atoms, ions or molecules) are present at all
the corners of a cube. This is shown in Fig. 18 (a). It is clear from Fig. 18 (c)
that atom present at each corner contributes 1/8 to each cube because it is
shared by 8 cubes. Now, there are 8 atoms at the corners.
Fig. 17. A body centred atom in any| Thus, the number of atoms present in each unit cell =
cubic unit cell is not shared by any |
other unit cell. S$ corner atoms xX atom per unit cell = 1 atom.

I atom

(c) Actual portion of atoms belonging to

one unit cell
Fig. 18. Simple cubic arrangement and number of spheres per unit cell.
SOLID STATE 1/15 [
Thus, simple or primitive cubic unit cell has one atom per unit cell.
(it) Body centred cubic unit cell
It has points at all the corners as well as at the body centre of the cube. It
is shown in Fig. 19. It is clear from the figure that there are eight atoms at
the corners and each is shared by 8 unit cells so that the contribution of each
atom at corner is 1/8. In addition, there is one atom in the body of the cube
as shown in Fig. 19 (c) which is not shared by any other cube.

(a) Open structure (6) Space filling structure (c) Actual portion of atoms belonging
to one unit cell

Fig. 19. Body centred cubic unit cell.

Thus, the number of atoms present at the corners per unit cell
1
= 8 corner atoms x 3 atom per unit cell = 1
The number of atoms present at the centre of the cube = 1
Total number of atoms in bcc arrangement = 1 + 1 = 2.
Thus, a body centred cubic unit cell has two atoms per unit cell.
(iit) Face centred cubic unit cell.
This is also called cubic close packed unit cell. It has points at all the corners
as well as at the centre of each of the six faces. It is shown in Fig. 20. In this
arrangement, there igs one atom at each of the eight corners. It is clear from
Fig. 20 (c) that atom present at each corner contributes 1/8 to each cube
because it is shared by 8 cubes. In addition, there are six atoms at the faces
of the cube and each is shared by two unit cells. Therefore, the contribution
of each atom at the face per unit cell is 1/2 [Fig. 20 (c)].

(a) Open structure (6) Space filling structure (c) Actual portion of atoms belonging
to one unit cell
Fig. 20. Cubic close packed or face centred cubic arrangement and share of each atom per unit cell.

Thus, the number of atoms present at corners per unit cell =

1
8 corner atoms x 8 atom per unit cell = 1

The number of atoms present at faces per unit cell =

1
6 atoms at the faces x 9 atom per unit cell = 3
 MODERN’S abc + OF CHEMISTRY
-XII

. Total number of atoms in ccp or fec arrangement = 1+ 3 = 4

Thus, a face centred cubic unit cell has four atoms per unit cell.
@® Can you guess the contribution The contribution of atoms and total number of atoms in different types
of an atom at the edge centre? of cubic unit cells are summarized below :
An atom present on the edge is
at corner
shared by four unit cells as shown
below:

Therefore, contribution of each

atom on the edge = 1/4
at body centre
How many atoms will be 1 _
present in an end centred Contribution — at corners and — at face Contribution of 1 at the body centre
orthorhombic unit cell? centres of the atoms in a face centred cell
An edge centred orthorhombic unit
Fig. 21. Contribution of atoms in a cubic unit cell.
cell has eight atoms at the corners
and two atoms at the centres of two
Unit cell No. of atoms No.ofatoms No.ofatoms Total
end faces.
at corners at faces in centre

Simple cubic or primitive cell 8 x -

Body centred cubic 8x —

Face centred cubic 8 x

Therefore, total number of atoms

per unit cell in end centred unit
It is important to remember that the atoms (or spheres) at the corners of a
cell is
simple cube touch each other [Fig. 22 (a)]. However, the atoms at the corners of
8 (corners) x i + 2 (end centres) face centred cube and body centred cube donot touch each other. It may be seen that
e in the face centred cube, the atoms along the face diagonal of the cube
x — =2 atoms. touch each other [Fig. 22(5)].
2
in the body centred cube, the atoms along the body diagonal of the cube
It may be noted that there is no
touch each other [Fig. 22(c)].
end centred cubic unit cell.
However, for simplicity, the atoms (or spheres) are shown only at the corners in
the figures.
(atoms at corners Rem (atoms along face diagonal
touch each other) i ae touch each other)
/ ; eo

(atoms along body diagonal

touch each other)

The blue coloured spheres represent the spheres which are touching each other.
(a) Simple cubic (b) Face centred cubic (c) Body centred cubic
Fig. 22
SOLID STATE 1/17 [
RELATIONSHIP BETWEEN THE NEAREST NEIGHBOUR DISTANCE (d)
AND RADIUS OF ATOM (r) AND THE EDGE OF UNIT CELL (a) FOR PURE
ELEMENTS
1. Simple cubic
Inasimplecubicarrangement,theatomsatthe ja@
corners touch each other [Fig. 23]. Therefore,
Distance between the nearest neighbours,
d=AB=a
Radius, r = d/2 = a/2
; REMEMBER
2. Face centred cubic Fig. 23 Simple cubic.
The relationship between the nearest
In a face centred cubic arrangement, the three atoms along the face
neighbour distance and radius of atom (for
diagonal touch each other [Fig. 24]. Therefore,
crystals of pure elements) and the edge of
Distance between the nearest neighbours, d = = unit cell (a) is summed up below :
Now in right angled AABC a” 2Td Dinausen Radios
AC? = AB? + BC? | between (7)
AC? =a? +4+a?2=2a? or AC= J2a nearest
J2a cl neighbour

:
d=—_
d
2 ==
a
=p =
(d)

Radius, r= —= Pw} Simple cubic

: Fig. 24 Face
3. Body centred cubic centred cubic. Face centred
In a body centred cubic arrangement, three atoms along the body
diagonal touch each other [Fig. 25]. Therefore,

Distance between nearest neighbours, d = ~

In right angled AABC
AC? = AB? + BC? or

AC? =a? +a? or AC= J2a aoe 0.866a 0.4334

Now in right angled AADC,
AD? = AC? + DC?
AD? = (J2a)’
+a? = 8a?
or AD = 3.
d
Fig. 25 Body
3
centred cubic.
Radius, r= — = V3 a:
2 4

SOLVED EXAMPLES

LJ Example 4
—
A cubic unit cell is made up of X and Y elements. If X Ifthree elements P, Q and R crystallise tn a cubic solid
are present on the corners of the cube and Y are present lattice with P atoms at the corners, @ atoms at the cube
on centres of faces of cube, then find the formula of the ele geolla ies 2 sich Of oie eaaes; ten
compound. (Hr. S.B. 2018) (Pb. S.B. 2002)
Solution: In acube, X atoms are at the 8 corners, each Solution: As P atoms are present at the 8 corners of the
shared by 8 cubes. Therefore, cube. Therefore,
The number of X atoms in the unit cell is 8/8 = 1.
Novof Pigtatiean Hie umes bye
Y atoms are at the centres of 6 faces and each face is shared 8
by two cubes. Therefore, @ atoms are present at the cube centres,
The number of Y atoms = 6/2 = 3 No. of Q atoms in the unit cell = 1
K atoms are present at the edges. Since there are 12 edges
The formula of the compound = XY..
and atom at each edge is shared by four atoms.
 MODERN’S abc + OF CHEMISTRY-XII

Therefore, Solution: Ifais the edge length of bcc unit cell, then radius
No. of R atoms in the unit cell = 12 x — =3 of an atom,
4 . J3
.. The formula of the compound = PQR,. r= a

L}) Example 5 Here, a = 316.5 pm

Calculate the number of unit cells in 8.1 g of aluminium if % ae V3 A105 pm
it crystallizes in a face-centred cubic (fc c) structure. (Atomic 4
mass of Al=27g mol). (A.I.S.B. 2017, D.S.B. 2017) =137.04 pm
Solution : L) Kxample 7
Moles of aluminium = = mol Aluminium crystallizes in a fee structure. Atomic
radius of the metal is 125 pm. Calculate the edge length
8.1
37
No. of atoms of Alin 8.1 g = => x 6.022 x 1075 of the unit cell of the metal?
No. of atoms in one unit cell = 4(fcc) (A.LS.B. 2013, Karnataka S8.B.2014)
81 6.022102 Solution : In a face centred cubic structure, radius (r), is
No. of unit cells = O7 . A related to length of the side (a) as:

= 4.5 x 107". m4 aE
LJ Example 6
Tungsten crystallizes in body centred cubic unit cell. = a = 2rV2
If edge of the unit cell is 816.5 pm, what is the radius r= 125pm
of the tungsten atom ? 4 a = 2x 125x 1.414
(D.S.B. 2012, CBSE Sample Paper 2017-18) = 353.3 nm.

I iil =
Ly A cubic solid is made up of two elements X and Y. Atoms Y are present at the
corners of the cube and atoms X at the body centre. What 1s the formula of the
compound ? (D.S.B.2006, CBSE Sample Paper 2008)
. When atoms are placed at the corners of all 12 edges of a cube, how many atoms
are present per unit cell ?
» A unit cell consists of a cube in which there are A atoms at the corners and
B atoms at the face centres and A atoms are missing from 2 corners 1n each unit
cell. What is the simplest formula of the compound ? (Pb. S.B. 2011)
. Acompound of X and Y crystallizes in the cubic structure in which Y atoms are at
the corners and X atoms are at the alternate faces of the cube. Find the formula
of the compound. (Pb. S.B. 2011, Meghalaya S.B. 2013)
. Gold crystallizes in the face centred cubic lattice. Calculate the approximate
number of unit cells in 2 mg of gold. (atomic mass of gold = 197 u).
Answers to Practice Problems . Xenon crystallizes in the face centred cubic lattice and the edge of the unit cell
is 620 pm. What is the nearest neighbour distance and radius of xenon atom ?
Ly » The length of the unit cell edge of a body centred cubic metal crystal is 352 pm.
2.1 Calculate the radius of an atom of the crystal. (Nagaland S.B. 2013)
» Calculate the atomic radius of elementary silver which crystallises in face centred
3. AB,
cubic lattice with unit cell edge length 4.086 x 10-1°m. (Assam S.B. 2016)
4, XY . Asolid has a structure in which W atoms are present at the corners of the cubic
5. 1.528 x 101° unit cells unit cell, O atoms are located at the cube edges and Na atoms are present at
cube centres. What is the formula of the compound ?
6. 4358.6 pm, 219.25 pm
10. CsCl crystallizes in cubic structure in which Cl ions are at the corners and Cs*
7. 152.416 pm ions occupy centre of the unit cell. [fradiu of Cs* and CI ions are 1. 69A and 1.81A
8.1.44 x 107° m respectively, calculate the edge length of the unit cell.
11. Tungsten crystallizes in body centred cubic lattice. Calculate the number of unit
9. NaWO;
cells in 1.5 g of tungsten (Atomic mass of tungsten = 184 wu). (Pb. S.B. 2013)
10. 4.04 A 12. Sodium crystallizes in a bce unit cell. Calculate the approximate number of unit
11. 2.45 x 107! unit cells cells in 9.2 g of sodium (Atomic mass of Na = 23 wu).
12. 1.2044 x 10*9 unit cells (C_LB.S.E. Sample Paper 2011, Assam S.B. 2013)
135. Gold (atomic radius = 0.144 nm) crystallizes in face centred unit cell. What is
13. 0.407 mm
the length of the side of the cell? (Meghalaya S.B. 2017)
14. A,B,, 14, In a face centred cubic arrangement of A and 5 atoms, A atoms occupy the corners
Hints & Solutions on page 57 and B atoms occupy the face centres of the unit cell. If one of the atoms is missing
from the corner in each unit cell, what is the simplest formula of the compound?
SOLID STATE

CLOSE PACKED STRUCTURES

In the formation of crystals, the constituent particles (atoms, ions or
molecules) get closely packed together. The closely packed arrangement is
that in which maximum available space is occupied leaving minimum vacant
space. This corresponds to a state of maximum possible density. The closer
the packing, the greater is the stability of the packed system.
We know that the constituent particles of crystals may be of varying shapes
and, therefore, the mode of closest packing of particles will vary according
to their shapes and sizes. However for understanding, we can use identical
hard spheres of equal size to represent atoms in a metal in terms of closest
packing of identical spheres.
We can build up the three dimensional structure in three steps :
(a) Close Packing in one Dimension
There is only one way of arranging spheres in one dimensional close packed
structure in which the spheres are placed in a horizontal row touching each

00000000
other. This is shown in Fig. 26.

Fig. 26. Close packing of spheres in one dimension.

As can be seen in this arrangement, each sphere is in contact with two ofits neighbours.
The number of nearest neighbours of a particle is called its co-
ordination number.
Thus, in one dimensional close packed arrangement, the coordination
number is 2.
(6b) Close Packing in two Dimensions
Two dimensional close packed structure can be generated by placing the
rows of close packed spheres. The rows can be combined in the following two
ways with respect to the first row to build a crystal plane.
(4) Square close packing or AAA... type arrangement in two
dimensions.
The spheres are packed in such a way that the rows have a horizontal as
well as vertical alignment. In this arrangement, the spheres of second row
are exactly above those of the first row. The second row is exactly same as
the first one. If we label the first row as ‘A’ type, the second row is also ‘A’
type. Similarly, we may place more rows to get AAA.... ..... type arrangement
as shown in Fig. 27 (a). In this arrangement, the spheres are found to form
squares. This type of packing is also called square close packing in two
dimensions.
(74) Hexagonal close packing or ABABA... type arrangement in two
dimensions.
The spheres are packed in such a way that the spheres in the second row
are placed in the depressions between the spheres of the first row. Similarly,
the spheres in the third row are placed in the depressions between the spheres
of the second row and so on. In this arrangement, the second row is different
from the first row. But the spheres in third row are aligned with those of the
first row. Similarly, the spheres of fourth row are aligned with those of second
row. If the arrangement of spheres in first row is called ‘A’ type, the one in the
second row is different and may be called ‘B’ type. Now, the arrangement of
spheres of third row is same as that of first row, and therefore, it is also called
‘A’ type. Similarly, fourth row is called ‘B’ type. Hence the arrangement is

. MIDI"
(MK KX KX KX YX
A AAA POA
CEKKKKKKN
Arrangement I Arrangement IT
(a) Square close packing occupies 52.4% of available space (6) Hexagonal close packing occupies 60.4% of available space
Fig. 27. Packing of spheres in two dimensions.
 MODERN'’S abc + OF CHEMISTRY
-XII

called ABAB......... type. This type of arrangement is also called hexagonal close
packing of spheres in two dimensions and is shown in Fig. 27.(6) (arrangement II).
A comparison of two ways of packing of spheres shows that in arrangement
I, the spheres are less closely packed than in arrangement II. It has been
calculated that in arrangement I, only 52.4% of the available space is occupied
by the spheres. In the second arrangement, 60.4% of the space is occupied.
Therefore, the arrangement I] is more efficient and leaves less space unoccupied
by spheres. Thus, arrangement IT is more economical and it represents a close
packing of spheres.
It can be seen that in arrangement I, each sphere is in contact with four other
spheres as shown in Fig. 28 (a). On the other hand, each sphere is in contact with
six other similar spheres in arrangement I] as shown in Fig. 28 (0).
Fig. 28. (a) A sphere in square Thus, in two dimensional close packing, the co-ordination number of each
close packing is in contact with four sphere in arrangement I (square close packing) is four and in arrangement
spheres. (6) A sphere in hexagonal
II (hexagonal close packing) is six. Thus, the arrangement II represents
close packing is in contact with six
spheres. closest packing of spheres in a layer.

(c) Close Packing in Three Dimensions

We can now build other layers over the first layer to extend the packing
in three dimensions. This can be done by building layers on square packed
and hexagonal close-packed arrangement of first layer. Let us see what types
of three dimensional close packing can be obtained from these two types of
arrangements. Let us mark the sphere in the first layer as A.
(4) Three dimensional close packing from two dimensional square
close packed layers
For placing the second square close packed layers above the first row, follow
the same procedure that was followed when one row was placed adjacent to the
other row. The second layer is placed over the first layer such that these spheres
of the second layers are exactly above those of first layer. In this arrangement,
spheres of both layers are perfectly aligned horizontally as well as vertically.
Similarly, we may place more layers one above the other. This is shown in
Fig. 29 (a). If the arrangement of spheres in the first layer is called ‘A’ type,
the other layers will also be ‘A’ type because they have same arrangement.
This type of packing is referred to as AAA......type. This type of packing is
also called simple cubic packing and its unit cell is the primitive unit cell
as shown in Fig. 29 (5).
(ii) Three dimensional close packing from two dimensional
hexagonal close packed layers.
As we have already seen that for two dimensional packing, hexagonal
close packing is more efficient packing. Let us consider a three dimensional
packing above this layer.
Let us mark the spheres in the first layer as A. It is clear from Fig. 30(q@)
that in the first layer there are some empty spaces or hollows called voids.
These are triangular in shape. These triangular voids are of two types marked
as a and 0b. All the hollows are equivalent but the spheres of second layer may
(b)
be placed either on hollows which are marked a or on other set of hollows
Fig. 29. Simple cubic lattice formed
marked 0. It may be noted that it is not possible to place spheres on both
by AAA.... arrangement.
types of hollows. Let us place the spheres on hollows marked 6 to make the
second layer which may be labelled as B layer. Obviously the holes marked
a remain unoccupied while building the second layer. The second layer is
indicated as dotted circles in Fig. 30 (0).
SOLID STATE

Fig. 30. Packing of second layer (5) on first layer (a).

It is clear from Fig. 30 (6) that the two types of voids are not similar.
The ‘c’ type of voids are triangular but ‘a’ type of voids of the second layer
are a combination of two triangular voids (one each of first layer and second
layer) with the vertex of one triangle upwards and the vertex of other triangle
downwards.
Whenever a sphere of second layer
is placed above the void of first layer, a
tetrahedral void is formed. These voids
are called tetrahedral voids because a
tetrahedron is formed when the centres
of these four spheres are joined. The
voids ‘ec’ represent tetrahedral voids.
The voids ‘a’ are double triangular
voids. The triangular void in the second
layer are above the triangular voids in
the first layer and the triangular shapes
of these voids donot overlap. Such voids
are surrounded by six spheres and are hep arrangement
called octahedral voids. Fig. 31. ABABA... or Acp arrangement of spheres. Metals like magnesium, zinc,
Now the third layer can be build up etc. adopt this type of arrangement.
by placing spheres above tetrahedral
voids marked (c) or octahedral voids marked (a).
(4) Covering tetrahedral voids
>» Number of atoms per unit cell
When a third layer is to be added, again there are two types of hollows
in hep.
available. One type of hollows marked ‘a’ are unoccupied hollows of the first
O In hep arrangement, Fig. 31 (0d),
layer. The other type of hollows are hollows in the second layer (marked c).
there are 12 atoms at the corners,
Thus, there are two alternatives to build the third layer.
2 at face centres and 3 atoms are
The third layer of spheres may be placed on the tetrahedral voids marked (c) present in the body. In hep, each
of the second layer. In this arrangement, the spheres of the third layer lie corner is shared by six unit cells,
directly above those in the first layer. In other words, third layer becomes therefore, contribution of atom at
exactly identical to the first layer (labelled A). This is shown in Fig. 31. This the corner is 1/6; each atom at the
type of packing is referred to as ABABA.... arrangement. This type of packing face centre is shared by 2 unit cells
is also known as hexagonal close packing. It is abbreviated as Aep. For and therefore, contribution of atom
simplicity, hep arrangement can be drawn as shown in Fig. 31 (0). at the face centre is 1/2; the atom
Metals like magnesium, molybdenum, beryllium, zinc, etc. adopt this type of within the body contributes to that
arrangement. unit cell only. Thus,
(ii) Covering octahedral voids No. of atoms per unit cell =
The second way to pack spheres in the third layer is to place them 12 (at corners) “= + 2 (face) x=
over octahedral voids marked ‘a’ (unoccupied hollows of first layer). This
gives rise to a new layer labelled as C. However, it can be shown that the + 3 (body)
x1
spheres in the fourth layer will correspond to those in the first layer. This =2+41+43
=6 atoms/unit cell.
is shown in Figs. 32 (a) and 32 (6). This gives the ABCABCA.....type of
a 1/22 MODERN'S abc + OF CHEMISTRY-XII
arrangement. It is also known as cubic close packing and is abbreviated as
eep. For simplicity cep arrangement can be drawn as shown in Fig. 32(c). It is
clear from Fig. 32 (c) that there is a sphere at the centre of each face of the cube.
Therefore, this arrangement is also known as face centred cubic arrangement
and is abbreviated as fee. Metals like copper, iron, nickel, aluminium, gold and
silver crystallise in this type of structure.
It may be noted that both types of packing are equally economical though
these have different forms. In both cases, 74% of the available volume is
occupied by the spheres.

cecp arrangement

(c)
Fig. 32. ABCABCA... or cep arrangement of spheres.

INTERSTITIAL VOIDS OR INTERSTITIAL SITES

In the close packing of spheres, certain hollows or voids are left vacant.
These holes or voids in the crystals are called interstitial voids or interstitial
sites. Two important interstitial voids are (i) tetrahedral (ti) octahedral.
We have learnt during packing of spheres that after arranging two layers
(A and B) we find two types of voids (marked a and c). The void ‘c’ is created

TE
by four spheres and is called tetrahedral void. The void ‘a’ is created by six
oe’ &
ine
oS. spheres in contact and is called octahedral void. These are shown in Fig. 33
marking them as ¢ and o. These are discussed below :
(i) Tetrahedral void or site . A sphere in the second layer is placed above three
spheres touching one another in the first layer. This is shown in Fig.34. The
centres of these spheres lie at the apices of a tetrahedron. It may be noted that
the shape of the void is not tetrahedral, but the arrangement around this void
Fig. 33. Tetrahedral and octahedral is tetrahedral. Thus, the vacant space among four spheres having tetrahedral
voids in close packing arrangement. arrangement is called tetrahedral void or tetrahedral site.
Tetrahedral void © Tetrahedral void
Learutug Plus
The presence of interstitial voids or
interstitial sites play an important
role in chemistry of transition
metals. The transition metals can Geometrical shape of void
easily accommodate the small non- Fig. 34. Tetrahedral void.
metallic atoms such as hydrogen,
boron, carbon and nitrogen because (ii) Oetahedral void or site. This type of void or site is formed at the
of spaces between the metal atoms. centre of six spheres. It is shown in Fig. 35. From the figure, it is clear that
These compounds are called each octahedral void is produced by two sets of equilateral triangles which point
interstitial compounds. in opposite directions. Thus, the void formed by two equilateral triangles with
SOLID STATE ee [
Octahedral void Octahedral void

Octahedral
hole

Geometrical shape of void

Fig. 35. Octahedral void.

apices in opposite direction is called octahedral void or octahedral site.

This void is, therefore, surrounded by 6 spheres lying at the vertices of a
regular octahedron.
Number of octahedral and tetrahedral voids or sites. There are
two tetrahedral voids for each sphere and there is only one octahedral void
for each sphere. Thus, in a close packed structure of N spheres, there are:
tetrahedral voids = 2N
octahedral voids = N
total number of tetrahedral and octahedral voids = 3N
Coordination Number
The number of spheres which are touching a given sphere is called the
coordination number. Thus, coordination number is
the number of closest (or nearest) neighbours of any constituent
particle in the crystal lattice.
As already discussed in Aep and ccp arrangements, a sphere is in direct
contact with 6 other spheres in the same plane of the central atom. It touches
three spheres in the layer above it and three spheres in the layer below it. Thus,
its coordination number in Acp and ccp arrangements is 12 as shown in Fig. 36.
It may be noted that coordination numbers of 4, 6, 8 and 12 are very
common in Various types oft crystals. Fig. 36. Coordination number of 12

EFFICIENCY OF PACKING OR PACKING EFFICIENCY in Acp and cep arrangement.

In whatever way, the constituent particles (atoms, molecules or ions) are
packed, there is always some free space left in the form of voids. The packing
efficiency is
the percentage of total space filled by the particles.
Alternatively, it may also be expressed as packing fraction. It is the
fraction of total space filled by the particles. Both types of close packing
(hep and cep) are equally efficient and occupy 74% of the available volume. On
the other hand, in body centred cubic structure, the efficiency is 68% while
in simple cubic structure, it is only 52.4%.
Let us calculate the packing efficiencies in different structures.
(a) In cubic close packing or face centred cubic arrangement
Suppose the edge length of the unit cell = a
and radius of each sphere =r
It is clear from the figure that there are 8 spheres at the corners and six
spheres at the faces.
No. of spheres
in unit cell = 8 x +6x 5 =o
As spheres along face diagonal are touching, it is evident from the figure,
AC = 4r
top view of ccp arrangement
Consider AABC. Since it is right angled triangle,
(spheres along face diagonal are
AC? = AB? <4 BO =@ 4027 = 2a touching)
Face diagonal, AC J2.a
Ar
J/2.a=4r or a eet |
V2 a
 MODERN'S abc + OF CHEMISTRY
-XII

Volume ofa unit cell = a®=(2J2r8=16/2r3

Total volume of 4 spheres = 4x Ras = 16s
3 3
Packing efficiency = Volume of four spheres in the unit cell , 100
Total volume of unit cell
16 3
=
al x 100
16V2 r°

= —* _ x 100 x 100
=74%
~ 3xJ2 ~ 3x1.414 —
Volume occupied in fce or cep arrangement = 74%
(6b) In hexagonal close packing (hcp) arrangement
Suppose radius of each sphere = r
From the figure, it is clear, that a = 2r
Volume of unit cell can be calculated as:
Volume of unit cell = Base area x Height (h)
Base area of regular hexagon = 6 x Area of equilateral triangle

= 6x 8

= 6 x Y3(an? = axa

Height of unit cell = ar..|?

3

Volume of unit cell 68 r? x ar. = 24/9 r°

No. of atoms in Acp unit cell 12 x ~(corners) +2x =(facecentres)

+—2r—_ >
hexagonal close packed arrangement + 3 (in body) = 6
Volume of 6spheres = 6x =n r? = 80 r°

Volume occupied by spheres in unit cell

Packing efficiency = x 100
Volume of Aep unit cell
8nr° Tt 3.142
24/2 tn aeI Eg Aa x 100

= 0.74 x 100 = 74%

.. Volume occupied in hep arrangement = 74%
(c) In body centred cubic (bcc) arrangement
Suppose the edge length = a
Radius of each sphere = r
It is clear from figure that there are 8 spheres at the corners and one in the
body of the unit cell. 1
No. of spheres per unit cell = 8 x = +1=2

It is evident from the figure that spheres along body diagonal are touching
so that,
AD = 4r
Consider right angled AABC,
AC? = AB?+BC?%=a?+a?
i AC? = 2a?
Similarly in right angled AACD,
Body diagonal, AD? = AC?+CD?
view of AD AIr = 96*40°=30"
bcc arrangement (spheres along body
AD = ,3.a
diagonal are touching)
Ree: Ar
SOLID STATE

4r
or a= B

3 4r \ _ 64r°
Volume of unit cell = a°= (<z)
V3 ~ 33
Volume of asphere = tr?
4 8
Total volume of two spheres = 2 x 3 c= 3a

Volume of two spheres in the unit cell

Packing efficiency = x 100
Total volume of unit cell
8
—tr 3 :
= =e x 100 = m3 x 100
64 3 Q
—_$—
3/3
_ SET x 100 = 68%
Volume occupied in bce arrangement = 68%
(d) In a simple cubic unit cell
Suppose the edge length of the unit cell =a
Radius of the sphere =r
Since the spheres are touching each other along the edge, a = 2r
Now, there are eight spheres at the corners of the cube.
Each sphere at the corner is shared by eight unit cells and the contribution
per unit cell is 1/8 so that —
Number of spheres per unit cell is 8 x 8 = 1 (spheres along the edge are
touching)
4
Volume of sphere = 3 tr?

Volume of cube = a®=(2r)? = 8r®

Packing efficiency = ___Volumepronge

sphere
Day x 100
Total volume of cubic unit cell
4 3
3 3.142 «100
= 3 * 100 =,= Ax 100 =
gr° 6 6
= 52.57% or 52.4%
”. Volume occupied in simple cubic arrangement = 52.4%
CL—————_
SIZES OF TETRAHEDRAL AND OCTAHEDRAL VOIDS
As we have already learnt, in the close packed structures (hep or ccp), simple cubic arrangement
there are two common types of voids :
(4) octahedral voids
(it) tetrahedral voids
The radii of the voids in these close packed structures are related to the
sizes of the spheres present in the packing. Let us calculate the radii of these
voids in relation to the radii of the atoms in close packing.
Relationship between radius of octahedral void and radius of
atoms in close packing.
An octahedral void is shown in Fig. 37. Though an octahedral void is
surrounded by six spheres, only four are shown. The spheres present above
and below the void are not shown. Let us assume that the length of the unit
cell is @ cm and radius of octahedral void (shown by sphere) is r and the
radius of sphere is R. Octahedral void with radius r
If the length of the unit cell is a cm, then
In right angled AABC, Fig. 37. A cross-section of an
AB = BC =a cm octahedral void.
 MODERN’S abc + OF CHEMISTRY-XIl

The diagonal AC is:

AC = ¥AB?+BC? =Ja% +a? = 2 4
also AC = v2 i = v2
AB a 1
Now, AB = 2R
AC =R+2r+R=2R42r
QR+2r — V2
2R 1
or tba = v2
R 1
or = = /29-1 =1.414~-1=0.414
or r=0.4)74K
Thus, for an atom to occupy an octahedral void, its radius must be 0.414
times the radius of the sphere.
Relationship between radius of the tetrahedral void and radius of
atoms in close packing.
A tetrahedral void may be represented by placing four spheres at the
alternate corners of a cube as shown in Fig. 38. It may be noted that a stable
tetrahedral arrangement has four spheres at the corners touching each other.
However, for simplicity, the spheres are shown by distant circles. Actually all
the spheres are touching one another. Let us assume that the length of each
side of the cube is @ em and radius of tetrahedral void (shown by a sphere)
Body diagonal
is r and the radius of sphere is R.
In the figure, AC is a face diagonal.
In right angled AABC,
AC? = AB? + BC?
a AC = | AB? + BC?

2 ore
Fig. 38. A tetrahedral void. = Ja? +a? = v2a
As spheres A and C at the face diagonal (though shown by distant circles)
are actually touching each other so that
AC=R+h=2R

2R = J2aorR= = ..(Z)
Now in the right angled triangle, AACD, AD is body diagonal and
AD? = AC? + CD?

AD = /AC?+CD? = J2a?2+a? = J3.a

The tetrahedral void is present at the centre of the body diagonal AD so that
half the length of this diagonal is equal to the sum of the radii of R and r. Thus,

R+re= AD = v8a cut th)

Dividing eq. (11) by eq. (2), we get
R+r 3a 2 V3
— x
R /2a 2

1+
Al
|

rd|~
or
i) S1
SOLID STATE 1/27 [
_
1.732 —1.414
— 0.225
1.414
or r= 0.225 R
Thus, for an atom to occupy a tetrahedral void, its radius must be 0.225
times the radius of the sphere.
Thus, we observe that a tetrahedral void is much smaller than the
octahedral void.
Radius Ratio of Cations and Anions and Stability of Ionic Solids
In case of ionic solids, usually anions are present in the close packed
arrangement and cations occupy voids. The number of oppositely charged
ions surrounding each ion is called its coordination number. Therefore,
the relation between the size of the void and the sphere in the close packed
arrangement is expressed in terms of radius of cation to that of anion. = 7
The ratio of the radius of the cation to the radius of the anion Competition ys)Cus |
is called radius ratio. The structures of crystals are
. _ Radiusofthecation — r, also expressed by various planes
Thus, Radius ratio = Radius of the anion ~ Se described by a set of integers known
as Miller indices. For detail, refer
For cations occupying the tetrahedral voids, Competition File (Page 79)
r, = 0.225 r_ or r/r_ = 0.225
For cations occupying the octahedral voids,
r, = 0.414 r_ or ee
The ratio of the radius of cation and the radius of anion /.e., radius ratio
(r,/r_)plays an important role in determining the structures ofionic solids and
coordination number of ions. As is clear, for the cations to occupy tetrahedral
void, the limiting lowest value of r,/r_ is 0.225 and to occupy octahedral
void, itis 0.414. In other words, for tetrahedral coordination, the radius ratio
should be in the range of 0.225 — 0.414. Similarly, it has been calculated that
for stable arrangement of cations occupying octahedral voids (i.e., coordination
number 6), the radius ratio should be more than 0.414 in the range of
0.414_0.732. If the radius ratio (r,/r_) is more than 0.732 (in the range
0.732—1.0), the cations occupy cubic voids (coordination number 8). Similarly,
below 0.225, the cations occupy simple trigonal voids. The possible coordination
numbers and structural arrangements of anions around cations for different
r,/r_ values are given below :

Radius ratio Possible coordination Structural Structural type Examples

(r/r_) number arrangement

0.165 — 0.225 3 Trigonal planar Eee |B Oe

0.225 — 0.414 A Tetrahedral “ns #05, CuCl, CuBr, Cul
Bas, Hgs
esEyMes Bs i)Cary 6 Octahedral NaCl NaCl, MgO, NaBr,
CaS, CaO
ioe — 1 8 Cubic CeCl CsCl, CsBr, TIBr, NH,Br

The application of radius ratio rule may be illustrated by the following examples :

SOLVED EXAMPLES
LJ Example 8
The radius of Na* ion is 95 pm and that of Cl are tf r(Na*) 5
ion is 181 pin. Predict whether the coordination eee ae, yr (cr) 181 uae
number of Nat ton is 6 or 4. (Pb. S.B. 2017) 7
The radius ratio lies between 0.414 — 0.732. Hence, Na* ions
Solution: Radius of Nat = 95 pm prefer to occupy octahedral holes having coordination
Radius of Cl = 181 pm number 6.
 MODERN'’S abc + OF CHEMISTRY
-XII

LJ Example 9 = Hadius of tetrahedral hole = 0.225 x Pa

Br ions form a close packed structure. If the = 0.225 x 195 = 43.875 pm

radius of Br ion is 195 pin, calculate the radius For the cation A* with radius, 82 pm
of the cation that just fits into the tetrahedral Raviewaatia ool 82pm 0.4206
hole. Can a cation having a radius of 82 pm be r 195 pm
slipped into the octahedral hole of the crystal Since the radius ratio (r,/r_) lies in the range
A*tBr ? (A.LS.B. 2003) 0.414—0.732, hence the cation A* can be slipped into octahedral
Solution: Radius of the cation just fitting into the hole of the crystal A*Br.
tetrahedral hole

= Answers to Practice Problems = 15. The atomic radii of Cs* and Cl ions are 1.69 A and 1.81 A respectively. Predict
15. & cubic the coordination number of Cs* ion and structure of CsCl.
16. A solid AB has NaCl structure. If the radius of cation Ais 100 pm, what is the
16. 136.6 to 241.6 pm.
radius of anion B ? (Pb.S.B.2017)
pe erat 2 1 aaa 17. If the radius of Br ion is 0.182 nm, how large a cation can fit in each of the
Hints & Solutions on page 57 tetrahedral hole ?

FORMULA OF A COMPOUND AND NUMBER OF VOIDS FILLED

In the case of simple ionic compounds, generally two types of arrangements
are possible. These are cubic close packed (ccp) or face centred cubic (fcc)
arrangement and hexagonal close packed (hcp) arrangement. The larger ions
(i.€., anions) adopt these arrangements. The other kinds of ions (i.e., cations)
occupy different voids. As we have learnt, there are two types of voids :
tetrahedral and octahedral; which are generally occupied.
From the description of the close packed structures and the types of voids
occupied, we can easily draw inferences regarding the structures of simple
ionic compounds. For example, consider a compound of general formula AB
in which the B ions form a close packed lattice. There are two possibilities:
(4) Since there is only one octahedral void per atom in a close packed
lattice, all the octahedral voids will be occupied by A* ions. In this

(8) Competition Plus case, the number of A* ions and B ions will be same. Sodium chloride
has this type of structure in which Cl ions form a cubic close packed
The arrangement of atoms, ions or structure and Nat ions occupy all the octahedral voids.
moleculesin crystals is determined by (ii) There are two tetrahedral voids per atom in a close packed lattice.
X-rays diffraction studies. For detail, This means that there are two tetrahedral voids available for every
refer Competition File (Page 79). B- ion. To form the compound AB, only one half of the tetrahedral
voids will be occupied. Zinc blende (ZnS) has this type of structure,
in which S* ions form cubic close packed lattice and Zn** ions occupy
one half of the tetrahedral voids.
If, on the other hand, the formula of the compound is A,B in which B- ions
adopt cubic close packed lattice, then all the tetrahedral voids will be occupied
by At ions. Since there are two tetrahedral voids per atom, and all the voids
are occupied, there will be two A* ions for each B- ion. Sodium oxide adopts
this type of structure. This structure is also known as antifluorite structure.
Alternatively, if At ions (though smaller in size than B~ ions) adopt cubic
close packed structure and B- ions occupy all the tetrahedral voids, then the
formula of the compound is AB, Calcium fluoride has similar type of structure.
The structure is known as fluorite structure.
The structures of some common ionic solids are summed upin Table 4
ahead.*

* These structures are not in CBSE syllabus. These are given to supplement your knowledge.
SOLID STATE 29)

| Learning Plus
STRUCTURES OF SOME COMMON IONIC COMPOUNDS
CF ion
Octahedrally J = a.
surrounded by ~/ an ov r Sodium chloride (NaCl)
sige se ;
six Na* ions * Cl ions have cep or fcc arrangement
(ze. Cl ions occupy all the corners and all
the face centres of the cube)
¢ Nat ions occupy all octahedral sites
(7.e. Na* ions are present at the body centre
and edge centres)
* C.N. of Nat = 6
See Nat ion octahedrally > SUEY | :
Se surrounded by six 9 * CN, of Cl = 6
CF ions

Cs* ion
surrounded by 8 Ck
q@ Cs

Cesium chloride (CsCl)

¢ Cl ions have simple cubic arrangement
(1.e. present at all the corners of the cube)
* Cs* ions occupy cubic sites
(1.e. occupy the centre of the cube)
* C.N. of Cs* = 8
by 8 Cs* ions
* CN. of Cl =8

Cesium chloride (CsCl)

Zinc sulphide (ZnS)

¢ §* ions have cep or fee arrangement
(i.e. S*- ions occupy all the corners
and all the face centres of the cube)
72 ion ¢ Zn** ions occupy half of the tetrahedral
tetrahedrally 7 _-F/ ws a | pata pes
surrounded by [UO ) ¢ C.N. of Zn** = 4
four S* ions’ | ) ¢ CIN. of S* =4
tetrahedrally It may be noted that ZnS exists in two
surrounded by forms; zinc blende and wurtzite. In
four 7n@* ions ; :
7n@* ions of second zinc blende, S* ions have cep or fce
unit cell arrangement (as shown) but in wurtzite
: rae ‘ i S* ions have hcp arrangement. The
Zing pea yn) arrangement of Zn** ions is same in both
Calcium fluoride (CaF,) i.e. occupy half the tetrahedral sites.
* Ca** ions in cep arrangement jan aurundiod by
(i.e. Ca** ions occupy all the corners
and all the face centres of the cube)
¢ F ions occupy all tetrahedral sites
+ C.N. of Ca”* = 8
¢ CIN. of F =4
| This structure is called fluorite structure.
Sodium oxide (Na,O) has structure reverse
of fluorite structure. O?- ions are arranged
in eccp arrangement and Na‘ ions occupy all
the tetrahedral sites. Itis called antifluorite
structure.
Calcium fluoride (CaF,)
 MODERN'’S abe + OF CHEMISTRY
-XII

Table 4. Summary of the structures of ionic solids.

Compound Co-ordination number Other Examples
NaCl ccp arrangement of CI, Li, Na, K
Nat‘ in all the octahedral sites halides, AgCl,
AgBr, MgO, CaO
Ans ccp arrangement of S*, cs Bes, CuCl,
(Zine blende) | Zn** in alternative tetrahedral sites | cs CuBr, Cul
CsCl Simple cubic arrangement of CI, = CsBr, Csl
Cs* in cubic sites =§ T1Cl, TlBr
a ee ee is gage ais mm

F- occupy all tetrahedral sites CaF,, CdF,

eo ee 2 Am A

Nat occupy all tetrahedral sites

Effect of Temperature and Pressure on Crystal Structures

At ordinary temperatures and pressures, chlorides, bromides and iodides of Li, Na, K and Kb as well as some of the halides
of silver possess the sodium chloride type structure. In this, the coordination number of both the negative and positive ions
are 6: 6. On the application of high pressure, these change to CsCl type structure in which the coordination number of ions
become 8 : 8. Therefore, the high pressure increases the coordination number. On the other hand, on heating to about
760 K, the CsCl structure transforms to the NaCl structure.

NaCl structure — ———— CsCl structure

(6 : 6 coordination) . (8 : § coordination)
Similarly, NH,Cl, NH,Br and NH,I transform from CsCl structure to the NaCl structure at 457 K, 411 K and 253 K
respectively.

>» Structure of diamond.

O Diamond has same overall geometry as zinc blende but with all atoms identical. It has face centred cubic (fcc) structure
with four more atoms which are present in alternate tetrahedral voids.
There are 8 carbon atoms per unit cell in diamond as calculated below:
Diamond has § carbon atoms at the corners (each contributing 1/8), 6 atoms at faces (each contributing 1/2) of the cube
and 4 atoms at tetrahedral sites (not shared by any other). Thus

Total number of atoms per unit cell=8 (at corners) x - + 6 (at faces) x : + 4 (at tetrahedral sites) x 1

—- 14+5+4+4=8 atoms

== SOLVED EXAMPLES
LU) Example 10 sites are occupied by atoms of element A, then for each atom of
A compound is formed by two elements P and @. _ B, the number ofA atoms will be 2 x 2/3 = 4/3.
Atoms of Q (as anions) make hep lattice and those of 4
the element P (as cations) occupy all the tetrahedral Ratio of atoms A and B = ao -4:3
voids. What ts the formula of the compound?
.. Formula of compound : A,B.
(Kerala S.B. 2014)
LJ Example 12
Solution : Atoms @ adopt Acp arrangement and there are
two tetrahedral sites per Q atom. Since all the tetrahedral sites In a cubic close packed structure of mixed oxides,
are occupied by P atoms, this means that there are two P atoms the lattice is made up of oxide ions, one-eighth of
for each Q atom. tetrahedral voids are occupied by divalent ions (A**)
Thus, the formula of the compound = P,Q. while one-half of octahedral voids are occupied by
O Example 11 trivalent ions (B*+). What is the formula of the oxide ?
Atoms of element B form hep lattice and those of the Solution : In a close packed arrangement, there is one
octahedral and two tetrahedral voids corresponding to each atom
element A occupy 2/8rd of the tetrahedral voids. constituting the lattice. Therefore, if
What ts the formula of the compound formed by these
Number of oxide ions (O) per unit cell = n
elements AandB? {N.C.E.R.T) (Assam S.B. 2017)
Number of tetrahedral voids per oxide ion in lattice
Solution : Atoms 5 adopt hcp arrangement and there are
=mx2=2n
two tetrahedral sites per atom of B. Since 2/Srd of the tetrahedral
SOLID STATE 1/31 a
1 ° ae | , | noid |
ee ee ee whileAl°* tons occupy the octahedral voids. Calculate
8 4 the percentage of
Number of octahedral voids per oxide ion in lattice
(i) tetrahedral voids occupied by Mg** ions
ts a — (iit) octahedral voids occupied by Al** ions.
No. of trivalent (B**) ions =n x = = — Solution : According to the formula MgAl,O,, there are
2 2 4 oxide ions, 1Mg** and 2 Al** ions per formula unit. If 4 oxide
p.n _ ff, ions are in ccp arrangement, there will be 4 octahedral voids and
sccumeleaonatined cai 4°20 " 8 tetrahedral voids. Thus, 1 Mg** ion is present in one of the
ee er 8 tetrahedral voids and 2 Al** ions are present in 2 octahedral
voids out of 4 available.
2 Formula of the compound = AB,O,.
(i) Percentage of tetrahedral voids occupied by Mg** ions
LJ Example 13
= = x 100 = 12.6%
The mineral spinel has the molecular formula 7
Mg AlsO4. In this, oxide ions are present in cep (11) Percentage of octahedral voids occupied by Al** ions

arrangement, Mg* ions occupy the tetrahedral voids = , x 100 = 50%

Learning Plus |
LOCATING TETRAHEDRAL AND OCTAHEDRAL VOIDS
We have learnt that close packed structures have both tetrahedral and octahedral voids. Let us visualize these voids in
ccp (or fcc) structures.
» Locating Tetrahedral Voids
Let us consider a unit cell of ccp or fcc lattice. It has atoms at all the corners of the cube and at the centre of each face as
shown in Fig.1(a). If we see carefully, we observe that the unit cell has eight small cubes. Each small cube has atoms at alternate
corners. Therefore, each small cube has 4 atoms. When joined to each other, they make a regular tetrahedron. The centre of
the small cube becomes tetrahedral void. Thus, there is one tetrahedral void in each small cube. Since there are eight small
cubes and therefore, there are eight tetrahedral voids in ccp unit cell.
We know that ccp structure has 4 atoms per unit cell. Thus, the number of tetrahedral voids is twice the number of
atoms. In Fig. 1(a@) only one tetrahedral site is shown while in Fig 1 (0) eight tetrahedral voids in ccp structure are shown.

Tetrahedral

i
t
i
|
'-Q+ i»if i]
‘ i hi i
th,

I
i
i,
z. *1
I
i eS
aRe
me
ee
=====
]
i
\ *

1 ba

i # | “ | -

a a a a a fz
rT FE eee
ee Cy
|

(a) One tetrahedral void in cep structure. (6) Eight tetrahedral voids in cep structure.
Fig.1. Locating tetrahedral voids in ccp structure.
> Locating Octahedral Voids
Let us consider the unit cell of cep or fcc lattice. It has atoms at all the corners and at the centre of each face as shown in
Fig. 2(a). If we carefully see, we observe that the body centre of the cube, O, is not occupied but it is surrounded by six atoms
on centre of six faces. If these face centres are joined, they make an octahedron. Thus, the centre of this octahedron 1.¢., point O
becomes octahedral void.
In addition to body centre, there is an octahedral void at the centre of each edge as shown Fig. 2(5). It is also surrounded by
six atoms as shown in Fig. 2(0d).
Thus in a ccp unit cell, there are 12 octahedral voids located on edges and 1 at the body centre of the cube. Now, each edge
of the cube is shared between four adjacent unit cells, so 1s the octahedral void located on it. This means that 1/4th of each void
belongs to a particular unit cell.
Thus, in ecp structure, the number of octahedral voids are :
Octahedral void at the body centre of the cube = 1
 MODERN'S abe + OF CHEMISTRY
-XII

Octahedral voids at the edges = 12 x - —2

.. Total number of octahedral voids = 14+5=4

We know that in ccp structure, each unit cell has 4 atoms. Therefore, the number of octahedral voids are same as the
number of atoms.

Octahedral arrangement
around one void at the

(a) Octahedral void at body centre of ccp unit cell (6) 12 octahedral voids at the edges in ccp unit cell (shown @)
Fig.2. Locating octahedral voids in cep structure.

18. A solid is made of two elements X and Y. Atoms X are in fec arrangement and
Y atoms occupy all the octahedral sites and alternate tetrahedral sites. What is
the formula of the compound ?
19. A compound is formed by two elements X and Y. Atoms of element Y (as anions)
make ccp and those of the element X (as cations) occupy all the octahedral
voids. What is the formula of the compound? {VU
20. A compound is formed by two elements M and N. The element N rE ecp
and M atom occupy 1/3 of the tetrahedral voids. What is the formula of the
hs ee ofhpouied 7 (Pb.S.B. 2013, D.S.B. 2015)
19. XY. 21. In a erystalline solid, anions Y are arranged in ccp arrangement. Cations X
20. M.N,. are equally distributed between tetrahedral and octahedral voids. If all the
| octahedral voids are occupied, what is the formula of the solid ?
21. X,Y. 22. In a metallic oxide, oxide ions are arranged in cubic close packing. One sixth of
22. PQO,. the tetrahedral voids are occupied by cations P and one third of octahedral voids
22. AlO.. are occupied by the cations @. Deduce the formula of the compound. (Pb.S.5. 2018)
——————— Ss 23. In corrundum, oxide ions are arranged in /icp arrangement and the aluminium
Hints & Solutions on page 57 ions occupy 2/3 of the octahedral voids. What is the formula of corrudum ?

Accelerate Your Potential

(for JEE Advance)
m rc In a face centred lattice of X and Y, X atoms
in
BER? Cation X* are equally formate Bereces ie PECRCTIUREES Coenen EeeohleN GLuninaen ae iace centres.
octahedral and tetrahedral voids. If all the octahedral (a) What is the formula of the compound ?
voids are occupied, whatis the formula of the compound? (6b) What would be the formula of the compound if :
Suppose the number of anions, Y =N (tz) one of the X atoms is missing from a corner
Then number of octahedral voids = N in each unit cell,
Number of tetrahedral voids = 2N (ii) two atoms of X are missing from the corners,
Since octahedral and tetrahedral voids are equally occupied (111) one of the X atoms from a corner is replaced by
by cations X* and all the octahedral voids are occupied, then N Z atoms (also monovalent) ?
cations X* are present in octahedral voids and N cations X* are (a) No. of X atoms in the unit cell =8 x 1/8 =1
present
in tetrahedral voids. Thus, Wa ade spare fai ps crore celll a ee 3
No. of cations present = N+N=2N Formula = XY, 2
Ratio of cations and anions = 2:1 (:) If one X atom is missing, no. of X atoms = 7/8
Formula of the compound = X,Y. Formulas X__Y,, or A_Y¥.,
SOLID STATE 1133 [
(1) If two X atoms are missing, no. of X atoms = 6/8 = 3/4 No. cfoctahedral sites — 4
Formula = a td > No. of tetrahedral sites = 4x2=8
it) No. of X atoms = 7/8, No. of Z at = 1/8
- ‘5oe - Bent Rees ae (:) No. of tetrahedral sites occupied = 8 xs al
Formula = X_,,.Y.,Z,, or X,Y,,Z 1
BEES Un a normal spinel structure, 0? ions form No. of octahedral sites occupied = 4 Ne ie
fee packing and 1/8 of the tetrahedral sites are occupied ee a eae
by divalent metal, A** ions and half of the octahedral sites - SeSEAER TA FIEH z i rs ar
are occupied by trivalent metal B* ions, what is the ratio Octahedral sites 2
of gfe en ae (it) No. of tetrahedral sites unoccupied = 8—1=7
(ii) not oceupied in spinel structure No. of octahedral sites unoccupied = 4—-2=2
Since O*- ions form fec structure, there will be four delraniyiyal sites a ang 0
O*- ions per unit cell. Therefore, Octahedral sites 2

Conceptu uUesTIONS =—1

Q.1. A metal crystallizes in a body centred cubic structure. If 'a' is the edge length of its unit cell, 'r' is the
radius of the sphere. What is the relationship between 'r' and 'a'? (CBSE Sample Paper 2017-18)

Ans. r= = a
Q.2. If the radius of the octahedral void is 'r' and radius of the atoms in close packing is 'R'. What is the
relation between 'r' and 'R'? (CBSE Sample Paper 2017-18)
Ans. r=0.414 KR.
Q.3. In a close packing of N spheres, how many
(1)tetrahedral, and (11) octahedral sites are present?
. (1) Tetrahedral = 2N, (iz) Octahedral = N.
. Arrange simple cubic, body centred cubic, face centred cubic and hexagonal close packing in the
increasing order of packing efficiency.
. Simple cubic < body centred cubic < face centred cubic = hexagonal close packing.
. (a) What is meant by the term coordination number ?
(b) What is the coordination number of atoms:
(4) in a cubic close packed structure (zz) in a body centred cubic structure ?
. (a) Coordination number is the number of nearest neighbours of any constituent particle in the crystal lattice.
(6) (4) 12 (it) 8.
. The ions of NaF and MgO all have the same number of electrons and the internuclear distances are
about the same (235 pm and 215 pm). Why then are the melting points of NaF and MgO so different
(992°C and 2642°C) ?
- In MgO, both the ions carry two units of charge (Mg**, O7-) whereas in NaF, each ion carries only one unit charge
(NatF). Therefore, there are stronger electrostatic forces of attraction in MgO and, hence, more energy is required
to overcome these forces. Thus, its melting point is high.
» Name the (7) most symmetrical and (i7) most unsymmetrical crystal system.
(4) Most symmetrical crystal system : Cubic
(zt) Most unsymmetrical crystal system : Triclinic.
. How many atoms can be assigned to its unit cell if an element forms (1) a body centred cubic cell and
(11) face centred cubic cell ? (A.LS.B. 2005)
Ans. (i) 2 (21) 4.
Q.9. What is the maximum coordination number of an atom in a hep crystal structure of an element. ?
(D.S.B. 2005)
Ans. 12.
Q.10. Which network solid is an exceptionally good conductor of electricity?
Ans. Graphite, a network solid is a good conductor of electricity.
Q.11. How are unit cell and space lattice related ?
Ans. Space lattice is obtained by repeating the unit cell in three dimensions. The spatial arrangement, stoichiometry
and density of unit cell and space lattice are equivalent.
 MODERN'S abc + OF CHEMISTRY
-XII

Q.12. Pick out the odd ones from the following sets:
(t) Sulphur, Argon, Solid CO,, Diamond; (i) SiC, Quartz, BaO, Graphite
Ans. (z) Diamond because all others are molecular solids.
(11) BaO because all others are covalent solids.
Q.13. What is the two dimensional coordination number of a molecule in square packed layer ?
N.C.E.R.T. (Meghalaya S.B. 2017)
Ans. A.
Q.14. Solid A is very hard electrical insulator in solid as well as in molten state and melts at extremel
high temperature. What type of solid is it ? \N.C.E.R.T.
Ans. Covalent or network solid like quartz (510,) or 51C.
Q.15. What type of solids are electrical conductors, malleable and ductile ? N.. C.E.R.T
Ans. Metallic solids.
Q.16. How many octahedral voids are there in 1 mole of a compound having cubic closed packed
structure ? (CBSE Sample Paper 2007)
Ans. 1 mole
Q.17. What is the total number of atoms per unit cell in a face centred cubic structure ?
(A.LS.B., 2008, D.S.B. 2008)
Ans. A.
Q.18. Some of the very old glass objects appear slightly milky instead of being transparent. Why ?
(A.L.S.B.2007)
Ans. This is because of some crystallization in that region.
Q.19. An ionic compound AB, possesses CaF, type crystal structure. Write the co-ordination numbers of A**
and B ions in crystals of AB,,. (D.S.B. 2000)
Ans. C.N. of A**=8;C.N. of B =4.
Q.20. An iron oxide crystallizes in a hexagonal close packed arrangement of oxide ions with two out of every
three octahedral voids occupied by iron. Give the formula of the iron oxide. (Meghalaya S.B. 2014)
Ans. In a close packed arrangement, there is one octahedral site corresponding to each atom constituting the lattice.
Therefore,
No. of oxide ions per unit cell in hep arrangement = 6
No. of octahedral holes = 6x1=6
No. ofironions = 6x : =4
Formula of the compound = Fe,O, or Fe,O,.
Q.21. If three elements X, Y and Z crystallize in a cubic solid with X atoms at the corners, Y atoms at the cube
centres and Z atoms at the faces of the cube, then write the formula of the compound.
Ans. Atom X per unit cell = 8 x Fe 1
Atom Y per unit cell = 1
1
Atom 4 per unit cell = 6 x a=2
.. Formula of the compound = XYZ,
Q.22. In asolid ‘AB’, ‘A’ atoms have ccp arrangement and5 atoms
occupy all the octahedral sites. If all the face centred
atoms along one of the axes are removed, then what will
be the resultant stoichiometry of the compound?
Ans. In ccp type structure, there are 8A at the corners of the cube
and 6A atoms on the face centres. If all the face centred atoms
along one of the axes are removed, it means removal of 2A
atoms. Therefore, only 4 atoms will be left on faces.

No. of A atoms per unit cell = 8 x - +4x - =3

No. of B atoms in ccp structure are 12 at edge centred and 1 at
body centre. Therefore,
No. of B atoms per unit cell= 12 x 7 +1=4
B A
.. Stoichiometry of compound = A.B,
2(A)atoms along one axis are removed.
Q.23. Both diamond and rhombic sulphur are covalent solids but the latter has very low melting point than
the former. Explain why ?
Ans. Diamond is a network covalent solid with strong interatomic forces whereas sulphur is a molecular solid consisting
of puckered eight membered rings (S,) held together by weak van der Waals forces.
SOLID STATE 1/35 [
Q.24. Write a feature which will distinguish a metallic solid from an ionic solid. (D.S.B. 2010)
Ans. Metallic solids are good conductors of heat and electricity whereas ionic solids are insulators in solid state but
conductors in molten state and in aqueous solution.
Q.25. Write a distinguishing feature of metallic solids. (A.L.S.B. 2010)
Ans. Metallic solids are good conductors of heat and electricity.
Q.26. What is the difference between glass and quartz while both are made up from 510, tetrahedral? Under
what conditions could quartz be converted into glass ?
Ans. Glass is an amorphous solid while quartz is a crystalline solid. On melting quartz and then rapidly cooling i.e.,
annealing, quartz is converted to glass.
Q.27. What difference in behaviour between the glass and sodium chloride would you expect to observe if
you break off a piece of either cube ?
Ans. The glass (an amorphous solid) would break irregularly, usually in curved shapes because its component molecules
are not arranged in an ordered pattern. On the other hand, sodium chloride (an ionic solid) would break off along
flat surfaces parallel to the faces of the cube because the planes of its component ions are parallel to the faces of the
crystalline cube.
Q.28. KF has cep structure. Calculate the radius of the unit cell if the side of the cube or edge length is 400
pm. How many F' ions and octahedral voids are there in the unit cell ? (CBSE Sample Paper 2011)

ee OL 400
Ans. For ccp lattice, = 141.4 pm
— 2f2 2x«1.414
There are four F ions and four octahedral voids.
Q.29. What is the relationship between the edge length (a) of the unit cell and radius (r) of an atom in a face
centred unit cell? (Meghalaya S.B. 2013)
a
Ans. |
2v2
Q.30. How will you show that glass is a supercooled liquid ?
Ans. On being heated, glass has the property to flow like liquids. If we examine carefully the window panes of old buildings,
we observe that they become slightly thicker at the bottom than at the top. This is because glass flows down very
slowly and makes the bottom portion slightly thicker. Hence, glass is called supercooled liquid.

CALCULATIONS INVOLVING UNIT CELL DIMENSIONS

From the dimensions of the unit cell, it is possible to calculate the volume
of the unit cell. From the knowledge of the density of unit cell, we can calculate
the mass of atoms in the unit cell or vice-versa.
If we know the edge of a cubic crystal of an element or compound, we can
easily calculate its density as described below :
Consider a unit cell of edge ‘a’ (cm) ‘ 5
The length of the edge of the cell = @ cm edge = a cm
Volume of unit cell = a? cm®

Density of unit cell = ee ren

Mass of unit cell
= Number of atoms in a unit cell x Mass of each atom = Z x m we (it)
where Z = number of atoms in unit cell and
m = mass of each atom
Mass of an atom present in unit cell,
_ Atomic mass _M It may be noted that the relation
~ Avogadro number _ Ny considers the cubic crystals of
M elements. However, for cubic crystals
Mass of unit cell = Z x — of ionic compounds, the formula is
Substituting in eq. (7), we get the same except that in the case of
ionic compounds, Z is the number of
formula units present in one unit cell
and M is formula mass.
 MODERN'’S abc + OF CHEMISTRY
-XII

If edge length ‘a’ is in pm, then

Edge length = a pm
KEY FORMULAE AND UNITS =-ax10"’m-=ax 107) cm
Density of unit cell (and hence den- Volume of unit cell = (a x 10°19 cm)? = a? x 10-8 em?
sity of a crystal), So, the formula becomes
AxM 3
ZAxM Density of unit cell = g cm
a* x10" XN,
= a’ xN,
where ‘a’ is in pm.
where a is edge of unit cell in cm In terms of SI units, if a is in metres and M is in kg mol", then
N, = Avogadro number (6.022 x ZxM
1024)
Density =/] ae mm
ct xN,
M = Atomic mass of element
or formula mass of the Density of unit cell is the same as the density of the substance. If the
compound. density of the element is known by other method, Avogadro number or number
“4 = No. of atoms present per unit of atoms in a given amount of element can be easily calculated.
cell or formula units The density of solids can be used in different ways.
e.g. for foc, 4 = 4,
for bee, Z = 2,
for simple cubic, 4 = 1.

SiO]
AYE 1D = O40)
2d

A. Unit Cell Dimensions and Density

LJ Example 14
or = 361.42 x 10° cm
An element having bcc geometry has atomic mass 50u.
Since the lattice is fec, the number of copper atoms per
Calculate the density of the unit cell, if its edge length
umit cell, Z = 4.
is 290 pm. (Mizoram S.B. 2015, Pb. S.B. 2015, 2016)
Density, P= a
3
Solution: Length of edge,a = 290 pm a XN,

= 200x 10%em M = 63.66 u, N, = 6.02 x 107°

Since it is bcc arrangement,
463.55
No. of atoms in the unit cell, Z = 2 pP —. eS

(361.42 x 1071")? x (6.02 x 107")

Atomic mass of the element, M = 60g mol!
= 8.94 ¢g cm?
Density = ORs
a xN,
LJ Example 16
2x50 g¢mol? Sodium has body centred cubic structure having
nearest neighbour distance 365.9 pm. Calculate its
density. (Atomic mass of sodium = 28 g mol-1.)
6.81 g cm™~. Solution : For the bcc structure, edge length is related to
nearest neighbour distance (d) as
LI Example 15
Copper crystallizes with face centred cubic unit cell. d=
adeh
—a or
2d
a=—>
Ifthe radius of copper atom is 127.8 pm, calculate the Fy V3
density of copper metal. (Atomic mass of Cu = 63.55 u
2365.9
and Avogadro’s number, N, = 6.02 x 10° mol). a = ———— — 429.5 pm = 422.6 x 107° cm
1.732
(A.LLS.B. 2012)
Solution : For a fcc unit cell, edge length (a) is related to Density, p= a
a xN,
radius of atom as :
. a Z = 2 (for bcc), M = 23 g mol’, N, =6.02 x 10”
" * oe 2x23
or a=2/2.p =2%x1.414~x 127.8
(422.5 x10 1°)* x(6.02x 10”) .
= 361.42 pm
SOLID STATE

L} Example 17. Atomic mass of Cr, A = 52 g mol

An element crystallizes in a fcc lattice with cell edge Density of metal, p = 7.2 g em?
of 250 pm. Calculate its density if300g of this element ZxM
Now, = |
contain 2 x 1074 atoms. (D.S.B. 2016) a” x Ny
Solution : Length of edge, a = 250 pm = 260 x 10°"m Zx52 g mol!
7.2 em SS ———$<$—<—$$—
= 260 x 107 cm = (289 x 107M em)? x (6.022 x 107° mol")
Volume of unit cell = (260 x 10-1 em)?
7 (7.2 g em) x (289 x 10°’ em)? x (6.022 x 1077 mol!)
15.626 x 10 cm? or =". 9f—_ ie cos,
(52 2 mol)
Mass of unit cell =
No. of atoms in unit cell
x Mass of each atom = 2.01
Since the element has fcc arrangement, the number of atoms Since the unit cell contains 2 atoms, it is body centred
per unit cell, Z = 4 cubic (bee).
300 LJ Example 20
Mass of an atom =
2x10"° An element with molar mass 27 g mol forms a cubic
300 unit cell with edge length 4.05 x 10° cm. If its density
Mass of unit cell = x4-6.0x10~¢ is 2.7 g cm, what is the nature of the unit cell ?
2x10**
Mass of unit cell (D.S.B. 2015)
Density of unit cell ZxM
Volume of unit cell Solution : Density of unit cell, p =
a” xN,
6.0x10-~g p = 2.7 g cm, a = 4.06 x 10°* cm, M = 27 g mol},
15.625 10“ em? Nx = 6.022 x 105
38.4 g cm wx27
lL) Example 18 a: = ea ee)° x gs
(4.05107
ANA
6.022 x10
A metal having atomic mass 50 g mol has a body —8 3 23
m Z ?.7x(4.05x107~ ) x 6.022 x10 _40
centred cubic crystal structure. The density of metal
is 5.96 g cm. Find the volume of the unit ceil. rats

(H.P.S.B. 2001, Pb S.B. 2016 Mizoram S.B. 2018, 2018) Since Z = 4, the unit cell is face centred cubic (fcc) unit cell.
Solution : Ifa is the edge length of the unit cell, then volume
of unit cell, V =a? . Atomic Mass and Number of Atoms from Density
Density of unit cell, p = 5.96 g em and Unit Cell Dimensions
Atomic mass of the metal, M = 50 g mol LJ Example 21
No. of atoms per unit cell, Z = 2 (bcc) An element with density 11.2 g cm forms a fcc lattice
Now, Density = - with edge length of 4 x 10% cm. Calculate the atomic
a xN,
mass of the element. (D. S. B. 2014, Pb. S.B. 2016)
_ _ Z£xM Solution: Edge length of the unit cell
DP" VXN, a = 4x10%cem
Density = 11.2 gcm™>
ae _ Z£xM
No. of atoms per unit cell in fcc lattice, Z = 4
— pxN,
Density, 0 = —_
2x (50 g mol™!) a” xN,
Vaune = OTe
—{~—_ =
(5.96 g em) x (6.022 x 107? mol!)
a ils eS
(4 x 10°%em)?x
(6.02 ¥ 107° mol”
)
27.86 x 10-*4 cm*,

. Lattice Type from Density and Unit Cell Dimensions

4
lL} Example 19 = 107.9 g mol!
The density of chromium metal is 7.2 gcm~. If the unit Atomic mass of element = 107.9 u.

cell ts cubic with edge length of 289 pm, determine the LJ Kxample 22
type of unit cell (simple, body centred or face centred)
An element has a body centred cubic (bcc) structure
[Atomic mass of Cr =52a.m.u., N, = 6.02 x 10°? mol).
with a cell edge of 288 pm. The density of the element
(Pb. S. B. 2014, 2017)
is 7.2 gem, How many atoms are present in 208 g of
Solution : Length of the edge = 289 pm = 289 x 1077 m the element ? (D.S.B. 2006, Pb.S.B. 2007)
= 289 x 10°" cm
 MODERN'S abc + OF CHEMISTRY
-XII

Solution: Edge length of the unit cell = 288 pm Solution: Sodium chloride has face centred cubic structure.
= 288 x 10°19 cm Therefore, the number of formula units or molecules per unit
Volume of the unit cell = (288 x 107-1")? em? cell, Z=4
= 2.39 x 107% em? Let Avogadro number Na
Mass of element = 208 g Molar mass of NaCl = 23 + 35.5 = 68.6 g mol}
Density of element = 7.2 g cm™= Since distance between Na* and Cl ions is 281 pm,
the length of edge is double the distance between Na* and
M
Volume of 208 g of the element = males CI ions.
Density
Edge of unit cell = 2 x 281 pm = 562 pm
or — 662 x 107! m — 662 x 10°’ em
Volume of element = cd a = 28.89 cm?
2g¢cem~ : ZxM
Density, » J Se N,
Number of unit cells in this volume
7 Volume of element 9165 scm? = bY
4x (58.5
Se
1+
~ Volume of unit cell (562 107~*cm) xN,

28.89 cm® 4x (58.5 IF

~ 2939x10-em / unit cell or nN, = { gamers
(2.165 g em™) x(562x107 em)?
= 12.08 x 1079 unit cells
6.09 x 10° mol-1,
Since the structure is bcc, number of atoms present in a unit
cell = 2
. Unit Cell Dimensions and lonic Radii from Density
The number of atoms in 208 g of the element
= 2x 12.08 x 10% = 24.16 x 107° atoms UL) Example 25
or = 2.416 x 1074 atoms
The compound CuCl has fee structure like ZnS. Its
LJ Example 23 density is 3.4 g em. What is the length of the edge of
An element E crystallizes tn body centred cubic the unit cell ? (Mizoram S.B. 2014)
structure. Ifthe edge length of the cell is 1.469 x 10-19 m Solution : CuCl has cubic close packed or face centred cubic
and the density is 19.3 g cem-, calculate the atomic structure like ZnS. The number of formula units or molecules of
mass of this element. Also calculate the radius of an CuCl per unit cell = 4.
atom of the element. (CBSE Sample Paper 2007)
Let length of each edge = acm
Solution : Edge length of the unit cell, a = 1.469 x 107° m
Volume of the cube = a® cm?
= 1.469 x 10% cm
Density ofthe cell = 3.4¢ em
Density, p = 19.3 g em™®
Formula mass of CuCl, M = 63.5 + 35.5 = 99
Since it is body centred, Z = 2
AxM . ZxM
Density p= xN,
p= a*xN,
2xM 4x (99 g mol)
19.3 g em = ____<""f & @/ 3.4¢en° = SS
(1.469x10 °cm)* x (6,022 10™ mol) d a? x (6.022 x10" mol)
(19.3 g cm) x (1.469x 10 °em)* «(6.022 x 10”* mol) or a 4x (99 g mol”)
or M 5
= 18.42 g mol? (3.4 g em) x (6.022 x10” mol)
Atomic mass = 18.42 u. 193.4 x 10-*4 em?
For a bcc structure, radius of an atom, a = §.78 x 10° cm or 578 pm.
. _ 48) _ 1.732x1.469x10m L] Example 26
4 ea 4 An element A crystallises in fec structure. 200g of this
— 6.36 x 1071! m element has 4.12 x 1074 atoms. The density of A is
7.2 gem. Calculate the edge length of the unit cell.
D. The Avogadro Constant from Density and Unit Cell (A.LLS.B. 2001)
Dimensions
Solution : Let length of each edge = a cm
LJ Example 24 Volume of unit cell = a? cm?
Calculate the value of Avogadro number from the Density = 7.2 ¢cem™°
following data : 200
Density of NaCl = 2.165 g cm, distance between Nat Mass of each atom =
4.1210"
and CT tons in NaCl crystal = 281 pm.
(A.LS.B. 2004, H.P.S.B. 2005, Pb. S.B. 2011, Hr. SB. 2017 = 48.54 x 10" g
Nagaland S.B. 2018) No. of atoms per unit cell = 4 (fcc)
SOLID STATE

Mass of unit cell = 4 x 48.54 x 10-4 owe a 4x58 g mol

= 194.16x 10* g
me BE “3 x (6,022.
10 mol)
N Sian Se Mass
See = Maine s____—4x58gmol*
24 (2.48 g em™) x (6,022 x 10” mol")
7.2 — 196.16x10"" = 156.3 x 10-4 em?
a
a = (166.3 x 10-4)
24
or ao 194.16 x10" — 96.97 x 10-4 em? or a = 6.376 x 107° em or 637.5 pm
Te Now, if radius of Fis r,- and radius of K* is r,., then
a = 2.999 x 10% cm = 299.9 pm. according to the figure, edge of unit cell,
or
a= 7,+ Jee
LU) Example 27
= Arye T;,-)
Niobium crystallizes in body centered cubic structure.
If density is 8.55 g cem~, calculate atomic radius of or iets = i:
niobium given its atomic mass 93 tu. | 2

Solution : Density = 8.55 gcm™ Thus, distance between K* and F ions will be half the edge
length in the unit cell.
Let length of the edge =a cm
Number of atoms per unit cell, Z = 2 (bcc) Thus, the distance between Kt and F- ions = a
Atomic mass, M =98 g molt = 268.8 pm.
: ZAxM
Density, p= axN, LJ Kxample 29
Aluminium crystallizes in a cubic close packed
| -1
8.65 gems = —“*8 Emo) _ structure. [ts metallic radius ts 125 pm.
a” x(6,02210™mol™) (a) What ts the length of the side of unit cell?
73 - 2x (93 g mol‘) (6) How many unit cells are there in 1.00 cm?
~ (8.55 g em) x(6.022x 10”? mol) of Al ?
(D.S.B. 2005, ALLS.B. 2005, Meghalaya S.B. 2018)
= 36.12 x 10-** cm?
Solution: For a cubic close packed structure, length of the
Edge length, a = (36.12 x 10-4)" = 3.306 x 10° cm side of unit cell is related to radius.
= 3.306 x 10°"m r = ra

Now, radius in body centred cubic, r =

V3
a a 2/2
or a =rx2J/2
-10 126 x 2 x 1.414 pm = 363.5 pm
as10 ™ _ 1.431 x 109m Volume of unit cell = (353.5 x 10°7° em)? = 4.42 x 10° em?
1
0.143 nm. No. of unit cells in 1 em® =
LJ Example 28 4.42 x103
KF has NaCl structure. What ts the distance between — 2.26 x 107 unit cells.
K* and F- in KF if density is 2.48 g em~ ? LJ Example 30
(Hr. S.B. 2005) Silver has atomic mass 108 a.m.u. and density
Solution : KF has NaCl (fec) structure, therefore, the 10.5 gem, If the edge length ofits unit cell is 409 pm,
number of KF molecules per unit cell, Z = 4
identify the type of unit cell. Also calculate the radius
Molar mass of KF = 68 g molt of an atom of silver.
Let the edge of unit cell = a cm
Solution : Edge length of unit cell
Density, p = 2.48 g em
a = 409 pm
AxM
Density, p = A = 409 x 10°19 em
A
Density, p = 10.6¢em>
Atomic mass of silver = 108 u
ZxM
ows P= BxN é
Z x(108¢g mol
10.6 gem? = ue
(409 x10! cm)? x(6.022 x 10% mol)
or 4 =
+
108¢ mol?
+—/,.-+2NF, +1--—+
Z=4.0
 MODERN'S abe + OF CHEMISTRY
-XII

Since the unit cell contains 4 atoms per unit cell, it is face LJ EKxample 32
centred cubic (fcc) unit cell.
The density of lead is 11.35 g cm and the metal
For jcc, r= — = SPM 144.6 pm crystallizes with fee unit cell. Estimate the radius
2/2 -2x1.414 of lead atom. (At. Mass of lead = 207 g mol! and
UI Example 31. N, = 6.02 x 1078 mol-*) (D.S.B. 2011)
Silver metal crystallises with a face centred cubic Sn lotten: Let length of edge = a cm
lattice. The length of the unit cell is found to be Density = 11.35
g em™®
4.077 x 10° cm. Calculate atomic radius and density No. of atoms per unit cell in fee lattice = 4
of silver. (Atomic mass of Ag = 108u, N, = 6.02 x 107° Atomic mass, M = 207 g mol
mol-1), (C.B.S.E. Sample Paper 2012, H.P.S.B. 2016) “ixM
Solution : Edge length of unit cell, a = 4.077 X 10° cm i ey a’ xN,
For fcc lattice, radius of an atom is related to edge length, . <i
Q AB: 11.35 g em? = __ 4x(207gmol™)
- 4.077x1078 , s a” 3 x (6.022 x 107° a mol)F
"= 98 ~ ~exiaia
; “A41*20 0 om 4 4x(207 g mol™) a
Density, p . _2xM “> (11.35 gem) x (6.022 x 10" mol)
a®’xN, = 121.14 x 10-*4 em
4108 Edge length,a = (121,14)"* x10° = 4.948 x 10° cm
(4.077 x 10-8)? x (6.02 x 10”3) or — 4.948 x 10-2°m
(-~ Z=4 for fec) or = 494.8 x 10°” m = 494.8 pm
_ at
= aa eee Now, radius in fcc = ae = onan = 174.96 pm
2/2 2x1.414

24. An element X (At. mass = 40 g mol) having f.c.c. structure, has unit cell edge
length of 400 pm. Calculate the density of ‘X’ and the number of unit cells in 4 g
of ‘X’. (N, = 6.022 x 107? mol) (A.L.S.B. 2018)
25. An element crystallizes in a f.c.c. lattice with cell edge of 400 pm. The density of
the element is 7 g cm-°. How many atoms are present in 280 g of the element?
(A.L.S.B. 2016)
26. Tungsten has body centred cubic lattice. Each edge of the unit cell is 316 pm and
density of the metal is 19.36 g cem-*. How many atoms are present in 50 g of the
element ? (Pb.S.B. 2011)
27. CsCl has body centred cubic lattice with the length of a side of a unit cell 412.1
pm and aluminium is face centred cubic lattice with length of the side of unit
cell 405 pm. Which of the two has larger density ? (Atomic mass of Cs = 182.9,
i = Al = 26.9, Cl = 35.5)
= Answers to Practice Problems _= 28. Unit cell of an element (atomic mass = 108 amu and density = 10.5 g em“) has
24. 4.16 g em, 1.505 x 10 edge length 409 pm. Deduce the type of the crystal lattice.
25. 2.5 x 10% atoms | . | (Nagaland aa 2016, Pb.S.B.2017)
29. Iron has a body centred cubic unit cell with a cell dimension of 286.65 pm. The
26. 1.64 x 10™ atoms. density of iron is 7.874 gcm™. Use this information to calculate Avogadro number.
27. Density of CsCl = 3.995 g cm, (At. mass of Fe = 55.846 u) (A.[.S.B. 2009; D.S.B. 2009)
density of Al = 2.69 g em. CsCl 30. Gold (atomic mass = 197 y, atomic radius = 0.144 nm) crystallizes 1n a face centred
has larger density. unit cell. Determine the density of gold, (N ‘4 = 8.022 x 107° mol).
28. Z =A, fee (C_.B.S.E. Sample Paper 2010)
29. 6.022 xx 1023 31. An element (atomic mass = 60) having face centred cubic structure has a density
ie of 6.23 g em™?. What is the edge length of the unit cell ? (Pb.S.B. 2015)
pa egies 32. An element with density 10 g cm™ forms a cubic unit cell with edge length of
31. 400 pm 3 x 10° em. What is the nature of the cubic unit cell if the atomic mass of the
32. bec element is 81 g mol"! ? (A.L.S.B. 2015)
33. 12.7 g¢em> ge. Lead (II) sulphide crystal has NaCl structure. What is its density ? The edge
Hints & Solutions on page 57 length of the unit cell of PbS crystal is 500 pm. (atomic masses : Pb = 207,
S = 32) (Pb.S.B. 2008)
SOLID STATE

34, Formula mass of NaCl is 58.45 g mol! and density of its pure form is
2.167 g em. The average distance between adjacent sodium and chloride ions
in the crystal is 2.814 x 10-8 em. Calculate the Avogadro number.
oo. Copper crystallizes into a fcc lattice with edge length 3.61 x 10-* cm. Show that
the calculated density is in agreement with its measured value of 8.92 g cm.
36. Crystalline CsBr has a cubic structure. Calculate the unit cell edge length if the
density of CsBr crystal is 4.24 g cm™ (atomic masses : Cs = 133, Br = 80).
of. The unit cell of an element of atomic mass 108 and density 10.5 g cm™ is
a cube with edge length of 409 pm. Find the structure of the crystal lattice
(simple cube, fcc or bcc). Avogadro’s number = 6.023 x 107°.
(Pb. S.B. 2014, Meghalaya S.B. 2015)
38. What is the distance between Nat and CI ions in NaCl crystal if the density is
2.165 g em’. Molar mass of NaCl = 68.6 g mol, (N, = 6.02 x 10” mol.)
(A.L.S.B. 2006)
og. A compound AB crystallizes in bec lattice with unit cell edge length of 380 pm.
Calculate
(z) the distance between oppositely charged ions in the lattice.
(it) radius of At if radius of B- is 175 pm.
40. Thallium chloride T1Cl crystallises in either a simple cubic lattice or a face
centred cubic lattice of CI ions with Tl* ions in the holes. If the density of the
solid is 7.00 g em™® and edge of the unit cell is 3.85 x 10° cm, what is the unit
cell geometry ? (Atomic mass of Tl = 208.37 and of Cl = 35.5).
41. Cesium chloride crystallizes as cubic lattice and has a density of 4.0 gem*®. = Answers to Practice Problems =
Calculate the length of the edge of the unit cell of cesium chloride. (Molar mass 84. 6.06 x 1023
of CsCl = 168.6 g mol) (D.S.B. 2003)
, . 35. 8.96 g cm?
42, An element having atomic mass 107.9 u has FCC lattice. The edge length of its
unit cell is 408.6 pm Calculate density of the unit cell. [Given, N, = 6.022 x 10° 36. 436.9 pm.
mol] (Karnataka S.B. 2018) 37. fcc type
43. Calculate the Avogadro number from the following data of AB when AB has NaCl 38. 282 pm
type structure- 39. (i) 329.1 pm
Density of AB = 2.48 gem", M=58 (ii) 154.1 pm
Distance between A’ and B ions in AB = 269 pm (Hr.S.B. 2005) AN. Gat. Sarai alte
44, X-ray diffraction studies show that copper crystallizes in a fee unit cell with cell Al. 412
edge of 3.61 x 10-* cm. In a separate experiment copper is determined to have a : ee e
density of 8.92 g cm™. Calculate the molar mass of copper. (H.P.S.B. 2005) 42. 10.506 g cm
45. Chromium crystallizes in a body centred cubic lattice whose density is 43. 6.007 x 10°°.
7.20 g/ cm?. The length of the edge of unit cell is 288.4 pm. Calculate the Avogadro 44, 63.2. g mol
number (atomic mass of chromium = 62). (Pb S.5. 2015, Meghalaya S.B. 2016) A5. 6.02 x 1028
46. An element has atomic mass 93 g mol and density 11.5 g cm. Ifthe edge length Pi igre
of its unit cell is 300 pm, identify the type of unit cell. (D.S.B. 2017)
Hints & Solutions on puss 57

Accelerate Your Potential

(for JEE Advance)

— Lithium borohydride (LiBH,) crystallizes 4 x (22g¢mol!)

in an orthorhombic system having 4 molecules per unit ~ (6,81 1078 x 4.43x 10-8 x 7.17 x 1078 em3)
cell. The unit cell dimensions are: a=6.81 A, b= 4.43 Aand x (6.022 x 107? mol +)
c=7.17A. Calculatethe density ofthe crystal (At.mass of Li=7, = 0.676 g cm
B=11,H=1u).
Problem [6X Iron crystallizes in several forms. At 1185 K,
Since orthorhombic unit cell has all the angles, fe oninn centred cubic o-form of iron changes to the face
a=6=y=90°, then centred cubic y-form of iron. Assuming that the distance
Volume of unit cell =axbdxec between the nearest neighbours is the same in two forms
Molar mass of LiBH, = 7+ 11+4x1=22gmol". at the transition temperature, calculate the ratio of
AxM the density of w-form to that of y-form at the transition
P= @xbxoNa temperature.
 MODERN'S abc + OF CHEMISTRY
-XII

For body centred o-form ro ltr

| | or Na*
eee cr a ..(t)
— SE or a= 20 Tcl-
4 3 =
No. of atoms of per unit cell, Z = 2 Na. = 9:71
ir
1
1Si of w-form =e ee, ae 2xM Ke
Density ofiron = is 3 = Nax4r/ BF But Pyat = Moy X 0.62 = 0.62 roy

For face centred y-form, O.52r__

- asa = 0.71
a J Kt
r=—— or a=2v2r
2/2 e
| Cee K* — 0.52
No. of atoms of per unit cell, Z= 4 or A Of

Naw?” Na xv? fe
: ZixM 4xM
Density of y-form ofiron = t——~ = ——— = r
9/008
Density of a-form of iron _ 2 . (2./2r)? ao
Density of y-formof iron (4r/./3)° 4 T ai A- _ 0.52+0.71_ 1.23 Es
_ 2x 3v8 x 16V2 vf. jiieee Ora
64x 4 Dividing eq. (ii) by eq. (2)
3x 1.732 x 1.414 ae
=” 0.918 pongo 2 eee

i) KCl and NaCl crystallize in the same form Twat or O41 152
r r '
and Na” = 0.52 and —-N@* =0.71 <
Fin ek or 2 = 114
Cl K a

Calculate Gs
(i) ratio of the side of the unit cell for KCl] to that for . Side of unit cell for KCl _ 114
NaCl. ~ Side ofunit cell for NaCl
(74) the ratio of density of KCl to that of NaCl. 7%M
(:) Both KCl and NaCl crystallize in face centred (i) Density = 4 Ny
cubic arrangement in which the face length is related to radii of Z
almost: Since Z and N, are same for both KCI and NaCl

aq ond ; a’ Density o< ae

teat Tor = 5 ANd Tet to = | =

ne _ (KCl) — (KCI) , [a(NaChP

4D ae ae “p(NaCl) ~ M(NaCl) [a(KCDP
clr |
=
io
————— | ———
ol ) (ee
(NaCl) 1
or Nat +1 —/ eo = 98.0 fen al KCl) 1.14)
a
qa (adding 1 on both sides) = 0.86

IMPERFECTIONS IN SOLIDS
Crystalline solids are formed by regular repetition of large number of
unit cells in all directions. An ionic crystal which has the same unit
cell containing the same lattice points throughout the whole of
erystal is known as ideal crystal. However, such ideal crystals exist
only at absolute zero (0 K) temperature. At any temperature above 0 K,
the crystals have some departure from complete ordered arrangement. In
actual practice, it is very difficult to grow a perfect or an ideal crystal.
A solid consists of a number of many small individual crystals or grains,
each of which is deformed because it is highly packed among other deformed
crystals. Even single crystals which are grown with all care and which appear
to be perfect may contain some internal irregularities.
Any deviation from completely ordered arrangement of constituent
particles in a crystal is called disorder or a defect.
SOLID STATE

The crystal may have additional defects due to the presence of some
impurities. The term disorder or imperfection is generally used to denote
departure from perfectly ordered state of the constituents of the crystals.
These imperfections will not only change the properties of the crystals but
also give rise to new properties.
TYPES OF DEFECTS
Broadly speaking, there are two types of defects:
(1) Point defects (it) Line defects
(i) Point defects
The defects which arise due to the irregularity or deviations from
ideal arrangement of atoms around a point or an atom in a crystalline
substance are called point defects or atomic imperfections.
(ii) Line defects
The defects which arise due to irregularities or
deviations from ideal arrangement in entire row of vacann ©) QO Q ©)

oe °_—
lattice points are called line defects.
These irregularities are called crystal defects or Q
erystal imperfections. In the present unit we shall confine
our discussion to point defects only.
POINT DEFECTS IN SOLIDS C) Q Q
The point defects arise due to any one of the following
causes
(4) Vacancy defect. When some of the lattice sites are Q C) OQ QO :
vacant, the crystal is said to have vacancy defect (Fig. 39).
Fig. 39. Vacancy defect.
The unoccupied positions are called vacancies. This defect
results in decrease in density of the substance. This type
of defect may
and therefore,
(ii)
ene
also develop when a substance
it 1s also called thermodynamic Gd
is heated
defect
Interstitial defect. When some constituent
0000.0Pata. (2 occupying
interstitial
particles (atoms or molecules) occupy vacant interstitial Particle C) CQ QQ OQ peasition
positions, the crystal is said to have interstitial defect occupying
(Fig. 40). This defect increases the density slightly. interstitial
It may be noted that vacancy and interstitial defects position 99 OQ e OQ
are shown by non-ionic solids. On the otherhand, ionic
solids must always maintain electrical neutrality.
The point defects in ionic crystals may be classified as: VGWV0O00
A. Defects in stoichiometric crystals.
B. Defects in non-stoichiometric crystals. Fig. 40. Interstitial defect.
C. Impurity defects
A. Point Defects in Stoichiometric Crystals
Stoichiometric compounds are those in which the number of positive
and negative tons are exactly in the ratios indicated by their chemical formulae.
For simplicity, we can consider the compounds of the type AB having equal
number of A* and B- ions. The defects in these types of compounds are called
stoichiometric defects. In these compounds two types of defects are generally
observed. These are :
1. Schottky defect.
2. Frenkel defect.
1. Schottky defect
This defect was discovered by German scientist Schottky in 1930. It arises
if some of the atoms or tons are missing from their normal lattice sites. The
lattice sites which are unoccupied are called lattice vacancies or holes. Since
the crystal is to remain electrically neutral, equal number of cations and Fig. 41. An ideal crystal.
anions are missing. The ideal AB crystal is shown in Fig. 41. The existence
 MODERN'S abc + OF CHEMISTRY
-XII

of two holes one due to a missing cation and the other due to a missing anion
Cation vacancy Anion vacancy is shown in Fig. 42. This is basically a vacancy defect in ionic solids.
Conditions causing Schottky defects. This type of defect is usually
observed in strongly ionic compounds having
(1) high co-ordination number, and
(it) tons (cations and anions) of almost similar sizes.

For example, NaCl, KCl, KBr, CsCl and AgBr ionic solids have Schottky
defects. It has been observed that in NaCl, there are about 10° Schottky
pairs per cm® at room temperature. In one cm®, there are about 10” ions
and this means that there will be one Schottky defect per 101° ions in
NaCl. Because of the presence of large number of vacancies in crystals,
its density is markedly lowered.
Fig. 42. The Schottky defect in
crystals. 2. Frenkel defect
This defect was discovered by a Russian scientist Frenkel in 1926. It arises
Cation in when an ton ts missing from its normal position (causing a vacancy or a hole)
Cation vacancy — Interstitial site
and occupies an interstitial site between the lattice points. The existence of
one hole due to a missing cation from its normal position and occupying an
interstitial position is shown in Fig. 48. In this case also, the crystal remains
electrically neutral because the number of anions and cations remains the same.
This defect is also known as interstitial defect. It creates a vacancy defect
at its original position and an interstitial defect in its new location.
Conditions causing Frenkel defects. This defect generally occurs in
compounds in which
(1) co-ordination number is low,
(it) anions are much larger in size than the cations.
Fig. 43. A Frenkel defect. In pure alkali metal halides, these defects are not very common because
the ions cannot get into interstitial positions due to their large sizes. These
defects can be found in silver halides such as AgCl, AgBr, AglI, ZnS, etc.
Because of the small size of the Ag* ion and Zn** ion, these ions can go into
the interstitial sites.
We observe that vacancies or holes are present in crystals with Schottky as
well as Frenkel defect but the former leads to decrease in the overall density of
It may be noted that in certain ionic the substance but the latter does not.
solids such as AgBr, both Schottky It may be noted that in addition to two basic types of defects (Schottky and
and Frenkel defects occur. Frenkel), another hybrid type of defect can also arise from a combination of the two.
Consequences of Schottky and Frenkel Defects. Schottky and Frenkel
defects in crystals lead to some interesting consequences. These are given
below :
1. Because of the presence of these defects, the electrical conductivity of
crystals increases. When an electric field is applied, a nearby ion moves from
its lattice site to occupy a ‘hole’. This results in creating a new ‘hole’ and
another nearby ion moves into it and so on. This process continues and a hole,
thereby, moves from one end to the another end. Thus, it conducts electricity
across the whole of the crystal.
2. Due to the presence of holes in the crystal, its density decreases. However,
it may be noted that density decreases only for crystals having Schottky defects.
3. The presence of ‘holes’ also decreases the lattice energy or the stability
of the crystal. The presence of too many holes may cause a partial collapse
of the lattice.
4. The closeness of similar charges in Frenkel defects tends to increase
the dielectric constant of the crystals.
SOLID STATE

Differences between Schottky and Frenkel Defects

Schottky defect Frenkel defect

1. It is produced because of missing It is produced when some atoms or ions

atoms or ions from their normal are displaced from their normal sites and
crystal sites. occupy interstitial sites.
. The presence of Schottky defect It does not affect the density ofthe crystal.
lowers the density of the crystal.
. Itis generally shown by ionic solids It is generally exhibited by ionic solids
having high co-ordination number having low co-ordination number and
and in which cations and anions are in which anions are larger in size than
of equal sizes e.g., NaCl, CsCl. cations e.g., AgCl, ZnS.

B. Point Defects in Non-Stoichiometric Crystals

The compounds in which the ratio of positive and negative tons present
in the compound differs from that required by tdeal chemical formula of the
compound are called non-stoichiometric compounds. * The defects in
these compounds are called non-stoichiometric defects. Vanadium oxide,
for example has, the formula VO, where x lies between 0.6 and 1.3. Similarly,
iron (IJ) oxide of ideal composition FeO are difficult to obtain. Normally, we
get samples of more oxygen atoms than iron atoms (composition of Fe,,. O
but it may range from Fe,9, O to Fe,,, O). ZnO usually has excess of zinc
atoms than oxygen atoms, ZnO, (x < 1). However, it may be noted that in each
case, the electrical neutrality of the crystal is maintained. Non-stoichiometric
behaviour is most commonly found for transition metal compounds. It is also
found for some lanthanoids and actinoids.
These are of two types depending upon whether positive ions are in excess
or negative ions are in excess. These are also known as metal excess defects
and metal deficiency defects respectively. Some of these examples are
given below :
(A) Metal Excess Defects
In these defects, the positive ions are in excess. These may arise due to
the following two ways :
(4) anionic vacancies
(it) presence of extra cations in interstitial sites.
(4) Anion vacancies. In this case, negative ions may be missing from
Electron
their lattice sites leaving holes in which the electrons remain entrapped to remains
maintain the electrical neutrality. This is shown in Fig. 44. Evidently, there is trapped
in anion
an excess of positive (metal) ions although, the crystal as a whole is electrically vacancy
neutral. This type of defect is observed in those crystals which are likely to
form Schottky defects.
In alkali metal halides, anion vacancies are produced when alkali metal
halide crystals are heated in the atmosphere of the alkali metal vapours. For Fig. 44. Metal excess defects due to
example, when crystal of NaCl are heated in an atmosphere of sodium vapour, anion vacancy.
the excess of sodium atoms are deposited on the surface of the crystal. The
Cl ions diffuse to the surface of the crystal and combine with Na atoms to
give NaCl. This happens by the loss of electrons by sodium atoms to form
Nat ions. The electrons, thus produced by the ionisation of the sodium atoms
diffuse into the crystal and get trapped at the anion vacancies. The electrons
trapped in anion vacancies are referred to as F-centres (from German word
farbenzenter meaning colour centre). They impart yellow colour to the crystals The electrons trapped in anion
vacancies are called F-centres
of NaCl. The colour results by excitation of these electrons when they absorb
because they impart colour to crystals.
energy from the visible light falling on the crystals. Similarly, excess of
* Non-stoichiometric compounds are sometimes called berthollides after the name of French
inorganic chemist Claude Louis Berthollet, who studied such compounds.
 MODERN'S abc + OF CHEMISTRY
-XII

potassium in KCl makes the crystal appear violet (or lilac), excess of lithium
in LiCl makes the crystal appear pink.
Cation and (71) Excess cations occupying interstitial sites. In this case, there
electron tn are extra positive tons occupying interstitial sites and the electrons in another
interstitial
interstitial sites to maintain electrical neutrality. This is shown in Fig. 45.
sites
The defect may be visualised as the loss of non-metal atoms which leave their
electrons behind. The excess metal ions occupy interstitial positions.
This type of defect is found in crystals which are likely to develop Frenkel
defect. The common example is zinc oxide. Zinc oxide (ZnO) is white in colour at
room temperature. On heating, it loses oxygen reversibly at high temperatures
Fig. 45. Metal excess defects due to and turns yellow in colour.
extra cation.
JInQ —Heat_, Ae + =O, f 2e-

The excess Zn** ions are trapped in interstitial sites and equal number
of electrons are trapped in the neighbourhood to balance the electrical charge.
These electrons give rise to enhanced electrical conductivity.
Consequences of Metal Excess Defects
acquiring 1. The crystals with metal excess defects conduct electricity due to the presence
higher charge of free electrons. However, the conductivity is very low because of the number
of defects and therefore, the number of free electrons is very small. Because
of low conductivity as compared to conductivity of metals, these are called
semiconductors. These compounds
are also called n-type semi-conductors
Fig. 46. Metal deficient defect due to since the current is carried by the electrons in the normal way.
cation vacancy. 2. The crystals with metal excess defects are generally coloured. For
example, non-stoichiometric sodium chloride is yellow, non-stoichiometric
potassium chloride is violet.
(B) Metal Deficient Defects
REMEMBER
These contain less number of positive ions than negative ions. These arise
Because of metallic lustre of some due to two ways :
minerals of iron pyrites, they shine
like gold and have been nick named
(4) Cation vacancies
as fool’s gold. (it) Extra anions occupying interstitial sites
(1) Cation vacancies. In some cases, the positive ions may be missing
from their lattice sites. The extra negative charge may be balanced by some
nearby metal ion acquiring two positive charges instead of one. This is shown in
Fig. 46. This type of defect is possible in metals which show variable oxidation
states. The common examples of compounds having this defect are ferrous oxide,
ferrous sulphide, nickel oxide etc. In case of iron pyrites (FeS), for example,
two out of three ferrous ions in a lattice may be converted into Fe** state and
the third Fe** ion may be missing from its lattice site. Therefore, the crystal
contains Fe** and Fe** ions. This gives rise to exchange of electrons from one
Fe*+ ion to Fe** ion in which Fe** changes to Fe** and Fe®*+ changes to Fe*+
Anion occupying
interstitial site
ion. As a result, the crystal has metallic lustre. Because of the natural colour
of iron pyrites and metallic lustre some samples of minerals shine like gold
and have been nick-named as fool’s gold. Similarly, FeO is mostly found with
a composition of Fe, ,.O. It may actually range from Fe, .,0 to Fe, ,,0. In
crystals of FeO, some Fe** ions are missing and the loss of positive charge is
. Metal acquiring made up by presence of required number of Fe** ions. Moreover, since there
<~ higher charge is exchange of electrons, the substances become conductors.
(ii) Extra anions occupying interstitial sites. In this case, the extra
anions may be occupying interstitial positions. The extra negative charge is
balanced by the extra charges (oxidation of equal number of cations to higher
oxidation states) on the adjacent metal ions. This is shown in Fig. 47. Such
Fig. 47. Metal deficient defect due to type of defect is not common because the negative ions are usually very large
extra anion.
and they cannot easily fit into the interstitial sites.
SOLID STATE

Consequences of Metal Deficient Defects

Crystals with metal deficient defects are semiconductors. The conductivity
is due to the movement of electron from one ion to another. For example, when
an electron moves from ion At, it changes to A**. It is also called movement
of positive hole and the substances are called p-type semiconductors.
(C) Impurity Defects
These defects in tonic crystals arise due to the presence of some impurity
tons at the lattice sites (in place of host tons) or at the vacant interstitial sites.
For example, if molten NaCl containing a little amount of SrCl, is allowed
to crystallise, some of the sites of Nat ions are occupied by Sr** ions. For
each Sr2* ion introduced, two Na* ions are removed to maintain electrical Fig. 48. Introduction of a cation
neutrality. One of these lattice site is occupied by Sr** ion and the other vacancy in NaCl by substitution of
Nat by Sr**.
remains vacant. This is shown in Fig. 48. Therefore, these vacancies result
in increased electrical conductivity of the solid. Similar defect and behaviour
is observed when CdCl, is added to AgCl.

SOLVED EXAMPLES ;

LU) Example33
( of Nit = = 0.98 x 100 = 96%
If NaCl is doped with 10% mol% of SrCl,, what is the
concentration of cation vacancy ? NCERT
% of NiS* = 4%
L) EKxample 35
Solution : One cation of Sr** would create one cation vacancy If Al** replaces Na* ion at the edge centre of NaCl lattice
in NaCl. Therefore, the number of cation vacancies created in then calculate the vacancies in I mole of NaCl.
the lattice of NaCl is equal to the number of divalent Sr** ions
Solution : 1 mol of NaCl contains 1 mol of Nat ions z.e.
added.
~. Concentration of cation vacancy on being doped with 10-7 6.022 x 107° Na? ions.
mol % SrCl, NaCl has fee arrangement of Cl ions and Na? are
in |
= 10% mol% = 10” = 10 mol present at the edge centres and body centres.
100
Since there are 12 edges and each edge is shared by 4 unit
No. of Sr2* ions in 10 mol 10 x 6.023 x 1079
cells, then contribution of Cl ions present at the edge centres is
= 6.023 x 101% Sr** ions
No. of cation vacancies = 6.023 x 107°. x12 =3 .Contribution of Na‘ ion present at the body centre = 1
LU) Example 3s4
Thus, for every 4 Nat ions, the ions present at the edge centres
Analysis shows that nickel oxide has the formula
Nio.9801.00 What fractions of the nickel exist as Ni** and = 3.
Ni** ions in given oxide? The Na* ions which have been replaced by Al** ions
(Pb.S.B. 2018)
Solution : Ni, 4,0, 9, = =x6.022 x10” = 4.5165 x10”
Let Ni** be x so that Ni®* will be 0.98 — x. Total charge on To maintain electrical neutrality, 1 Al** ion will replace
the compound must be zero so that
3 Nat ions. This means that 1 position will be occupied
+ 2x +3(0.98-—x)—-2 = 0
and remaining 2 will be vacant.
2x + 2.94 —3x—-—2 = 0 -- No. of vacancies in 1 mole of NaCl
—x = — 0.94
or x = 0.94
: =x 4.5165 x10” = 3.011 x 10?3

_Answers
to Practice Problems =
47. The composition of a sample of wustite 1s Fe,9, O, 997.What mass percentage of
AT. 11.5%
iron is present in the form of Fe(IIT) ions ?
48, 91.67, 8.33
48. Analysis shows that a metal oxide has the empirical formula M, ,, O, ,9- Calculate
the percentage of M?* and M** ions in the crystal. (C_B.S.E. Sample Paper 2007) Hints & Solutions on page 57
 MODERN’S abc + OF CHEMISTRY
-XII

Accelerate Your Potential

(for JEE Advance)

Problem ih a = 0.560 nm. Calculate the density of the — @ xXNa

metal if it contains 0.1% Schottky defects. (Atomic mass of Z, = 4 (fec), M=23 + 36.6 =68.6 g mor,
metal = 40 g mol)
a = 662.6 pm or = 562.6 x 10-*° cm, N, = 6.022 x 10°
Due to Schottky defect, the vacant spaces will 4x 58.5
a
increase ;
resulting arr,
decrease : number of| atoms per unitit cell.
in ci p = ___
(662.6 x 107)? x (6.022 x10) _ 9 1 89 g oem

; 4x01
Inthiscase, Z = 100 = 8.996 Observed density = 2.158 gem
. Since observed density is less than theoretically calculated
Density We ZxM value, this means that some Na* and CI ions are missing from
' Na xa their lattice sites 1.e. the crystal has Schottky defect.
7 3.996 x (40g mol7!) bs (iz) Actual formula units of NaCl per unit cell can be calculated
(0.560 x 10~" cm)? x (6.022 x 10** mol!) , rae a® xN, Xp
= 15l¢ sae M
_ 662.6x 107 !°cm)® x (6.022 x 1078 mol!) x(2.158 g em7*)
adelTensth ofsodium chloride is found to ie 562. 6 pm. The
(58.5 g mol*)
density of NaCl is observed to be 2.158 g cm.
= 3.956
(i) Predict the type of defect present in the crystal.
Formula units missing per unit cell = 4—3.956 =0.044
(ii) Calculate the percentage of Na‘* and CI ions
missing. 0.044
% missing unit cells= x100 =1.1%
(1) The density can be calculated as

PROPERTIES OF SOLIDS
There is a close relationship between the properties of a solid and its composition
and structure. Some important properties of solids are discussed below :

1. Electrical Properties of Solids

Solids exhibit an interesting range of variation of electrical conductivities
extending over 27 orders of magnitude ranging from 10-7 to 10’ ohm! m"!
which no other physical property show.
On the basis of electrical conductivity, solids can be classified into three
types:
(1) conductors
(11) insulators
(111) semiconductors.
(1) Conductors. The solids which allow the passage of electric current are
called conductors. They have conductivities in the range 10* to 10’ ohm! m1.
For example, metals have conductivities of the order of 10’ ohm mand hence
are the best conductors of electricity. Conductors are of two types : metallic
conductors or electrolytic conductors.
(a) Metallic conductors are those which allow the electricity to pass through
REMEMBER them without undergoing any chemical change. For example, copper, silver
etc. Metals conduct electricity in solid as well as in molten state. In metallic
e Metals conduct electricity through
the movement of electrons.
conductors, the conductance is due to the movement of electrons under the
influence of an applied electric potential. The streams of electrons constitute
e Electrolytes conduct electricity due the current. The conductivity of metals depends upon the number of valence
to movement of ions. electrons avatlable per atom.
e Metals conduct electricity in the (6) Electrolytic conductors are those which allow the electricity to pass
solid as well as molten state. through them by undergoing chemical change. The conduction in ionic solids is
e Electrolytes conduct electricity only due to the migration of ions or other charged particles under the applied field.
in aqueous solution or molten state. Due to strong electrostatic forces of attraction, the ionic solids do not conduct
electricity. However, these conduct electricity to a good extent when they are
SOLID STATE

in their molten state or in the form of their aqueous solutions. In these states, REMEMBER
the ions of the electrolyte become free and they conduct electricity due to the
Range of conductivity
movement of ions.
e Conductors PG te hoe
(it) Insulators. The solids which do not allow the passage of electric ohm nr?
current through them are called insulators. They have very very low eSemiconductors : O-* te. 107
conductivities ranging between 10-“° to 10-'° ohm! m1. For example, wood, ohm-!m-!
sulphur, phosphorus, rubber etc. e Insulators : 10° to 10-19
(iit) Semiconductors. The solids whose conductivity lies between those ohm!m-t
of typical metallic conductors and insulators are called semiconductors.
The semiconductors have conductivity in the range of 10-° to 10* OQ? m1. The
conductivity of semiconductors is due to the presence of impurities and defects.
Effect of Temperature on Conductivity
In general, with increase in temperature the conductivity of metals decreases
REMEMBER
while that of semiconductors increases. However, there is very little increase
in the conductivity of an insulator as the temperature is increased. With increase in temperature
electrical conductivity of
The electrical behaviour of some typical transition metal oxides as metals
e metals decreases
(M), insulators (1) and oxides showing transition from metal to insulators
e® semiconductors increases.
behaviour (T) at a certain temperature are given below :
TiO (M) VO (T) MnO() FeO) CoO) NiO(I) CuO()
Ti,0,(T) V,0,(T) Cr,0,() Mn,0, (1) _— Fe, (1)
Vo, (T) CrO,@) Mn0O, dd)
TiO, V,0, D It is very interesting to note that
transition metal monoxides (MO),
Similar behaviour is exhibited by sulphides. all of which have similar NaCl
structures show very marked
Mechanism of Electrical Conduction
differences in their electrical
The conduction in most of the solids is through electron movement under an
properties.
electric field. However, in some ionic solids, the conduction is by ions. Therefore,
in the solids where the conduction is by the movement of electrons, the electrical e TiO is metallic, MnO, FeO, CuO,
conductivity depends on the number of electrons available to participate in etc. are insulators while VO is
the conduction process. The difference in electrical conductance behaviour of metallic or insulator depending
conductors, insulators and semiconductors can be explained with the help of upon temperature.
band model. CrO, 1s metallic, MnO, is
insulator while VO, is metallic
BAND THEORY FOR EXPLAINING THE BEHAVIOUR OF METAL or insulator depending upon
CONDUCTORS, SEMICONDUCTORS AND INSULATORS temperature.
The bonding in metals can be explained by extending the simple molecular
ReO, is metallic, while VO, and
orbital theory to metals, called band theory. The basis of band theory is that
TiO, are metallic or insulator
a metal lattice has an extremely large number of atoms. The atomic orbitals of
depending upon temperature.
these metal atoms overlap to form a large number of molecular orbitals which
are so close in energy to each other that they form energy bands. > Thus, transition metal oxides
Let us consider an example of lithium metal. Ignoring inner 1s-electrons show marked differences in
which do not involve in bonding, 2s-orbitals of lithium atoms may combine to form electrical properties.
molecular orbitals. We have learnt that in case of Li, (two atoms) 2s AOs on two To sum up
lithium atoms combine to give two MOs; one bonding MO and one anti-bonding
MO [Fig. 49 (a@)]. If we have three lithium atoms, three 2s AOs would combine to OTi0, CrO,, ReO, are metallic.
form three MOs; one bonding, one antibonding and one non-bonding [Fig. 49 (b)]. O MnO, FeO, CuO, are insulators
The energy of non-bonding MO is in between the bonding and antibonding VO, VO,, V,0,, TiO, etc. change
MO, exactly at the same level as the energy of the AOs. Similarly, in case of from metallic to insulator at a
four lithium atoms, four 2s AOs would combine to form four MOs; two bonding certain temperature.
and two antibonding MOs [Fig. 49 (c)]. Similarly, if we have N atoms of lithium
(N is Avogadro number, 6.02 x 107° atoms), 2s AOs of N atoms would combine
O Rhenium oxide, ReO, has
appearance as well as
to give N MOs. As the number of molecular orbitals is large, the energy levels
conductivity like copper.
of MOs are so close together, that they may almost be treated as continuous.
 MODERN'’S abc + OF CHEMISTRY
-XII

Such a group of energy levels is known as energy band and is responsible

for the name band model for metals.
The energy levels in a band is equal to the number of atoms in the metal.
The formation of an energy band depends upon :
(i) the close proximity of large number of atoms.
(iz) the energy difference between the pure atomic orbitals.
Thus, 2s-atomic orbitals give rise to one energy band, the 2p-atomic orbitals
also form a band of closely spaced energy levels. The various energy bands from
different atomic orbitals may overlap or be separated from each other depending
upon the relative energies of the atomic energy levels.

Antibonding MO

Bonding MO

Antibonding MO

Non-bonding MO

Bonding MO

;Antibonding MOs

:Bonding MQOs

N Closely
spaced MOs
(d) Li, (Metal)

The energy bands formed by the overlap of 1s, 2s and

2p AQOs of lithium metal are shown in Fig. 50.
2p AOs 2p Band The arrangement of electrons in different energy
N Atoms bands determine the characteristics of a metal. Now,
———— tOverlapping in the case of Li atom, the electronic configuration is
—_¥_- of 2s and 2p band 1s? 2s!. The 1s energy band will be completely filled.
2s AOs These electrons do not contribute towards bonding and
NAtoms — 2s Band may be ignored. As already learnt, in case of Li,, there
will be 2 valence electrons and there are two MOs.
Since each MO can accommodate two electrons (Pauli’s
exclusion principle), only bonding molecular orbital
N Atoms will be completely filled. Similarly, in case of Li,, the
four valence electrons would occupy only the two lowest
Fig. 50. Formation of energy bands in lithium atoms.
bonding MOs.
SOLID STATE

Thus, in these cases, half of the molecular orbitals remain unoccupied.

Similarly, N 2s atomic orbitals give N 2s molecular orbitals (energy band). Since
Li atom has only one valence electron, only half of the molecular orbitals will be
filled. In other words, only one half of the 2s band, will be filled in the lithium
metal. This is shown in Fig. 51. (It may be noted that the bands are displaced -
laterally for clarity). Thus, there are many empty levels into which electrons CO
=
can move. This movement of electrons from one level to another constitutes an = 2p Band
electric current. Z.
es
Thus, lithium is good conductor. At the same time, if we heat one end of
metal, electrons at that end gain energy and move to empty energy bands
2s Band
where they can travel easily to another part of the metal. This accounts for
thermal conduction of metals. Fig. 51. The band structure for Li metal.
We can apply the same arguments to beryllium. In beryllium, there are two
valence electrons and therefore, N atoms of beryllium will have 2N electrons from
2s AOs. Therefore, in beryllium metal, the 2s band will be completely filled
(Fig 52) There are no empty orbitals in 2s energy band into which electrons
can move. However, 2p energy band is completely empty and it overlaps the
2s energy band. When some electric field is applied, the electrons can move
into the empty band.
Thus, tf the band is partially filled or tt overlaps with a higher energy
ENERGY 2p Band
unoccupied band, then electrons can easily flow under an applied electric field
and metal shows conductivity. For example, a partially filled band is shown
in Fig. 58. (a) and overlapping bands are shown in Fig. 53(0) found in metals.
Therefore, when some electric field is applied electrons can easily move 2s Band

within partially filled band or empty overlapping band and this movement is Fig. 52. The band structure for Be metal.
responsible for electrical conductance of the substance. This type of behaviour
is shown by metals.
In general, the electrical conductance of solids depends upon
the energy gap between the filled valence bands and next higher
vacant energy band.
e The outermost filled energy band ts called valence band and
e the next (lowest lying) empty band in which electrons can move Overlapping
is called conduction band.
The spaces between valence band and conduction band
represent energies forbidden to electrons and are called energy
gaps or forbidden zone. The valence band and conduction bands
for metals, semi-conductors and insulators are shown in Fig. 54. Partially filed band
(t) In metals, the conduction band ts close to valence band and, (a) Overlapping bands
therefore, the electrons can easily go into the conduction band. (b)
Therefore, metals are good conductors. Fig. 53. Partially filled and overlapping bands.
(it) In insulators, the energy gap
between valence band and conduction
band is very large. Therefore, the
electrons from valence band cannot
jump into the conduction band. Hence,
the insulators have extremely low
conductivity. Overlapping or — omall Very large
(iit) Several solids have properties | very small energy energy gap
intermediate between metals and —A i SPSTEY BA7
insulators. These are called semi- ra} j
metals or semiconductors. They have
only small difference in energy between ,
the filled valence band and empty Conductor
: (Metal) Semi-conductor
conduction band. Therefore, some (Semi-metal) Insulator
electrons may jump to conduction band
Fig. 54. Valence and conductance bands in metals, semi-conductors and insulators.
and hence they show some conductivity.
 MODERN'’S abc + OF CHEMISTRY
-XII

Klectrical conductivity of semi-conductors increases with rise in temperature

because more electrons can jump to the conduction band. Substances like silicon
—s—$— $4
| | t |
and germanium show this type of behaviour.
Conduction of Electricity in Semiconductors
a ae a a Germanium and silicon are the most important commercial examples of
semiconductors. Atoms of both germanium and silicon have four electrons
ee in the outermost shell. Therefore, each atom is covalently bonded with four
ae a a neighbouring atoms. There are no free electrons in this structure and therefore
for practical purposes, the conductivities of pure germanium and silicon are very
(a) Network of pure silicon low and they behave as insulators. The energy gap between valence band and

A kk
conduction band for Ge and Si are 68 kJ mol and 106 kJ mol" respectively
| at room temperature.
These can behave as semi-conductors in two types :
| < wae (1) Intrinsic conduction
| GI e~— | (11) Axtrinsic conduction
a a a (t) Intrinsic conduction
—si— Si®: Si—Si— Pure silicon or germanium are poor conductors because they have network
1 | Gi | or lattice of four strong covalent bonds. [Fig. 55 (a)] When a sufficient amount
of energy by increasing temperature is supplied to the crystal, some covalent
(6) Intrinsic semi-conduction in silicon bonds may break due to thermal vibrations and electrons are released. When
the crystal is connected to the elecric current, these electrons move leaving
Fig. 55. (a) Pure silicon (5) Silicon behind a positive charge or a ‘positive hole’ at the site of missing electron. The
showing positive holes and negative crystal will now be able to conduct electricity because when electric field is
electrons.
applied, the electrons move in one direction and the ‘positive holes’ move in
the other direction. The electrons move through the interstices of the lattice
and the positive holes jump from one bond to another as shown in Fig. 55 (0).
This is known as intrinsic semiconductivity of the crystal. The intrinstic
semiconductor contains equal number of current carrying holes and electrons.
(41) Extrinsic semi-conduction
The conductivity of the intrinsic semiconductors is too low to be of practical
use. Their conductivity is increased by adding an appropriate amount of
suitable impurity. This process is called doping. The conductivity of silicon
and germanium increases drastically by doping it with certain other elements.
The impurities are of two types :
(i) Electron rich (or donor) impurities and
(ii) Electron deficient (or acceptor) impurities.
(4) Electron rich (or donor) impurities. The electron rich (or donor)
impurities provide electrons in the following way:
Silicon and germanium belong to group 14 of the periodic table and have
four valence electrons. In their crystals each atom forms four covalent bonds
(as discussed above) with its neighbours (Fig. 55).
Let us consider that some atoms with five valence electrons (of group
15) such as arsenic (As) are added to the silicon crystal. As a result, silicon
atoms at some lattice sites are replaced by As atoms with five electrons in
their outermost shell. As a Si atom is substituted by an atom of As, four of
the electrons in arsenic form covalent bonds with surrounding Si atoms and
the fifth electron remains free. Hence, an extra electron, over and above the
number required for forming the four covalent bonds, gets introduced in the
crystal. This extra electron which is not needed for bonding becomes delocalised
and can serve to conduct electricity and therefore, silicon containing traces of
arsenic (or arsenic doped silicon) exhibits high electrical conductivity. This
type of conduction is known as n-type semi-conduction where ‘n’ stands for
negative because electrons are responsible for semiconducting behaviour. This
Fig. 56. Arsenic doped silicon is shown in Fig. 56. Doping of a germanium or silicon semiconductor with other
semi-conductor.
) group-15 elements such as P, Sb or Bi also give n-type semiconductors.
SOLID STATE

(zz) Electron deficient or Acceptor Impurities. An electron deficient

or Acceptor impurity helps in conduction in the following way :
Suppose some atoms of silicon are doped with acceptor atoms having only
three outer shell electrons such as indium (of Group 18). As a result, silicon
atoms at some sites are replaced by indium atoms with three electrons in
their outermost shell. Each indium atom uses its three electrons to form three
bonds in the lattice and some sites normally occupied by electrons will be left
empty and gives rise to electron deficiencies. The electron deficient sites are
called electron vacancies or electron holes. An electron from neighbouring
atom can jump to fill up this electron hole, but in doing so it would create
an electron hole at its original position. As it continues, it would appear as
if the electron hole has moved in the direction opposite to that of electron
which filled it. When an electric field is applied, the electrons move towards
the positively charged plate through electron holes and electron holes move
towards the negatively charged plate as if they carry positive charge. This type
of semiconductors are called p-type semiconductors because holes (positive
in charge) appear to be responsible for the semiconducting properties. Doping
Fig. 57. Indium doped silicon
of silicon or germanium with other group-13 elements such as B, Al or Ga semiconductor.
also give p-type semiconductors. This is shown in Fig. 57.
Thus, doping of germanium or silicon with traces of arsenic (or other
group-15 element) gives rise to n-type semi-conductor and that with
indium (or other group 13 element) gives rise to p-type semiconductor.
Both n-type and p-type semiconductors are electrically neutral because
each atom of impurity added is neutral in itself containing equal number
of protons and electrons.
Applications of n-type and p-type semiconductors.
n-type and p-type of semiconductors are shown in Fig. 58. Various
combinations of n-type and p-type semiconductors are possible which are used
to make electronic components. For example,
e A diode is a combination of n-type and p-type semi-conductors and is
used as a rectifier.
e Transistors which are p-n-p or n-p-n ‘sandwich’ semi-conductors are
used to detect or amplify radio or audio signals.
e A solar cell is a photo diode used for converting radiant energy (of b) p-type
light) into electrical energy.
e Now, alarge variety of solid materials have been prepared by combination Fig. 58. Conduction in n-type and
of elements of group-13 and 15 or 12 and 16 which have average valence p-type of semiconductors.
of 4 as in Ge or 81. Typical examples of group 13-15 compounds are AIP,
GaAs or InSb. Gallium arsenide (GaAs) semiconductors have gained
much response and have revolutionised the design of semiconductor
devices. The examples of group 12—16 compounds are ZnS, CdS, CdSe
and HgTe. In these compounds, the bonds are not perfectly covalent (M) Competition Plus
and the ionic character depends upon the electronegativity differences
Superconducting materials are those
between the two elements. which offer no resistance to the
It is interesting to learn that transition metal oxides show marked passage of electricity. For detail, refer
differences in electrical properties. TiO, VO, CrO, and ReO, behave like typical Competition File (Page 79).
metals. Rhenium oxide, ReO, behaves metallic like copper in conductivity and
appearance. Certain other oxides like VO, VO,, VO, and Ti0, show metallic
or insulating properties depending upon temperature.

2. Magnetic Properties of Solids

The microscopic (observable) magnetic properties of materials are due to
the magnetic moments associated with individual electron. Kach electron in an
atom has magnetic moment which originates from two sources :
(t) Orbital motion around the nucleus.
(it) Spin of electron around its own axts.
 MODERN'’S abc + OF CHEMISTRY
-XII

A moving electron may be regarded as a small current loop generating a

Magnetic small magnetic field and having a magnetic moment along its axis of rotation as
moment shown in Fig. 59 (a). The magnetic moment which originates from electron spin
Electron
is directed along the spin axis. The spin magnetic moments are generally shown
by up and down direction as shown in Fig. 59 (0). Thus, each electron in an atom
may be regarded as a small magnet having permanent orbital and spin magnetic
Atomic moments. The fundamental magnetic moment is the Bohr magneton [L, which is
nucleus
equal to 9.27 x 10-4A m’. For each electron in an atom, the spin magnetic moment
(a) is + [lp depending upon the two possibilities of the spin. The contribution of the
orbital magnetic moment is equal to m, lly where m, is the magnetic quantum
Magnetic
moment number of the electron.
The magnetic properties of solids are also related to their electronic structures.
Electron Materials can be divided into the following types depending upon their response
to magnetic field :
Direction
(4) Diamagnetic materials. The substances which are weakly repelled by
of spin
the magnetic field are known as diamagnetic substances. For example, NaCl,
(b) water, benzene, etc. are diamagnetic substances. The property thus exhibited is
Fig. 59. (a) An orbiting electron. called diamagnetism. Diamagnetism arises when all the electrons are paired.
(6) A spinning electron. Pairing of electrons cancels their magnetic moments and they lose their magnetic
character.
(ii) Paramagnetic materials. The substances which have permanent
magnetic dipoles and are attracted by the magnetic field are known as
paramagnetic substances. These consist of atoms, ions or molecules having one
or more unpaired electrons. The common examples are Cu**, Fe**, Cr°*, O,, TiO,
Ti,0,, VO,, CuO, ete. They lose their magnetism in the absence of magnetic field.
Solids like TiO, which are expected to be diamagnetic often show paramagnetism
due to the presence of slight non-stoichiometry.
(iii) Ferromagnetic substances. The substances which are strongly
attracted by the magnetic field and show permanent magnetism even when the
magnetic field is removed are known as ferromagnetic substances. Once such
a material is magnetised, it remains magnetised permanently. Iron is the most
common example. Other examples are cobalt, nickel, gadolinium (Gd), CrO,,
etc. at room temperature. These substances are very important in technology.
For example, CrO, is the oxide used to make magnetic tapes for use in cassette
recorders.
In solid state, the metal ions of ferromagnetic substances are grouped together
into small regions called domains. Thus, each domain acts as a tiny magnet. In
an unmagnetized piece of ferromagnetic substance, the domains are randomly
oriented and their magnetic moments get cancelled. When the substance is placed
in a magnetic field all the domains get oriented in the direction of magnetic field.
Depending upon the alignment of magnetic moments of domains in ferromagnetic

Pty (a) Ferromagnet

substances, these are divided into three types :
(a) When there ts spontaneous alignment of magnetic moments of domains in
the same direction, we get ferromagnetism [Fig. 60 (a)]. These have strong

Ntitt
magnetic effect. This ordering of domains persists even when the magnetic
field is removed and the ferromagnetic substance becomes a permanent
magnet.
(b) Anti-ferromagnet (b) If the alignment of magnetic moments of domains is in a compensatory

Tlit)
way so as to give zero net magnetic moment because of cancellation of the
individual magnetic moments then we get anti-ferromagnetism in the
material. The common example is MnO. A pattern of alignment of magnetic
(c) Ferrimagnet domains in anti-ferromagnetic substance is shown in Fig. 60 (0d).
Fig. 60. Alignment of magnetic (c) When the magnetic moments of domains are aligned in parallel and anti-
moments in (a) Ferromagnet (5) Anti- parallel directions in unequal numbers resulting in net magnetic moment,
ferromagnet (c) Ferrimagnet. we get ferrimagnetism. This is shown in Fig. 60 (c). They are weakly
SOLID STATE 1/55 [
attracted by magnetic field as compared to ferromagnetic substances. REMEMBER
For example, Fe,O, (magnetite) and ferrites of formula M?*Fe,O is
It may be noted that each
M = Mg, Cu, Zn, etc. show ferrimagnetism. These substances also lose
ferromagnetic substance has a
ferrimagnetism on heating and become paramagnetic. ; characteristic temperature above
It may be noted that all the magnetically ordered solids (ferromagnetic, anti- which no ferromagnetism is
ferromagnetic and ferrimagnetic) transform to paramagnetic state at a higher observed. This is known as Curie
temperature due to randomisation of their spins. For example, temperature.
(1) VO, transforms from anti-ferromagnetic state to paramagnetic state
at 150 K.
(11) Fe,0,, becomes paramagnetic from ferrimagnetic at 850 K. ®) C OM LeCTLITLOU Plus
Magnetic properties of some transition metal oxides are shown Solids have dielectric properties.
below (where p = paramagnetic, af = anti-ferromagnetic, fe = ferrimagnetic, f= For detail, refer Competition File
ferromagnetic and d = diamagnetic) (Page 79).
TiO (p) VO (p) MnO (af) FeO (af) CoO (p) NiO (p) CuO (p)
Ti,0,(p) V,0,(af) Cr,O,(af) Mn,O,(af) —*Fe,0, (af
TiO,(@) VO,~@) Cro, MnO, (af) Fe,0, (fe) Co,0, (af)
V,0, (d)

add on c 9 2 © = ZN bo

Q.1. Analysis shows that FeO has a non-stoichiometric composition with molecular formula Fe, ,.O. Give
reason. (A. S.B. 2018)
Ans. It shows metal deficiency defect. In FeO, some Fe** ions are replaced by Fe** ions. Three Fe** ions are replaced by
two Fe** ions to maintain electrical neutrality.
Q.2. Following is the schematic alignment of magnetic moments:
ro : ne J,

—sf , a: =
—7 fs
=] = || —F ke

| i z

Identify the type of magnetism. What happens when these substances are heated ?
(CBSE Sample Paper 2017-18)
. Ferrimagnetism. These substances lose ferrimagnetism on heating and become paramagnetic.
. Name any one solid in which both Frenkel and Schottky defects occur.
. Silver bromide, AgBr has both Frenkel and Schottky defects.
. What is the effect of temperature on the conductivity of metals and semi-metals ?
. In general, with increase in temperature, the conductivity of metals decreases and that of semi-metals increases.
. What is photovoltaic cell ?
. The process in which electricity is produced by shining sunlight on certain substances. Amorphous silicon acts as
a typical photovoltaic cell.
. Why is Frenkel defect not found in pure alkali metal halides ?
. Frenkel defect is not found in alkali metal halides because the ions cannot get into the interstitial sites due to their
larger size.
. What is the effect of presence of Schottky defects on the density of the crystal ?
. The overall density of a crystalline substance decreases due to Schottky defects.
. What is the difference in the semi-conductors obtained by doping silicon with As or with Ga?
» Semi-conductor produced by doping silicon with As is n-type semiconductor in which : : :
flow of current _ due to seta ails silicon doped with Ga is p-type semiconductor e ee "5 © eo
in which flow of current is due to positive holes.
. Identify the type of defect shows in the following figure:
What type of substances show this defect ? (CBSE Sample Paper 2017-18)
Ans. Schottky defect.
This type of defect is shown by ionic compounds in which
(1) the ions have high coordination number and
(21) 1ons (cations and anions) are of almost similar sizes.
 MODERN'’S abc + OF CHEMISTRY
-XII

Q.10. Classify each of the following as being either a p-type or n-type semiconductor :
(1) Ge doped with In.
(17) Si doped with B. (CBSE Sample Paper 2011)
Ans. (1) Ge belongs to group 14 and In belongs to group 13.
Therefore, an electron deficient hole is created and it is a p-type semiconductor.
(11) B belongs to group 13 and Si belongs to group 14. Therefore, an electron deficient hole is created and it is a
p-type semiconductor.
Q.11. Name a salt which is added to AgCl so as to produce cation vacancies. (A.L.S.B. 2003, DSB. 2004)
Ans. CdCl.
Q.12. Which point defect lowers the density of a crystal ? (A.LS.B. 2004)
Ans. Schottky defect.
Q.13. How does the electrical conductivity of semi-conductors vary with temperature ? (Pb.S.B. 2006)
Ans. The electrical conductivity of semi-conductors increases with increase in temperature.
Q.14. Name the non-stoichiometric point defect responsible for colour in alkali metal halides.
(A.LS.B. 2006)
Ans. Metal excess non-stoichiometric point defects.
Q.15. CaCl, will introduce Schottky defect when added to AgCl crystal. Explain. (Pb.S.B. 2003)
Ans. CaCl, on adding to AgCl introduces impurity defect. The addition of one Ca** ion will replace two Ag* ions to maintain
electrical conductivity. One of the position of Ag* will be occupied by Ca?* ion and other will be left as a hole. Thus,
a hole is created similar to Schottky defect.
Q.16. Why does ZnO appear golden yellow at high temperature? Explain.
(Meghalaya S.B. 2013, Kerala S.B. 2018))
Ans. When ZnO is heated it loses oxygen as :
. 1
ZnO —Heat__ 792+4 5 On + Be"
The Zn** ions are entrapped in the interstitial sites and electrons are entrapped in the neighbouring interstitial
sites to maintain electrical neutrality. This results in metal excess defect. Due to the presence of electrons in the
interstitial void, the colour is yellow.
Q.17. The electrical conductivity of metals decreases with rise in temperature while that of a semiconductor
increases. Explain. (H.P.S.B. 2003)
Ans. In case of metals, with increase in temperature, the kernels start vibrating and therefore, they offer resistance to
the flow of electrons. Hence, conductivity of metals decreases with rise in temperature. On the other hand, in case
of semi-conductors, the conducitivity is due to the presence of impurities and defects. As the number of defects (such
as holes) increases with rise in temperature, the conductivity increases.
Q.18. Why does zinc oxide exhibit enhanced electrical conductivity on heating ? (D.S.B. 2005 C)
Ans. On heating, zinc oxide loses oxygen as :
3
FnO _ Heat 72+ 4 51 On + 6°

The zine ions thus formed are entrapped into the interstitial sites while the electrons are entrapped in the
neighbouring interstitial sites. The entrapped electrons enhance the electrical conductivity of ZnO.
Q.19. Give reason :
(a) Why is Frenkel defect found in AgCl ?
(b) What is the difference between phosphorus doped and gallium doped silicon semiconductors ?
(CBSE Sample Paper 2011)
Ans. (a) Due to small size of Ag* ion, it can fit into interstitial sites.
(b) Phosphorus doped silicon are n-type semiconductors while gallium doped silicon are p-type semiconductors.
Q.20. Why does LiCl acquire pink colour when heated in Li vapours ? (CBSE Sample Paper 2011)
Ans. On heating LiCl in Li vapours, the excess of Li atoms deposit on the surface of the crystal. The Cl ions diffuse to
the surface of the crystal and combine with Li atoms to form LiCl. The electrons produced by ionisation of Li atoms
diffuse into the crystal and get trapped at anion vacancies called F-centres. These absorb energy from visible light
and radiate pink colour.
SOLID STATE

Hints & Solutions for

Practice Problems
. As Y atoms are at the corners of the cube and contribution LJ 8. For fee unit cell, radius
of each = 1/8, therefore, no. of Y atoms/unit cell a
"= ole
= Sis ; = 1. There can be only one X atom at the body

centre. ~10
> — 4086 x10" Ms 144 x 10-9 m.
Hence, formula = XY. 2x1414
. There are only 8 corners so, no. of atoms per unit cell _) 9. No. of W atoms = 8 x 1/8 =1
= 8x a 1
8 No. of O atoms= 12x7=3
. No. of A atoms at the corners = 8
No. of Na atoms= 1
No. of A atoms missing from corners = 2
No. of A atoms present = 8-2-6 Formula = NaWOz;
_J10. We assume that the closest Cs* to Cl ion distance is
the sum of ionic radii of Cs* and CT ions.
No. of A atoms per unit cell = == 3/4
Nearest neighbour distance = 1.69 + 1.81 = 3.50A
This distance is one half of the body diagonal of the cube
No. of B atoms per unit cell = 6x + 3
Body diagonal = 3a
Formula = A,,,B, = AB,
v3a = 35.50
. There are 8 Y atoms at the corners and contribution 2
of each is 1/8. or a= 3.50 x2 = 4.04A,
V3
No. of Y atoms per unit cell = g x = 1 (J 11. 1 mol of tungsten = 184g = 6.022 x 10*° atoms
|
6.022 x10 23 wi
There can be only two X atoms at alternate faces and
No. of atoms in 1.5g of tungsten = oO
contribution of each of them is 1/2. 184
—- 4.909 x 1072
No. of X atoms per unit cell = 2x = 1
A bee unit cell contains 2 atoms per unit cell.
Hence, formula is XY. 4,909 x 1074
No. of unit cells = — 2.45 x 107!
1 mole of gold = 197 g = 6.02x 107 atoms
No. of atoms in 2 x 10° g of gold O12. 1 mol of sodium = 23 g = 6.022 x 107° atoms
_ |6.02 x10123 2102 No. of atoms present in 9.2 g of sodium
197 6.022 x 1078
= a x 9.2 = 2.4088 x 1077
= 6.11 x 10* 23
Since face centred cubic unit cell contains 4 atoms, A dce unit cell contains 2 atoms, 38
therefore, number of unit cells present , 2.4088 x10
No. of unit cells present = nr
_ 6.11x10" — 1.528 x 107* unit cells = 1.2044 x 107"
7 4
. Distance between nearest neighbour. _J 13. For face centred unit cell, radius of atom
ne
- 35
_ 620 ~ 438.5 pm
d = <=
a7 2 ° or a= 2J2.r
d r= 0.144 nm
r= 5 = 219.25 pm
a= 2x 1.414 x 0.144

. For dcc crystal, r = 8a = 0.407 nm.

LJ) 14. No. of atoms of A at corners = 7 (because one A is
missing).
_, SSEOO! _ 459.416 pm
4 Contribution of atoms Ain a unit cell =7 x 1_i
8 8
se MODERN’S abc + OF CHEMISTRY
-XII

No. of atoms of B at face centres = 6 Ratio of cations X and anions Y = 2N:N

er: Be]
Contribution of atoms B in a unit cell = 6x .-3 Thus, the formula of the compound will be X,Y.

A:B=1:3 or 7:24 Suppose the number of oxide ions = N

No. of octahedral voids = N
Simplest formula = A,B,, No. of tetrahedral voids = 2 N
oan 1.69A No. of cations P present = * boZ T Z
LI) 1s: Oe = 0.934
fi 1.81A
Since the radius ratio les between 0.732 to 1, the No. of cations Q present = x Zz I|
=
|
o>
oo co
|co
|=
coordination number of Cs* is 8 and the geometry of
Ratio P :-4jee O7-
CsCl is cubic.
r _ =
r At to
rAt
Nod -Ie for 1:1:38
3 3
0.414 0.732
Formula of compound = PQO,,.
241.6 to 136.6 pm
. In hep arrangement, there is one octahedral void
O17. For a cation to fit into a tetrahedral hole corresponding to each atom in the close packing.

Since 4 of the octahedral voids are occupied by

< 0.414
aluminium ions, therefore, for each oxide ion there
or rn, < 0.414 xr
will be : aluminium ions.
< 0.414 x 0.182 nm
Therefore, ratio between aluminium ion and oxide
r. < 7.63x 107 nm
10N 18 : |
+

) 18. For each X atom, there are one octahedral and two
tetrahedral sites. CJ -l or 2:38
3
No. of Y atoms in octahedral sites = 1 per X atom Formula of corrundum = Al,QOs.
Since alternative (i.e., half) tetrahedral sites are d= =
_] 24,
occupied, a” xN,
No. of Y atoms in tetrahedral sites = 1 per X atom
7 4x40
Total Y atoms = 2 per X atom ~ (400 x107!°)? x 6.022 x10”
Formula = XY,,. = 4.15 g em™
O19. Suppose number of atoms of Y in ccp = N 40 g of element = 6.022 x 10” atoms
No. of octahedral voids = N eur | 6.022 x 107° Pl
No. of atoms ofX = N gof element = ry, x
Formula : XY = 6.022 x 10” atoms
U 20. Since N forms ccp arrangement, it will have For fee, Z = 4
4 atoms in a unit cell. 1 unit cell = 4 atoms
Number of N atoms in unit cell = 4 -neo 22
For each atom, there are two tetrahedral voids so that No. of unit cells in 4g = a ,
there are 8 tetrahedral voids per unit cell.
= 1.505 x 107”
df 8
No. of M atoms — x $= —
3 3 _] 25. Edge length = 400 pm = 400 x 107° em
Volume of unit cell = (400 x10°-*°)? = 64 x10-** em?
Formula = M,N,
or = M,N.. Volume of 280 g of element = cad © = 40 em®
7g cm
L) 21. Suppose the number of anions Y = N
No. of octahedral voids = N Number of unit cells in this volume
40
No. of tetrahedral voids = 2 N = ———z, = 6.25 x 10”
Since octahedral and tetrahedral voids are equally 64 x10
occupied by cations X and all the octahedral voids For fcc, number of atoms per unit cell = 4
are occupied (as given) then N cations X are present -. No. of atoms in 280 g of element = 6.25 x 10” x 4
in octahedral voids and N cations X are present in
tetrahedral voids. Therefore, = 2.5 x 10** atoms
No. of cations present = N + N = 2N
SOLID STATE

LJ 26. Volume of 50 g of element

a0 a = 2J2r=2x1.414x0.144
19.35 — 0.407 nm = 0.407 x 10°’ em
— 269 cm
Volume of unit cell = (3.16 x 107°)° 4x(197 g mol ')
= $1.6 10% ev a (0.407 x107' cm)’ x (6.022 x 10** mol’)
No. of unit cells in this volume =
2.09 = 19.41 g cm”
31.6 x 10+
L) 31. Density = aa
= 8.2 x 10” a xN,
Since bcc arrangement has 2 atoms per unit cell, Z = A (for fcc)
Total no. of atoms = 2 x 8.2 x 1077 = 1.64 x 10”. TA 4x60

O 27. Volume of unit cell of CsCl= (4.121 x 10°°)° a x 6§.02210"

a. SA
= 4x60
= 69.99 x 10°*4 em?
6.23
x 6.022 x107
AXM
Density = — 64 x 10-*4
a’ xN,
a- 4x10%cm
“ = 1 (for bcc)
= 4x 107'° m=400 pm.
Formula mass = 132.9 + 35.5 = 168.4
AxM
The unit cell contains one Cs* ion and one CI ion 2.e., L) 32. Density, p = 3 <N,
one formula unit of CsCl.
p = 10gem”,M = 81g mol?
1x 168.4 a = 3x 10*%cm,N, = 6.022 x 10”
Density (CsCl)
(412.1 x 1071)? x (6.022 x1073) <0 Zx81
3.995 g cm™ ~~ (3x 107°)?
x 6.022 x 1078
For Al,Z =4 —§ 53 | oo 23
ae 7 10x(3x10™)° x 6.02210 ey,
4x 26.9 81
ss (405 x 1072°)? x (6.022 102°) -. Nature of cubic unit cell is bee.
2.690 g cm”. ZAXxXM
LJ 33. Density = —
CsCl has larger density. ct x Na

ZxM
L) 28. p= M = 207 + 32 = 239
7 4x239
a = 409 pm = 409 x10" cm
~ (500x 107°)? x (6.022 x 1079)
Zx108
10.5 = = 12.70 g cm?
(409 x 107°)" x (6.022 x 10°*)
O) 34. Edge of unit cell = 2 x 2.814 x 10° cm
10.5 x (409 x 10710)" x (6.02210) — 6.628 x 10° cm
= 4.0
108 Z=aA4
.. fee type structure
If N, is Avogadro number,
O 29. Density, J Yr , ZAxM
a xNy Density = ——_
a xNa
a = 286.65 x 10° em, Z = 2 (for bcc)
M = 202 + 37 = 239
M = 56.845 u, P = 7.874 g em™®
4x 58.5
- 2x 55.845 een (5.628 x 107°)? x Ny
(286.65x1071)? x Ny N. - 458.5
_ 2x 55.845 A (5.628 x 107)? x 2.167
or N, — 6.022 x 1078
(286.65 x107"°)? x 7.874 — 6.06 x 1078
ZAxM
UY 30. Density, p= ; 4x 63.5
a*xN, L) 35. Density =

Foror fcc
fe unitit cell, cell, r r = —=
2/8
8.96 g cm”
— 1/60 MODERN'S abc + OF CHEMISTRY-XII

LJ 36. Molecular mass of CsBr = 133 + 80 = 213 % x 243.87

100 = — Oo
= (3.85 x 10°) x (6.022 x 10”)
Density SS Rit eo -8,3 23
a’ x Ny 7.00 x (3.85 x 10°)” x (6.022 x 10°")
or = —— e—_—_—_—_—_—_—
on | 243.87
1x 213 = 0.99 or 1
AGA = —— . A unit cell of TIC] contains one formula unit of TIC1.
a’ x6,022 x10" 7
It is a simple cubic arrangement.
eae ss a O) 41. Density = 4.0 g cm?
6.022 x 10™ x 4.24 Z = 1 (for cubic lattice)
_ ~23

a = 4.369 x 10% cm = 436.9 pm a* x 6.02210

ZxM or (| 3 168.5
St rr
L) 37. Density = —= 4,00 x 6.022 x1078
a xN,
| = 69.9 x 10-4 em?
A108 -
10.6 = (409 x 10-1)3 x 6.022 x 1023 a = 4.12x 10° cem= 412 pm

Z= 10.5 x (409x 10°)? x 6.022 x 10% y/ ay hae

108 a = 408.6 pm = 408.6 x 1077? cm

a Density = =
.. fee type structure. a” x Ng
_ 4 x (107.9)
408.6 x 10cm)? x 6.022 x 107°
L) 38. Density = — vem ony e
aa — 10.506 g em?
2165 — 4x 98.9 O 43. If N, is Avogadro number,
a
a’ x 6.022 x 10
ian Z =A (for fec)

“3 = 4x58.5 Density - 2*M

2.165 x 6.022 x 10 a xN,

a° = 179.48 x 10 em? Edge of unit cell = 2 x 269 = 538 pm

or a = 6.64x 10° cm = 6388 x 10° cm
In NaCl structure, a = 2 (ry.+ + Tar) ; 248 — 4x58
.. Distance between Na* and CI ion, (538 x 107") x Ny

es 4x58
ac):
Peat To =_ ay = 282 pm|
me 2.82 x 10~™ 8 cm
a2 A (538x100)? x 2.48

= 6.007 x 107°
LJ 39. In a bcc lattice,
body diagonal = 3a J 44, If M is the molar mass of copper,

Now, 2 (r7y++ 7, = /3a Danis = om

ee x Na

ee
J/3__ _ 1.732x380 m=
“9 “an
aaa
BS0.1 pm 7, = 4 (for fer)

r,+ = 329.1 —r, = 154.1 pm Cell edge, a = 3.61 x 10° cm, N, = 6.022 x ig

LJ 40. Formula unit mass of TIC] = 208.37 + 35.5 = 243.87 892 — 4xM
7? (3.61 x10)? x 6.022 x 10”

ZxM 8.92
x 6.022 x10” x (3.61x 107°)
Density = A.0CeCeomrKXrl_—X—X—X—X—— — 63.2 mol,
SOLID STATE 1/61 [

L) 45.
—C—lT
aE
If N, is Avogadro number O47. Fe,5;O,, is non-stoichiometric and is a mixture of Fe**
Edge of unit cell = 288.4 pm = 288.4 x 107° em and Fe** ions. Let x atoms of Fe** ions are present in
x Boe he the compound. This means that x Fe** ions have been
= replaced by Fe** ions.
Density = — = No. of Fe** ions = 0.93 — x
alia For electrical neutrality, positive charge on the
790 = ee compound = Negative charge on the compound
oS BBAXIOTY xXNg 2(0.98 — x) + 8x = 2
2x52 SG “y = 2
or N= Pon eoe ane.
= 7.20 x (288.4 x 107") or x =0.14
_ 6.02 x 107 ”. Fraction of Fe** = 0.14, Fe** = 0.93 — 0.14 = 0.79
—_ Thus, the given formula may be represented as
ZxM 1,3 2-
L) 46. a = Feo79 Feo O19
. A
Total molar mass = 0.93 x 566 + 1 x 16 = 68.08¢
a = 300 pm = 300 x 10" m=3 x 10° cm 0.14 x56
% of iron present as Fe (IIT) = x 100 = 11.5%
M = 93 g mol’, p = 11.5 gem™
) 48. Let M** ions in the crystal be x so that M** ions in the
Zx 93 ¢ mol! crystal will be 0.96 — x. Total charge on the compound
11.5 gem™® =
(3x 10%em)? x (6.022 10”* mol!) must be zero, so that
42 xx+39 (0.96 —x)-2=0
2x — 2.88 —38x-—2 =0
ce
(11.5 gem™) x (3 x10%em)*
7
x (6.022 10” mol")
=I or x = 0.88
mo
( . 2 % of M2* = 0.88 x 100 = 91.67
~9Q1 0.96
It is bee type % of M** = 100 — 91.67 = 8.33.

|”Key Terms & Laws , |

© Isotropicsubstances. The substances which show same physical properties (electrical conductivity, thermal conductivity,
refractive index etc.) in all directions are called isotropic substances.
© Anisotropic substances. The substances which show different physical properties (electrical conductivity, thermal
conductivity, refractive index, etc.) in different directions are called anisotropic substances.
® Crystal lattice or space lattice. It is the regular arrangement of the constituent particles (atoms, ions or molecules)
of a crystalline solid in three dimensional space.
® Unit cell. It is the the smallest three dimensional repeating portion of a space lattice which when repeated over and
again in different directions produces the complete crystal lattice.
® Close packing. The arrangement in which maximum available space is occupied leaving minimum available space.
© Interstitial voids or sites. The holes or voids in the crystal lattice are called interstitial voids or sites.
® Coordination number. It is the number of nearest (or closest) neighbours of any constituent particle in the crystal
lattice.
® Radius ratio. The ratio of the radius of the cation to the radius of the anion (z.e. r,/r_) 1s called radius ratio.
® Disorder or defect. Any deviation from completely ordered arrangement of constituent particles in a crystal is called
disorder or defect.
® Schottky defect. The defect in ionic solids in which equal number of cations and anions are missing from their
normal sites.
® Frenkel defect. The defect in ionic solids in which some cations are missing from normal lattice sites and occupy
intertitial sites.
sa MODERN'S abe + OF CHEMISTRY
-XII

QUICK CHAPTER ROUND UP

SOLIDS

Crystalline Solids Amorphous Solids

* Constituent particles have definite * Constituent particles do not have
geometric arrangement regular arrangement
* long range order * short range order
» NaCl, Cu, Fe, 5 >»glass, rubber, plastics

e Constituents: +ve © 4+ve ions in a sea

and —ve ions of electrons
Non polar
e Strong electrostatic e Metallic bonding e Covalent bonds
e Dispersion
forces » Cu, Ag, Fe, Mg » SiC, quartz, (Si0,)
forces
>» NaCl, MgO, CaF, diamond, graphite, AIN
bar
solid CO,

14 Bravais
CRYSTAL SYSTEMS
lattices

Orthorhombic Triclinic Rhombohedral

azwobx#e avobise a=b=e
a-#B2#y=2 90° a=B=y
2 90°

P, F,B,E P P

No. of atoms per cubic unit cell Relationship between nearest distance (d) and radius of atom (r)
Simple = 1 Simple cubic @=a r= me
Body centred = 2 a
Face centred = 4 Face centred cubic C= = SS
A
End centred = 2

Body centred cubic

. of tetrahedral sites = 2 per atom

. of octahedral sites = 1 per atom

CLOSE PACKING

Cubic close or face Hexagonal close

centred cubic packing
SOLID STATE 1163 [
The limiting radius ratio (r,/r,) and the
coordination numbers in different crystals

0.155 — 0.225 Planar triangular _—e.g., B,O,)

0.225 — 0.414 Tetrahedral (e.g., ZnS)
0.414 — 0.732 Octahedral (e.g., NaCl)
0.732 —1 ! Body centred cubic (e.g, CsCl)

#4 for
Mass of atoms of unit cell = No. of atoms in unit cell (4) x Mass of atom
fee=A4
Molar mass (M) Bee £2
Mazs of atom = ——_———
Avogadro number (N, } simple cubic = 1
ZixM
Density of unit cell =
a xNg

DEFECTS IN CRYSTALS

Frenkel defect Schottky defect Metal excess type Metal deficient type
® cations missing from *® equal number of cations ® anion Vacancies or * cations vacancies or
normal sites and occupy and anions missing from interstitial cations interstitial anions
interstitial sites normal sites ® n-type semiconductors ® p-type semiconductors
e does not cause change in e density decreases
density >» NaCl, KCl, CsBr, AgBr
b AgCl, AgBr, Agl, ZnS

In AgBr, both Frenkel and Schottky defects occur

SOLIDS ON THE BASIS OF ELECTRICAL PROPERTIES

Conductors Semiconductors Insulators

Electrical conductivity: Electrical conductivity: Electrical conductivity:
107 to 10° ohm ‘tm? 10% to 10* ohm m™? 10° to 10°?° ohm m7?

«n-type semiconductors: Group 14 elements doped with group 15 elements, free electrons increase conductivity.
« p-type semiconductors: Group 14 elements doped with group 13 elements, presence of holes increase conductivity.

MAGNETIC PROPERTIES OF SOLID

Paramagnetic Diamagnetic Ferromagnetic Anti-ferromagnetic Ferrimagnetic

permanent magnetic weakly repelled by remain permanently, zero magnetic moment magnetic moments are
dipoles and attracted by || magnetic field magnetized even in the due to equal number of aligned in parallel and
magnetic field > benzene, NaCl, TiO,, absence of magnetic field magnetic moments in anti-parallel directions
> O,, Cu", Fe**, TiO V,0, > Fe, CO, Ni, CrO, opposite directions. in unequal numbers
Cuo. TiO.. VO >» MnO, FeO, Cr,O, giving net small magnetic
; i moment .
> MgFe,O,
« Curie temperature: Temperature above which ferromagnetism is not observed.
iss MODERN'S abc + OF CHEMISTRY
-XII

Ni@aan oy Solved
In-text Question |/

Q.1. Why are solids rigid ? of the ions in the crystal is destroyed and the ions are in a
Ans. In solids, the particles are closely packed and the position to move about when an electric current is applied.
empty spaces between the particles are very small. Therefore, Hence, ionic solids conduct electricity in molten state.
solids are incompressible and they maintain their own shape Q.9. What type of solids are electrical conductors,
when subjected to outside force. Hence, solids are rigid. malleable and ductile ?
Q.2. Why do solids have a definite volume ? Ans. Metallic solids.
Ans. The intermolecular forces between the particles in Q.10 Give the significance of lattice point.
the solid state are very strong. Therefore, they are strongly Ans. Lattice points represent the positions of the constituent
held at fixed positions and particles cannot separate from one particles (atoms, molecules or ions) in a crystal lattice.
another. Hence, solids have a definite volume. Q.11. Name the parameters that characterize a unit
Q.3. Classify the following as amorphous or crystalline cell.
solids : Ans. A unit cell is characterized by the two types of
Polyurethane, naphthalene, benzoic acid, teflon, parameters:
potassium nitrate, cellophane, polyvinylchloride, fibre (1) Dimensions along the three edges represented as a, b
glass, copper. and c.
Ans. Refer Solved Example 1 (Page 8). (11) Angles between edges « (between 5 and c), 6 (between
Q.4. Why is glass considered a super cooled liquid ? a and c) and y (between a and 5b).
Ans. Glass is an amorphous solid. Like liquids, it has a Hence a unit cell is represented by six parameters a, b,
tendency to flow, though very slowly. Moreover, glass is obtained c, &, B, and y.
when molten silicates are allowed to cool rapidly. Therefore, Q.12. Distinguish between :
glass is considered as a super cooled liquid.
(1) Hexagonal and monoclinic unit cell
Q.5. Refractive index of a solid is observed to have
(177) Face centred and end centred unit cell
the same value along all directions. Comment on the
Ans. (1) Hexagonal unit cell has two edges of equal length
nature of this solid. Would it show cleavage property ?
(a = 6 # c) while monoclinic unit cell has all the three edges
Ans. Since refractive index of the solid has same value
of unequal length (a # b #c).
in all directions i.e., isotropic, 1t 1s an amorphous solid. It
In hexagonal two angles are of 90° and one angle of 120°
will not show cleavage property. When cut with a sharp edged
(ao = B = 90, y = 120). In monoclinic, two angles are of 90° but
tool (knife) it will cut into two pieces with irregular surfaces.
one is not of 90° (a = y = 90°, B # 90°).
Q.6. Classify the following solids in different
(it) Face centred unit cell has points at the corners as
categories based on the nature of intermolecular forces
well as at the centre of each face. It has 4 atoms per unit cell.
operating in them :
End centred unit cell has points at all the corners and at
Potassium sulphate, tin, benzene, urea, ammonia,
the centre of any two opposite faces. It has 2 atoms per unit cell.
water, zinc sulphide, graphite, rubidium, argon, silicon
carbide. Q.13. Explain how much portion of an atom located at:
Ans. Potassium sulphate : 1onic solid, tin : metallic solid, (7) corner and (ii) body centre of a cubic unit cell is
part of its neighbouring unit cell ?
benzene : molecular solid, urea : molecular solid, ammonia :
molecular solid, water : molecular solid, zinc sulphide : ionic Ans. (1) 1/8 part of an atom located at corner belongs to
solid, graphite : covalent solid, rubidium : metallic solid, neighbouring unit cell
argon : molecular solid, silicon carbide : covalent solid. (it) No part.
Q.7. Solid A is very hard electrical insulator in solid Q.14. What is the two dimensional coordination
as well as in molten state and melts at extremely high number of a molecule in square close packed layer ?
temperature. What type of solid is it ? Ans. 4.
Ans. Covalent or network solid like quartz (S10,), 51C or Q.15. A compound forms hexagonal close packed
C (diamond). structure. What is the total number of voids in
Q.8. Ionic solids conduct electricity in molten state 0.5 mol of it ?How many of these are tetrahedral voids ?
but not in solid state. Explain. Ans. An atom in hep structure has three voids, one
Ans. In solid state, the ions are present in fixed positions octahedral and two tetrahedral
in the crystal lattice and cannot move when electric field is No. of atoms in 0.5 mol = 0.5 x 6.022 x 107°
applied. However, when melted, the well ordered arrangement — 3.011 x 10”
SOLID STATE

Total number of voids = 3 x 3.011 x 107° Ans. Electronic imperfections.

= 9.033 x 107 These defects affect electrical conductivity. It increases
Number of tetrahedral voids = 2 x 3.011 x 107 with rise in temperature.
— 6.022 x 1078 Q.20. What type of stoichiometric defect is shown by:
Q. 16. A compound is formed by two elements M and @) ZnS (ii) AgBr
N. The element N forms ccp and M atoms occupy 1/3
Ans. (1) ZnS : Frenkel defect.
of tetrahedral voids. What is the formula of the
compound ? (it) AgBr : Frenkel defect as well as Schottky defect.
Ans. Since N forms ccp arrangement, it will have Q.21. Explain how vacancies are introduced in an
4 atoms in a unit cell. ionic solid when a cation of higher valence is added as
Number of N atoms in unit cell = 4 an impurity in it ?
For each atom, there are two tetrahedral voids so that Ans. When a cation of higher valence is added to an ionic
there are 8 tetrahedral voids per unit cell. solid, 1t results into impurity defect and cationic vacancies are
introduced to maintain electrical neutrality. For example, when
No. of M atoms = 1.3.8
3 3 molten NaCl is allowed to crystallise in the presence of SrCl,,
Formula = M,N, some of the Nat ions are replaced by Sr** ions. Each Sr** ion
or = M,N,. replaces two Na’* ions to maintain electrical neutrality. One
Q. 17. Which of the following lattices has the highest of the site is occupied by Sr** ion and the other site remains
packing efficiency (7) simple cubic (11) body centred cubic vacant. Hence, cationic vacancies are produced equal to the
and (i711) hexagonal close packed lattice ? number of Sr** ions.
Ans. The packing efficiencies are : Q.22. Ionic solids which have anionic vacancies due
simple cubic = 52.4% to metal excess defect develop colour. Explain with the
help of a suitable example.
body centred cubic = 68%
hexagonal close packed = 74% Ans. When crystals of alkali metal halides such as NaCl
are heated in the atmosphere of sodium vapour, the excess
.. Hexagonal close packed lattice has highest packing
of sodium atoms are deposited on the surface of the crystal.
efficiency.
The Cl ions diffuse to the surface and combine with sodium
Q.18. An element with molar mass 2.7 x 107
atoms to form NaCl. This happens by the loss of electrons by
kg mol forms a cubic unit cell with edge length 405 pm.
Na atoms to form Na‘ ions. The released electrons diffuse into
If the density is 2.7 x 10° kg m~. What is the nature of
the crystal and occupy anionic sites. As a result, the structure
the cubic unit cell ?
has an excess of sodium.
Ans. Edge length = 405 pm = 405 x 10" m
The crystals acquire yellow colour because when visible
Density of the cell = 2.7 x 10° kgm™®
light falls on the crystals, they absorb energy from the visible
Molar mass = 2.7 x 10° kg mol?
region to excite the electrons. Hence, they are coloured. Similarly,
“AxM excess of Li makes LiCl crystals pink and excess of K makes
Now,ow, density
density = a xN,
KCl crystals violet.
Z-?
Q.23. A group 14 element is to be converted into
Z x 2.7x107kg mols
27x10: kgm? — ——-*: -f$ See 7 n-type semiconductor by doping with a suitable impurity.
x 10° Kg m= 7505x10 mRt6.022.x10 mol) To which group should this impurity belong ?
_g _ (27x 10°kg m™) x (405x 107"
m)? x (6,022 x10"? mol) Ans. Group 15
2.7x107%kg mol! e.g., P, As.
- 4.0 Q.24. What type of substances would make better
Since the unit cell contains 4 atoms, it is cubic close permanent magnets, ferromagnetic or ferrimagnetic ?
packed structure, ccp. Justify your answer.
Q.19. What type of defect can arise when a solid is Ans. Ferromagnetic substances. When the substance is
heated ? Which physical property is affected by it and placed in a magnetic field, all the domains get oriented in the
in what way ? direction of the magnetic field.

Textbook Exercises ||
Q.1. Define the term ‘amorphous’. Give a few examples Q.2. What makes a glass different from a solid such
of amorphous solids. as quartz ? Under what conditions could quartz be
Ans. A solid is said to be amorphous if the constituent converted into glass ?
particles are not arranged in any regular fashion. They may have Ans. Quartz is a crystalline solid in which SiO, tetrahedral
short range order. For example, glass, plastics, amorphous silica. units are arranged in an orderly arrangement. Glass is a
Tse
supercooled liquid and is an amorphous solid. In which S10, Ans. (i)
MODERN'’S abe + OF CHEMISTRY
-XII

tetrahedral units are not arranged in any regular order.

Hexagonal close packing Cubic close packing
Quartz can be converted into glass by melting the quartz
and then cooling it rapidly. (1) In hep, the spheres of the | (2) In cep, the spheres of the
third layer are exactly third layer are not aligned
Q.3. Classify each of the following solids as ionic,
aligned with those of the with those of the first layer
metallic, molecular, network (covalent) or amorphous.
first layer. This arrange- or second layer. The layers
(a) Tetra phosphorus decoxide (P,O,,) ment is represented as of fourth layer are aligned
(6) Graphite (c) Brass AG AB........... type: with those of the first layer.
(d) Ammonium phosphate (NH,),PO, This pattern is represented
as ABCABC .......
(e)SiC (PRb (g)I, (DLiBr (@)P, (Si (&) Plastic (it) InAecp, the tetrahedral voids |(ii) In ecp, the third layer may
Ans. Refer Solved Example 2 (Page 8). of the second layer may be be placed above the second
Q.4. (a) What is meant by term ‘coordination number’? covered by the spheres of layer in a manner such
(6) What is the coordination number of atoms : the third layer. that its spheres cover the
octahedral voids.
(4) in a cubic close packed structure
(14) in a body centred cubic structure. (it) The three dimensional arrangement of constituent
particles of a substance (atoms, ions or molecules) is called
Ans. (a) Coordination number gives the number of nearest
crystal lattice.
neighbours with which a given atom is in contact. In case of
ionic crystals, coordination number of an ion in the crystal is The smallest repeating pattern in a crystal lattice which
the number of oppositely charged ions surrounding that ion. when repeated in three dimensions gives the crystal is called
unit cell.
(6) @) 12 (it) 8
(221) A void surrounded by four spheres is called a
Q.5. How can you determine the atomic mass of an
tetrahedral void while a void surrounded by six spheres is called
unknown metal if you know its density and the dimension
an octahedral void.
of its unit cell ? Explain.
Q.8. How many lattice points are there in one unit
Ans. Refer Text ; page 35.
cell of each of the following lattice ?
p x a®xN A
Atomic mass, M = (a) face centred cubic (b) face centred tetragonal
Z
(c) body centred.
Q.6. ‘Stability of a crystal is reflected in the magnitude
of its melting points’. Comment. Collect melting points Ans. (a) In face centred cubic arrangement, number of
of solid water, ethyl alcohol, diethyl ether and methane lattice points are :
from a data book. What can you say about the inter- 8 (at corners) + 6 (at face centres)
molecular forces between these molecules ? Lattice points per unit cell = 8x -+6x -=4
Ans. The melting point of a crystal depends upon the
magnitude of forces holding the constituent particles together, (6) In face centred tetragonal, number of lattice points are:
which determine the stability. Higher the melting point, greater = 8 (at corners) + 6 (at face centres)
are the forces holding the constituent particles together and
hence greater is the stability. For example, ionic crystals such Lattice points per unit cell = 8 x 46 yt =
as NaCl, KNO,, etc. have very high melting points and are
(c) In body centred cubic arrangement number of lattice
stable. On the other hand, molecular solids such as naphthalene,
points are :
iodine, etc. are less stable because they have low values of
= 8 (at corners) + 1 (at body center)
melting points.
The melting points of some compounds are : Lattice points per unit cell = 8 x -+1=2
Water = 273 K, ethyl alcohol = 155.8 K, diethyl ether
Q.9. Explain : (a) The basis of similarities and
= 156.8 K and methane = 90.5 K.
differences between metallic and ionic crystals.
The intermolecular forces in water and ethyl alcohol are
(6) Ionic solids are hard and brittle.
mainly hydrogen bonding. The higher melting point of water than
ethyl alcohol indicates that the hydrogen bonding in water is Ans. (a) Basis of similarities
stronger than in ethyl alcohol. Diethyl ether is a polar molecule (1) Both ionic and metallic crystals have electrostatic forces
and, therefore, the intermolecular forces in diethyl ether are of attraction. In ionic crystals, these are between the oppositely
dipole-dipole interactions. On the other hand, methane is a charged ions while in metals, these are among the valence
non-polar molecule and the only forces present in them are the electrons and the kernels. That is why both ionic and metallic
weak van der Waals forces (London dispersion forces). These crystals have high melting points.
are weaker than dipole-dipole interactions and hence methane (it) In both cases, the bond is non-directional.
has very low melting point than diethyl ether. Basis of differences
Q.7. How will you distinguish between the following (z) In ionic crystals, the ions are not free to move and
pair of terms: therefore, they do not conduct electricity in the solid state.
(1) Hexagonal close packing and cubic close packing They conduct electricity in the molten state or in their aqueous
(it) Crystal lattice and unit cell. solution. However, in metals, the valence electrons are free
(itt) Tetrahedral void and octahedral void. to move and hence they conduct electricity in the solid state.
SOLID STATE

(12) Ionic bond in ionic crystals is strong due to electrostatic re 4 x 63.5 = 8.96 g cm™
forces of attraction. However, metallic bond may be weak or (3.61x 10%)? x 6.022 x 10°
strong depending upon the number of valence electrons and
This value is close to measured value.
the size of the kernels.
Q.16. Analysis shows that nickel oxide has formula
(b) Ionic crystals are hard because there are strong
Ni, 9801.00 What fractions of nickel exist as Ni** and
electrostatic forces of attraction among the oppositely
charged ions. They are brittle because the ionic bond is Ni** ions ?
non-directional. Ans. Refer Solved Example 34 (Page 47).
Q.10. Calculate the efficiency of packing in case of Q.17. What is a semiconductor ? Describe the two main
a metal crystal for types of semiconductors and contrast their conduction
(a) simple cubic (b) body centered cubic (c) face mechanism.
centered cubic Ans. The substances whose conductance les between that
(with the assumptions that atoms are touching each of conductors (metals) and insulators are called semiconductors.
other). They have conductivity values ranging from 10° to 10*Q71m7.
Ans. Refer Text ; page 25-25. Two main types of semi-conductors are n-type and p-type. For
Q.11. Silver crystallizes in fcc lattice. If edge length details Refer Text, page 52-53.
of the cell is 4.077 x 10° cm and density is 10.5 g em™. Q.18. Non-stoichiometric cuprous oxide, Cu,O can be
Calculate the atomic mass of silver. prepared in laboratory. In this oxide, copper to oxygen
(A.LS.B. 2008, Uttarakhand S.B. 2015) ratio is slightly less than 2: 1. Can you account for the
ZxM fact that this substance is a p-type semi-conductor ?
Ans. Density, p= ——— Ans. Since the ratio of Cu : O in Cu,O 1s less than
a” xN,
2: 1, therefore, Cu,O is non-stoichiometric crystal. This means
_ M- — 3 Na that some Cu* ions have been replaced by Cu?* ions. To maintain
electrical neutrality, every two Cu* ions will be replaced by
one Cu*' ion thereby creating a hole. Since the conduction will
Z =A (fcc lattice), p = 10.5 g em™®, N, = 6.022 x 10”,
be due to the presence of these positive holes, it is a p-types
(a = 4.077 x 10° em) semi-conductor.
\_ 10.5 x (4.077 x107*)° x 6.022
ee x10” Q.19. Ferric oxide crystallizes in a hexagonal close
4 packed array of oxide ions with two out of every three
= 107.12 g molt. octahedral holes occupied by ferric ions. Derive the
Q.12. A cubic solid is made of two elements P and Q. formula of the ferric oxide.
Atoms of Q are at the corners of the cube and P at the body Ans. In a close packed arrangement, there is one octahedral
centre. What is the formula of the compound ? What are site corresponding to each atom constituting the lattice.
the coordination numbers of P and Q ?
No. of oxide ions per unit cell in Acp arrangement = 6
Ans. As atoms Q are present at the 8 corners of the cube,
No. of octahedral holes = 6
therefore, number of atoms of @ in the unit cell = 8x :=]
No. of ferric ions = 6xo=4
As atoms P are present at the body centre, therefore,
Formula of the compound Fe,O, or Fe,Qg.
number of atoms P in the unit cell = 1
.. Formula of the compound = PQ Q.20. Classify each of the following as being either
a p-type or a n-type semiconductor :
Coordination number of each P and @ = 8
(4) Ge doped with In (74) B doped with Si
Q.13. Niobium crystallizes in body centered cubic
structure. If density is 8.55 g cm™, calculate atomic Ans. (1) Ge belongs to group 14 and In belongs to group 153.
radius of niobium using its atomic mass 93 u. Therefore, an electron deficient hole is created and its is
Ans. Refer Solved Example 27 (Page 39). a p-type semiconductor.
Q.14. If the radius of the octahedral void is r and (iz) B belongs to group 13 and Si belongs to group 14.
radius of the atoms in close packing is R. Derive relation Therefore, there will be a free electron and it is a n-type semi
between r and R. conductor.
Ans. Refer Text ; page 25-26. Q.21. Gold (atomic radius = 0.144 nm) crystallizes
Q.15. Copper crystallizes into a fcc latice with edge in a face centered unit cell. What is the length of a side
length 3.61 x 10° em. Show that the calculated density of the cell.
is in agreement with its measured value of 8.29 g cm™. Ans. For face centred unit cell, radius of atom
ZxM pao
Ans. Density, p =
ty, P a® XN, 2/2
or ae ar J/2
For fcc lattice, Z= 4
r= 0.144 nm
Atomic mass, M of copper = 63.5
a = 2x 0.144x 1.414 =0,.407 nm.
a=3.61 x 10° cm
ca Q.22. In terms of band theory, what is the difference
MODERN'S abc + OF CHEMISTRY

Ans. Refer Text pages 45, 44, 45.

-XII

(1) between a conductor and an insulator (ii) between a Q.24. Aluminium crystallizes in a cubic close packed
conductor and a semi-conductor ? structure. Its metallic radius is 125 pm.
Ans. (1) The energy gap between the valence band and the (a) What is the length of the side of the unit cell ?
conduction band in an insulator is very large. As a result, under
(b) How many unit cells are there in 1.00 cm?’ of
an applied electric field, the electrons cannot jump from valence
aluminium ?
band to conduction band and therefore, such a substance has
very small conductivity and behaves as an insulator. On the Ans. Refer Solved Example 29 (Page 39).
other hand, in a conductor the energy gap is either very small Q.25. If NaCl is doped with 107° mol% of SrCl,. What
or there is overlapping between valence band and conduction is the concentration of cation vacancies ?
band. Therefore, under an applied electric field, the electron can Ans. Refer Solved Example 33 (Page 47).
jump from valence band to insulator band and the substance
Q.26. Explain the following with suitable examples:
shows conductivity.
(a) ferromagnetism (6) paramagnetism
(1) In a conductor, the energy gap between valence band
(c) ferrimagnetism (d) antiferromagnetism
and conductance band is very small or there is overlapping
between valence band and conduction band. But in a semi- (e) 12-16 and 13-15 group compounds.
conductor, there is always a small energy gap between them. Ans. Refer Text page 54 [for (a) to (d)/.
(see Fig. 54 on page 51). (e) The solid binary compounds prepared by combining
Q.23. Explain the following terms with suitable elements of group 12 and 16 are called 12 — 16 compounds. For
examples : example, Cd5, ZnS, etc. The compounds prepared by combining
(4) Schottky defect (ii) Frenkel defect elements of group 13 and 15 are called 13-15 compounds.
For example, AIP, GaAs, etc. These compounds are used as
(711) Interstitials (iv) F-centres
semiconductors.

_ Exemplar Problems THT|

Subjective Questions

>) Soe . Why are liquids and gases categorised as fluids?

5. Why is FeQ(s)
composition?
not formed in stoichiometric

Ans. In the crystals of FeO, some of the Fe** cations are

_ The liquids and gases have a property to flow i.e. the replaced by Fe** ions. To balance the charge, three
molecules of liquids and gases can easily move past Fe* ions are replaced by two Fe** ions to make up for
and tumble over one another freely. Because of the loss of positive charge. As a result, there would be
their tendency to flow, these have been categorised less amount of metal as compared to stoichiometric
as fluids. proportion.
2. Why are solids incompressible? 6. Why does white ZnO (s) becomes yellow upon
Ans. The internuclear distances between the constituent heating?
particles (atoms, molecules or ions) 1n solids are very Ans. When ZnO is heated it loses oxygen as :
less. On bringing them further closer, there will be
large repulsive forces between electron clouds of these 7nQ —Heat_, 72+ 4 50; 4+ 2e-
particles. Therefore, solids cannot be compressed. The Zn** ions are entrapped in the interstitial sites and
3. Inspite of long range order in the arrangement electrons are entrapped in the neighbouring interstitial
of particles why are the crystals usually not sites to maintain electrical neutrality. This results in
perfect? metal excess defect and F-centres are created. Due to
Ans. During the crystallisation process, some deviations from the presence of electrons in the interstitial voids, the
the ideal ordered arrangement may occur. As a result, colour is yellow.
crystals are usually not perfect. 7. Why does the electrical conductivity of
4, Why does table salt, NaCl, some times appear semiconductors increase with rise in temperature?
yellow in colour? Ans. According to band model, the gap between conduction
Ans. The yellow colour of sodium chloride crystals is due band and valence band is small in semiconductors as
to metal excess defect. In this defect, the unpaired shown in Fig. 54 (Page 51).
electrons get trapped in anion vacancies. These sites are Therefore, electrons from the valence band can jump
called F-centres. The yellow colour results by excitation to the conduction band on increasing temperature.
of these electrons when they absorb energy from the Thus, they become more conducting as the temperature
visible light falling on the crystals. increases.
SOLID STATE

8. Explain why does conductivity of germanium one-third of the tetrahedral voids present.
crystals increase on doping with gallium. Determine the formula of the compound formed
Ans. On doping germanium with gallium, some of the by M and N?
positions of lattice of germanium are occupied by Ans. N atoms make up ccp arrangement and there are two
gallium. Gallium atom has only three valence electrons. tetrahedral sites per atom of N.
Therefore, fourth valency of nearby germanium atom No. of N atoms per unit cell = 4
is not satisfied and this site remains vacant. This
No. of tetrahedral sites =4x2=8
place is deficient of electrons and is called electron
hole or electron vacancy. Electron from neighbouring No. of sites occupied by M = a =
co
OO
|
atom moves to fill the gap, thereby creating a hole in
its original position. Under the influence of electric No. of M atoms per unit cell =
oo
G0
|
field, electrons move towards positively charged plates Formula M,N, or M,N,, or M,N,
through these holes and conduct electricity. The holes
10. Under which situations can an amorphous
appear to move towards negatively charged plates. The
substance change to crystalline form?
movement of electrons (or electron holes) results in
increase in conductivity of germanium. On heating, amorphous solids become crystalline at
some temperature. For example, some glass objects
In a compound, nitrogen atoms (N) make cubic
from ancient civilisations are found to become milky
close packed lattice and metal atoms (M) occupy
in appearance because of some crystallisation.

Memory TEST W
“ea say True or False Complete the missing links
1. Tetragonal and orthorhombic crystal systems have same The number of atoms for primitive unit cell is ............. ;
axial angles. for body centred cubic unit cell is ............. and for face
In a fee unit cell, the distance along one of the faces of centred cubic unit cell is ............. ,
the unit cell is 2.828 times the radius of the atoms.
The electrical conductivity of metals ............. with
In a face centred cubic system, number of atoms at
decrease in temperature.
facesis 4.
The substances which are strongly attracted by the
Copper crystallises in a fcc lattice. If radius of copper
atom is 130 pm, then the edge length of the unit cell will magnetic field and show permanent magnetism even
be 450.32 pm. when magnetic field is removed are called .............
The percentage of vacant space in bcc unit cell and simple substances.
cubic unit cell are 26% and 32% respectively. The formula of a compound is ............. in which atoms
Number of atoms per unit cell in fec and bce unit cells of element B form /cp lattice and those of the element
are 4 and 2 respectively. A occupy 2/3rd of tetrahedral voids.
re For bcc metallic unit cell, the edge length (a) and radius A group 14 element is to be converted in to n-type
(7) of atom are related as : a = a r. semiconductor by doping it with a suitable impurity
V3 belonging to group ............. of the periodic table.
8. The volume of a fee unit cell with atomic radius of atom If electrical conductivity is found to be same in all
100 pm is 2.26 x 10-79 m®. directions through a solid, the substance is ............. and
9, The two ions A* and B” have radii 90 and 200 pm this property is called .............
respectively. In close packed crystal of a compound AB,
The coordination number of each sphere in hep 1s .............,
the coordination number of A” is 4.
WGC IE aeecdacex and in bcc packing 1s ............. ;
10. Number of Na* and CI ions in a unit cell are 6 and 6
The packing fraction of a simple unit cell is ............. :
respectively.
The empty space in /icp 1s ............. and thatin bce packing
1_ Schottky defect results in the decrease in the density of
the crystal.
i): eee ee
12. Number of octahedral voids in 1 mole of a compound In a body centred cubic crystal, the nearest neighbour
having ccp and bcc arrangement are 24.08 x 107° and distance is ............. times the edge of the crystal and ina
12.04 x 107° respectively. face centred cubic crystal, the nearest neighbour distance
1: eon times the edge of the crystal.
13. The edge length of an ionic crystal XY having sodium
chloride type structure is the sum of the radius of P and Q. 11. An octahedral void is ....... ...... times larger than a
14, hep arrangement has 6 atoms per unit cell. tetrahedral void.
15. Ferromagnetic and antiferromagnetic solids change into 12. In a body centred cubic arrangement ............. atoms along
paramagnetic at high temperature. the body diagonal touch each other.
| 170 MODERN'S abc + OF CHEMISTRY
-XII

135. The compound aii both Frenkel and Schottky . In a crystalline solid, anions B are arranged in a cep.
defects 18 ............. Cations A are equally distributed between octahedral
14, If there is a large energy gap between the filled valence and tetrahedral voids. If all the octahedral voids are
band and empty conduction band, the substance acts as oocupied, the formula of the compound 1s A,B/A,B.
. Ina body centred cubic unit cell of elements, the radius
of an atom is 0.455/0.354 times the edge length of the
. Ina bday centred cubic crystal of an element, the ratio of
unit cell.
edge of the unit cell to the radius of the atomis.............
. For a hep unit cell, the number of atoms per unit cell is
» NaCl crystals have yellow colour due to the presence of 6/4.
-» CdCl, added to AgCl erystal will introduce Schottky
defect /Frenkel defect.
Choose the correct alternative
MnO, is antiferromagnetic/ferromagnetic substance.
Lithium, sodium, potassium and rubidium crystallize in 10. Ferrimagnetism/ferromagnetism arises due to unequal
the bce /fee structure. number of domains in opposite direction resulting in net
Most unsymmetrical crystal system is monoclinic / magnetic moment.
triclinic. 11. The substance showing both Schottky defect and Frenkel
Orthorhombic has 4/38 types of lattices. defect is AgBr/Zn8.
Total number of tetrahedral and octahedral voids in hep 12. When silicon is doped with arsenic, n-type/p-type
arrangement are 12/18. semiconductor is produced.

Answers

Say True or False

True. Both have axial angles « = 6 = y= 90°. No. of octahedral voids in cep or bcc arrangement
» True. In fcc unit cell, the face diagonal is = 6.023 x 107°
4dr = /2.a 135. False. A(XY) = Ary. +ry-)

or ee ee
14. True. 15. True.
2 Complete the missing links
2x 1414r=2.828r
& False. No. of atoms at faces = 3 1 1,2,4 2. increases
False. Edge length (a) = 2,/2 r 3. ferromagnetic 4, A,B,
= 2x 1.414 x 130 = 367.64 pm 5. 16 6. amorphous, isotropy
False. In bcc vacant space = 32% and in simple cubic 7. 12,12,8 8. 52.4%
unit cell vacant space = 48%.
1
True. 7. True. 9. 26%, 32% 10. X83 © 366) , — (0.707)
True. For fcc arrangement, r = —_—
2 V2
a 11. 0.414/0.225 = 1.84 12. three
a = 2V2.r =2x1414x100x 102m
= 2.828 x 10° m 13. AgBr 14, insulator
”. Volume of unit cell = a? = (2.828 x 10-7 m)? 15. ——a ~ =(2,309)
4 16, F-centres
= 2.26x 10 m® 3% ~ VB
r(A*) 90pm
False. = (2.46 Choose the correct alternative
r(B-) 200 pm
bee 2. triclinic 3. 4
Since it lies in the range of 0.414 to 0.782, the coordination
18 5. A,B 6. 0.433
number of A* will be 6.
10. False. No. of Na* ions = 4, No. of CI ions = 4.
6 8. Schottky defect
antiferromagnetic 10. ferrimagnetism
11. True.
12. False. 1 mole of compound in ccp or bcc arrangement » AgBr 12. n-type
has 6.02 x 107° atoms.
SOLID STATE

Higher Order Thinking Skills & nq tie

lvanced Leve
QUESTIONS WITH ANSWERS

Q.1. Diamond and solid rhombic sulphur both are edge not covered by atoms = @g-—2r
covalent solids but the latter has very low melting point
In bee, body diagonal _ VBa
than the former. Explain why ?
Ans. Diamond is a three dimensional network covalent solid 3
4r=V3a orr = x8
having very strong interatomic forces while, rhombic sulphuris a
molecular solid consisting of puckered eight membered rings (Sg)
.. Edge not covered by atoms= q-—2x Wy
held together by weak van der Waals' forces.
Q.2. Why does the window glasses of the old buildings
look milky ? e 2-8
Ans. Due to heating during the day and cooling at night (7.e., 7 2 ) 21.732
= 0.134%
annealing) over a number of years, glass acquires some crystalline Fea!
a 2
character and hence looks milky.
Q.8. Aface centred cubic lattice ofasingletype of atoms
Q.3. Can cubic lattice have end-centred unit cell ?
has same defects and its one corner and one face centre
Ans. No, because a cubic unit cell must have all the faces to
is left unoccupied per unit cell. Calculate the packing
be same.
fraction of such solid.
Q.4. Silver iodide crystallizes in the cubic close packed
Ans. Suppose the edge length of unit cell is a and radius of
zine sulphide structure. Assuming that ions occupy the
lattice points, what fraction of the tetrahedral sites is each atom is r.
occupied by Ag* ions ? No. of atoms perunit
cell = Tx 45x—= =
Ans. To maintain stoichiometry, Ag* ions occupy half the
tetrahedral sites because there are two tetrahedral sites occupied For face centred unit cell, a = 2/2r
for each I"ion.
Volume of unit cell, a? = (2V2r)? = 16V2 r°
.. 60% tetrahedral sites are occupied.
Q.5. An element "X' has bcc lattice as shown below: Total volume of of atoms = a x i tr = : mr®
The unit cell length, a is 306 pm. 8 8 3 2
(a) What is the distance between
nearest neighbours ?
9a!
Packing fraction = Ee
(6) What is the distance between
next nearest neighbours ?
9n 9x3.142
(c) How many nearest neighbours
does each X atom have? ~ 32/2 32x1.414
(d) How many next nearest neighbours does each X = 0.625
have? Q.9. The CsCl has cubic structure of CI ions in which
Ans. (a) The body diagonal is V3 .a =1.732 x 306 = 530 pm Cs* ion is present in the body centre of the cube. Its density
Nearest neighbours along body diagonal are half the body is 3.99 g cm™.
diagonal. 530) (7) Calculate the length of the edge of unit cell.
Distance between nearest neighbours = a 265 pm (71) What is the distance between Cs* and CI ions?
(6) The next nearest neighbours are along the edge. (iii) What is the radius of Cs* ion if the radius of CI ion
.. Distance between next nearest neighbour = 306 pm is 180 pm?
(c) 8, because the body centre is next to 8 corners. Ans. The unit cell of CsCl has cubic arrangement of CI ions
and Cs*ionis presentin the body centre of the cube. Therefore, the
(d) 6, because each corner has neighbours along each edge.
unit cell contains one Cs* andone CTI ionorone CsCl unit,i.e.,Z=1
Q.6. For a cubic crystal, the face diagonal is 4,25A.
Molar mass of CsCl, M = 133 + 35.5 = 168.5 gmol?
Calculate its face length.
ZxM
Ans. Ifa is the length of the face, then Density,p =
ap a’ xN,
face diagonal = Va*+a* = 2a
Face diagonal — 4.25 301A 1x (168.5 ees
”. Face length, a = 3.99gcem” = oe
2 (1.414 a? x (6.022 x10”? mol!)
Q.7. What fraction of edge is not covered by atoms in F 1x (168.5 g mol)
bcc arrangement? ~ (3.99 g em™) x (6.022 x 10” mol!)
Ans. Ifa is the edge length of bcc unit cell and ris the radius 7.02 x 10°73 em?
of atom, then
| 72, MODERN'’S abc + OF CHEMISTRY
-XII

(i) Letlength ofthe edge ofunit cell = a 2 Atomic mass of metal

d(bec) = a
a® = 7.02x 10 em®=70.2x 10“ cm® N, x(3.0A)
a (70.2 x 10-4 em)"
d(fcc) 4 (8.0)°
= 4.12x10%em=412 pm = emo = 1.26.

d( bcc) 2 (3.5)°
(11) Asshownin the figure, Cs‘ ion is presentin the centre
Q.11. You are given marbles of diameter 10 mm. They
of unit cell andisin contact with 8 CI ions at the corners. Itis clear
are to be placed such that their centres are lyingin asquare
that the length of the body diagonal is equal to twice the distance
bound by four lines each of length 40 mm. What will be
between centre of Cs* and centre of Cl ion. The body diagonal
the arrangement of marbles in a plane so that maximum
can also be calculated as :
number of marbles can be placed inside the area ? Sketch
If length of unit cell edge is a, then face diagonal AC, is
the diagram and derive an expression for the number of
AC = JAB?+BC? = Var +a = 2a molecules per unit area. (LL.T. 2003)
The body diagonal AD is: Ans. Area of square = 40 x 40 = 1600 mm?
To have maximum number
AD = JAC? +CD? = J2a" +a” = 3a
of spheres, packing must be
Acp. As shown in the figure, the
maximum number of spheres of
diameter 10 mm are=18
Area = 1600 mm? = 16 em”
. No. of spheres per cm?

oF16 1,125
Now, Q.12. Acompound AB has rock salt type structure. The
2 (Distance between Cs* and Cl) = Ba formula weight of AB is 6.023 Y amu and the closest A—B
distance is Y“? nm, where Y is an arbitrary number.
or Distance between Cs* and Cl v3. a
(a) Find the density of the lattice.
2
v3 x 412
— pm _= 1.732 x 206 pm (b) If the density of lattice is found to be 20 kg m™,
predict the type of defect. (L1.T. 2004)
356.8 pm.
Ans. (a) Density of a crystal is
(tii) Let the radius of Cl be r(CT) so that “7.x Formula mass of substance
rmCs*)+r(Cl) = 356.8 pm d =
Na, Xx a’
r(Cl) = 3656.8— 180 =176.8 pm. Now AB has rock salt type structure 1.e., fcc so that
Q.10. A metal crystallizes into two cubic phases, face Z=A
centred cubic (fcc) and body centred cubic (bcc), whose Formula mass =6.023Y x 10° kg,a =2Y"? nm=2Y"" x 10°m
unit cell lengths are 3.5 Aand3.0A respectively. Calculate 4 x 6.023 Y x10“°kg
the ratio of densities of fec and bcc. Dengsi = oD LLL EOC ae
'y 6.023 x 107° x (2Y" x 10°m)?
Ans. Density of a crystal is
ee 4 x Formula mass of substance = 5.00kgm”.
7 Nx a” (6) Since the observed density (20 kg m™) is higher than
Now, forfec,4Z = 4andforbcc,Z=2 the calculated value (5 kg m™°), the compound must has either
“Formula mass of substance interstitial impurity defect or substitutional impurity defect.
d(fcc) —_,... x. 4 ©
Ny x(305A)°

= Revision Exercises
>» Very Short Answer Questions <4 4, Why is Frenkel defect not found in pure alkali metal
halides ?
1. Crystalline solids are anisotropic in nature. What does
5. What is the coordination number of Acp and ccp
this statement mean? (D.S.B. 2011)
structures ? (Jammu S.B. 2015)
2. Define a unit cell. How many atoms are present in a simple 6. State the type of crystal defects shown by AgBr.
cubie unit cell ? (Meghalaya S.B. 2017)
3. In a close packed arrangement of N spheres, how many 7. What is meant by point defects in crystals?
() tetrahedral and (iz) octahedral sites are present ? (Jharkhand S.B. 2011)
SOLID STATE

»>
What is meant by ‘doping’ in a semiconductor ?
CBSE QUESTIONS <4
8.

(D.S.B. 2012)
What is the radius ratio (r*/r-) for an ion to occupy
od. Which point defect in crystals lowers the density of a
9,

tetrahedral site ?
crystal? (AJ_S.B. 2009, Assam S.B. 2013, 2015)
10. Explain the nature of crystal defect produced when
34, What type of semiconductor is obtained when silicon is
sodium crystal is doped with MgCl, ?
doped with arsenic ? (A.L.S.B. 2010)
11. What is the effect of Frenkel structural defect on the
oo. What type of interactions hold the molecules together in
electrical conductivity of a crystalline solid?
a polar molecular solid ? (A.L.S.B. 2010)
12. Why does Frenkel defect not change the density of AgCl
crystals? 356, Which stoichiometric defect in crystals increases the
13. What makes alkali metal halides sometimes coloured, density of a solid ? (D.S.B. 2011, AJS.B. 2012)
which are otherwise colourless ? (D.S.B. 2004) of. How the conductivity of an intrinsic semiconductor be
14. What is meant by coordination number? increased ? (A.LS.B. 2012)
(Uttarakhand S.B. 2014) 38. What is the formula of a compound in which the element Y
15. How does temperature influence the conductivity of a forms hep lattice and atoms X occupy 2/3rd of tetrahedral
semi-conductor ? (Pb.S.B. 2007)
voids ? (A.LS.B. 2075)
16. What type of substances exhibit anti-ferromagnetism? oo. Analysis shows that FeO has a non-stoichiometric
composition with molecular formula Fe, ,.O. Give
(D.S.B. 2008)
reason. (A.S.B. 2078)
17. Name an element with which silicon should be doped to
given n-type of semiconductor. (D.S.B. 2008C)
18. How does electrical conductivity vary in metals with
ate Boards’ Questions
temperature? (Pb.S.5. 2008)
40). Close packing is maximum in the crystal which is
19. What is the relationship between the edge length (a) of the
(a) bec (b) fee
unit cell and the radius (7) of an atom in a face-centred
(c) simple cubic (d) end centred cubic
unit cell? (Meghalaya S.B. 2013)
(A.P. S.B. 2013)
20 ' Which point defect in crystals of a solid does not change
41. In a solid lattice, the cation has left a lattice site and is
the density of the solid ? (D.S.B. 2009, 2010)
located at an interstitial position. The lattice defect is
21. How does ferromagnetism arise ? (Pb.S.B. 20171)
(a) n-type (b) p-type
22. A compound forms /ficp structure. Calculate the total (c) Frenkel defect (d) Schottky defect
number of voids in 0.5 mol of it. (Assam S.B. 2017)
(H.P.S.B. 2013)
23. Write a point of distinction between a metallic solid and
The coordination number of metal crystallizing in a
an ionic solid other than metallic lustre. (D.S.6. 2012) hexagonal close packing structure are
24, How many lattice points are there in one unit cell of each (a) 12 (b) 4
of the following lattices? (c) 8 (d) 10
(t) Face centred cubic lattice (A.P.S.B. 2013, Mizoram S.B. 2015)
(it) Body centred cubic lattice. (Pb.S.B. 2012) In a body centred unit cell, the number of atoms present
20. Identify each of the following as being either a p-type or 18
n-type semiconductor: (a) 1 (b) 2
(1) Ge doped with In (c) 3 (d) 4
(it) Si doped with As. (Pb.S.B. 2012) (Hr. S.B. 2013, 2018, Mizoram S.B. 2014,
26. How many atoms are there in a unit cell of a metal AP. S.B. 2016, 2017, Nagaland S.B. 2018)
crystallizing in fee structure ? In a trigonal crystal
(D.S.B. 2013, Meghalaya S.B. 2015, Tripura S.B. 2016) (qj)a=H=c, a=f=72 90°
27. What type of stoichiometric defect 1s shown by AgCl? (bba=b4e, 2=f=y7=90°
(D.S.B. 2013) (cja2zb47e, a= Bp=y=
50°
28. What type of substances would make better permanent
(Ja =b#ce, a=f6=90°,y= 120° (Ar. S.B. 2013)
magnets: ferromagnetic or ferrimagnetic? (D.S.5. 2013)
The appearance of colour in solid alkali metal halides is
29. What is the formula of a compound 1n which the element Y
generally due to
forms ccp lattice and atoms of X occupy 1/3 of tetrahedral
(a) Schottky defect (6) Frenkel defect
voids ? (D.S.B. 2015)
(c) F-centre (d) Interstitial position
30. What are the coordination number of Na* and CI ions in
(Mizoram S.B. 2013, H_P. S.B. 2016)
NaCl? (Nagaland S.B. 2016)
46. In a body centred cubic structure, the space occupied is
ol. What is Frenkel defect? How does it affect density of the
about
solid? (Karnataka S.B. 2018)
(a) 74% (6) 20%
o2. What is the coordination number of particles present in fcc
(c) 68% (d) 62.4%
crystal structure? (Kerala S.B. 2018)
(Maharashtra S.B. 2013, H.P. S.B. 2015, 2018)
| 74 MODERN'’S abc + OF CHEMISTRY
-XII

47, Some polar crystals when heated produce small electrical og. Due to Frenkel defect, the density of the ionic solids
current. The phenomenon is called (a) increases
(a) Ferroelectricity (6) Anti-ferroelectricity (6) decreases
(c) Pyroelectricity (d) Piezoelectricity. (c) does not change
(Manipur S.B. 2014) (d) depends on pressure (Mizoram S.B. 2017)
The empty space within Acp arrangement is 60. Which of the following is an amorphous solid?
(a) 34% (b) 47.6% (a) graphite (6) glass
(c) 32% (d) 26% (c) chrome alum (d) silicon carbide
(H.P. S.B. 2015, Meghalaya S.B. 2015) (AP. 5B. 2OTF)
49, A crystal system with axes a #b +c and angles a#B#y#90° 61. In a face-centred cubic unit cell, the edge length is
corresponds to 4 4
(a) monoclinic (a) —=r a> r
(6) triclinic
V3 V2
(c) cubic (d) tetragonal
(Mizoram S.B. 2016) (c) 2r (d) 8
50. The number of Cl ions present around each Na* ion in
NaCl crystal lattice is (Meghalaya S.B. 2018)
(a) 3 (b) 4 62. Amorphous solid is
(c) 8 (d) 6 (a) rubber (6) plastic
(Jharkhand S.B. 2016, West Bengal S.B. 2018) (c) glass (d) all
ol. To get n-type semiconductor from silicon, it should be doped (Ar. S.B. 2018)
with an element having valence electrons of
(a) 2 (6) 1
»> Short Answer Questions <4
(c) 3 (d) 5 (Meghalaya S.B. 2016) . Howare the solids classified on the basis of
bonding in them ?
o2. Volume occupied by atoms in fcc is Give the constituents and one example of each type.
(a) 74% (b) 68% (J.K.S.B. 2011)
(c) 52.4% (d) 76% » What do you understand by the terms ‘space lattice’ and
(4_.P. S.B. 2018, Mizoram S.B. 2018) ‘unit cell' ? (Pb.S.B. 2015)
oo. Percentage empty space in a bcc arrangement is » Explain with the help of diagrams the structural differences
(a) 74% (b) 68% between three types of cubic crystals. (J.A.S.B. 2011)
(c) 32% (d) 26% (Hr. S.B. 2017) » What are crystalline solids? Give two examples.
o4, To get p-type semiconductor, impurity to be added to silicon (Ar.S.B. 2017)
should have which of the following number of valence . What are crystalline and amorphous solids? Give four
electrons? important differences between crystalline and amorphous
(a) 2 (b) 3 solids. (H.P.S.B. 2005, Pb. S.B. 2013)
(c} 1 (d) 5 (Meghalaya S.B. 2018) . Explain:
oo. A ferromagnetic substance becomes a permanent magnet
(a) Zine oxide is white but it turns yellow on heating and
when it is placed in a magnetic field because
becomes highly conducting.
(a) all the domains get oriented 1n the direction of magnetic
(6) CdCl, will induce Schottky defect if added to AgCl
field.
crystal.
(6) all the domains get oriented in the direction opposite
to the magnetic field. » If the radius of an octahedral void is r and the radius
(c) domains get oriented randomly. of atoms in close-packed arrangement is h, derive the
(dq) domains are not affected by magnetic field. relationship between r and R.
(Manipur S.B. 2017) . What is meant by coordination number ? What is the
56. The presence of F-centres in a crystal make it coordination number of atoms in a
(a) conducting (6) non-conducting (a) cubic close packed structure
(c) coloured (d) colourless (6) body centred cubic structure.
(Nagaland. S.B. 2017) . What is the radius ratio (r*/r_) for an ion to occupy :
o7. The number of tetrahedral voids in the unit cell of a fee (t) tetrahedral void. (22) octahedral void ?
lattice of similar atoms is
10. What are the differences between Schottky and Frenkel
(a) 4 (b) 6
defects ? (Pb.S.B. 2013, H.P.S.B. 2013, Hr. S.B. 2013)
(c) 8 (d) 10
11. Explain the Schottky defects in stoichiometric crystals.
(Ar. S.B. 2017, Meghalaya S.B. 2017)
What are the important consequences of Schottky and
58. Fe, Co and Ni are Frenkel defects? (Uttarakhand S.B. 2012)
(a) ferrimagnetic materials
12. Differentiate between n-type and p-type extrinsic
(6) anti-ferromagnetic materials
semiconductors.
(c) ferromagnetic materials
13. Account for electrical conductivity in ionic compounds having
(d) diamagnetic materials (Meghalaya S.B. 2017)
(1) metal excess defects (11) metal deficient defects.
SOLID STATE

14. Name the types of semiconductors produced when (a) A unit cell of sodium chloride has four formula units
germanium (Ge) is doped separately with boron (B) and (number of atoms per unit cell). The edge length of unit
arsenic (As). Which one will be a better semiconductor and cell is 0.664 nm. Find out the density of sodium chloride.
why ? (Manipur S.B. 2014) (6) Define Frenkel defect and Schottky defect. What is
15. () Explain Schottky defect in sodium chloride crystal. the difference between these two?
(it) Explain electric properties of semiconductors on the (Uttarakhand S.B. 2013)
basis of band theory. (Uttarakhand S.B. 2014) 29. (a) NaCl has fee structure. Calculate the number of NaCl
16. (a) Calculate the packing efficiency in simple cubic lattice. units in a unit cell of NaCl.
(Karnataka S.B. 2018) (6) Calculate the density of NaCl if edge length of NaCl
(6) Whatis Frenkel defect ? Give an example. unit cell is 564 pm. (Molar mass of NaCl = 58.5 g mol)
(Karnataka S.B. 2014) (Kerala S.B. 2013)
17. In terms of band theory, what is the difference between a0. (a) What type of semiconductor is obtained when silicon
(a) a conductor and an insulator is doped with boron?
(6) What type of magnetism is shown in the following
(6) a conductor and a semiconductor.
alignment of magnetic moments?
18. Explain the following :
T Fae Bs T iT
(tz) Why is Frenkel defect not found in pure alkali metal
(c) What type of point defect is produced when AgCl is
halides ? (Meghalaya S.B.2014)
doped with CdCl,? (D.S.B. 2013)
(71) Anti-ferromagnetic substances have unpaired electrons
but their dipole moment is zero. (Ar. S.B. 2006) ol. Examine the given defective crystal
19. What are semiconductors? How does electrical conductivity aA eb fF At 6B COAT
of semiconductors vary with temperature? Give one example Bo O B At B
of intrinsic semiconductor. AY B A O At
Or B AT B AX B
What are paramagnetism and ferromagnetism? What Answer the following questions:
type of substances would make better permanent (1) What type of stoichiometric defect is shown by the crystal?
magnets—ferromagnetic or ferrimagnetic? (it) How 1s the density of the crystal affected by this defect ?
(111) What type of ionic substances show such defect ?
(Assam S.B. 2018)
(D.S.B. 2014)
20. Write two differences between ferromagnetic substances
ous Explain the following
and antiferromagnetic substances. (Pb.S.5. 2009, 2014)
(1) F-centres
21. Explain the following terms : (zz) Doping (A.P.S.B. 2015)
(1) Schottky defects
oo. Write any two differences between crystalline and
(it) Frenkel defects
amorphous solids. (A.P.S.B. 2015, D.S.B. 2017)
(Uttarakhand S.B. 2015, Jammu S.B. 2016)
oA, Distinguish between crystal lattice and unit cell.
22. Explain the following terms with examples :
(Hr.S.B. 2015)
(1) Metal excess defects
(it) Metal deficiency defects (Ar. S.B. 2011) oe (a) Briefly discuss Schottky defect and give examples.
23. (a) What are imperfections in solids ? (6) Calculate the density of copper crystal which crystallises
(6) What are F-centres ? (H.P.S.B. 2011) in fec arrangement with edge length of 3.61 x 10° cm.
24, (a) Define ferromagnetism and ferrimagnetism.
(Hr.S.B. 2015)
(6) Differentiate between metals, insulators and ob. Define ferromagnetism and ferrimagnetism.
semiconductors on the basis of band theory. (Pb.S.B. 2015)
(Ar.S.B. 2012) ods Unit cells can be divided into two categories, primitive
25. (a) Why does Frenkel defect not change the density of and centred unit cells.
AgCl crystals ? (a) Differentiate between unit cell and crystal lattice.
(6) Why does electrical conductivity of a semiconductor (6) Calculate the number of atoms per unit cell in the
increases with rise in temperature ? (Pb.S.B. 2012) following:
(1) body centred cubic unit cell (bcc)
26. (1) What is a semiconductor? Mention two main types of
(12) face centred cubic unit cell (fcc)
semiconductors.
(Kerala S.B. 2015)
(11) Sodium crystallizes in a body centred cubic (bcc) unit
cell. Calculate the approximate number of unit cells oO. Calculate packing effciency in simple cubic lattice.
in 9.2¢ of sodium. (Atomic mass of Na = 23) (Karnataka S.B. 2018)
(Assam S.B. 2013) oO”. Explain
27. (a) Give two differences between ferromagnetic and anti- (t) radius ratio (it) unit cells
ferromagnetic substances. (111) Ferromagnetism (iv) Ferrimagnetism
(6) Tungsten crystallizes in body centred cubic lattice. (v) F-centre (vz) Doping
Calculate the number of unit cells in 1.5 g of tungsten.
(H.P.S.B. 2018)
(At. mass of tungsten = 184) (Pb. S.B. 2013)
| 176 MODERN'S abc + OF CHEMISTRY
-XII

40). (a) Defince the following terms: How will you distinguish between the following pairs
(i) F-centre of terms :
(1) Tetrahedral and octahedral voids
(it) Unit cell (Ar. S.B. 2018)
(it) Crystal lattice and unit cell (A.f.S.B. 2014)
(6) Explain Schottky defect with an example
Do. (1) Write the type of magnetism observed when the
(Ar. S.B. 2018) magnetic moments are oppositely aligned and cancel
41. Differentiate between Schottky and Frenkel defects. out each other.
(Pb S.B. 2016) (it) Which stoichiometric defect does not change the
42. Differentiate between crystalline and amorphous solids. density of the crystal ? (A.f.S.B. 2014)
(Pb S.B. 2016) 56. (a) Based on the nature of intermolecular forces, classify
the following solids: Benzene, silver.
.» What is Schottky defect? Find out the packing efficiency
(6) AgCl shows Frenkel defect while NaCl does not. Give
in a simple cubic lattice. (Kolkata S.B. 2016)
reason.
» (a) Which of the following is a molecular solid?
(c) What type of semiconductor is formed when Ge 1s doped
(4) Diamond (it) Graphite
with Al ? (A.L.S.B. 2017)
(111) Ice (cv) Quartz
o7. An element ‘X’ (At. mass = 40 g mol”) having f.c.c.
(6) Unit cells can be classified into primitive and centred
structure, has unit cell edge length of 400 pm. Calculate
unit cells. Differentiate between primitive and centred
the density of ‘X’ and the number of unit cells in 4 g of
unit cells.
(c) Presence of excess sodium makes NaCl crystal ™*. (Ny = 6.022 x 10° mol") (A.L.S.B. 2018)
coloured. Explain on the basis of crystal defects.
(Kerala S.B. 2016) »> Long Answer Questions <4
. Write short notes on the following : 1. What do you understand by imperfections 1n solids? Explain
(1) Schottky defect stoichiometric defects in solids.
(11) Ferromagnetic substances. (H.P.S.B. 2017) 2. Discuss briefly the following properties of solids:
46. (a) Based on the nature of intermolecular forces, classify (1) electrical properties (ii) magnetic properties
the following solids? oe (a) An element has atomic mass 93 g mol? and density
(i) SiO, (ii) Ice 11.5 gem”. If the edge length of its unit cell is 300 pm,
identify the type of unit cell.
(b) ZnO turns yellow an heating. Why ?
(6) Write any two differences between amorphous solids
(Kerala S.B. 2018)
and crystalline solids.

CBSE QUESTIONS <4 OR

(a) Calculate the number of unit cells in 8.1 g of aluminium
47, Assign reasons for the following : if it crystallizes in a fee structure. (Atomic mass of Al
(t) Phosphorus doped silicon is a semiconductor = 27 g mol‘)
(11) Schottky defect lowers the density of a solid (b) Give reasons :
(111) Some of the very old objects appear slightly milky (1) Instoichiometric defects, NaCl exhibits Schottky defect
instead of being transparent. (A.1.S.B. 2007) and not Frenkel defect.
. Explain the following properties with suitable examples: (it) Silicon on doping with phosphorus forms n-type
(1) ferromagnetism (12) paramagnetism semiconductor.
(111) ferrimagnetism (A.IS.B. 2008) (111) Ferrimagnetic substances show better magnetism than
antiferromagnetic substances. (D.S.B. 2017)
. How do metallic and ionic substances differ in conducting
electricity ? (A.L.S.B. 2009) (1) Following is the schematic alignment of magnetic
50. Explain how you can determine the atomic mass of an moments:
unknown metal if you know its mass, density and the
dimensions of unit cell of its crystal.
(A.S.B. 2011, Manipur S.B. 2012)
ol. Calculate the packing efficiency of a metal crystal for a Identify the type of magnetism. What happens when
simple cubic lattice. (alior 2oe| these substances are heated ?
o2. Account for the following:
(it) If the radius of the octahedral void is ‘r’ and radius of
(6) Schottky defects lower the density of related solids. the atoms 1n close packing is ‘h’. What is the relation
(c) Conductivity of silicon increases on doping it with between ‘r’ and ‘h’.
phosphorus. (A.2.S_B8. 2073) (111) Tungsten crystallizes in body YY -Y(VX -)
tse (a) What change occurs when AgCl is doped with CdCl,? centred cubic unit cell. If the eee TY -Y-Y -)
(6) What type of semiconductor is produced when silicon edge length of the unit cell is YK- OIC -
is doped with boron? (A.FS_B. 2073) 315.5 pm, what is the radius of YX -X-X- XX -YX -)
tungsten atom?
o4, (1) What type of non-stoichiometric point defect is
responsible for the pink colour of LiCl ? OR
(11) What type of stoichiometric defect is shown by NaCl? (i) Identify the type of defect shown |(_)
in the following figure:
Cir
What type of substances show this defect ?
SOLID STATE

»> CBSE QUESTIONS <4

(z1) A metal crystallizes in a body centred cubic structure.
If ‘a’ is the edge length of its unit cell, ‘r’ is the radius of
the sphere. What is the relationship between ‘r’ and ‘a’? 9, Calculate the distance between Na* and Cl ions in NaCl
(111) An element with molar mass 63 g/ mol forms a cubic crystal if its density is 2.165 g cm°. (Molar mass of NaCl
unit cell with edge length of 360.8 p.m. If its density is = 68.6 gmol*,N, =6.02x 10" mol). (AJLS.B. 2006)
8.92 g/ cm®. What is the nature of the cubic unit cell ? 10. Iron has a body centred cubic unit cell witha cell edge of 286.65
(CBSE Sample Paper 2017-18) pm. The density of iron is 7.86 g cm. Use this information
to calculate Avogadro's number. (A./.S.B. 2009)
»> NUMERICAL PROBLEMS << 11. Silver crystallizes with face centred cubic unit cells. Each
side of the unit cell has a length of 409 pm. What is the
. Potassium iodide has cubic unit cell with cell edge of radius of an atom of silver ? (Assume that each face atom
705 pm. The density of KI is 3.12 g em *®.How many is touching four corner atoms). (A.L.S.B. 2009)
K* and I ions are contained in the unit cell ? 12. Tungsten crystallizes in a body centred cubic lattice.
Calculate the number of unit cells in 1.5 g of tungsten.
[Ans. 4K* and 4T]
Atomic mass of tungsten = 184 u. (A.I.S.B. 2009)
The unit of an element of atomic mass 96 and density 15. The well known mineral fluorite is chemically calcium
10.3 g em™ is a cube with edge length of 314 pm. Find the fluoride. It is Known that in one unit cell of this mineral
structure of the crystal lattice (simple cubic, FCC or BCC) there are 4 Ca** ions and 8 ions
F and that Ca** ions are
(Avogadro's constant, N,= 6.023 x 107° mol) arranged in a fcc lattice. The F ions fill all the tetrahedral
holes in the face centred cubic lattice of Ca** ions. The edge
[Ans. BCC]
of the unit cell is 56.46 x 10° cm in length. The density of
KCI and NaCl have fec lattice. Calculate the ratio of density the solid is 3.18 g em™. Use this information to calculate
of NaCl to that of KCl if the ratio of edge of NaCl to that of Avogadro’s number (Molar mass of CaF’, = 78.08 g mol +).
KCl is 0.875. [Ans. 1.172] (ATSB. 2070, D.S_6. 2070)
Lithium metal has a body centred cubic structure. Its density 14, The density of copper metal is 8.95 g cem™. If the radius
is 0.53 g cm™ and its molar mass is 6.94 g mol+. Calculate of copper atom be 127.8 pm, is the copper unit cell simple
cubic, body-centred cubic or face-centred cubic ?
the volume of a unit cell of lithium metal.
(Given : atomic mass of Cu = 63.54 g mol and N, = 6.022
[Ans. 4.356 x 10-2% em*] x 107° mol) (A.LS.B. 2010, D.S.B. 2010)
Iron has body centred cubic unit cell edge of 286.65 pm. 15. Copper crystallises with face centred cubic unit cell. If the
The density of iron is 7.87 g cm’. Use this information radius of copper atom is 127.8 pm, calculate the density of
to calculate Avogadro's number (At. mass of iron = 56 ¢g copper metal. (Atomic mass of Cu = 63.55 u and Avogadro's
mol *) (D.S.B. 2010) number N, = 6.02 x 10*° mol*) (A.I.S.B. 2012)
16. Aluminium crystallizes in an fcc structure. Atomic radius of
An element crystallizes in a structure having fcc unit cell the metal is 125 pm. What is length of the side of the unit
of an edge 300 pm. Calculate its density if 180 g of this cell of metal ? (A.LS.B. 2013)
element contains 3.708 x 10** atoms. (Pb.S.B. 2012) [Ans. 353.3 pm]
An element (density 7.2 g ecm’) crystallizes in a body 17. An element with density 10 g em™® forms a cubic unit
centred cubic structure having its unit celll edge length cell with edge length of 3 x 10° cm. What is the nature
2.88 A. Calculate the number of atoms present in 156 g of of the cubic unit cell if the atomic mass of the element is
the element. (Tripura Board 2016) 81 g mol ?? (A.L.S.B. 2015)
[Ans. bec]
Silver crystallizes in a fee lattice. The edge length of its
18. An element crystallizes in fcc lattice with cell edge of 400
unit cell is 4.07 x 10° em and its density is 10.48 g em”.
pm. The density of the element in 7 gcm™°. How many atoms
Calculate the relative atomic mass of silver (N, = 6.022 x
are present in 280 g of the element ? (A.L.S.B. 2016)
107° mol’). (Kolkata S.B. 2016)

yyw
ints & Answers
; for Revision Exercises
15. Conductivity ofa semi-conductor increases with temperature.
17. P
18. Conductivity of metals decreases with increase in
(z) 2N (az) N 5. 12,12 temperature.
Schottky and Frenkel defects 19. a= 2/or 22. 1 mol
0.225 — 0.414 24, (z)4 (21) 2 25. (i) p-type (11) n-type
. Electrical conductance increases. 26. A 27. Frenkel defect
. Metal excess defect due to anion vacancies. 28. ferromagnetic 29. X,Y,
| 178 MODERN'’S abc + OF CHEMISTRY
-XII

350. Nat =6, Cl =6 o2. six 2x(56 g mol)

oo. Schottky defect 34, n-type
(7.87 g em™)x (286.65 x 107? em)*
oo. Dipole-dipole forces 36. Interstitial defect
38. X,Y, 40. (5) Al. (c) 42, (a) 43. (b) = 6.04 x 1077 mol".
44, (a) 45. (c) 46. (c) A7. (c) 48. (d)
6. Mass of unit cell = ee x4=194.17x10°-~
49, (dD) 50. (d) 51. (d) 52. (a) 53. (c) 3.708 x 10
o4, (dD) 55. (a) 56. (c) as. Le) 58. (c) 194.17x 10-4 =7.19 P
Density = gcm
509. (c) 60. (0). G1. (5) 62. (d). (300x10° 2°)
Numerical Problems 7. Volume of unit cell = (2.88 x 10° em)*
£95 SOW cm”.
AxM
¢ 1. Density= a 156 ¢
xN, Volume of 156 g of element = 5 = 21.67 cm’
7.22 cm
M = 39 + 127 = 166
— 21.67
“ = No. of formula units No. of umit cells in this volume = ae.
7 Zx166 23.89 x 107
3.12
(705 x 107°)? x (6.022 x 10?) — 0.907 x 1074
For bce, number of atoms per unit cell = 2
3.12 x (705 x 1072°)? x (6.022 x 107")
a 166 No. of atoms in 156 g of element = 0.907 x 10% x 2
= 3.96 or 4 = 1.814 x 10**
4 K* and 4T ions per unit cell. 8. Refer Solved Example 31 (page 40).
9. Refer Solution of Practice Problem 38 (page 60).
+ 2. Density = —— 10. Refer Solution of Practice Problem 29 (page 59).
a xN,
Zx 96 11. For fee unit cell, radius , r = a
eS oe
ad de
(314 x 107" em)" x (6.022 x 10™) 2/2
— 409
~10,3 23
52 10.3 x (314 x10
ee 96
ee.
x 6.022 x10”
a 2x1.414
= 144.6pm
.. bce structure 12. 1 mol of tungsten = 184 g = 6.022 x 10° atoms
M(KCl) 23
No. of atoms in 1.5 g of tungsten = 8.08 x10" 51.5
+ 3. d(NaCl) = oe
Pn Na
A body centred cubic cell contains 2 atoms.
a’ (KCl)
M(KCl) No. of unit cells present
6.023 x 1078 x1.5
184 x2
N
d(KCl) = 4-4 = 2.45 x 107!
a’ (KCl)
AxM
d(NaCl) _ M(NaC) , a (KCI) 13. Density
a®xNa
d(KCl) M(KCl) a (NaCl)
4 x 78.08g mol”
3 3.18 gem? =
: 88 (4 = 1.172 (5.46 x 10° °cm)*’ x Ny
74.5 \0.875.
N, = 6.02 x 108
ZxM
+ A, Density = 2 At 14, Assuming fcc lattice for copper,
For bec, “4 = 2
iL 2/2 r
0.53 2x694
~~ a8 6.022 x 10° —~ 2x 1.414 x 127.8 x 10% em
2x 6.94 = 3.614 x 10° cm
3 —_ ss 29 5
a = 053x6.022x10" = 4:86 x 10° cm . 4 x 63.54
Volume =a? = 4.35 x 10-7? em? Density, P = ©614x10 cm) x(6.02 x10")
+ 5. For bcc arrangement,Z=2, p= 7.87 gem”, = 8.94 gem”
M =56 g mol? Since the density is same as observed, the lattice is fee
Edge length, a = 286.65 x 10° m = 286.65 x 10°? em lattice.
15. Refer Solved Example 15 (page 36).
7 AxM
7 a® x N, 16. Refer Solved Example 7 (page 18).
17. Refer Solution of Practice Problem 32 (page 59).
*xM
or N, = ree 18. Refer Solution of Practice Problem 24 (page 58).
pla
SOLID STATE

(‘ompetition >:
eo, 0

| tle Additional Useful Information and Objective Questions

ADDITIONAL USEFUL INFORMATION

Structure of Magnetite (Fe,O,)
>» X-RAYS DIFFRACTION STUDIES
Magnetite may be considered as having the composition
X-rays studies have helped to know the arrangement
FeO. Fe.0O3. This composition can be obtained if we convert
of atoms, ions or molecules in crystals. The phenomenon of
2/3 of Fe** ions in FeO into Fe** ions (for every three Fe** ions
X-rays by the crystals was studied by W.L. Bragg and W.H.
Bragg. By analysing the diffraction patterns, Bragg deduced a two Fe** ions). In Fe,O,, the oxide ions are arranged in cubic
simple relationship between the distance between the planes close packing arrangement. Fe** ions occupy octahedral sites and
of constituent particles in the crystal (d), the wavelength of the Fe** ions are equally distributed between octahedral and
X-rays used (A) and the angle of diffraction (9). This relation tetrahedral sites. This structure is known as inverse spinel
is known as Bragg equation and is given as: structure. Fe,O, is the load stone used by ancient travellers to
nha = 2d sin 8, find the direction. Another example of this structure is MgFe,O,
where 20 = angle made by a diffracted X-ray beam in which Fe™* ions of Fe,O, are replaced by Mg** ions.
with the direction of incident beam. Normal Spinel Structure
n = positive integer (1, 2, 3.... ete,) which A spinel is an important class of oxides consisting of two
stands for serial order of diffracted types of metal ions with the oxide ions. The general formula
beams. of the compounds adopting spinel structure is AB,O, such
Using Bragg's law, we can calculate the distance between as MgAl,O, and ferrites such as Zn Fe,O,. In this case, the
rows of constituent particles in a crystal. These distances oxide ions are arranged in cubic close packing arrangement,
are characteristic of a crystal and depend upon the size and the divalent cations (Mg** or Fe**) are in tetrahedral sites and
geometry or arrangement of these particles. trivalent ions (Fe**, Al°*) are in octahedral sites. In normal
spinel structure, one-eighth of the tetrahedral holes are occupied
> LAW OF CONSTANCY OF INTERFACIAL by divalent metal ions and one-half of the octahedral holes are
ANGLES occupied by trivalent metal ions. Many of the ferrites which
Crystals are bound by plane faces. The angle between any have spinel type structures are important magnetic materials
two faces is called an interfacial angle. It is measured by an used in telephones or memory loops in computers.
instrument known as goniometer. The law of constancy of
> DIELECTRIC PROPERTIES OF SOLIDS
interfacial angles states that
Depending upon the alignment of dipoles, the crystals have
irrespective of the size and shape of the crystals
the following dielectric properties:
(which depend upon the conditions of their
formation), the angles between any two corresponding (a) Piezoelectricity in which the dipoles align themselves
faces of the crystal of a particular substance are in an ordered manner such that there is a net dipole
always the same. moment in the crystal, e.g., titanates of barium and lead,
lead zirconate (PbZrO,), ammonium dihydrogen phosphate
This is also known as Steno’s law.
(NH,H,PO,), quartz.
> STRUCTURE OF METALS (6) Ferroelectricity in which the dipoles are permanently
aligned up even in the absence of electric field and the
The crystal structures adopted by some metallic elements
direction of polarization can be changed by applying
at 26°C and 1 bar pressure are :
an electric field. e.g., barium titanate (BaT10,), sodium
Crystal structure potassium tartarate (Rochelle salt), potassium dihydrogen
hep Be, Cd, Co, Mg, Ca, Ti, 4n phosphate (KH,PO,), ete.
ice Ag, Al, Au, Ca, Cu, Ni, Pb, Pt (c) Pyroelectricity. Some polar crystals when heated produce
small electric current called pyroelectricity.
bec Ba, Cr, Fe, Ir, Alkali metals
(d) Anti-ferroelectricity. There is no net dipole moment in
Primitive cubic Po
some crystals inspite of small dipoles because of alignment
of dipoles in opposite directions and therefore they donot
>» PACKING IN OXIDES OF TRON show ferroelectric character, e.g., lead zirconate (PbZrO,).
The packing in oxides of iron such as FeO and Fe,O, is
very interesting. >» SUPERCONDUCTING MATERIALS
Structure of Iron oxide (FeQ) Ordinary metals conduct electricity and their conductivity
Iron oxide (FeO) has rock salt (NaCl) structure. In this case is of order of 10° ohm? m™. Superconducting materials are
O* ions adopt face centred cubic arrangement (fcc) and Fe** ions those which offer no resistance to the passage of electricity. In
occupy octahedral sites. This is the ideal arrangement. However, this state, the materials become diamagnetic and are repelled
this oxide is always non-stoichiometic i.e., the composition of by the magnets. Most metals become superconducting at very
Fe** and O* ions is not 1: 1. It has been found to be generally low temperatures (2-5 K). The highest temperature at which
Fe,,, O (wustite). This composition can be obtained if a small superconductivity was known till recently was 23 K in alloys
number of Fe** ions are replaced by two-third as many Fe* of niobium (e.g., Nb,Ge). Some organic compounds also become
ions in octahedral sites. superconducting at temperatures below 5 K.
0 MODERN'S abc + OF CHEMISTRY
-XII

The common examples of some superconducting materials a b/2 c/2

along with their temperatures at which they become 1 1
superconducting are given below :
- 2 2
Material Temperature Miller indices (reciprocal of intercepts).
Alloys of niobium 23 K d. 2 2
Ba, 7K, 5B105 30 K i I i
La, gor, CuO, 40 K 1 2 y
Bi,Ca,Sr,Cu,0,, 105 K Alternatively, h, and 7 can be calculated as :
T1,Ca,Ba,Cu,O,, 125 K h = =
The important possible uses of super conducting materials
Intercept of plane along X-axis
are in electronics, building magnets, levitation, transportation, b
power transmission, etc.
‘ Intercept of plane along Y-axis
> DESIGNATION OF PLANES IN CRYSTALS : c
MILLER INDICES (A,2,1) 7 Intercept of plane along Z-axis
The structure of a crystalis also described by various planes
Then express /1, k, / as integers. For example, for the above
which pass through lattice points of the crystal. A number of
PQR plane making intercepts 2a, 3b and 2c we have
methods have been suggested to represent various planes in the
erystal. The method proposed by W.H. Miller is commonly used. ~_ wv eee a
In this method, the planes are described by a set of integers 8a’ — Bb? 2
1 1 1
(A, & and 7) known as Miller indices. The Miller indices of or — 3 = a

a plane of a crystal are the reciprocals of the intercepts 2 3 9

of that plane corresponding to unit length on the various .. Miller indices are 323.
axes. In this method, the unit lengths a, b and c along the three We can easily describe Miller indices of planes in a cube.
axes are choosen and the intercepts in terms of a, b and c are It may be noted that 1f a plane is parallel to one of the base
noted. The reciprocal of these numbers as simple integers are axes, its intercept with that axis would be infinity. Therefore,
the Miller indices. The simple procedure for determining Miller the Miller index for that plane will be zero (1/0 = 0).
indices for a plane is : For example, consider the shaded plane in a cube at unit length.
(1) Determine the intercept (expressed as a multiple of £

a, 6 and c) of the plane with X, Y and Z axes.

(zt) Invert all numbers.
(111) Clear fractions by taking LCM to obtain fh, k and /
values.
Let us illustrate this by some examples :
Consider a shaded plane PQR which makes intercepts 2a, 35
and 2c where a, 6 and c are unit lengths along X, Y and Z axes.
Intercepts of shaded plane PQR
2a 3b 2c ¥
It makes intercept only along X axis
or 2 3 2 (for unit lengths)
“. Miller indices (reciprocal of intercepts) are : Intercepts 1 a oe
1 i 1 ae ae 1 1 ik
Miller indices a = =
2 3 2
or 3 2 3 (by taking LCM) 1 0 0
Similarly, consider the following examples :

(z)

¥ Y
[Note : The numbers corresponding to intercepts i.¢., 2, 3
and 2 are also called Weiss indices].
Intercepts
Let us consider another example in which the plane makes
fractional intercepts. Miller indices
The unit length a, 6 and c are shown by dotted lines.
Intercepts of shaded plane along X, Y and 4 axes are Rey
RP RR ee
SOLID STATE 1/81 a

Intercepts us u 1
2 2
7 ae 2 2 1
Miller indices a — =
x 7c if 1
(zz)
2 2 1

OBJECTIVE TYPE QUESTIONS , |

Hl]
i
}
I LT
Hil Hl I if
A7. The co-ordination number in ccp and /icp arrangement of
metal atoms are respectively
(a) 6,6 (b) 12,6
Select the Correct Answer: (c) 8,6 _ (d) 12,12 ;
i A8. A metal crystallizes in accep structure. Its metallic radius
Space Lattice, Unit Cell and Crystal Systems is 141.6 pm. The number of unit cells in 64 cm? ofthe metal
Al. The crystal system of a compound with unit cell —
dimensions, a = 0.387, 6 = 0.387 and c = 0.604 nm and (a) 2x 10° (6) 1.6 x 10°
oa =fB=90° and y= 120° is (c) 1x 10%4 (d) 1.5 x 10”
(a) cubic (6) hexagonal A9. The portion ofedge length not occupied by atoms for simple
(c) orthorhombic (d) rhombohedral cubic, fcc and bcc are respectively (a is edge length)
A2,. In which of the following pair, both the crystals are not of (. 43) 1
the same type (a) O; “oe - a (1-45)
(a) Ice, solid CO, (6) NaCl, BaO
(c) SiC, diamond (d) Mg, Ar (, 3) 0: a{2_
A3. Which of the following statements is not true about sat 2)? v2
crystalline solids?
(a) Polar molecular solids have higher enthalpies of (c) 0; o{1- 5) ; a ae y
vaporisation than those ofnon-polar molecular solids.
(b) Graphite, though covalent solid is a good conductor (d) a:Wea: 3 e
of electricity. 2
(c) Ionic solids are conductors in molten state. A10. Total volume of atoms present in face centred cubic unit
(d) Non-polarmolecular
solids have London forces between cell of metal is (r is atomic radius)
the constituents and have higher melting points than (a) 24 3 (b) 2a
polar molecular solids. 7
A4, The most unsymmetrical and symmetrical systems are (c) 2 (d) 2 nr®
respectively
All. Ina face centred cubic unit cell of close packed atoms, the
(a) tetragonal, cubic
radius of atom (7) is related to the edge length (a) of the
(6) triclinic, cubic
unit cell by the expression
(c) rhombohedral, hexagonal
a
(d) orthorhombic, cubic (a) r= wc} (6b) r=-—
A5. The packing fraction for a body centred cube is ; ua
(a) 0.42 (6) 054 (ce) 0.68 (d) 0.74 (c) r= aap (d) r=
A6. The number of atoms in bcc and fcc arrangement are | ;
respectively : Al12. The number of atoms een ieaceeenal close packed
(6) 2,4 (c) 4,2 (d) 2,1 unit cell is
(a) 12
(a) 4 (6) 6 (c) 8 (d) 12

; Al. (6) A2 (d) Ads. (d) A4. (5) A5. (c) <A6. (0) A7. (d) A8. (c) AX (c) AO (ce)
All. ic) Al3. (5)
ea MODERN'S abc + OF CHEMISTRY
-XII

Al3. Ina hep arrangement, each atom at the corner contributes A** cations and 1/2 of the octahedral holes are occupied
to the unit cell equal to by cations B**. The general formula of this compound is
(a) 1/2 (b) 1/8 (c) 1/6 (d) 1/4 (a) A,BO, (6) AB,O,
Al4, A metal crystallizes in bcc lattice. The percentage of edge (ck) 46,0 (dq) A,B,O
length not covered by atoms is
» Acrystalline solid has a cubic structure in which tungsten
(a) 12.4% (b) 13.4% (W) atoms are located at the cubic corners of the unit cell,
(c) 87.6% (d) 50.0% oxygen atoms at the edges of the cube and sodium atoms at
Al5. A metal crystallizes in fcc lattice and edge of the unit cell the cube centre. The molecular formula of the compound is
is 620 pm. The radius of metal atom is (a) Na, WO, (6) NaWwo,
(a) 2656.5 pm (6) 310 pm (c) NaWO, (dq) Na,WO,
(c) 219.2 pm (d) 438.6 pm
» A mineral of titanium (perovskite) is found to contain
Al6. How many unit cells are present in a cubic shaped ideal calcium ions at the corners, oxygen atoms at the face
crystal of NaCl of mass 1.0 g? centres and titanium atoms at the centre of the cube. The
(a) 2.67 x 107! (6b) 1.28 x 1074 oxidation state of titanium in the mineral is
(c) 1.71 x 1077 (d) 6.14 x 1074 (a) +1 (6b) +3 (c) +4 (dq) +2
Interstitial Voids, Structure and Density of Ionic » The number of tetrahedral and octahedral holes in a
solids hexagonal primitive unit cell are
(a) 8,4 (b) 6,12 ic) 2,1 (d) 12,6
Al7. For tetrahedral co-ordination, the radius ratio (r,/r_) » In which of the following structures, the anion has
should be: maximum co-ordination number ?
(a) 0.166 — 0.225 (6) 0.226 — 0.414 (a) NaCl (5) ZnS (c) CaF, (d) Na,O
(c} 0.414—0.782 (fq) 0O.782—1
. Ina/fcc arrangement of P and @ atoms, where P atoms are
Al18. A compound formed by elements A and 5 crystallises in
at the corners of the unit cell, Q atoms at the face centres
the cubic structure where A atoms are at the corners of a and two atoms are missing from two corners in each unit
cube and B atoms are at the face centre. The formula of cell, then the formula of the compound is
the compound is:
(a2) P,Q, (6) P,Q © P,Q @) PQ,
(a) AB, (6) A,B (c) AB, (d) A,B,.
. The pyknometer density of sodium chloride crystal is
A119. The number of second nearest Na* ions neighbour of a 2.165 x 10° kg m™ while its X-ray density is 2.178 x
Na?* ion in NaCl structure is 10° kg m™®. The fraction of the unoccupied sites in sodium
(a) 12 (b) 6 (c) 8 (d) 4 chloride crystal is
(a) 5.96 (b) 5.96 x 107
. The cubic unit cell of Al (molar mass = 27 g mol) has an
edge length of 405 pm. Its density is 2.7 g cm*.The cubic
(c) 5.96 x 107 (d) 56.96 x 10%
unit cell is . Three elements A, B and C crystallise into a cubic solid
(a) body centred (6) primitive lattice. Atoms A occupy the corners, B occupy the cube
(c) edge centred (d) face centred centres and C occupy the edges. The formula of the
. Inmagnetite, O7 have ccp arrangement with Fe** ions in compoundis
1/8 tetrahedral voids and Fe** ions in 1/4th octahedral (a) ABC (6) ABC,
and 1/8 tetrahedral voids. The formula of magnetite is (c) ABC, (d) ABC,
(a) FeO, (Sees. » Aelement cystallizes in fcc lattice and edge length of unit
(c) FeO (dq) Fe,O, cell is 400 pm. If density of unit cell is 11.2 g cm”, then
. An alloy of Cu, Au and Agis found to have Cu constituting atomic mass of the element is
the ccp lattice. If Ag atoms occupy edge centres and Au is (a) 215.6 (b) 431.2
present at body centres, the alloy has formula: (c) 107.8 (d) 98.6
(a) Cu, Ag, Au (6) Cu, Ag, Au . An element (atomic mass = 60 g mol*) having fcc unit cell
(c) Cu, Ag, Au (d) Cu Ag Au has density 6.23 g cm’. The edge length of the unit cell
is (N, = 6.02 x 10*°)
A23. In spinel structure, O* ions are cubic-closed packed, (a) 300 pm (6) 250 pm
whereas 1/8th of the tetrahedral holes are occupied by
(c) 400 pm (d) 160 pm

Answer
Al3. (c) <Al4, (6b) Al5. (ce) Al6. (a) AI. (6) Al18. (a) Al9. (a) <A20. (d) A221. (a) A222. (c)
A23. (6b) A224. (c) A25. (c) A26. (d) A27. (d) A28. (d) A29. (d) A380. (ce) ASB. (ce) A82. (ce)
SOLID STATE

A33. The cell edge of a fec crystal is 100 pm and its density is (a) ferromagnetism (0) anti-ferromagnetism
10.0 gem°. The number of atoms in 100 g of this crystal (c) ferrimagnetism (dq) diamagnetism.
18 A37. Fe,O, is ferrimagnetic at room temperature but at
(a) 1x10 (5) 2x 10" 850 Kit becomes :
(c) 3x10” (d) 4x10” (a) diamagnetic (6) ferromagnetic
. Copper crystallizes in a cubic lattice structure. Atomic (c) non-magnetic (d) paramagnetic
radius of copper is 128 pm and its atomic mass 1s 63.5. » lron (IJ) oxide has cubic structure and each unit cell has
The density of copper is side 6A. Ifthe density ofthe compound is 4 gem“, calculate
(a) 10.71gem™ (6b) 4.93 gem” the number of Fe** and O* ions present in each unit cell.
(c) 89¢gem™ (dq) 112¢em° (molar mass of FeO = 72 g mol’, N, = 6.02 x 10” mol")
(a) 1 (6) 2
Defects in Crystal Structures, Magnetic and (c) 4 (d) 6
Electrical Properties . The appearance of colour in solid alkali metal halides is
A365. Which of the following is not an example of 13-15 generally due to
compound? (a) Sehottky defect (6) Frenkel defect
(a) InSb (6) GaAs (c) Interstitial position (d) F-centres
(C_B.S.E PMT. 2006)
(c) CdSe (d) AIP.
A40. An example of a ferromagnetic oxide is
» If the alignment of magnetic moments in a substance is
(a) CrO, (6) TiO,
in a compensatory way so as to give zero net magnetic
moment, then the substance is said to be im FeoV, (d) Mn,O.

Answers
AS3. (d) A384. (c) A35. (c) A386. (6) A387. (d) Ass. (c) A389. (d) A40. (a)

MULTIPLE CHOICE QUESTIONS (c) 1g: Ba: 2a (d) 1a: J3a:J2a

from Competitive Examinations (C_B.S.E. PMT 2008)
B4, Lithium metal crytallises in a body centred cubic crystal.
AIPMT & Other State Boards’ If the length of the side of the unit cell of lithium is 351
Medical Entrance pm, the atomic radius of the lithium will be :
Bl. If NaClis doped with 10~* mol % of SrCl,, the concentra- (a) 161.8 pm (6) 76.5 pm
tion of cation vacancies will be (N, = 6.02 x 1077 mol) (c) 300.5 pm (d) 240.8 pm
(a) 6.02x10?° mol? (6b) 6.02 x 10) mol (C_B.S.E. PMT 2009)
(c) 6.021014 mol! (d) 6.02 x 10" mol B5. A metal crystallises with a face-centred cubic lattice. The
(C.B.S.E. PMT. 2007) edge of the unit cell is 408 pm. The diameter of the metal
atom is
B2. The fraction of total volume occupied by the atoms present
(a) 288 pm (6) 408 pm
in a simple cube is
(c) 144 pm (dq) 204pm (ALP.M.T. 2012)
E It
(a)
S () 7 = B6. A metal has a fcc lattice. The edge length of the unit cell
is 404 pm. The density of the metal is 2.72 g cm”. The
al
molar mass of the metal is:
(c) | (d) y (C_B.S.E. P.M.T. 2007)
(Avogadro's constant, N, = 6.02 x 107° mol*)
. If ‘@ stands for the edge length of the cubic systems :
simple cubic, body centred cubic and face centred cubic, (a) 27 gmol* (6) 20gmol*
then the ratio of the radii of the spheres in these systems (c) 40g mol? (d) 30gmol’ (NEET 2013)
will be respectively : B7. The number of carbon atoms per unit cell of diamond unit
1 1, cell is
(a) ae
1.48). “aie
1 (b) ,
-q: 8a:
J2 (a) 6 (6) 1

—_ (c) 4 (d) 8 (NEET 20138)

B1. (3) B2. (d) B38. (a) B44. (a) BS. (a) B6. (a) B7. (d)
 MODERN'S abc + OF CHEMISTRY
-XII

. [fais the length of the side of a cube, the distance between (c) Frenkel defect is favoured in those ionic compounds
the body centered atom and one corner atom in the cube in which sizes of cations and anions are almost equal.
will be
(d) FeO, ,ghasnon-stoichiometric metal deficiency defect.

aes VB (NEET 2017)

B16. Iron exhibits bee structure at room temperature. Above
(c) 84 (d) are (AIPMT 2014) 900 °C, it transforms to fee structure. The ratio of density
of iron at room temperature to that at 900 °C (assuming
B9. The vacant space in bcc lattice unit cell is: molar mass and atomic radi of iron remain constant
(a) 239% (b) 32% with temperature) is
(c) 26% (d) 48% (AIPMT 2015) (a) V3 (b) 43
B10. The correct statement regarding defects in crystalline V2 3/2
solids is: (ce) 3v3 (zy 1 (NEET 2018)
(a) Frenkel defect is a dislocation defect. 4/2 2
(6) Frenkel defect is found in halides of alkaline earth B17. Total number of tetrahedral and octahedral voids in
metals. 0.6 mol of a compound forming /cp structure are :
(c) Schottky defects have no effect on the density of (a) 6.022 x10” (6) 3.011 x 10”
crystalline solids. (c) 9.033 x 10° (d) 4.616 x 10”
(d) Frenkel defects decrease the density of crystalline (A.M.U Med. 2010)
solids. (AIPMT 2015) B18. Which one of the following compound exhibits both
Schottky and Frenkel defects ?
Bll. Agiven metal crystallises out with a cubic structure having (a) NaCl (b) AgCl
edge length of 361 pm. If there are four metal atoms in
(c) AgBr (dq) Agl (A.M.U. Med. 2010)
one unit cell, what is the radius of one atom ?
B19. The mass percentage ofiron present as Fe(IIT)in Fe, 5,0, ,
(a) 80 pm (6b) 108 pm is
(c) 40 pm (d) 127 pm (AIPMT 2015) (a) 8.3% (6) 9.6%
B12. Lithium has a dcc structure. Its density is 530 kg m™ and (c) 11.5% (d) 17.7% (A.M.U. Med. 2013)
its atomic mass is 6.94 g mol+. Calculate the edge length
of a unit cell of lithium metal. (N, = 6.02 x 107° mol”) JEE (Main) & Other State Boards’
(a) 627 pm (6) 264 pm Engineering Entrance
(c) 1564 pm (d) 352 pm (NEET 2016)
B20. In a compound, atoms of element Y form ccp lattice and
B13. The ionic radii of At and B~ ions are 0.98 x 107!" m and those of element X occupy 2/3rd of tetrahedral voids. The
1.81 x 107!" m. The coordination number of each ion in formula of the compound will be
AB is
(a) X,Y, (0) X,Y,
(a) 8 (ob) 3
(c) 6 (d) A (NEET 20716) ic) X,Y. (d) X,Y (A.LE.E.E. 2008)
B14, In calcium fluoride, having the fluorite structure, the B21. The edge length of a face centred cubic cell of an ionic
coordination numbers for calcium ion (Ca**) and fluoride substance is 508 pm. If the radius of the cation is 110 pm,
ion (F) are the radius of the anion is :
(a) 4and2 (6) B6andé (a) 618 pm (6) 144 pm
(c) 8and4 (d@) 4and8 (NEET 2016)
(c) 288 pm (dq) 398 pm (AJLE.E_E. 2010)
B15. Which is the incorrect statement ?
B22. Percentage of free space in cubic close packed structure
(a) Density decreases in case of crystals with Schottky and in body centred packed structure are respectively :
defect.
(a) 32% and 48 % (b) 48 % and 26%
(6) NaCl(s)is insulator, silicon is semiconductor, silver
is conductor, quartz is piezoelectric crystal. (c) 30 % and 26 % (d) 26% and 32%
(A.LE.E.E. 2010)

As wele
B8. (d) B9. (5) B10. (a) Bll. (d) B12. (d@) Bis. (c) B14. (c) B15. (c,d) BiG. (c) BT. (ec)
B18. (c) B19. (c) B20. (5) B21. (5) B22. (d)
SOLID STATE

B23 In a face centred cubic lattice, atom A occupies the corner B31. Which type of ‘defect’ has the presence of cations 1n the
positions and atom B occupies the face centre positions. interstitial sites?
If one atom of B is missing from one of the face centred (a) Schottky defect (6) Vacancy defect
points, the formula of the compound is (c) Frenkel defect (d) Metal deficiency defect
(a) A,B (6) AB, (JEE Main 2018)
B32. Anionic compound is expected to have tetrahedral structure
(c) A,B (d) A,B, (AIEEE 2011) ifr,/r_ lies in the range of
B24, Copper crystallises in fcc lattice with a unit cell edge of (a) 0.155 to 0.225 (6) 0.732 to 1
361 pm. The radius of copper atom is: (c) 0.414 to 0.732 (d) 0.226 to 0.414
(Karnataka C.E.T. 2008)
(a) 108 pm (6) 128 pm
B33. A solid compound contains X, Y and Z atoms in a cubic
(c) 157 pm (d) 181 pm (AIEEE 20117)
lattice with X atoms occupying the corners, Y atoms in
B25. Lithium forms body centred cubic structure. The length the body centred position and Z atoms at the centres of
of the side of its unit cell is 351 pm. Atomic radius of the faces of the unit cell. What is the empirical formula of the
lithium will be compound?
(a) 300 pm (6) 240 pm (a) XY,Z, (b) XYZ,
(c) 152 pm (dq) 76pm (ALE_E_E. 2012) (c) XLY,Z, (d) X,YZ,
B26. Experimentally it was found that a metal oxide has formula
(e) XYZ (Kerala P.E.T. 2008)
M,,930- Metal M is present as M** and M** in its oxide. B34, KCI erystallizes in the same type of lattice as does NaCl.
Fraction of the metal which exists as M** would be Giventhat "y,+ /%- = 0-55 and r,. /r%- = 0.74, calculate
(a) 5.08% (b) 7.01% the ratio of the side of the unit cell for KC] to that of NaCl.
(c) 4.08% (d) 6.05% (JHE Main 2013) (a) 1.123 (6) 0.891
B27. CsCl erystallises in body-centred cubic lattice. If ‘a’ is (ce) 1.414 (d) 0.414
its edge length then which of the following expression is
(e) 1.7382 (Kerala P.E.T. 2008)
correct ?
(a) Toet loa = V3 a (0) rat + lq = 3a B35. The white ZnO turns yellow on heating because of
od (a) Frenkel defect
(Cc) Ta.# + lor = my (dq) rot +lor= 5
(6b) Metal excess defect
(JEE Main 2014) (c) Metal deficiency defect
(d) Schottky defect (A.M.U. Engg. 2010)
B28. Sodium metal crystallizes in a body centred cubic lattice
with a unit cell edge 4.29 A. The radius of sodium atom B36. In face-centred cubic lattice, a unit cell is shared equally
1s approximately by how many unit cells?
(a) 6.72A (b) 0.93 A (a) 6 (b) 4
(c) 1.86A (d) 3.22 A (JEE Main 2015) (c) 2 (d) 8 (Karnataka C_E.T. 2013)
B29. Which of the following compound is metallic and B37. Potassium dichromate belongs to which crystal system?
ferromagnetic?
(a) Tetragonal (6) Orthorthombic
(a) TiO, (b) Cro, (c) Triclinie (dq) Hexagonal
(c) VO, (d) MnO, (JEE Main 2016)
(e) Monoclinic (Kerala PET 2014)
B30. A metal crystallises in a face centred cubic structure. If B3s. Which one of the following is used as a piezoelectric
the edge length of its unit cell is ‘a’, the closest approach material ?
between two atoms in metallic crystal will be (a) Silicones (6) Graphite
(a) 2a (b) 2/2a (c) Silica gel (d) Kieselguhr
(e) Quartz (Kerala PET 2014, Karnataka CET 2016)
(c) J2a (d) 5 (JEE Main 2017)

Ainsuets
B23. (d) B24. (5) B25. (c) B26. (c) B27. (d) B28. (c) B29. (5) B30. (d) B3l. (ce) B32. (d)
B33. (6) B34. (a) B35. (5) B36. (a) B37. (c) B38. (e)
6 MODERN’S abc + OF CHEMISTRY
-XII

B39. Suppose the mass of a single Ag atom is ‘m’. Ag metal (d) Trapping of proton in the lattice leads to the formation
erystallizes in fcc lattice with unit cell of length ‘a’. The of F-centres. (Karnataka CET 2017)
density of Ag metal in terms of ‘a’ and ‘mm’ is B46. Which of the following crystals has unit cell such that
@) o) = a#zb#zcanda#Bp+#Y+90°?
a) KoCr.0. (6) NaNO,
(c) (d) a (WB JEE 2015) (c) KNO, (d) A,B,
a a
B40. The unit cell with crystallographic dimensions, a # 5 #c¢, (Karnataka CET 2017)
a= y= 90° and B # 90° is
B47. In a face centred cubic arrangement of A and B atoms
(a) monoclinic (6) tetragonal
in which ‘A’ atoms are at the corners of the unit cell and
(c) triclinic (d) orthorhombic
‘B’ atoms are at the face centres. One of the ‘A’ atoms is
(Karnataka CET 2015) missing from one corner in unit cell. The simplest formula
B41. Ionic solids with Schottky defect may contain in their of compound is
structure (a) AB, (6b) A.B,
(a) cation vacancies only (c) A,B, (d) A,B,
(6) cation vacancies and interstitial cations (Karnataka CET 2017)
(c) equal number of cation and anion vacancies B48. A compound formed by elements X and Y crystallises in
(d@) anion vacancies and interstitial anions the cubic structure, where X atoms at the corners of a cube
(WB JEE 2016, Karnataka CET 2016) and Y atoms are at the centres of the body. The formula
of the compound is
B42. In a face centred cubic unit cell, what is the volume
occupied? (a) XY (6) XY,
wi X,Y. (d) XY,
(a) =m?
3
(6) ony
3 (WB JEE 2018)
3 B49. Edge length of a cube is 300 pm. Its body diagonal would
(c) 1%5,2 (qd) 84 (MH-CET 2016) be
3 3/3
(a) 600 pm (6b) 423 pm
B43. An element crystallising in body centred cubic lattice (c) 519.6 pm (d) 450.5 pm
has an edge length of 500 pm. If its density is 4 g (Karnataka CET 2018)
cm, the atomic mass of the element (in g mol“) is B50. Which of the following is not a conductor of electricity?
(consider N, = 6 x 10°) (a) Solid NaCl (6) Cu
(a) 100 (6b) 250 (c) Fused NaCl (d@) Brine solution
(Karnataka CET 2018)
(c) 126 (d) 150

(e) 50 (Kerala PET 2016) JEE (Advance) for ITT Entrance

B44, The contribution of a particle at the edge centre of a
particular unit cell is, B51. In a solid ‘AB’ having NaCl structure, ‘A’ atoms occupy the
corners of the cubic unit cell. If all the face-centred atoms
(a) 1 (oy 1 along one of the axes are removed, then the resultant
2 4 stiochiometry of the solid is

(ce) 1 (d) , (Karnataka CET 2016)

(a) AB, (6) A,B
ick 7B. (dq) A,B, (LL.T. 2001)
B45. The correct statement regarding defect in solids is B52. In which of the following crystals alternate tetrahedral
(a) Schottky defect has no effect on the physical properties voids are occupied ?
of solids (a) NaCl (6) Zns
(6) Frenkel defect is a dislocation defect (c) CaF, (d) Na,O (1L.T. 2005)
(c) Frenkel defect is usually favoured by a very small
difference in the sizes of cations and anions

maswels
B39. (a) B40. (a) B41. (c) B42. (c) B43. (dq) B44, (b) B45. (6) B46. (a) B47. (6) B48. (a)
B49. (c) B50. (a) B51. (d) B52. (5)
SOLID STATE

B53. The packing efficiency of the two dimensional square unit (LET. Jt. 2012)
cell shown is: B55. The arrangement of X" ions around A* ion 1n solid AX is
given in the figure (not drawn to scale). If the radius of
X is 250 pm, the radius of A* is

*@

(a) 39.27% (b) 68.02%

(c) 74.05% (d) 78.64% (a) 104 pm (6) 125 pm
(.L.T. 2010) (c) 183 pm (d) 57 pm
B54. A compound M,X, has cubic close packing (cep)
(JEE Advance 2013)
arrangement of X. Its unit cell structure is shown
below. The empirical formula of the compound is B56. If the unit cell of a mineral has cubic close packed (ccp)
array of oxygen atoms with m fraction of octahedral holes
occupied by aluminium ions and n fraction of tetrahedral
holes occupied by magnesium ions, m and 7, respectively,

11 1
(a) 3 (b) La

« it (dy) 1.1 (WEE Advance 2015)

9°9 4’8

PAS Welsy
B53. (d) B54. (5) B55. (a) B56. (a)

Cs. In which of the following structures, the coordination

C MULTIPLE CHOICE QUESTIONS number of both the ions are same ?
with more than one correct answer (a) Cesium chloride
(6) Sodium chloride
C1. Which of the following is/are not true about hexagonal (c) Zine sulphide
close packing ? (d) Sodium oxide
(a) It has 26% empty space
C4, Which of the following is not correct for Frenkel defect in
(6) In this arrangement, third layer is identical to the
crystals ?
first layer.
(c) The coordination number in this arrangement is 6. (a) Itisdueto equal number ofcations and anions missing
from lattice sites.
(d) Itis as closely packed as body centred cubic packing.
(6) It has no effect on density of the crystal.
C2. Which of the following statements are correct ? (c) It occurs in crystals where the difference in the size
(a) The coordination number of each type of 10n in CsCl of cations and anions is small.
crystal is 8. (d) Silver halides show Frenkel defect.
(6) A metal that crystallizes in bee structure has
C5. The coordination number of eight for cation is found in
coordination number 12.
(c) A unit cell of an ionic crystal shares some of its ions (a) CsCl (b) NaCl
with other unit cells. (c) CaF, (d) Na,O
(d) The length of the unit cell in NaCl is 552 pm C6. Which of the following systems do not give correct
(r,,,+ = 95 pm, r,,cr” = 181 pm) description of axial lengths and axial angles ?
(a) Hexagonal : a=b#e, a= f= 980°, y= 120°

swlces
(6) Tetragonal: a=b#e, a= fB=90°, y#90°

Cl. (c), (d) C2. (a), (c),(d@) C3. (a), (6), (c) C4, (a), (c) C5. (a), (c) C6. (5), (c)
es MODERN'S abc + OF CHEMISTRY
-XII

(c) Monoclinic : abc, a= B=y#90° C9. Which type of defects are present in AgbBr and ZnS crystal
systems ?
(d) Cubic a=b=c, a= 6 =y=90°
(a) Frenkel and Schottky
C7. The correct statement(s) regarding defects in solidsis (are)
(a) Frenkel defect is usually favoured by a very small (6) Schottky and Frenkel
difference in the sizes of cation and anion (c) Frenkel and Frenkel
(6) Frenkel defect is a dislocation defect (d) Schottky and Schottky
(c) Trapping of an electron in the lattice leads to the (A.M_U. (Engg.) 2015)
formation of F-centre
C10. The correct statement(s) for cubic close packed (ccp) in
(d) Schottky defects have no effect on the physical
properties of solids. WUT-JEE 2009) three dimensional structure is(are)
C8. With respect to graphite and diamond, which of the (a) the number of the nearest neighbours of an atom
statement(s) given is(are) correct ? present in the top most layer is 12.
(a) Graphite is harder than diamond. (6) the efficiency of atom packing is 74%.
(6) Graphite has higher electrical conductivity than (c) the number of octahedral and tetrahedral voids per
diamond. atom are 1 and 2, respectively.
(c) Graphite has higher thermal conductivity than
diamond.
(d) the unit cell edge length is 2,/9 times the radius of
the atom.
(d) Graphite has higher C—C bond order than diamond.
(JEE Advance 2016)
WUT-JEE 2012)

Araswiess
C7. (0), (c) C8.(5), (d) C9. (b), (c) C10.(5), (c), (d)

D2. Gold crystallizes in a face centred unit cell. Its edge length
MULTIPLE CHOICE QUESTIONS
ts
is 0.410 nm. The radius of gold atom is
based on the given passage/comprehension (a) 0.205 nm (6) 0.290 nm
(c) 0.145 nm (d) 0.578 nm
Passage I.
Ds. In a cubic lattice of XYZ, X atoms are present at all corners
In the crystalline solids the smallest repeating partin the except one corner which is occupied by Y atoms. Z atoms are
latticeis known as unit cell. The unit cells are described as present at face centres. The formula of the compound is
simple (points at all the corners), body centred (points at all (a) X,YZ,, (6) XYZ,
the corners andin the centre), face centred (points at allthe
corners and centre of all faces), and end centred (points at (c) X,Yo4Z (a) Kove,
all the corners and centres of two opposite end faces) unit D4, The ionic radii of K*, Rb* and Br’ are 137, 148 and 195
cells. In two common types of packing ccp and /cp, 26% of pm. The coordination number of cation in RbBr and KBr
space is left unoccupiedin the form of interstitial sites. For structures are respectively
the stable ionic crystalline structures, there is definite (a) 8,6 (b) 6,4
radius ratio limit for a cation to fit perfectly in the lattice (c) 6,8 (d) 4,6
of anions, called radius ratio rule. This also defines the D5. A face centred cubic lattice of a metal M and a body centred
coordination number of an ion, which is the number of cubic lattice of metal N contain same number of 2.25 x
nearest neighbours of opposite charges. This depends 10” unit cells. If density of M is twice than that of N, the
upon the ratio of radii of two types ofions, r,/r_. This ratio ratio between the number of atoms per unit cell is
for coordination numbers 3, 4, 6 and 8 is respectively
(a) 4:1 (6) 1:1
0.155—-0.225, 0.225-0.414, 0.414—0.732 and 0.732-1
respetively. (c) 2:1 (d) 1:4
Passage II.
Answer the following questions : Density of a unit cell is same as the density of the
D1. The number of atoms per unit cell in simple (s), body substance. If the density of the substance is known,
centred (6), face centred (f) and end centred (e) unit cell number of atoms or dimensions of the unit cell can be
decreases as calculated. The density of the unit cell is related to its
(a) f>b>e>s8s (6) f>b=e>s8 mass (M), no. of atoms per unit cell (4), edge length
(c) b>f>s=e (d) f >b>e=s (a2 in cm) and Avogadro number N, as :
ZxM
p=
a®xN ,

Passage - I D1. (5) Dz. {(c) D3. (d) D4, (a) D5. (c)
SOLID STATE

Answer the following questions : Here, the top and bottom of the cell are regular hexagons
D6. An element crystallizes in a structure having a fee unit and three atoms are sandwiched in between them.
cell of an edge 100 pm. If 24 g of the element contains Aspace-filling model of this structure, called hexagonal close-
24 x 107° atoms, the density is packed (/icp), is constituted of a sphere on a flat surface
(a) 2.40 gem? (6) 40gem” surrounded in the same plane by six identical spheres as
(c) 4gem”? (d) 24gcem° closely as possible. Three spheres arethen placed over thefirst
layer so that they touch each other and represent the second
D7. The number of atoms present in 100 g of a bcc crystal
layer. Each one of the three spheres touches three spheres
(density = 12.5 g cm”) having cell edge 200 pm is
of the bottom layer. Finally, the second layer is covered with
(a) 1x10” (b) 1x 107 a third layer that 1s identical to the bottom layer in relative
position. Assume radius of every sphere to be ‘7’.
(c) 2x 1074 (d) 2x 107°
Answer the following questions :
. Ametal X (at. mass = 60) has a body centred cubic crystal
structure. The density of the metal is 42 g cm”. The D9. The number of atoms in this Acp unit cell is
volume of unit cell is (a) 4 (5) 6 (c) 12 hay VE

(a) 8.2x 10 em? (b) 4.76 x 10-°° em? D10. The volume of this Aep unit cell is

(c) 3.86 x 107 em? (d) 3.86 x 10°~° em? (a) 24,/2r3 (b) 16V2r°
(c) 12V2r 3 64 3
(d) eke
3/5"
Passage III.
In hexagonal systems of crystals, a frequently encountered D11. The empty space in this Acp unit cell is
arrangement of atoms is described as a hexagonal prism. (a) 74% (b) 47.6%
(ce) 32% (d) 26% (LL.T. 2008)

(AES
Passage-II D6. (5) D7. (c) D8. (bd)
Passage-III D9. (5) D10. (a) D11. (d)

: In ZnO, the excess Zn** ions are present in

Assertion Reason Type Questions Assertion
interstitial sites.
The questions given below consist of an Assertion and the Reason : Metal excess crystals have either missing
Reason. Use the following key to choose the appropriate answer. eation or anion in interstitial site.

(a) Ifboth assertion and reason are CORRECT and reason Assertion : FeO is non-stoichiometric with Fe, 5,0.
is the correct explanation of the assertion. Reason : Some Fe** ions are replaced by Fe** as 3Fe**
(6) Ifboth assertion and reason are CORRECT, but reason = 2Fe** to maintain electrical neutrality.
is NOT THE CORRECT explanation of the assertion. Assertion : In CaF,, F ions occupy all the tetrahedral
(c) If assertion is CORRECT but reason is INCORRECT. sites.

(d@) If assertion is INCORRECT but reason is CORRECT. Reason : The number of Ca2* is double the number of
F” ions.
(e) If both assertion and reason are INCORRECT.
Assertion : Size of cation is larger in tetrahedral void than
1. Assertion : In any ionic solid (MX) with Schottky defects, in octahedral void.
the number of positive and negative ions are Reason : The cations occupy more space than anions
same. in crystal close packing
Reason : Equal number of cation and anion vacancies Assertion : Frenkel defect is shown by silver halides.
are present. U.1.T. 2001) Reason : Silver ions are small in size and can easily fit
2. Assertion : ZnS has a tetrahedral arrangement. in interstitial sites.
Reason — : In ZnS, S* ions occupy the tetrahedral sites Assertion : In Frenkel defect, density of the crystalline
while Zn** ions form cubic close packed solid does not change.
structure. Reason : In Frenkel defect, no cation or anion leaves
3. Assertion : In CsCl structure, the co-ordination number the crystal.
of Cs* ion is 8. 10. Assertion : Frenkel and Schottky defects are stoichiometric
Reason : Cl ions in CsCl have body centred cubic defects.
arrangement. Reason : Both defects change the density of the

(1) —(a) (2)—(e) @)—-() (4)—-() )—-@) (6)-(e) ()—-(e) (8)-@ (9)—-(@) (10) — (c)
80 MODERN'’S abe + OF CHEMISTRY
-XII

3. Match the distribution of particles A and B in List I with

Matching Type Questions formula given in List II.

Each question has matching list. The codes for the lists List I List
have choices (a), (b), (c) and (d) out of which only one is correct. P. Ainccp and B equally 1. A,B,
1. Match the type of crystal system given in List I with its distributed in octahedral
and tetrahedral
description given in List II.
@. Binfep and A occupy 2/3rd 2. A,B
List I List IT
of octahedral voids
P. Monoclinic l. a2#b4¢e,04+P2+7280° R. A atthe corners and face centres 3. AB
@. Tetragonal 2. £A04eo,.0=b=—7—o0" and B at edge centres and body centre
R. Triclinic 3. a#b4c,a=y=90°,8 490° S. Bincep and A occupy all the 4. AB,
5S. Khombic 4. =p 4e,8=C—7—-or octahedral and tetrahedral sites

P Q R 5 B Q RK 5
(a) 3 4 2 1 (a) 4 1 3 2
(0) 4 3 1 2 (b) 4 1 2 3
(c) 3 2 i! A
(c) 3 4 1 2 (d) 4 2 3 i
(d) 2 3 4 1
4, Match the entries of column I with appropriate entries of
2. Match the type of crystal given in List I with example in column II.
List IT. Compound Magnetic property
List I List II (A) NaCl (p) Ferrimagnetic
P. Ionic 1. AIN (B) MnO (gq) Paramagnetic
@. Network 2. Mg (C) CrCl, (r) Ferromagnetic
R. Metallic 3. MgO (D) CrO, (s) Diamagnetic
5. Molecular 4. Solid CO,
(EZ) MgFe,O, (t) Antiferromagnetic
P Q R 5 A B C D &E
(a) 3 1 4 2 (a) p r g t os
(0) 3 1 2 4 (b) t q r p s
(c) i 3 2 A (c) r i gq p s
(d) s t q rp
(d) 4 2 3 1
(e) s ' t qQ p

Answers (Kerala PMT 2015)

tes 2. (bd) 3. (a) 4, (d)

p q sr s
Matrix Match Type Questions
entries of Column IJ. Each entry in - ()
Each question contains statements given in two columns, Column I may have one or more than p (P) (q) (r)
which have to be matched. Statements in Column I are labelled one correct option from Column II. The
as A, B, C and D whereas statements in Column II are labelled answers to these questions have tobe C (P) (q) ()
as p,g,r ands. Match the entries of Column I with appropriate appropriately bubbled as illustrated in
D
the given example.
1. Match the crystal system/unit cells mentioned in column I with their characteristic features mentioned in column II.

(A) Simple cubic and face centred cubic | (p) have these cells parameters a = 5 =c anda=fB=y
(B) Cubic and rhombohedral (g) are two crystal systems
(C) Cubic and tetragonal (r) have only two crystallographic angles of 90°
(D) Hexagonal and monoclinic (s) belong to same crystal system.
(L.T. 2007)

Answers
(1) :(A-@)(s)_ — (B) -@) (q) (C) —(q) (D) —(q) (r)
SOLID STATE

2. Match the imperfections in solids mentioned in column | with the characteristic features mentioned in column II.

(A) Schottky defects excess cations occupy interstitial sites

(B) Frenkel defects conduct electricity due to free electrons
(C) Metal excess defects act as p-type semi-conductors
(D) Metal deficient defects are non-stoichiometric defects

3. Match the type of arrangement in column I| with the characteristic feature mentioned in column II.

(A) Cubic close packing (p) occupy 74% of the space

(B) Hexagonal close packing (q) occupy 68% of the space
(C) Body centred cubic (r) have 1 atom per unit cell
(D) Simple cubic (s) have more number of atoms per unit cell than
simple cubic arrangement

Arsswets
(2) : (A) —(q) (B) —(p)(q) (C) —(p) (q) (s) (D) —(r) (s)
(3) : (A) —(p)(s) (B) —(p) (r) (s) (C) —(s) (D) —(q).

Integer Type or Numerical Value Type Questions 8. A compound is formed by two elements X and Y.
i A The element Y form ccp and atoms of X occupy 1/3 of
tetrahedral voids. If the formula of the compound is X,
Interger Type: The answer to each of the following question Y,, then value of a + 6 is
is a single-digit-integer ranging from 0 to 9. 9. A cubic unit cell has one atom on each corner and one
1. Silver (atomic weight = 108 g mol“) has a density of atom on each body diagonal. The number of atoms in the
10.6 g cm’. The number of silver atoms on a surface of unit cell is
area 107° m “ can be expressed in scientific notation as 10. The number of hexagonal faces that are present in a
y x 10*. The value of x is (L.T. 2010) truncated octahedron is (LL.T. 2011)
2. In NaCl structure, Cl ions have cep arrangement and 11. Acrystalline solid of a pure substance has a face centred
Na‘ ions occupy all the octahedral sites. The total number cubic structure with a cell edge of 400 pm. Ifthe density of
the substance in the crystal is 8 g cm”, then the number
of Na* and CI ions per unit cell is :
of atoms present in 256 g of the crystal is N x 10**. The
3. A metal ‘X’ crytallizes in a unit cell in which the radius of value of N is (JEE Advance 2017)
atom (7) is related to edge of unit cell (a) as r = 0.3536 a. Numerical Value Type: Give the correct numerical value
The total number of atoms present per unit cell is (in decimal notation truncated/rounded off to the second
decimal place).
4, The radius ratio of an ionic solid r,/r_is 0.624. The
coordination number of this type of structure is 12. Consider anionic solid MX with NaCl structure. Construct
5. Atoms of element N form hcp arrangement and those of a new structure (7) whose unit cell is constructed from
the unit cell of MX following the sequential instructions
element M occupy 2/83rd of tetrahedral voids. The total
given below. Neglect the charge balance.
number of M and N per formula unit is
(1) Remove all the anions (X) except the central one
6. In hexagonal close packing, the difference in the number
of tetrahedral and octahedral voids per unit cell is (2) Replace all the face centred cations (M) by anions (X)

7. The ratio of coordination number of each sphere in ccp (3) Remove all the corner cations (M)
and hcp in three dimensions is (4) Replace the central anion (X) with cation (M)

The value of Se osee| in 418

Answecs DEDEDE CAMONE/ (SEE Advance 2018)

1. 7 2. 8 ao. A 4, 6 a. 7 6. 6 te il 8. 5 9, 5 10. 8

11. 2 12. 3.00

 MODERN'S abc + OF CHEMISTRY
-XII

Exemplar Problems T/T|

Objective Questions

<@
(c) same arrangement of constituent particles in different
directions.
» Which of the following conditions favours the existence of (d) different arrangement of constituent particles in
a substance in the solid state? different directions.
(a) High temperature (6) Low temperature . lodine molecules are held in the crystals lattice by
(c) High thermal energy (d) Weak cohesive forces
» Which of the following is not a characteristic of a crystalline (a) London forces
solid ? (6) dipole-dipole interactions
(a) Definite and characteristic heat of fusion. (c) covalent bonds
(6) Isotropic nature. (@) coulombic forces
(c) Aregular periodically repeated pattern of arrangement » Which of the following is a network solid?
of constituent particles in the entire crystal. (a) SO, (Solid) (6) I,
(d) A true solid (c) Diamond (d) H,O (Ice)
» Which of the following is an amorphous solid ? 10. Which of the following solids 1s not an electrical conductor?
(a) Graphite (C) (6) Quartz glass (510,) (A) Mg(s) (B) TiO(s) (C) L{s) (D) H,O(s)
(c) Chrome alum (d) Silicon carbide (SiC) (a) (A) only (6) (B) Only
.» Which of the following arrangements shows schematic
(c) (C) and (D) (d) (B), (C) and (D)
alignment of magnetic moments of antiferromagnetic
substances ? 11. Which of the followingis not the characteristic of ionic solids?

“OOODOO®
(a) Very low value of electrical conductivity in the molten state.
(6) Brittle nature.

»VYOUDY
(c) Very strong forces of interactions.
(d) Anisotropic nature.
12. Graphite is a good conductor of electricity due to the

“OOVOOY
presence of
(a) lone pair of electrons (5) free valence electrons

“—OYUOOOD
(c) cations (d) anions
» Which of the following oxides behaves as conductor or
insulator depending upon temperature ?
» Which of the following is true about the value of refractive (a) TiO (b) SiO, (c) TiO, (d) MgO
index of quartz glass? 14, Which of the following oxides shows electrical properties
(a) Same in all directions like metals ?
(6) Different in different directions (a) SiO, (6) MgO (c) SO0,(s) (d) CrO,
(c) Cannot be measured 15. The lattice site in a pure crystal cannot be occupied by
(d) Always zero
» Which of the following statement is not true about (a) molecule (6) ion
amorphous solids? (c) electron (d) atom
(a) On heating they may become crystalline at certain 16. Graphite cannot be classified as
temperature. (a) conducting solid (6) network solid
(6) They may become crystalline on keeping for long time. (c) covalent solid (d) ionic solid
(c) Amorphous solids can be moulded by heating. 17. Cations are present in the interstitial sites in
(d) They are anisotropic in nature. (a) Frenkel defect (6) Schottky defect
. The sharp melting point of crystalline solids is due to (c) Vacancy defect (d) Metal deficiency defect
18. Schottky defect is observed in crystals when
(a) aregular arrangement of constituent particles observed (a) some cations move from their lattice site to cafemseael
over a short distance in the crystal lattice. sites.
(b) aregular arrangement of constituent particles observed (b) equal number of cations and anions are missing from

HE
over a long distance in the crystal lattice. the lattice.
(ce) some lattice sites are occupied by electrons.
(d) some impurity is present in the lattice.
1. (5) 2. (d) a. (5) eae 5. (a) 6. (d) 7. (b) 8. (a) Saale) 10. (c)
11. (a) 12. (d) eee) 14. (d) 15. (c) 16. (d) 17. (a) 18. (5)
SOLID STATE

19. Which of the following is true about the charge acquired (c) Frenkel defects
by p-type semiconductors ? (d) Electronic defects
(a) positive 29. Silicon doped with electron-rich impurity forms
(5) neutral (a) p-type semiconductor
(c) negative (6) n-type semiconductor
(d) depends on concentration of p impurity (c) intrinsic semiconductor
20. To get a n-type semiconductor from silicon, it should be (d) insulator
doped with a substance with valence :
a0. Which of the following statements is not true ?
(a) 2 (6) 1 (c) 3 (d) 6
(a) Paramagnetic substances are weakly attracted by
21. The total number of tetrahedral voids in the face centred
magnetic field.
unit cell is
(a) 6 (6) 8 (c) 10 (d) 12 (0) Ferromagnetic substances cannot be magnetised
permanently.
22. Which of the following point defects are shown by AgBr(s)
crystals ? (c) The domains in antiferromagnetic substances are
oppositely oriented with respect to each other.
(A) Schottky defect
(d) Pairing of electrons cancels their magnetic moment in
(B) Frenkel defect
the diamagnetic substances.
(C) Metal excess defect
ol. Which of the following is not true about the ionic solids?
(D) Metal deficiency defect
(a) (A) and (B) (6) (C) and (D) (a) Bigger ions form the close packed structure.
(c) (A) and (C) (d) (B) and (D) (5) Smaller ions occupy either the tetrahedral or the
23. In which pair most efficient packing is present? octahedral voids depending upon their size.
(a) hep and bcc (6) hep and ccp (c) Occupation of all the voids is not necessary.
(c) bec and cep (d) bce and simple cubic cell (d) The fraction of octahedral or tetrahedral voids occupied
24, The percentage of empty space in a body centred cubic depends upon the radii of the ions occupying the voids.
arrangement is : OZ. A ferromagnetic substance becomes a permanent magnet
(a) 74 (6) 68 when it is placed in a magnetic field becuase
(c) 32 (d) 26 (a) all the domains get oriented in the direction of aimenetie
25. Which of the following statement is not true about the field.
hexagonal close packing ? (d) all the domains get oriented in the direction opposite
(a) The coordination number is 12. to the direction of magnetic field.
(6) It has 74% packing efficiency. (c) domains get oriented randomly.
(c) Tetrahedral voids of the second layer are covered by (d) domains are not affected by magnetic field.
the spheres of the third layer. oo. The correct order of the packing efficiency in different types
(d) In this arrangement spheres of the fourth layer are of unit cells is
exactly aligned with those of the first layer. (a) fee < bcc < simple “
26. In which of the following structures coordination number (6) fee > bcc > simple cubic
for cations and anions in the packed structure will be same? (c) fee < bcc > simple cubic
(a) Cl ions form fcc lattice and Na‘* ions occupy all (d) bee < fec > simple cubic
octahedral voids of the unit cell.
34, Which of the following defects is also known as dislocation
(b) Ca** ions form fec lattice and F ions occupy all the defect?
eight tetrahedral voids of the unit cell.
(a) Frenkel defect
(c) O* ions form fcc lattice and Na‘ ions occupy all the
eight tetrahedral voids of the unit cell. (6) Schottky defect
(d) S* ions form fcc lattice and Zn** ions go into alternate (c) Non-stoichiometric defect
tetrahedral voids of the unit cell. (d) Simple interstitial defect
27. What is the coordination number in a square close packed oo. In the cubic close packing, the unit cell has
structure in two dimensions ? (a) 4 tetrahedral voids each of which is shared by ‘our
(a) 2 (6) 3 adjacent unit cells.
(c) 4 (d) 6 (6) 4 tetrahedral voids within the unit cell.
28. Which kind of defects are introduced by doping? (c) 8 tetrahedral voids each of the which is shared by four
(a) Dislocation defect adjacent unit cells.
(6) Schottky defect (d) 8 tetrahedral voids within the unit cells.

(asta
19. (5) 20. 21. (5) 22. (a) rid (b) 24, Le) 25. (d) 26. (a, d) Pale) 28. (d)
29. (d) 30. . 31. (d) siPog Ty! oo. (0) 34, (a) 35. (d)
is MODERN'’S abc + OF CHEMISTRY
-XII

36. The edge lengths of the unit cells in terms of the radius Od. Which of the following represents correct order of
of spheres constituting fcc, bcc and simple cubic unit cell conductivity in solids?
are respectively
(a) B etale 77 “ineulatore ~ “comiconductors
Ar Ar
(a) 2V2r,
—, 2r (6) ——, 04/or
, Or (5) Kinetale =e hy asulators < Senenerpaees peerre
V3 /3 (c) « metale=k semiconductors al i
— zero

(c) 2r,eJor,4r (dj) 2 3. 24/9r (d) Lae < Bsiteriedhictats > Pec ulatore # Zero

V3 V3

| 36. (a) 37. (a)

»> Multiple Choice Questions (Type-ll) (c) The gap between valence band and conduction band
cannot be determined.
Note: In the following questions two or more options may be (d) Valence band may remain partially filled.
correct. 42. Under the influence of electric field, which of the following
38. Which of the following is not true about the voids statements is true about the movement of electrons and
formed in three dimensional hexagonal close packed holes in a p-type semiconductor?
structure ? (a) Electron will move towards the positvely charged plate
(a) A tetrahedral void is formed when a sphere of the through electron holes.
second layer is present above triangular void in the (0) Holes will appear to be moving towards the negatively
first layer. charged plate.
(b) All the triangular voids are not covered by the spheres (c) Both electrons and holes appear to move towards the
of the second layer. positively charged plate.
(c) Tetrahedral voids are formed when the triangular voids (d) Movement of electrons is not related to the movement
in the second layer lie above the triangular voids in of holes.
the first layer and the triangular shapes of these voids 45. Which of the following statements are true about
do not overlap. semiconductors?
(d) Octahedral voids are formed when the triangular voids (a) Silicon doped with electron rich impurity is a p-type
in the second layer exactly overlap with similar voids semiconductor.
in the first layer.
(b) Silicon doped with an electron rich impurity is an
39. The value of magnetic moment is zero in the case of n-type semiconductor.
antiferromagnetic substances because the domains
(c) Delocalised electrons increase the conductivity of doped
(a) get oriented in the direction of the applied a hctic
silicon.
field.
(d) An electron vacancy increases the conductivity of
(b) get oriented opposite to the direction of the applied n-type semiconductor.
magnetic field.
. An excess of potassium ions makes KCl crystals appear
(c) are oppositely oriented with respect to each other
violet or lilac in colour since
without the application of magnetic field.
(a) some of the anionic sites are ceeapied by an unpaired
(d) cancel out each other’s magnetic moment.
electron.
40. Which of the following statements are not true?
(a) Vacancy defect results in a decrease in the density of
(b) some of the anionic sites are occupied by a pair of
electrons.
the substance.
(c) there are vacancies at some anionic sites.
(b) Interstitial defects results in an increase 1n the density
of the substance. (d) F-centres are created which impart colour to the
crystals.
(c) Impurity defect has no effect on the density of the
substance. 45. The number of tetrahedral voids per unit cell in NaCl
crystal is
(d) Frenkel defect results in an increase 1n the density of
the substance. (a) 4
41. Which of the following statements are true about metals ? (b) 8
(a2) Valence band overlaps with conduction band. (c) twice the number of octahedral voids.
(6) The gap between valence band and conduction band (d) four times the number of octahedral voids.
is negligible.

mmswels
38. (c), (d) 39. (c),(d) 40. (c),(d) = 41. (a), (8), (d) 42. (a), (0) 43.(6),(c) 44. (a),(d) 45. (5), (c)
SOLID STATE

46. Amorphous solid can also be called 48. Which of the following statements are correct?
(a) pseudo solids (6) true solids (a) Ferrimagnetic substances lose ferrimagnetism on
(c) super cooled liquids (d) super cooled solids heating and become paramagnetic.
A7. A perfect crystal of silicon (Fig.1) is doped with some (6) Ferrimagnetic substances do not lose ferrimagnetism
elements as given in the options. Which of these options on heating and remain ferrimagnetic.
show n-type semiconductors? (c) Antiferromagnetic substances have domain structures
similar to ferromagnetic substances and their magnetic
moments are not cancelled by each other.
Silicon atom #
= &
* 2.
#

Li - :‘@
(d) Inferromagnetic substances all the domains get oriented
in the direction of magnetic field and remain as such
even after removing magnetic field.
49, Which of the following features are not shown by quartz
glass?
(a) This is a crystalline solid.
Lt
#*
= =
Ld
'a
(6) Refractive index is same in all the directions.
Fig. 1. Pure crystal (c) This has definite heat of fusion.
(d) This is also called super cooled liquid.

(a)
©0000
@@:2:@: b) 06:6
eoee ‘@:
50. Which of the following cannot be regarded as molecular solid?
(a) SiC (Silicon carbide)
(c) Diamond
(6) AIN
(d) I,
51. In which of the following arrangements octahedral voids
606 06:6: @e@6 6: are formed?
(a) hep (b) bee
(c) simple cubic (d) fee
52. Frenkel defect is also known as
(a) stoichiometric defect
@@ 06 6: ®@@06:@: (6) dislocation defect

” @@:e ‘@: o @:6 1:6: (c) impurity defect

(d) non-stoichometric defect
©6000 ©8680 53. Which of the following defects decrease the density?
©6066! 0080660: (a) Interstitial defect (6) Vacancy defect
(c) Frenkel defect (d) Schottky defect

A8. (a), (d) 49. (a), (c) 50. (a@),(0),(c) 451. (a), (d) 52. (a),(6) 538. (8), (d)

Column I Column IT
»> Matching Type Questions
(a) Simple vacancy defect (2) shown by non-ionic solids
Note: In the following questions match the items given in and increases density of the
Column I with the items given in Column IT. In some solid.
questions more than one item of Column I and Column (6) Simple interstitial (it) shown by ionic solids and
IT may match. defect decreases density of the
solid.
54. Match the defects given in Column I with the statements
(c) Frenkel defect (iit) shown by non ionic solids
in given Column II.
and density of the solid
decreases.
(d) Schottky defect (iv) shown by ionic solids and
density of the solid remains
the same.
6 MODERN'’S abc + OF CHEMISTRY
-XII

55. Match the type of unit cell given in Column I with the 56. Match the types of defect given in Column I with the
features given in Column II. statement given in Column II.

Column I Column If Column I Column IT

(a) Primitive cubic unit cell. (1) Kach of the three (a) Impurity defect. (2) NaCl with anionic sites
perpendicular edges called F-centres.
compulsorily have the (6) Metal excess defect. (ii) FeO with Fe**.
different edge lengthz.e., (c) Metal deficiency defect. (iii) NaCl with Sr** and some
ab #¢: eationic sites vacant.
57. Match the items given in Column I with the items given
(6) Body centred cubic unit (zi) Number of atoms per
in Column II.
cell. unit cell is one.
Column I Column IT
(c) Face centred cubic umt (iii) Each of the three
cell. perpendicular edges (a) Meg in solid state. (t) p-Type semiconductor.
compulsorily have the (6) MgCl, in molten state. (ii) n-Type semiconductor.
same edge length i.e., (c) Silicon with phosphorus. (iii) Electrolytic conductors.
ee os (d@) Germanium with boron. (iv) Electronic conductors.
(d) End centred (iv) In addition to the
58. Match the type of packing given in Column I with the
orthorhombic. contribution from unit items given in Column II.
cell the corner atoms
the number of atoms Column I Column IT
present in a unit cell (a) Square close packing (1) Triangular voids.
is one. in two dimensions.
(5) Hexagonalclose packing (i1) Pattern of spheres is
(v) In addition to the
in two dimensions. repeated in every
contribution from the
fourth layer.
corner atoms the
(c) Hexagonal close packing (121) Coordination number 4.
number of atoms
in three dimensions.
present in a unit cell
(d) Cubic close packing (iv) Pattern of sphere is
is three.
in three dimensions. repeated in alternate
layers.

nswices
54. (a)-(111); (BH); (Hiv); (Hat) = 55. (a) Hi, 111); (B)Hit, 1); (e)Htit, v); (dH, wv) ~=56. (aH); (0)H1); (eH it)
57. (a)tv); (6)Hizt); (c)H11); (Ha) 58. (@)Hi1it); (b)H(1); (c)H iv); (d)-(11)

<q 60. Assertion : Graphite is a good conductor of electricity

however diamond belongs to the category of insulators.
In the following questions a statement of assertion Reason : Graphite is soft in nature on the other hand
followed by a statement of reason is given. Choose diamond is very hard and brittle.
the correct answer out of the following chotces. 61. Assertion : Total number of octahedral voids present in
(a) Assertion and reason both are correct statements and unit cell of cubic close packing including the one that is
reason is correct explanation for assertion. present at the body centre, is four.
(b) Assertion and reason both are correct statements but Reason : Besides the body centre there is one octahedral
reason is not correct explanation for assertion. void present at the centre of each of the six faces of the unit
(c) Assertion is correct statement but reason is wrong cell and each of which is shared between two adjacent unit
statement. cells.
(d) Assertion is wrong statement but reason is correct 62. Assertion : The packing efficiency is maximum for the fcc
statement. structure.
59. Assertion : The total number of atoms present in a simple Reason : The cordination number is 12 in fcc structures.
cubie unit cell is one. 63. Assertion : Semiconductors are solids with conductivities
in the intermediate range from 10° — 10* ohm7?m?.
Reason : Simple cubic unit cell has atoms at its corners,
each of which is shared between eight adjacent unit cells. Reason : Intermediate conductivity in semiconductor is
due to partially filled valence band.
Araswets
59. (a) G60. (bd) G1. (c) 62. (bd) 63. (c)
SOLID STATE

tions for
Hints & E xplana Difficult Objective Type Questions

A. mcq with only one correct answer A20. (d) : d= ZxM

a®xN,
A8. (c) f= 2/2 a 27 = Axaql
= 2x 1.414 x 141.5 = 400 pm
Volume of unit cell (406 «10719 ) x (6.02 x 10°8)
= (400x 107° em)? =6.4x 10° em?
No. of unit cells in 64 em? 2.7 x (406 x 10-*°) x 6.02 x 1078
Z =a =4
. — 1 x 10% unit cells ra
6.4x10 .. Lattice is fee.
A9. (c) For simple cubic, distance between nearest
neighbours = a . May No. of O* ions in ccp = 4
Empty space = 0 There will be 8 tetrahedral sites and 4 octahedral
sites
For fcc distance between nearest neighbours,
No. of Fe** ions = =x8 —]
a =
v2 1 No. of Fe** ions= SxB+—x4 =9
Empty
Pty space
sp = a——=
Ta = a[1-.|
ae
Formula of magnetite : Fe** Fe,*tO,” = Fe,O,
For bcc, d = vibe =e No. of Cu atoms = 4 (ccp arrangement)
1
No. of Ag atoms = 12 (edges) x 7 > 3
Empty space = eee afi
No. of Au atoms = 1 (body centre)
Al10. (c) No of atoms present in fcc unit cell =4
Formula Cu, Ag, Au
Total volume of atoms present in fcc unit cell
16 . (b): No. of O* ions in cep arrangement = 4
ae oe = — «Tr - No. of octahedral holes = 4
a 3
Al4, (5) : In bec, radius of atom, No. of B** ions = 4 x ; -9

r=
Ba No. of tetrahedral holes =4x2=8
where a is the edge length No. of A** ions = 8 x 7 =]
The edge length not covered by atoms = a — 2r 8
Formula A B,O,
3 28 . {c) No. of W atoms per unit cell = 1
= a a-2xX—a=a
re 3
No. of O atoms per unit cell = 12 x2 (edge centre)
_ a(2 7 — 0.134a =3
No. of Na atoms per unit cell = 1 (cube centre)
Percentage of edge length not covered Formula NaWO,
1
= 0.1340 x100 = 13.4% . {c) No of Ca atoms per unit cell = 8 (corners) x 3 =
aq

a 620
A115. (c) = 219.20 pm O atoms per unit cell = 6 (face centres) x — 3
" * oJ ~ 2x1.414
Ti atoms per unit cell = 1 a
Al16. (a) : No. of NaCl molecules in a unit cell = 4 Formula of mineral = Ca TiO,
Suppose oxidation state of Ti be x
Nineechaniies.
Jass of unitcell = =
6.022 x 1022
+24x43(-2)=0 or x=+4
1x 6.022
x 107" . (d): No. of atoms per unit cell of hexagonal primitive
No.0. of UNIL unit Cells cellsinin
OF lg
£ = ——————_
conor unit cell = 6
No of tetrahedral holes = 6 x 2=12
= 257x107!
1 No. of octahedral holes = 6 x 1=6
A118. (a) : No. of A atoms per unit cell = 8 (at corners) x 8 - (d): No. of atoms at the corners = 6
a I Contribution of each atom = 1/8
No. of B atoms per unit cell /
1
’. No. of P atoms
= 6 x A = 3/4
= 6 (at the face centre) x 5 3
Formula AB, No. of atoms at the faces = 6
8 MODERN'S abe + OF CHEMISTRY
-AIl

Contribution of each atom = 1 d one “AxM

.. No. of Q atoms
= 6 x : =3 a? ~*~ Na
4x 63.6
Formula P3 Q, or PQ, 3
4 (362 x 10") x (6.02 x 10°)
A29. (d) Molar volume from pyknometer density
= 89gcem”
M
2.165 x 10° A838. (c) ad J SEN
a xN,
Molar volume from X-ray density
5 Ax 72
SS = / O
2.178 x 10° (5x 10-8) (6.021075)
m°”
.. Volume unoccupied = M ag = oa | 3
10? |2.165 2.178 A x (5x 10°) x (6.02 x 10”)
0.013 M x 107 i
No. of Fe** and O* ions present in each unit
~ 2.165 x 2.178
Fraction unoccupied =
0.013M x 10° / Mx107°
cell = 4

2.165 x 2.178 2.165 B. meq from Competitive Examinations

= 5.96 x 10°. Bl. (6) : One cation of Sr** would create one cation
1 vacancy in NaCl. Therefore, the number of cation
. te) No. of 'A' atoms= 8 x 8=1
vacancies created in the lattice of NaCl is equal to
No. of 'B' atoms = 1x1l=1 the number of divalent Sr** ions added.
No. of moles of cationic vacancies
No. of 'C' atoms = — 12=3
— 10+ = 10% mol
Formula = ABC,
10?
No. of cation vacancies
. he) d— 2xM_
a®xN, = 10° x 6.02 x 10%
Ax» M = 6.02 x 107"
OO ————— ao B2. (d) : Packing fraction of a simple cube
(400 x 10-*°) x (6.02 x 10°) _ Volume of one sphere
~ Volume of cubic unit cell
11.2x (400 x 10-1)" x (6.02 4 10”) Edge lengtha =2r or r=a/2
or M = = 107.8
ZxM * o(S 3
. Ley 3 d=
a®xN, .. Packing fraction =
a 2 _i
x: 6
4 =x 60
6.23 B3. (a) : For simple cubic, a= 2r_.. _——
a® x 6.02 x 107"
A x BO For bec, Ar =
5 =64x10™
6.23 x 6.02 x10?
bo|
sa|S
a =
a = 4x10%em=400pm For fcc,

. (d ) : Volume of unit cell =(100 x 10°?° em)? Ratio is:

—10-** em?
Mass of unit cell = V x d — 10-74 x 10.0 = 10-74 g oS a

es
po|
bo|e
100
No. of unit cells in 100 g = 10-22 B4 (a) : For bcc structure,
_ iy

Since lattice is fee and each unit cell has 4 atoms r= “8,= “85.351 151.98 pm
per unit cell.
B5. (a) : For jcc lattice, radius (r)is related to edge length(a)
No. of atoms = 4 x 10”. a
r = a = 408 pm
A34. (c) For jcc, r a 2/2’
2/2 408
or = I 2f/2r =2x 1.414x 128 ’ = Sie
362 pm -- Diameter = 2 x 144 = 288 pm
SOLID STATE

B6. @): d= XM a”*xN, Z(bec)xM (4r\

2x M

SSeS eR
d = 2.72 gem”, Z=4, d(bec)_ a3xNy _ \vB
a = 404 pm=4.04x 10% cm d(fec) Z(fec)xM 4xM
_ 4xM ax N, ee2) x0
(4 EN
2.12
(4,04 x 107°)? x 6.02 x 10” v2.
or M=27¢ mol?
__ 2xM a) iki
(cay
B7. (d) : Carbon has structure similarto ZnS (zinc blende).
Carbon forming fcc or ccp and also occupying half
tetrahedral sites.
Total no. ofcarbon atoms= 8 x i (corners)+ 6 x 7
8 |
(faces) + 4 (tetrahedral sites) = 8. 2\2° J2) 4v2
B8. (d) : The distance between body centred atom and one
B17. (c) For 1 mol of a compound, number of tetrahedral
corner atom is v3 @ (ie. half of body diagonal) and octahedral voids = 2+1=3
”. No. of voids = 8 x 0.5 x 6.022 x 107° = 9.033 x 107°
B9. (6) : In bce arrangement, volume of space occupied
= 68% B18. (c) AgBr shows both Schottky and Frenkel defects
.. Vacant space = 100 — 68 = 32% B19. (c) Let x atoms of Fe** ions are present. This means
B11. (d) : For Z=4, structure is fcc x Fe** ions have been replaced by Fe** ions.
»_ N2a _ 1414x8
_jo7
61om No. of Fe** ions = 0.93 — x
4 4 For electrical neutrality,
AxM 2(0.938 —x) + 3x =2
B12. d) : ————
1864+4x=2 or x = 0.14
For bce, Z = 2, M = 6.94 g mol Fraction of Fe** = 0.14, Fe** = 0.93 — 0.14 = 0.79

530 g x 10° Formula : Fe%,, Fe} 1,015

— 5630 ke m= = = 0.580 gem?
‘ . em? x 108 Total molar mass = 0.93 x 56+ 1x 16= 68.08
2x6.94 % of Fe (IIT) = 2:24*5® , 190 = 11.5%
12S) i
a® x 6.02 x 1078 68.08
B20. (5) : No. of Y atoms in a unit cell = 4
3 2x 6.94 No. of tetrahedral sites =4 x 2=8
tt
— Pee’
—
__s-3B 0°@* em?
0.53 x 6.02 x 107°
No. of X atoms in unit cell = 8 x = =
a = 38.62 x 10° em
= 352 pm
Formula : Xig¥, or X,Y, or Xy4Yz
B13.
™% — 0.98x107°m 3 3 4
(c) = 0.64
™ 1,81x107m B21. (5) : For jcc

Since the radius ratio lies between 0.414 — 0.732,

its coordination number is 6.
B15. (c) : In Frenkel defect the size of cation should be
smaller than that of anion.
(d) : isalsoincorrect because Fe,, O is metal deficient
non-stoichiometric compound.
B16. (c) For bee structure: 4r = 3 a

or a= al
3
A=2
For fee structure : 4r = /2q
or

eS
4r
/2 508
=—fF.= “9 ~ll0=14¢pm
Z=4
ea: MODERN'S abe + OF CHEMISTRY
-AIl

B22. (d) : Percentage of free space in ccp = 26% and in Daiisity Mass of unit cell
bec = 32%. B39. (a) :
Volume of unit cell
B28. (d) : No. of 'A' atoms at corners = 8 xe =] No. of atoms x Mass of each atom

1 i)
Volume of unit cell
No. of i]'B'1 atoms at face centres = 5x — = 9 For fcc, no. of atoms per unit cell = 4
Formula = AB... or A,B, 4xm
Density = 3
B24, (bd) In a fcc lattice a
B41. (e) In Schottky defect equal number of cations and
Ar = /2a
anions are missing from their lattice sites.
2 1.414 «361 B42. (e) No. of atoms in fec unit cell = 4
ae a8 = EE XOOL _aorar = 128 pm
B25. (c) For bee structure, Volume occupied by 1 atom = 5m

aV3 _351x1.7382 _ ip, sate Volume occupied by 4 atoms = 4 x 4? = a m®

4 4
B43. (d) :
_ 2x 3
B26. (c) Let fraction of metal which exits as M** be x ax Na
Fraction of metal as M** = 0.98 —x For bcc, Z = 2, a = 600 x 107° em
“. ox + 2(0.98 — x) = 2 d=4gcem™”
x+196=2 or x=0.04 2 xM

% of M3+ = 9:94 . 1009 = 4.08 (500 x 107° yx (6x 1078)

0.98
\3
B27. (d) : Body diagonal = ,/3 g 4 x (500 x10") x 6 x 10°
| ees, pay Sey
2
or 2rg.++2rq-= JB a = 160g mol?

3 a B44, (b) : Each particle at the edge centre is surrounded by

Tos tla = 75 four unit cells. Therefore, its contribution per unit
B28. (c) For bec lattice, cell is >
. _ Na _ 1782x429 53 4
4 4 B45. (Bb) : Frenkel defect is a dislocation defect.
B29. (6) : CrO, is metallic and ferromagnetic. B46. (a) : The dimensions; 746 #y#90° anda #b#c represent
triclinic crystal system. Among the given options
B30. (d) : Infecc, the closest approach distance between two
only K,Cr,O, exhibits triclinic crystal system.
atoms,
a 1 fT
| B47. (b) : No. of A atoms at the corners = 7 x Phe Ps
(2
No. of B atoms at face centres = 6 x 1 = 3
B31. (ce) In Frenkel defect, the cations are dislocated from
2
their normal sites to interstitial sites.
Ratio of A: B= : ae
: 1
B33. (5) : Atoms ofX per unit cell =8 x — =1
Formula of compound is A.B,,
Atoms of Y per unit cell = 1
, 1 | 1
Atoms of Z per unit cell = 6 x Py =3 B48. (a) : No. of X atoms = wer =]

.. Formula of the compound is XYZ,. No. of Y atoms = 1

re, an Formula : XY
B34. (a): —N8a_= 0.65; K" = 0.74
‘or fg B49. (e) Length of body diagonal = V3.a
Fe. fe = 1.732300
or 2 41= 0.66 +1, -K* = 0.7441
‘a- To = 519.6 pm
B51. (d) : No. of atoms (A) on the corners = 8
wat tor — 1.56, "xt or
or = 1.74
No. of atoms (A) on the face centres = 6
Tor ‘o- Removing face centred atoms along one of the axes
Edge length ratio is
means removal of 2A atoms so that
r+ oe ¥ Tor = ae —, ———
=

—~ 1.129
No. of A atoms per unit cell = 8 x 5+4x .=3
Tor Twat tor , Na* cl
No. ofB atoms per unit cell in NaCl type structure
=4
B36. (a) : Each unit cell is surrounded by 6 other unit cells
because a fcc unit cell has six faces. Formula = A,B,
SOLID STATE

B52. (5) : In ZnS, S* ions are present in all the corners and
centres of each face (fcc or ccp arrangement). Zn* C. mcq with more than one correct answer
ions occupy alternate tetrahedral sites.
Petters te
FL. ted) : A hexagonal close packing has coordination
B53. (d) : number 12 and is not as closely packed as bcc.
C2. (a,c,d): (6) is not correct because it has coordination
Ifa is the length of unit cell
number 8.
Face diagonal, AC = 2a ai. (acdc): Cs*(8), Cl (8); Na* (6); CI(6); Zn** (4), S*(4);
But AC = 4r Na‘ (4), O7(8).
J2a = 4r C9. (b,c) : £nS shows Frenkel defect while AgBr shows both
4r : Frenkel and Schottky defects. Therefore, options
a= —== 2,/2r (6) and (c) are correct.
/2
No. of particles = 4x2 +1=2 D. mcq based on passage/comprehension
Area occupied by particles = 2 x mr” Passage I.
; ; Qxnr? ot D1. (d) : The number of atoms per unit cell in different
”. Packing efficiency = = types of unit cells are:
i * * @ar 4
f=4,5=2,e=2ands=1
= 0.7857 or 78.57 %.
B54. (5) X are present at all the corners and face centres D2. (c) From geometry we can prove that, r = a
2/2
0.410 aade
No. of X atoms = 8x5 +6x5=4
"= 9x1.414 — 007m
M are present at 4 edges and at body centre D3. (d) : No. of X atoms = 7x ; = 7/8

No. of M atoms = 4xt41x1=2 1

No. of Y atoms =1x 8 = 1/8
The empirical formula of compound: M,X, or MX,

B55. (a) : Cation A* occupies octahedral void of arrangement No. of Z atoms =6x > =3
of X anions
Formula = a oo Z, = AVL,
r,
"At _0.414—> _A* _0.414 +
_ 250 D4. (a) : m(Rb") _ 148 _ 0 76(C.N. 8 above 0.732)
r(Br’) 195
or r,s =0.414 x 260 = 104 pm. + c
B56. (a) : For ccp arrangement, 4 = 4 MK) _ 187 _ 9700
r(Br) 195
.. No. of O atoms = 4 (C.N. 6 between 0.414 — 0.732)
No. of octahedral voids = 4 D5. (c) fcc arrangement has 4 atoms per unit cell while bcc
No. of tetrahedral voids = 4x 2=8 arrangement has 2 atoms per unit cell. Therefore,
ratio between atoms is 4: 2 or 2: 1. Here density
No. of Al®* ions = m x 4 does not make any difference.
No. of Mg** ions =n x 8 Passage II.
Thus the formula of mineral is
D6. (b) : Vol. of unit cell =(100 x 10-7? em)®
Al,,, Mgs, O4 =1~x 10 cm?
4m(+3) + 8n(4+2) + 4(-2) = 0 24.0)
Mass of an atom = =1x10*¢
12m+16n-8 = 0 24x10”
A(3m+4n—2) = 0 (No. of atoms in fcc = 4)
i om+4n = 2 Mass of unit cell =4x1x10%=4x10%¢
Possible values of m and n are 4x10
Densi
ensity —- ——,,
1x10 = 40 gcm ii
gxteaxt = 2 true
2 8 D7. (c) Vol. of unit cell = (200 x 10°7°)® = 8 x 10° em?
1 Volume of 100 g of element = a 2 8 em?
SX1+ 4x7 = 2 not true
12.5

No. of unit cell = ss —~]x 10"

gxisaxt = 9 not true 8x10
2 2
No. of atoms in 100 g = 2 x 1 x 107*=2
x 1074
gxtaaxt - 2 not true
4 8 (No. of atoms in bce unit cell = 2)
— |ano2 MODERN'S abe + OF CHEMISTRY
-AIl

——
7 reas

2x60
Ds. (b
(D) M ass offmt
unit ce eel sae
a
602x102 (
10.5. y"
No. of atoms in 1 cm? —- |——_N,
108
Density = _Mass 2
No. of atoms in 10° m? or 10% cm
Volume
rc 2x 60 = [PEN re
~~ 6.02 x10" xV 108
~~| x sis x 10 23 \75 ge
2
2x60
or V= ee = 4.75 x 10° cm’.
6.02 x10°° x 4.2
Passage III.
1.60 x 10°
D9. (bd) Effective no. of atoms present in unit cell of icp . Ener at
1 1 2. (8) : There are 4Na‘ion and 4CI ions per unit cell. Total Na*
=e =o tok Lal eS Hs
2 6 and CT ions are 8.
D10. (a) : Volume = Base area x Height 3. (4) : It corresponds to fee unit cell. Therefore, the number of
atoms present per unit cell is 4.
= 6x a? x2x [20
4 3 4. (6) : Since radius ratio lies between 0.414 — 0.7382, its
Puttinga = 2r coordination number is 6.
5. (7) : Suppose number of atoms N in /Acp lattice = n
as 2
6x ana x2x ,/—.2r No. of tetrahedral voids = 2n
4 3
No. of M atoms = =x an =
3 2
=6x 8. Ar? x 2/22r = 24,/27?
Formula = M,,N, or M4N, or M,N,.
8 3
Dll. (d) : Packing fraction in icp = 0.74
Total number of M and N atoms = 7.
-. Void fraction = 1 — 0.74 = 0.26 6. (6) : In one Aep unit cell, there are 6 atoms.
.. Empty space in icp unit cell = 26%. No. of octahedral voids = 6
No. of tetrahedral voids = 12
Assertion Reason Type Questions Difference = 12-6 =6.
2. (e): Correct assertion : ZnS has fcc structure. 7. (1): Coordination no. in cep = 12
Correct reason:S” ions adoptccp orfcc arrangement Coordination no. in hep = 12
and Zn** ions occupy alternate tetrahedral sites. Ratio = 12/12 = 1.
3. (c): Correct reason: Cl ionsin CsCl have simple cubic 8. (65): Suppose the atoms Y in ccp = n
arrangement. No. of tetrahedral voids = 2n
om (a) : Both assertion and reason are correct. No. of X atoms = 2n/3
6. (c): Correct reason : Since there are two tetrahedral Formul X,,.,Y,, or X,Y;
sites for each Ca** ion, the number of F ions are a+b=6
double the number of Ca** ions. : 1
9.(6): Contribution of atoms on the corners = 8x—=1.
7. (e): Correct assertion: Octahedral voidis larger in size
than tetrahedral void. Since atoms on the body diagonal are not shared by any
Correct reason: Cations are generally smaller than other unit cell and there are four body diagonals, their
anions and therefore occupy less space. contribution per unit cell = 4
8. (a): Both assertion and reason are correct. Total number of atoms in the unit cell = 4 +1=5.
9. (a): Both assertion and reason are correct. 10. (8): Atruncated octahedron has 14 faces (8 regular hexagons
10. (c): Correct reason : In Frenkel and Schottky defect, and 6 squares), 36 edges and 24 vertices.
the number of cations and anions remains the same. 11. (2) : Volume of unit cell = (400 x 107°)? em?
Mass of element = 256 g
Integer Type or Numerical Value Type Questions Density of element = 8 gcm™
25
Mags Volume of 256 g of element = = = 82 em?
1. (7): Density = Oo
” Volume o2
No. of unit cells = —~ 5 x 10~ unit cells
10.6 g/em® means in 1 cm? Ag = 10.5 g
(400x 10°)
. . 1056 Since the structure is fcc, number of atoms present in a
No.o.ofof ato
atoms in 1cm®?
1 cm = 108
——N 4
unit cell = 4
No. of atoms in 256 g=5 x 10% x4
No. of atoms in 1 cm
(225
—_N,
y" = 2 x 10** atoms
108 |
SOLID STATE

12. (3.00): MX having NaCl structure ol. (d): Opposite to the direction of magnetic field.
No. of M*ions=4 #£=™No. of X ions=4 eae (6): fee (74%) > bec (68%) > Simple cubic (52.4%)
For structure Z constructed from MX a4. (a): because cations are dislocated to interstitial sites.

(1) After removing all X ions except the centred one, oo. (d): Inccp, there are four atoms per unit cell and therefore
eight tetrahedral voids.
No. of M*ions=4 No. ofX ions =1
36. (a): Infec; a = ia or 2,/2r -in bcc a = ca and in cubic,
(ii) No. of face centred M* ions removed = 6x = 3 a = Zr. V2 V3
|
bo

No. of M* ions replaced by X ions = 3 oO”. (a): The conductivity of metals is much more than that
No. of M* ions left=1 No. ofX ions=1+3=4 of insulators but the conductivity of semiconductors
is less than metals and more than insulators.
(iii) No. of corners M* ions =8x ==1:
NCERT Exemplar Problems : MCQs Type-II
No. of M* ions left =1—1=0 No. of X ions = 4
40. (c, d): (c)is not true because impurity defect changes the
(iv) Replacing central X” by M* mass but not the volume and therefore, density
No. of M* ions = 04+1=1 No. ofX” ions =4—1=3 changes.
(d) Frenkel defect neither changes mass nor volume.
No.of
0.0 Xi= _ 3 _ 300 42. (a, b): (c)is wrong because electrons move towards anode
No.ofM’ ions 1 and holes move towards cathode.
(d) is also not true.
NCERT Exemplar Problems : MCQs Type-I 43. (b, ¢): (a) 1s false because silicon doped with electron rich
impurity is n-type semiconductor.
=. (6): Crystalline solids are not isotropic in nature. These (d) is false because conductivity of n-type
are anisotropic in nature. semiconductor increases due to extra electrons
A, (d): In antiferromagnetism, the magnetic moments are in and not due to vacancy.
a compensatory way so as to give zero net magnetic 45. (6, c): InNaCl, Cl ions havefcec arrangement and number
moment because of cancellation of individual magnetic of Cl ions per unit cell = 4. Number of tetrahedral
moments. voids will be 4 x 2 =8.
. (a2): Quartz glass is amorphous and therefore, refractive Tetrahedral voids are double the number of
index is same in all directions. octahedral voids.
12. (6): Graphite is a good conductor of electricity due to the
AZ. (a, c): Impurities of As and P when doped to silicon give
presence of free (m) electrons.
n-type semiconductor.
14, (d): CrO, show electrical behaviour as metals.
50. (a, b,c): 51C, ALN and diamond are covalent network solids.
1S. (6): The overall charge is neutral.
Doe (6, d): Vacancy defect and Schottky defect decrease the
20. (d): n-type of semiconductor is formed when silicon is
density.
doped with atoms having more than four electrons
(e.g. P, As). NCERT Exemplar Problems :
21. (6): Afee unit cell has 4 atoms per unit cell and each atom
has two tetrahedral sites. Therefore, the number of
Assertion Reason Type Questions
tetrahedral sites in fec unit cell is eight. 59. (a): Simple cubic unit cell has one atom because there
22. (a): AgBr shows both Schottky defect and Frenkel defect. are 8 atoms at the corners, each contributing 1/8.
23. (6): hep and cep occupy 74% of the available space and 60. (6): Graphite is a good conductor of electricity because
have most efficient packing.
of the presence of m electrons.
20. (d): Ithas AB AB AB type of arrangement and therefore,
61. (c): Reason is not correct though assertion is correct.
fourth layer is not aligned with particles of first layer.
26. (a), (d): In NaCl, both Na* and CI ions have six C.N. (d) is 62. (6): Both assertion and reason statements are correct but
also correct. The C.N. ofboth Zn** and S* ions are four. reason is not correct explanation for the assertion.
28. (d) : Electronic defects are introduced by doping. 63. (c): Assertion is correct but the reason is not the correct
explanation ofassertion. Thisis because intermediate
a0. (6): In ferromagnetic substances ordering of magnetic
conductivity of semiconductors is due to small energy
moments may persist even when magnetic field
is removed. Therefore, these can be magnetised gap between filled valence band and empty conduction
permanently. band.
O04
a 1/1104 MODERN’S abe + OF CHEMISTRY-XII

Init Practice Test

Time Allowed : 2 Hrs. Maximum Marks: 35

1. What is the maximum coordination number of an atom in a hep crystal structure of an element? (1)
2. Both diamond and rhombic sulphur are covalent solids but the latter has very low melting point than the former.
Why? (1)
3. Why is Frenkel defect not found in pure alkali metal halides? (1)
4, A group 14 element is to be converted into n-type semiconductor by doping with a suitable impurity. To which
croup should this impurity belong? (1)
5. How do the structures of quartz and quartz glass differ from each other. (1)
6. Calculate the packing efficiency for body centred cubic arrangement. (2)
7. Analysis of a metal oxide shows its empirical formula M,.,0,5.Calculate the percentage of M** and M** ions in
the crystal. (2)
8. What are Schottky and Frenkel defects? How does density of a solid get affected by these defects? (2)
9. What is the difference between anti-ferromagnetic and ferromagnetic substances? What is the cause of this
difference? (2)
10. Ferric oxide crystallizes in a hexagonal close packed array of oxide ions with two out of every three octahedral
voids occupied by ferric ions. Derive the formula of the ferric oxide. (2)
11. An element crystallizes in a body centred cubic structure with a cell edge of 288 pm. The density of the element
is 7.2 ¢ cm°. How many atoms are present in 208 g of the element ? (3)
12. Explain
(4) Some of the very old glass objects appear slightly milky instead of being transparent.
(iz) Zine oxide exhibits enhanced electrical conductivity on heating.
(vit) CdCl, will induce Schottky defect if added to silver chloride crystal. (3)
18. Explain the following terms with suitable examples:
(i) Ferrimagnetism
(iz) Intrinsic conduction of solids
(iit) Ferromagnetism. (3)
14. Niobium crystallizes in body centred cubic structure. If its density is 8.55 g em”, calculate atomic radius of
niobium given its atomic mass 93 u. (3)
15. Chromium metal crystallises in body centred cubic lattice. The length of the unit cell edge is found to be 287 pm.
calculate the atomic radius. What would be the density of chromium in g em™ ? (Atomic mass of Cr = 51.996).()
16. (a) Ifthe radius of octahedral void is r and the radius of the atoms in the close packing is R, derive a relationship
between r and R.
(6) Whatis a semiconductor ? Describe the two main types of semiconductors and contrast conduction mechanism
in them. (5)

To check your performance, see HINTS AND SOLUTIONS TO SOME QUESTIONS at the end of
Part I of the book.
 SOLUTIONS
0) 55) DOs MAYA DS A
Building on..... —_—e a Preparing for Competition.....
@ Understanding Text 1 @ Quick Memory Test with @ Additional Useful Information 98
Conceptual Questions 21, 34, 64 Answers 85 ¢@ Topicwise MCQs 100
¢ Advanced Level Problems 18, @ HOTS & Advanced Level @ Competitive Examination Qs
cheb, Ede Questions with Answer 87 >» AIPMT & Other State Boards'
SOLUTION FILE REVISION EXERCISES Medical Entrance 102
# Hints & Solutions for Practice (with Previous Years’ CBSE Qs > JEE (Main) & Other State
Problems 66 & Other State Boards Qs) 89 Boards' Engineering Entrance 105
CHAPTER SUMMARY & QUICK @ Hints & Answers for Revision » JEE (Advance) for ITT Entrance
CHAPTER ROUND UP 74 Exercises 94 108
NCERT FILE @ NCERT Exemplar Problems
@ In-text Qs & Exercises with (Objective Questions) 1138
Solutions Fl @ Hints & Explanations for
@ NCERT Exemplar Problems with a ataaataas 7 y ce Difficult Questions 118
Answers & Solutions (Subjective) 84

7 As we look around, we rarely come across pure substances in our day

“to day life. Most of these are mixtures containing two or more pure
“substances. The homogeneous mixtures of two or more substances
are called solutions. The air around us is a gaseous mixture of
\ primarily oxygen and nitrogen, our blood is a liquid mixture of
different components, the substances like milk, jaggery, sharbat
drink etc. which appear to contain only one type of substance
are, in fact, mixtures. Alloys such as brass, bronze, stainless
steel etc. which we use in our daily life are also mixtures.
| The homogeneous mixtures of two or more substances are
called solutions.
| The importance or utility of solutions depends upon their
compositions.
Many medicines dissolved in suitable non-aqueous
SeSesesessessess / solvents such as alcohol are given to patients. Saline glucose
Cer ssecverecese x : / is administered to persons suffering from dehydration, 1 parts
seesstesess ieee, ss COO / per million (ppm) of F ions in water prevents tooth decay and
a intravenous injections are always dissolved in water containing salts
we / at particular ionic concentration which match with blood plasma
concentrations and so on.
Si In the present unit we shall consider mostly liquid solutions and their
er
properties.
SOLUTIONS
A solution is the homogeneous mixture of two or more substances whose composition can be varied
within certain limits.
By homogeneous mixture we mean that its composition and properties are uniform throughout the mixture. The
substances making up the solution are called components of the solution. Depending upon the total components
present in the solution, it is called the binary solution (two components), ternary solution (three components),
quaternary solution (four components), etc. For simplicity, we shall consider only binary solutions. The components

an
| 22 MODERN'S abe + OF CHEMISTRY-AXIl

of a binary solution are generally referred to as solute and the solvent. In general,
a component which is present in the largest quantity is called the solvent while
the component which is present in lesser quantity is termed the solute.
In other words, a solute is a substance that dissolves and a solvent is a substance in which dissolution takes
place. For example, if a crystal of sugar is dropped into a beaker of water, it dissolves to form a solution. In this
case, sugar is solute and water is solvent. The solvent determines the physical state in which solution exists. In a
solution, the particles are of molecular size (about 1000 pm) and the different components cannot be separated by
any of the physical methods such as filtration, settling, centrifugation, etc.
TYPES OF SOLUTIONS
Depending upon the physical states of the solute and the solvent, the solutions can be classified into the following
types.
Table 1. Different types of solutions.

Solute Solvent Common Examples

Gaseous solutions
Gas Mixture of nitrogen and oxygen gases, air
Gas Chloroform mixed with nitrogen gas, water vapour in air (humidity)
Gas Camphor in nitrogen gas, dust or smoke particles in air
Liquid solutions
Liquid Oxygen dissolved in water, CO, dissolved in water
Liquid Ethanol or methanol dissolved in water
Liquid Sucrose or salt in water
Solid solutions
Solid Solution of hydrogen in palladium (phenomenon of adsorption of gases
over metals)
Solid Mercury with sodium (amalgams)
Solid Copper dissolved in gold (alloys)

Out of these nine types of solutions, three solutions, namely solid in liquid,
liquid in liquid and gas in liquid are very common. In all these three types of
solutions, liquid acts as solvent.
The solutionsin which water is the solvent are called aqueous solutions while
those in which the solvent is other than water are called non-aqueous solutions.
The common non-aqueous solvents are ether, benzene, carbon tetrachloride, etc.
METHODS FOR EXPRESSING THE CONCENTRATION OF
SOLUTIONS : UNITS OF CONCENTRATION
The concentration of a solution may be defined as
the amount of solute present in the given quantity of the solution.
The concentration of solution may be expressed by several ways as
discussed below :
1. Mass percentage or volume percentage
The mass percentage of a component in a given solution is the mass of
the component per 100 g of the solution.

Mazs % of component = component

_#880f the in thesolution _ 4)
Total mass of the solution

For example, if W, is the mass of component A and Wp is the mass of

component B in a solution, then

Mass percentage of A = a W, x 100 ---(1)

This can be expressed as w/w. For example, a 10% (w/w) solution of sodium
chloride means that 10 g of sodium chloride is present in 90 g of water so
that the total mass of the solution is 100 g or simply 10 g of sodium chloride
is present in 100 g of solution.
Volume percentage. In case of a liquid dissolved in another liquid, it is
SOLUTIONS

convenient to express the concentrations in volume percentage. The volume

percentage is defined as the volume of the component per 100 parts by
volume of the solution. For example, if V, and V, are the volumes of two
Mass percentage of a component
components A and B respectively in a solution, then => wiw
= Volume of A x 100 Volume| percentage of a component
a a Volume of A + Volume of B = p/p
This may be expressed as v/v. For example, 10% by volume of ethanol Mass by volume percentage of a
solution means that 10 mL of ethanol is dissolved in water such that the total component
volume of the solution is 100 mL. => wiv
Mass by volume percentage (w/v). Sometimes, we express the
concentrations as weight/volume. It is the mass of solute dissolved in 100
mL of the solution. For example, a 10% solution of sodium chloride (w/v)
means that 10 g of sodium chloride are dissolved in 100 mL of solution.
2. Parts per million
When a solute is present in very minute amounts (trace quantities), the
concentration is expressed in parts per million abbreviated as ppm. It is the
parts of a component per million parts of the solution. It is expressed as :
Mass of component A 6
Poms = Total mass of solution " ale?
Like percentage, concentration in parts per million can also be expressed
as mass to mass, volume to volume or mass to volume. For example, suppose
a litre of sea water (which weighs 1030g) contains about 6x10~ g of dissolved
oxygen (O,). Its mass percentage is :

Mass percentage of O, = 6 x 107 x 100 =5.8 x 107%

2 1030
Parts per million parts of dissolved O, is
6x10°
ppm of O, x 10° =5.8 ppm
1030
Thus, instead of expressing concentration of dissolved O, as 5.8 x 10+ %,
it is better to express as 5.8 ppm.
Atmospheric pollution in cities due to harmful gases is generally expressed
in ppm though in this case the values refer to volumes rather than masses.
For example, the concentration of SO, in Delhi has been found to be as high as
10 ppm. This means that 10 cm® of SO, are present in 10° cm® (or 10° L) of air.
The concentration of atmospheric pollutants in cities is generally expressed
in terms of ug/mL.

= SOLVED EXAMPLES
LI Example 1
If 11 g of oxalic acid are dissolved in 500 mL of solution (density = 1.1
g mL), what is the mass % of oxalic acid in solution ?
Solution : 11 g of oxalic acid are present in 600 mL of solution.
Density of solution = 1.1 g mL?
Mass of solution = (500 mL) x (1.1 g mL“)
= 650g
Mass of oxalic acid = 1lg
th
Mass % of oxalic acid = 550 x 100 = 2%.

3. Molarity of a solution
Molarity of a solution is defined as the number of moles of the solute
dissolved per litre of the solution. It is represented as ‘M’. Mathematically,
Moles of solute
Molarity = athahs
Volume of solution in litres
 MODERN'S abe + OF CHEMISTRY
-AXIl

It is convenient to express volume in cm? or mL so that

Moles of solute
Molarity is most common method for Molarity = x 1000 (+: 1 litre = 1000 mL)
expressing concentration of solutions. Volume of solution (in mL or cm®)
Solutions of different molarities are Thus, the units of molarity are moles per litre (mol L7“!) or moles
commonly expressed as:
per cubic decimetre (mol dm-).* The symbol M is used for mol L- or
1 M = Molar solution
mol dm.
- or 0.5 M = Semimolar solution Moles of solute can be calculated as:
Mass of solute
M ; : Mol f solute = ———@_—__—_—_-
aT or 0.1 M = Decimolar solution Partin pny Veneseneee Molar mass of solute

M For example, 0.25 M (or 0.25 mol L~) solution of NaOH means that 0.25
am or 0.01 M = Centimolar solution
mol (or 10g; molar mass of NaOH = 40) has been dissolved in one litre (or
one cubic decimetre) of the solution. If w g of the solute is present in V mL
— or 0.001 M = Millimolar solution (or cm®) of the solution, then
w
x 1000
ene Pe te Molar mass of solute x V
Molarity is one of the common measures of expressing concentration which
is frequently used in the laboratory. However, it has one disadvantage. I/t
changes with temperature because of expansion or contraction of the liquid
with temperature.

SOLVED EXAMPLES >

LJ Example 2.
2.46 g of sodium hydroxide (molar mass = 40) are dissolved in water
and the solution is made to 100 cm? in a volumetric flask. Calculate the
molarity of the solution.
Solution : Amount of NaOH = 2.46 ¢g
Volume of solution = 100 cm?
Moles of NaQH = pene aia
eae
Molar mass
KEY NOTE 2.46 g
= 0.0615 mol
From the discussion of molarity ~ 40gmol?
and molality, it is evident that in Moles of NaOH
Molarity = x 1000
molarity we consider the volume Volume of solution
of the solution while in molality
= eats x 1000 mL L'= 0.615 mol L“.
we take the mass of the solvent.
B T 0.615 M
: Moles of solute
Mulaoty =ayant ooealvent Ga a
4, Molality of a solution
Moles of solute
Molality of a solution is defined as the number of moles of the
ee Mass of solvent in kg solute dissolved per 1000 g (or 1 Rg) of the solvent.It is denoted by m.
Molality is considered better Mathematically,
for expressing the concen- Moles of solute
tration as compared to molarity Molality (m) .(4)
Mass of solvent in kg
because the molarity changes
or 7 Moles of solute 1000
with temperature because
of change in volume of the Mass of solvent in gram
solution due to expansion Thus, the units of molality are moles per kilogram i.e., mol kg. For
or contraction of the liquid example, 1.0 m solution of KCl means that 1 mol (74.5 g) of KCl is dissolved
with temperature. However, in 1 kg or 1000 g of water.
molality does not change with If w g of solute are dissolved in W g of solvent, then
temperature because mass of Ww
Molality, m = x 1000
the solvent does not change Molar mass of solute xW
with change in temperature.
* In SI units, volume is expressed as dm® and 1 litre = 1 dm*.
SOLUTIONS
26]
~SOLVED EXAMPLES >
L} Kxample 3.
Calculate the molality of a solution containing 20.7 g of potassium carbonate
dissolved in 500 mL of solution (assume density of solution = 1 g mL-4)
(A.LLS.B. 2005)
Solution : Mass of K,CO, = 20.7 g
Molar mass of K,CO, = 188 g mol

Moles of K,CO, = ——-8 —= 0.15 mol

138 g mol

Mass of solution = (600 mL) x (1 g mL7?) = 500 g

Amount of water = 500 — 20.7 = 479.3 ¢g

Moles of solute
— Mass of solvent in gram iad

0.15 mol -1
= ——— x1000
47993g © gk
= 0.313 mol kg? or = 0.313 m
LJ Kxample4
2.5 g of ethanoic acid (CH,COOH) ts dissolved in 75 g of benzene. Calculate
the molality of the solution. N.C.E.R.T. (Hr.S.B. 2012, Assam SB. 2012)
Solution : Molar mass of CH,COOH = 2 x 12+4x1+2x 16=60g mol

2.52
Moles of CH,COOH = = = 0.0417 mol
60 g mol
KEY NOTE
Mass of benzene = 75 g
Like mole fraction, the term mass
Moles of CH,COOH fraction is also used. Itis the mass
Molality of CH,COOH = 8 >* 1000
Mass of benzene (in g) of a given component per unit mass
of the solution. If W, and W, are
_ 0.0417 mol 1000
the masses of two components of the
45
solution, then mass fraction of A,
= 0.556 m
_ __Wa
ae Wa + We
5. Mole fraction
and mass fraction of B,
Mole fraction is the ratio of number of moles of one component to
the total number of moles (solute and solvent) present in the solution. Wp
Number of moles of the component
x
B= Wa+Wp
Mole fracti f An) Total numbe
arher afmoles Evidently, x, + xp = 1
in r of males of
ofall camuanents
all compo nenta
Mass fraction multiplied by 100
It is denoted by x and a subscript used on the right hand side of x denotes
gives mass percentage i.e. mass
the component. Let us suppose that a solution contains n, moles of solute
percentage of A=x, x 100
and n, moles of the solvent. Then,
n Like mass fraction, volume
Mole fraction of solute (x,) = A __ (5) fraction may also be defined.
Nha + Ip
If v, and v, are the volumes
n of two components A and B,
Mole fraction of solvent (xp) —__B__ me(5)
Na +Np VA
volume fraction of A =
The sum of mole fractions of all the components in a solution ts always
VA +UB
equal to one as shown below : volume fraction of B =
UB
n n UA +UR
Xy+Xp = A 5 —®_ =]
Volume fraction multiplied by 100
Thus, if the mole fraction of one component of a binary solution is gives volume percentage.
| 26 MODERN'S abe + OF CHEMISTRY
-AXIl

known, then that of the other can be calculated. For example, the mole fraction
x, 1s related to xp, as :

xX, =1-—Xp or Xp=1l—X,

Relationship between It may be noted that the mole fraction is independent of temperature
Normality and Molarity of and is unitless.
Solutions
The normality and molarity of a
solution are related as :
If a solution contains ‘i? number of components, we have
Normality = eed
; Molar mass DN
ey Equivalent mass
For acids, = = , ete.
Normality = Molarity x Basicity m+ Me cvneie EE Di
where basicity is the number of In general, for a solution containing ‘2’ number of components;
H* ions that a molecule of an acid
can give in solution. For example, x. = a
Normality of H,5O, DN
= 2 x Molarity of H,SO, X, +X, +... fax: ZB
Normality of H,PO,
= 3 x Molarity of H,PO,.
For bases, SOLVED EXAMPLES
Normality = Molarity x Acidity
where acidity is the number of LJ Example 5
OH ions that a molecule of base Calculate the mole fraction of ethylene glycol (C,H,O,) in a solution
can give in solution. For example, containing 20% of C,H,O, by mass. |
Normality of KOH (H.P.S.B. 2014, Meghalaya S.B. 2017) \N.C-E.R.T)
= 1 x Molarity of KOH
Normality of Ba(OH), Solution : 20% ethylene glycol solution means that 20 g of ethylene glycol is
= 2 x Molarity of Ba(OH), present in 100 g of solution or 20 g of ethylene glycol is present in 80 g of water.
For salts Molar mass of C,H,O, = 2x 12+6x1+2x16=62 g mol”
Normality = Molarity x Total
positive valency of metal 20 g ,
Moles of CF. 62 gmol = (1.322 mol
atoms because
Equivalent mass of salt =
80 |
Mol. mass of salt Moles of water = 5 _ = 4.444 mol
18¢ mol
Total positive valency
of metal atoms : _ Moles of C,H,O,
For oxidising and reducing glycol Moles of C,H,O, + Moles of H,O
agents
0.322
Normality = Molarity x No. —~ —~———— = 0.068
~ 0.822+4444 ©
of electrons lost or gained by
one molecule of the substance 4.444
because Nwater — 0.3224 4,444 — 08?
Equivalent mass of an oxidising
or reducing agent
or x water = 1— 0.068 = 0.932
Mol. mass
~ No. of electrons lost or
gained by one molecule 6. Normality
of the substance Normality of a solution is the number of gram equivalents of the
It may be noted that these days solute dissolved per litre of the solution. It is denoted by N.
the terms normality or equivalent
weight are not commonly used. Number of gram equivalents of solute
Normality (N) = ———W (7)
Volume of solution in litres
SOLUTIONS

Number of gram equivalents of solute

or Normality = ; -——- x 1000
Volume of solution in mL

Thus, the units of normality are gm equivalent per litre i.e.,

g equiv L7}.
Gram equivalents of solute can be calculated as :

M f solut
Gram equivalents of solute = Bicincdietainaanile
Equivalent mass

Like molarity, normality of a solution also changes with

temperature.

= = SOLVED EXAMPLES & Z

LJ Example 6
Calculate the normality of solution containing 31.5 g of hydrated oxalic
acid (H,C,0, 2H,O) in 1250 mL of solution.
Solution : Mass of oxalic acid = 31.5¢
31.5 _
Equivalents of oxalic acid = 63.” 0.5 (Eq. wt. 126/2 = 63)

Volume of solution = 1250 mL

Normality = 1559 1000

«1000 ==0.4 N,
Let us sum up different concentration units.

Molarity mol L-' or M moles of solute per litre of solution

Molality mol kg or m moles of solute per kilogram of solvent
Mole fraction (x) = number of moles of a component expressed as a fraction
of total number of moles
Mass percentage % mass of a component expressed as a percentage of total
mass
Volume percentage % volume of a component expressed as a percentage of
the total volume
Parts per million by mass ppm (by mass) mass in grams per million grams of the sample
Parts per million by volume) ppm (by volume) |volume in mL per 10° mL or 10° L of the sample

Sometimes, the concentrations ofionic substances are expressed as formality.

7. Formality
It is the number of formula mass of the solute dissolved per litre
of the solution. It is represented by F.

Number of formula masses of solute

a Volume of the solution in litre
...(8) WATCH OUT !
e Molarity of a solution changes
The term formalityis used to express the concentrations of ionic substances.
with temperature due to
The ionic compounds such as NaCl, KNO,, CuSO,, etc. do not exist as discrete
accompanied changes in volume
molecules. In such cases, we do not use the term mole for expressing the
of the solution.
concentration. The sum of the atomic masses of various atoms constituting
e Molality and mole fraction do
the formula of the ionic compounds is called gram formula mass instead
not change with temperature.
of molar mass.
| 28 MODERN'S abe + OF CHEMISTRY
-AIl

WD) Competition Plus Soltucug Numerical Probleme

> Relation between molarity and FORMULAE AND UNITS
molality, Moles of solute
Molarity (M) = tii
ee es Vol. of solution (in mL)
m M_ 1000 Moles of solute
Molality (mm) = eee eRe eee
> Relation between molarity and Mass of solvent (in g)
mole fraction, Gram equiv. of solute
_ X_x1000xp Normality (N) = — eS 100
Vol. of solution (in mL)
~ x,M, + x9My
Mol. mass
Normality Molarity x
> Relation between molality and y Eq. mass
mole fraction,
Moles of solute
_ 1000x, Mole fraction of solute (x,) =
Moles of solute + Moles of solvent
: x,M,
Mole fraction of solute + Mole fraction of solvent = 1
For details, refer Competition
File (Page 98). or Mole fraction of solvent = 1 — Mole fraction of solute.

L} EKxample 7. LI Kxample 9.
2.82 g of glucose (molar mass = 180) are dissolved A solution is 25% water, 25% ethanol and 50% acetic
in 80 g of water. Calculate (a) the molality (b) mole acid by mass. Calculatethe mole fraction of each
fraction of glucose and water. component. (A.P.S.B. 2011, 2015, 2018)
Solution : (a) Caleulation of molality of solution. Solution : Let the total mass of solution = 100 g
Mass of water = 25 g
Mass of glucose = 2.82 g
Mass of ethanol = 25 g
2.82
Moles of glucose = = (Molar mass = 180) Mass of acetic acid = 50 ¢

Mass of water = 30 ¢ Moles of water = = = 1.388

. Moles of glucose
—_ ——>—— x 1000
Molality Mass of water (.” Molar mass of H,O = 18)
2.82 x 1000 25
= “Ig0
x 30. ~ 0-022 m Moles of ethanol = 7 0.543

(6) Calculation of mole fraction ( Molar mass of C,H.OH = 46)

2.82
—~ —— 7).
aaa e ue 180 Moles of acetic acid = 7 = 0,833
Molesee of water = 2>=1.67 (.. Molar mass of CH,COOH = 60)

Mole fraction of glucose 157

= _ 0.0157 — 0.009 Total number of moles _= 1.388, + 0.543 + 0.8338
0.0157 + 1.67
= 2.764
Mole fracti f wat a 0.991 1.388
See any +167” Mole fraction of water = 3.764 = 0.502
L} Example 8.
Mole fracti f eth [ee ie
Calculate the molarity of pure water (density of water Ms gry emeeecee eteyar meee Sagi,
= 1g mL)
; : ; 0.833
Solution: Density of water = 1g mL Mole fraction of acetic acid = 2764 > 0.302
Mass of 1000 mL of water = Volume x Density
1000 x 1 = 1000 g L] Example 10.
Calculate the moles of methanol in 65 litres of its
Moles of water xi8 = 56.55 mol 2m solution, if the density of the solution ts 0.981
Now, 55.565 moles of H,O are present in 1000 ml or 1L kg L- (Molar mass of methanol = 32.0 g mol-).
of water
ane Molarity = 55.55 M.
SOLUTIONS
20
|
Solution : Mass of 5L solution = 6L x 0.981 kg L1 Solution : 15% H,SO,solution means that 15 g of H,SO,
= 4.905 kg = 4906 g are present in 100 g of solution in water.
Mass of 2m solution = 1000 g + 2 moles of methanol (1) Calculation of molarity of solution
= 1000 + 2 x 32 Weight of H,SO, per 100 g of solution = 15 g
1000 + 64 = 1064 g 15
Now 1064 g of solution contains methanol = 2 mol Gram moles of H,SO, = 98 mol

4905 g of solution contains methanol = x 4905 , Mass 100g _ ,,

Volume of solution = Density =T10 7 90.9 mL
= 9 oes mol.

LJ Example 11. / Moles of H,SO,

Molarity of H,SO, x 1000
Calculate the mass percentage of aspirin (C,H ,O,,) in ~ Volume of solution (mL)
acetontirile (CH,CN) when 6.5 g of C,H,O., is dissolved
15 x 1000
in 450 g of CH.CN. N.C.E.R.T. 1.68 M.
—~ 98e7 90.9 ~
Solution: Mass of aspirin (C,H,O,) = 6.5 g
(it) Calculation of normality
Mass of acetonitrile (CH,CN) = 460 g
Mol s 98 ,
Total mass of solution = 450 + 6.5 Equivalent mass of H,5O, = — 5 49
- 456.5 ¢
6.5 Mass of H,SO, _ 15
,
Mass irin
% aspirin = ——-~x100
1565 Gram equivalents of H,SO, = Equivalent mass 49
= 1.424 %
Gram equivalent of H,SO,
Normality _—— ee a l

LJ Example 12. Volume of solution (mL) aia

A solution of glucose (molar mass = 180 g mol-*) in 15 x 1000
water is labelled as 10% by mass. What would be = 49 x 90.9 = 286 N:
the molality and molarity of the solution ? (Density
(iit) Calculation of molality
of solution = 1.2 g mL-) (A.LS.B. 2014)
Weight of water in solution = 100 —- 15 = 8g
Solution : 10% (by mass) solution of glucose means that
10 g of glucose is present in 100 g of solution or 1n 90 g of water. 15
Moles
oles ofof H,SO,
H,SO, = —
98
(1) Calculation of molality
Mass of glucose = 10 ¢ Moles of H,SO,
_ —__________s"
4 epee
10 ey Wt. of solvent in gram nae
Moles of glucose = jg9 = 0.0556
15 x 1000
(Molar mass of glucose = 180) = 98
x 85 - 18 m

Mass of water = 90 g
LJ} Kxample 14.
Moles of glucose
Molahty = x 1000 A sugar syrup of weight 214.2 g contains 34.2 g of
Mass of water
sugar (C ,.H,,0,,. Calculate :
0.0556
== 790 x 1000 =_ 0.615 m. (t) molal concentration, and

(it) Calculation of molarity (it) mole fraction of sugar in the syrup.

Moles of glucose = 0.0556 (A.P.S.B. 2011, Pb. S.B. 2011)
Mass Solution : (i) Weight of sugar syrup = 214.2 g
Volume of solution
Density Weight of sugar in syrup = 34.2 g
100 Weight of water in syrup = 214.2 — 34.2 = 180.0 g
= —— =83.3 mL
1.20 4,2 |
Moles of sugar = “5 = 0.1 (Molar mass = 342)
Moles of glucose
Molarity = —W7>— xl
ae Vol. of solution as
Molality y =* 2:*
{80 x 1000 =oe
0.56 m
0.0556 |
= 33.3 * 1000 = 0.667 M
. *

r 34,2
(12) oles of of sugar
Moles 349 =0.1
= — 0
LU) Example 13.
A commercially available sample of sulphuric acid
is 15% H,SO, by weight (density = 1.10 g mL). Moles of water = ba = 10
18
Calculate (t) molarity (i) normality and
. 0.1
(iti) molality of the solution. (Pb.S.B. 2007, 20185) Mole fraction of sugar= = 0.0099.
10
+ 0.1
 MODERN'S abe + OF CHEMISTRY
-AXIl

LU) Example 15. Mass _ _ 100g

Volume of solution =
An antifreeze solution is prepared from 222.6 g Density 1.8 gmL!
of ethylene glycol, C,H,(OH), and 200 g of water.
66.6 mL
Calculate the molality of the solution. If the density
80 x 1000
of this solution be 1.072 g mL, what will be the Molarity of solution = =14.7M
98 x 55.5
molarity of the solution ? *R (D.S.B. 2007)
To calculate the volume of 14.7M H,SO, required to prepare,
Solution : (:) Calculation of molality 1 Lof 0.2 M H,50O,, we can apply molarity equation*:
Mass of ethylene glycol = 222.6 g M,V, =a M.V.
Molar mass of ethylene glycol = 2 x At. mass of C + 6 x At. 14.7 x Vi — 0.2 x 1000
mass of H + 2 x At. mass of O
0.2 x 1000 «|
=2x12+6x142x
16=62 Ni = ca = 13.60 mL

222.6 Volume of 14.7 M H,SO, required = 13.60 mL.

Moles of ethylene glycol = eg. 3.59 mol
LJ Kxample 18.
Mass of water = 200 g The mole fraction of benzene in a solution with toluene
; Moles of ethylene glycol __ is 0.50. Calculate the mass percent of benzene in the
Molal = —————___—— x 1000 solution.
ae Mass of water *
Solution : Let mass percentage of benzene in solution
3.59 is x. This means 100 g of solution contains x g benzene and
= 300 x 1000 = 17.95 m.
(100 — x) g of toluene.
Mass of benzene = xg
(11) Calculation of molarity
Moles of ethylene glycol = 3.59 mol Moles of benzene = = (Mol. mass of C,H, = 78)
Mass of solution = 200 + 222.6 = 422.6 g
Mass of toluene = (100-x)¢g
Volume of solution = ee
Moles of toluene = ~> 7

= sae = 394.22 mL (Mol. mass of C,H-CH, = 92)

Now mole fraction of benzene = 0.5

,1999
Molarity = Moles ofethylene glycol Moles of benzene 7
Moles of benzene + Moles of toluene

= yeD x 1000 — 9,11 M. *

18 7
x, 100-—x — 0.6
LJ Example 16. 78 92
What ts the mole fraction of the solute in 2.5 m
aqueous solution? x 78 X92
| 2S
Solution : 2.5 m aqueous solution means that 2.65 moles 78 |92x+78(100-<x)
of solute are present in 1000 g of water. Thus,
Moles of solute = 2.5 02x = 46x + 3900 — 39x

1000 86x = 3900

Moles of water = Te #55.6
x = 46.9

2.9 Mass percent of benzene = 45.9 wt.

Mole fraction of solute = 3545567 0.043.
LJ) Kxample 19.
LU) Example 17. A sample of drinking water was found to be severely
Calculate the volume of 80% H,SO, by weight (density contaminated with chloroform (CHC1,), supposed to
= 1.80 g mL) required to prepare 1L of 0.2 M H,SO,. be carcinogen. The level of contamination was 15
Solution : 80% H,SO, solution means that 80 g of H,SO, ppm (by mass).
are present in 100 g of solution in water. (1) Kxpress this in percent by mass.
80 (11) Determine the molality of chloroform in the water
Moles of H,SO, present = 98 mol
sample. N.C.E.R.T.
SOLUTIONS

Solution : 15 ppm (by mass) means 15 g of CHCl, is LJ Kxample 20.

present in 10° g of solution. The mole fraction of water in a sulphuric acid solution
Mass of chloroform is 0.85. Calculate the molality of the solution.
(1) Percent by mass x 100
Total mass Solution : Mole fraction of water in solution = 0.85.
2aree. x 100 =1.5 x 10°% Mole fraction of H,SO, in solution = 1 — 0.86 = 0.15.
If n, is the number of moles of water and 7, is the number
of moles H,5O, in the solution, then
(11) Calculation of molality
Mass of CHCl, = 15g Mole fraction of H,SO, = Me. 015
My + No

15
Moles of CHCl, = Molality of H,SO, solution means the number of moles of
119.5
H,5O, present in 1000 g of H,O. Thus, we have,
(Molar mass of CHCl, = 119.5)
1000 |
= 0.1255 mol w,= 1000 g or n, = 73 55.55, ny =?

Mass of water = 10°- 15 = 10° Ng 2

Moles of CHCl, 55.55+7, a?
Molality x 1000 n= 0.15 te + S.d025 or i, = 9.8
Mass of water

0.1255
x 1000 Alternatively,
~ 08
If 2, and n, are the number of moles of water and H,SO,
= 1.255 x 10+ m. respectively, then

Mater _
FL _.286 _G)
Ny + Ng

To calculate the volume of a given molarity of a solution, required to prepare solution of other molarity, we use molarity
equation:
MV, ms M,V,
where M, is the molarity of the given solution, M, is the molarity of the required solution, V, is the volume of given solution
and V, 1s the volume of the required solution.
Molarity equation is commonly used :
e to calculate the molarity of a solution after mixing two or more solutions.
UW If V, mL of a solution of molarity M, is mixed with V, mL of solution of molarity M,, then the molarity of the final
solution, M, is
M,V, + M.V. = M.(V, + V,)
M,V, + M2V3
or ns —
3 Vi + Vs
to calculate the volume of the solution of given molarity required to dilute to get solution of known molarity.
To dilute V, mL ofa solution of molarity M, to molarity M, so that the final volume is V., volume of water to be added
i.e., V,—V, will be
Nee Mae: M,
jv
This can be easily calculated as
M,V, (undiluted solution) = M,V, (diluted solution)

Vo (of diluted solution) M,V,

M,

-. Vol. of water to be added, We ie M,V,

M —V,
v= (Me)
M,-M, |V
= |———-

as)
to calculate the volume of reactants for reactions between two reactants.

where 7, and n, are their stoichiometric coefficients in the balanced chemical equation.

Like molarity equation, we have normality equation N,V, = N,V, (where N, and N, are the normalities of two solutions).
This can be used for dilution or reactions between two reactants.
ana. MODERN’S abc + OF CHEMISTRY

Now, HCl reacts with Na,CO, as :

-XII

XH.s0, = 2 =-0.85 =-1-085=015 ii)

My + Ng Na,CO, + 2HCl ————> 2NaCl + H,O + CO,
Dividing eq. (zi) by eq. (z)
NaHCO, + HCl ————> NaCl + H,O + CO,
Ng 0.15
According to the reactions, 1 mol of NaCO, will react with
ny 0.85
2 mol of HCl and therefore, 0.00526 mol of Na,CO, will
react with 2 x 0.00526 mol of HCl. Similarly,
Now, i= i = 50.00 1 mol of NaHCO, will react with 1 mol of HCl and therefore,
0.00526 mol of NaHCO, will react with 0.00526 mol of HCL
fe = ae x 55.55 = 9.8 moles Total mols of HCl required to react with mixture of NaHCO,
and Na,CO,
Hence, molality of solution = 9.8 m. = 2 x 0.00626 + 0.00526
LJ Example 21. = 0.01578 mol
How many mL of a 0.1M HCl are required to react To calculate volume of 0.1 M HCI corresponding to 0.01578
mol, we have
completely with 1 g mixture of Na,CO, and NaHCO,
0.1 mol of 0.1 M HCl is present in 1000 mL
containing equimolar amounts of two? |N.C.E.R.T.
Solution : Let the amount of Na,CO, be x in the mixture. 1000
0.01678 mol of 0.1 M HCl is present in 01 x 0.01578
Amount of NaHCO, =1--x
= 157.8 mL
x
Moles of Na,CO, = 106 U) Example 22.
A 6.90 M solution of KOH tn water contains 30% by mass
(Molar mass of Na,CO, = 106)
of KOH. Calculate the density of the KOH solution. (Molar
1-*x
Moles of NaHCO, = oa mass of KOH = 56 g mol-2). (AIS.B. 2006)
Solution : 6.90 M solution of KOH contains 6.90 moles of
(Molar mass of NaHCO, = 84) KOH in 1000 mL of solution.
Since number of moles of both are equal
Wt. of KOH in solution = 6.90 x 56 = 386.4 g
x 1-*x
Wt of KOH in 1000 mL solution = 386.4 g
106 84 Since the solution is 30% by weight, it means that 30 g of
84 x = 106 — 106x KOH are present in 100 g of solution.
190 x =106 .. x = 0.568 ; : 1
386.4 g of KOH is present in = x 386.4
0.558
Moles of Na,CO, = ae = 0.00526
= 1288 g of solution

1-—0.558 Weight
Moles of NaHCO, = ee Density =
Volume
1288
= 0.00526 (Moles are equal) —_
= 1000 =],1.288 g mL
— —1

. Calculate the percentage composition in terms of mass of a solution

obtained by mixing 300 g of a 25% and 400 g of a 40% solution by mass.
. 18 g of glucose (molar mass 180 g mol") is present in 500 cm? of of its aqueous
solution. What is the molarity of the solution? What additional data is required
if the molality of the solution is also required to be calculated ?
— Answers to Practice Problems — . A solution of glucose (C,H,,O,) in water is labelled as 10% by weight. What
would be the molality of the solution? (A.LS.B. 2013)
1. 33.57%, 66.45% - What volume of 10% (w/v) solution of Na,CO, will be required to neutralise
2. 0.2 M, density of the solution is 100 mL of HCI solution containing 3.65 g of HCI? (Assam S.B. 2012)
needed to calculate molality of
. What volume of 95 mass % sulphuric acid (density = 1.85 g/em*) and what mass
the solution.
of water must be taken to prepare 100 cm® of 15 mass % solution sulphuric
. 0.618 m
. 63.19 mL acid (density = 1.10 g em®) ?
. 9.4cm?, 92.6 g. . Calculate the mole fraction of ethanol and water in a sample of rectified spirit
Oo.
me
Ol
Co Ethanol = 0.88, water = 0.12 which contains 95% ethanol by mass.
(H.P.S.B. 2009, Pb. S.B. 2011, Meghalaya S.B. 2013)
SOLUTIONS

7. Calculate the mole fraction of water in a mixture of 12 g water, 108 g acetic — Answers to Practice Problems
acid and 92 g ethanol.
T. 0.16
8. One litre solution of N/2 HCl is heated in a beaker. It was observed that when 8. 0.6865 N
the volume of the solution is reduced to 600 mL, 3.25 g of HCl is lost. Calculate 9. 19.19 M
the normality of the new solution. 10. Molality = 0.2 m
. Concentrated sulphuric acid has a density 1.9 g/mL and is 99% H,SO, by weight Mole fraction = 0.00386
calculate molarity of sulphuric acid in the acid. (Pb. S.B. 2015) 11. 142.6 ¢
10. Calculate the molality and mole fraction of the solute in aqueous solution 12. 124M
containing 3 g of urea per 250 g of water. 13. 0.05 F
11. The molality of a solution of ethyl alcohol (C,H,OH) in water is 1.56 m. How 14. (2) 0.018 (22) 1M (2iz) 1.002 m.
many grams of ethyl alcohol are dissolved in 2 kg of water ? 15. 7.6 M;11.4m
12. Commercially available concentrated hydrochloric acid contains 38% HCl by 16. 0.81, 95.87%
mass and has density 1.19 g cm™. Calculate the molarity of this solution. 17. 6.02 x 1071 molecules.
(Pb.S.B. 2005, 2007, 2015) 18. 34.8%
15. Calculate the formality of sodium thiosulphate (Na,5,0,. 5H,O) solution, 19. (2) 0.256 M (iz) 0.24 m (212) 0.0043
1.24 g of which are dissolved in 100 cm? of the solution. . 0.25 M
14, 4.0 g of NaOH are contained in one decilitre of a solution. Calculate (2) mole 21. 0.55 M
fraction of NaOH (iz) molarity of NaOH (zzz) molality of solution. (density of . 2.29 m
solution = 1.038 g mL). (Pb. S.B. 2010) 23. 23.6 em?
15. Calculate the molarity and molality of a solution prepared by mixing equal 24, 6.135 m
volumes of 30% by weight of H,SO, (density = 1.218 g/mL) and 70% by weight . 0.427 M, 0.470 m
of H,SO, of solution (density = 1.610 g/mL). (Pb. S.B. 2010) Hints & Solutions on page 66
16. The concentration of solution of sulphuric acid is 18 M and has density
1.84 g cm’. What is the mole fraction and weight percentage of H,SO, in the
solution?
17. Calculate the number of molecules of oxalic acid (H,C,O,. 2H,O) in 100 mL of
0.2 N oxalic acid solution.
18. In a solution of benzene in chloroform (CHCI,), the mole fraction of benzene is
0.45. Calculate its percentage by weight in the mixture.
19. 8.0575 x 10° kg of Glauber’s salt is dissolved in water to obtain 1 dm? of solution
of density 1077.2 kg m-™. Calculate
(z) the molarity (zz) the molality and (zzz) mole fraction of Na,SO, in the solution
(Atomic masses : Na = 23.00, 5S = 32.10, O = 16.00, H = 1.01)
20. Calculate the molarity of a solution of CaCl, if on chemical analysis it 1s found
that 500 mL of CaCl, solution contain 1.505 x 10°° CI ions.
M
21. 100 mL of a solution containing 5 g of NaOH are mixed with 200 mL of 5 NaOH
solution. Calculate the molarity of the resulting solution.
22. The density of a 2.05 M acetic acid in water is 1.02 g em. Calculate the molality
of the solution. (Pb. S.B. 2005)
25. Concentrated HNO, used in the laboratory is usually 69% by mass of HNO,.
Calculate the volume of the solution which contains 23 g of HNO,. The density
of concentrated HNO, is 1.41 g em™.
24. Battery acid is 4.27 M H,SO, (aq) and has density of 1.25 g mL. What is the
molality of H,SO, in the solution ? (Pb. S.B. 2005)
26. Hundred gram of Al(NO,), [molar mass 213 g mol] is dissolved in 1L of water at
20°C. The density of water at this temperature is 0.9982 g cm™ and the density
of resulting solution is 0.9990 g cm. Calculate the molarity and molality of
this solution.

Accelerate Your Potential

td 540) 3)BY Be (for JEE Advance)

i How many mL of sulphuric acid of H,SO, so that total solution of 50 mass % ees a becomes
density 1.84 g mL” containing 95.6 mass % of (1000 + v) mL.
H,SO, should be added to one litre of 40 mass “% 100
Volume of solution of 95.6% H,5O
solution of H,SO, of density 1.31 g mL” in order 4~ 1.84
: . 1.84
to prepare 50 mass % solution of sulphuric acid Amount of H,S5O, in v mL of solution = 95.6 x 700 x
of density 1.40 g mL}. 100
Volume of solution of 40% H,SO
Let v mL of 95.6 mass % sulphuric acid of 4~ 131
density 1.84 g mL! be added to 1000 mL of 40 mass %
 MODERN'S abe + OF CHEMISTRY
-AIl

Amount of H,SO, in 1000 mL of solution = ee x 1000

How many grams of wet NaOH
containing 15% water is required to prepare 6L
100 of 0.6 M NaOH solution?
Volume of solution of 50% H,SO, = 740
1 L of 0.6 M NaOH contains = 0.5 mol NaOH
Amount of H,SO, in (1000 + v) mL of solution or 0.5 x 40 = 20 g NaOH
6 L of 0.6 M NaOH contains = 20 x 6 = 120 g NaOH
= 60 x =—"x(1000+v) Since wet NaOH contains 15% water, then
100
100 g of wet NaOH contain 85 g pure NaOH
Tage: 95.6 1.84x vu 7 40*1.31 «1000= or 865 g of NaOH is contained in 100 g wet NaOH
Pease pos v)
100 100
120 g of NaOH is contained in aus) x 120 = 141.18 g
175.90v + 562400 = 70000 + 70 uv
105.90 v = 17600 Wet NaOH required to prepare 6 L of 0.6 M NaOH
or v = 166.2 mL. - 141,18 g
=) Calculate the resulting molarity of a
Vol. of H,S5O, of density 1.84 containing 96.6 mass % of
solution obtained by adding 6.2 g of KOH to 500 mL
H,SO, to be added = 166.2 mL.
Calculate the density of H,SO, solution of = KOH solution (density = 1.06 g mL”!). The
whose molarity and molality are 10.8 M and 92.6 m density of resulting solution is 1.10 g mL".
respectively. 1000 mL of ~ KOH solution contains KOH
Molarity 10.8 means that 10.8 moles of H,SO,
= aearal
are present in 1L of the solution.
Let the density of the solution is d g mL“', then }
or x ob] 112
Mass of 1000 mL of solution= (1000 x d) g
(Molar mass of KOH = 56)
Mass of H,5QO, in solution = 10.8 x 98 = 1068.4 g . 119
600 mL of — KOH solution contains KOH = TAT x 500
Mass of water = (1000 d — 1068.4) g
10.8 = 6.6 g
oh ————— x 1000 = 92.6
(1000d — 1058.4) Mass of 500 mL of KOH solution = 500 x 1.06 = 5380 g
10800 = 92.6 x (1000 d — 1058.4) After adding 6.2 g of KOH,
Mass of KOH = 5.6+ 6.2 =11.8 ¢
1000 d — 1068.4 = suki = bo Mass of solution = 530 + 6.2 = 536.2 g

or 1000 d = 116.6 + 1068.4 = 1175 Volume of new solution = 536.2 = 487.45 mL

1175
= Ss i Rigleett yee
1000 56 x 487.45

SOLUBILITY OF GASES AND SOLIDS IN LIQUIDS

REMEMBER Solubility of a substance expresses the maximum amount of it
e Saturated solution. A solution which can be dissolved in a specific amount of solvent at a specified
which contains maximum temperature.
amount of solute which dissolves The solubility of a substance depends upon the nature of solute, nature
completely in a given solvent at of the solvent, temperature and pressure.
a particular temperature. Let us consider the effect of these factors on the solubility of a solid in a
Unsaturated solution. A liquid and a gas in a liquid.
solution which contains less Solubility of Solids in Liquids
amount of solute than required When a solid (solute) is added to the solvent, the solute dissolves because
for forming saturated solution. its particles go into the liquid and its concentration in the solution increases.
Supersaturated solution. A This process is known as dissolution. Some solute particles in solution collide
solution which contains excess with the solid solute particles and get precipitated out. This process is called
of solute than required for erystallisation. The process of dissolution continues until the solution attains
formation of saturated solution. a certain maximum concentration. Such a solution in which no more solute
» Added excess solute does not can be dissolved at a given conditions of temperature and pressure is called
dissolve. saturated solution. A solution in which more solute can be dissolved at the
same temperature is called unsaturated solution. At the saturated solution
stage, an equilibrium gets established between the process of dissolution and
crystallisation. Under such conditions, the number of solute particles going
into the solution will be equal to the number of solute particles separating
out and a state of dynamic equilibrium is reached.
Dissolution _
Solute + Solvent
Crystallisation_ Solution
~
SOLUTIONS

Therefore, in saturated solution, the concentration of solute in the solution

will remain constant under the given conditions i.e., temperature and pressure.
The maximum amount of solute that dissolves completely in a given amount
of solvent at a particular temperature is called its solubility.
Thus, the solubility of a substance at a given temperature is defined as
the amount of the solid that dissolves in 100 g of the solvent at a
given temperature to form a saturated solution.
The solubility is also expressed as molar solubility which gives the molar
concentration of a substance in a saturated solution i.e., mol dm-®. Thus,
the concentration of the solute has the highest value in a
saturated solution.
Factors affecting the solubility of a solid in a liquid.
The solubility of a solid in a liquid, in general, depends upon the
following factors:
(i) Nature of the solute and the solvent.
(it) Temperature
The pressure has almost insignificant effect on the solubility hoo o

of a solid in a liquid.
(4) Nature of the solute and the solvent. Every solid does
not dissolve in a given liquid. In general, a solid dissolves in a liquid —_ianSo

(solvent) ifthe intermolecular interactions are similar in solute and the

solvent. This is in accordance with basic rule “like dissolves like.”
This means that ionic (or polar) compounds dissolve more readily in —.Soo

polar solvents like water and are very little soluble or almost insoluble
in non-polar solvents like benzene, ether, carbon tetrachloride. Solvent)
Solute/100g
(g
solubility
Similarly, non-polar (covalent or organic) compounds are soluble in
non-polar solvents like benzene, ether, carbon tetrachloride but are
very little soluble in water (polar solvent). For example, common salt
(sodium chloride) and sugar dissolve readily in water and solubility
of common salt in water is much more than that of sugar (covalent
Temperature (°C)
compound). Their solubilities in water are 5.3 mol L~ and 3.8 mol L7*!
(a) Continuous solubility curves
respectively. However, naphthalene and anthracene (non-polar
compounds) are not soluble in water. On the other hand, naphthalene
and anthracene dissolve readily in benzene but sodium chloride and
sugar do not.
(11) Effect of temperature. Temperature has a marked effect on — hoo o
(61.8°C)
=
the solubility of a solid in a solvent. The solubility may increase or oO
if
% *
A
= +
o
decrease with increase in temperature. The variation of solubilities wv) ye
=H at Ko
of some common substances with temperature is shown in Fig. 1. Oo
So

We observe three types of trends in the behaviour of different 2

,

=
solutes : o
wv)
(a) The solubility of solutes increases with increase in =
temperature. The solubility of most of substances such as sodium iy
Fe
nitrate (NaNO,), potassium nitrate (KNO,), ammonium chloride = a
ro.
‘Lb
(NH,Cl), potassium chloride (KCl), sodium chloride (NaCl), silver
o
wv oe base
nitrate (AgNO,), potassium iodide (KI), etc. increase with rise onSo

in temperature. This is because the dissolution process for these

substances is endothermic (A_,H > 0).
Solute + Solvent + Heat =—— Solution A,,H = +ve
40 60 80 100
Since these substances absorb heat on forming solution and
Temperature (°C)
therefore, their solubility increases with increase in temperature (b) Discontinuous solubility curves
in accordance with Le-Chatelier’s principle. As is clear from Fig.
1.(a), the variation of sodium chloride with temperature is very Fig. 1. Variation of solubilities of some
small, though it also increases. substances with temperature.
 MODERN'S abe + OF CHEMISTRY-AXIl

(b) The solubility of solids decreases with increase in temperature.

In general
The solubility of some substances like lithium sulphate (Li,SO,), certum
if the solute dissolves with
sulphate [Ce,(SO,).], some calcium salts of organic acids, sodium carbonate
absorption of heat (endothermic
monohydrate (Na,CO,.H,O), etc. decrease with rise in temperature. This is
process), the solubility increases because their dissolution process is exothermic (A,,H < 0):
with rise in temperature.
Solute + Solvent —— Solution + Heat A,,H =—ve
if the solute dissolves with
Since these dissolve with evolution of heat, a decrease of solubility with
evolution of heat (exothermic
temperature is expected in accordance with Le-Chatelier’s principle.
process), the solubility decreases
It may be noted that in these two types, there is continuous increase or
with rise in temperature.
decrease with increase in temperature as shown in Fig. 1.(a).
(c) The solubility shows irregular behaviour with increase in
temperature. For some substances, the solubility behaviour is not regular. For
example, the solubility of sodium sulphate (Na,SO,) increases upto a certain
temperature and then decreases as the temperature is further raised. In this
case, the solubility curves are not continuous but discontinuous and show
breaks. The temperature corresponding to the break in the solubility curve is
known as the transition temperature. For example, the solubility curve of
sodium sulphate shows a sharp break at 32.8°C. This is due to change in one
ss
oO, solid form into another solid form. For example, in case of sodium sulphate at
So 32.8°C, there is an equilibrium between solid decahydrate Na,SO,.10H,O and
gion
anhydrous Na,SO,.
Na,SO, . 10H,O
above 32.8°C
Na,SO,
a below 32.8°C
ieom
oo

Below this temperature, only sodium sulphate decahydrate (Na,SO,. 10H,O)

oS
ie exists while above this temperature, anhydrous sodium sulphate (Na,SO,) exists.
=
i: The solubility curve for FeSO,.7H,O is also discontinuous and shows break
= at 61.8°C. At this temperature heptahydrate changes to tetrahydrate. The
curve for CaCl,.6H,O shows two breaks corresponding to
CaCl,.6H,0 —-> CaCl,.4H,0 —~ CaCl,.2H,O.
(zit) Effect of pressure. The effect of pressure on the solubility of solids
Temperature (°C) in liquids is generally very small or insignificant. This is because solids and
liquids are highly incompressible and practically remain unaffected by changes
Fig. 2. Solubility of N, and O, in in pressure. For example, a change of 500 atm in pressure increases the
water at 1 atm pressure. solubility of sodium chloride in water only by 2.3%.
Solubility of Gases in Liquids
Gases dissolve in liquids to form homogeneous solutions. Many gases
dissolve in water. Oxygen dissolves only to a small extent in water. The natural
Quantitatively, the effect of
water contains dissolved oxygen which is vital in sustaining all aquatic life
temperature on the solubility of a
gas in a liquid at constant pressure in lakes, rivers, sea, etc. The different gases are soluble in water to different
may be expressed as : extents. Some gases are also soluble in solvents like ethyl alcohol, ether, benzene,
dins AH etc. The solubility of a gas in a particular liquid may be expressed as the
at - RT? AG)
volume of the gas (in em? converted to S.T.P.) that can dissolve
where s is_ the solubility in moles in a fixed volume of the liquid to form the saturated solution at
per litre of the gas in the liquid and
a given temperature.
AH is the enthalpy of solution at
temperature T. If AH is regarded as The solubility of a gas may also be expressed in terms of molarity or
independent of temperature, then mole fraction of the gas.
integration of equation (1) gives Factors affecting the solubility of a gas in a liquid.
The solubility of a gas in a liquid depends upon:
(1) The nature of the gas and the solvent
(it) Temperature of the solution
where s, and s, are the solubilities at
(111) Pressure
temperature T, and T, respectively.
This expressionis similar to Clausius-
(4) Nature of the gas and the solvent. The solubility of different gases
Clapeyron equation which gives the
in the same solvent varies considerably. For example, gases like nitrogen,
effect of pressure on the boiling point hydrogen, oxygen, helium, etc. dissolve in water only to a small extent whereas
of a liquid. the gases like ammonia, sulphur dioxide, hydrogen chloride, etc. are highly
soluble in water. The solubility of the latter gases in water is due to the
SOLUTIONS

chemical reactions of these gases with water to form ammonium hydroxide,

sulphurous acid and hydrochloric acid respectively. Therefore, the most soluble
gases are those which chemically react with the liquid solvent.
Oxygen, nitrogen and carbon dioxide are much more soluble in ethyl
alcohol than in water at the same temperature and pressure. On the other
hand, gases like NH, and H,S are less soluble in ethyl alcohol than water at
the same temperature and pressure.
(11) Effect of temperature. The solubility of a gas decreases with increase
of temperature (Fig. 2). This is because, in general, gases dissolve in a liquid
with the evolution of heat i1.e., exothermic process.
Gas + Solvent — Solution + Heat.
Therefore, in accordance with Le-Chatelier’s principle, the increase in
temperature will result in decrease in the solubility of the gas. It is for this
reason that most of gases which dissolve without ionizing are readily expelled
from solutions by boiling.
It may be noted that there are certain gases such as hydrogen and inert
gases whose solubility increases slightly with increase of temperature
especially in the non-aqueous solvents such as alcohols, acetone,
hydrocarbons, etc.
(iit) Effect of pressure. The solubility of gases
PISTON
increases with increase of pressure. This behaviour is
also in accordance with Le-Chatelier’s principle.
To understand this, consider a gas in dynamic
equilibrium with a solution [Fig. 3(a)]. The lower part
represents the solution and the upper part is gaseous
system at a pressure p and temperature T. Since there
is dynamic equilibrium, the number of gas molecules
entering the solution is equal to the number of dissolved
molecules leaving the solution phase. Now increase the
pressure over the solution phase by compressing the gas
to a smaller volume as shown in Fig. 3 (6). This will
(a) Lower pressure of (6) Higher pressure of
increase the number of gaseous particles per unit volume
gas, lower solubility gas, higher solubility
over the solution. As a result, the more molecules will be
striking the surface of the liquid and hence more molecules Fig. 3. Effect of pressure on the solubility of a gas.
will dissolve and the solubility of gas will increase until
a new equilibrium is reached. Thus, increasing the pressure of a gas above the
solution, increases the solubility of the gas.
The concentration of the dissolved gas is proportional to the pressure on
the gas above the solution.
William Henry made systematic studies of the solubility of a gas in a
liquid. He gave a quantitative relationship between solubility of a gas in a
solvent and pressure which is known as Henry’s law. The law states that
the mass of a gas dissolved per unit volume of the solvent at a
constant temperature is directly proportional to the pressure of the
gas in equilibrium with the solution.
If m is the mass of the gas dissolved in a unit volume of the solvent and
p is the pressure of the gas in equilibrium with the solution, then
m cx p
or m= K. p (9)
where K is the proportionality constant. The magnitude of K depends on the
nature of the gas, nature of the solvent, temperature and the units of pressure.
Thus, Henry’s law may also be stated as: the solubility of a gas in a liquid at
a particular temperature is directly proportional to the pressure of the gas in
equilibrium with the solution.
Dalton, during the same period, also concluded independently that the
solubility of a gas in a liquid solution depends upon the partial pressure of
the gas. Now, if we use mole fraction of the gas in the solution as a measure
of its solubility, then mole fraction of the gas in the solution is proportional
lane to the partial pressure of the gas over the solution, 1.e.,
MODERN'S abe + OF CHEMISTRY
-AXIl

xo p
or x= hep

or Pp
= K’
Bt
| 7 |
or p = Kyx Ky = K’ ..(10)
5
eal
jioSoS=
where K,, is called Henry’s law constant. Thus, Henry’s law may alternatively
S
ir)
be stated as:
mm
Bo the partial pressure of the gas in the vapour phase is directly
/ proportional to the mole fraction of the gas in the solution.
am
Cae
= The units of K,, will be atm or bar (or & bar)
:
tr)
the
Thus, when we draw a graph between partial pressure of the gas against
mole fraction of the gas in solution at a given temperature, then a straight
ra
a line passing through the origin is obtained. The plot of experimental results for
"oa
ve the solubility of HCl gas in cyclohexane at 293 K is given in Fig. 4. The straight
= line graph shows the validity of Henry’s law. The slope of the line gives
a
7 0.010 0.020 the Henry’s law constant, K,,. Different gases have different K,, values at the
Mole fraction of HCl in its same temperature. This suggests that K,,is a function of the nature of the gas.
solution in cyclohexane When a mixture of a number of gases is brought in contact with a solvent,
each constituent gas dissolves in proportion toits own partial pressure. Therefore,
Fig. 4. Plot of solubility of HCl gas
Henry’s law is applied to each gas independent of the presence of other gas.
in cyclohexane at 293 K.
The Henry’s law constant values for some gases in water at 298 K are
given in Table 2 below.
Table 2. Henry’s law constants (K,) for some gases in water at different temperatures.

on Temp(K) K,,(kbar) Gas Temp(K) K,, (kbar)

295 144.97 CO, 298 AES iy
295 69.16 Ar 298 40.3
295 76.48 Methane 298 0.413
303 88.84 Vinyl chloride 298 0.611
293 34.86
FOO2ZAzma
ha
bo
Bo
303 46.82
From these values, it may be concluded that
R U Curious... N (7) Henry's law constant, K,, depends upon the nature of the gas.
(ii) Higher the value of K,, at a particular pressure, the lower is the solubility
Aquatic species like fish feel
more comfortable in lakes in of the gas in the liquid. (-" x = 7 .p; from Eq. 10).
winter than in the summer. H
| > Aquatic species require dissolved (iit) The value of K,, increases with increase in temperature indicating that
O, for breathing. As solubility the solubility of gases decreases with increase of temperature. (It is clear from
of gases decreases with increase Table 2 that K,, values of N, and O, increase with increase in temperature.)
of temperature, less oxygen is This is the reason that aquatic species are more comfortable in cold water
available in summer than in winter. rather than warm water.
Hence, they feel more comfortable
Limitation of Henry’s law. It has been observed that Henry’s law is
in winter (low temperature) when
valid if
the solubility of O, 1s higher.
(4) pressure is low. At high pressure, the law becomes less accurate and
|> In summer during hot day,
the proportionality constant shows considerable deviations.
temperature at the surface of water
is relatively high and therefore, the (iz) the temperature is not too low.
solubility of oxygen in the upper (iit) the gas is not highly soluble and
layer is less. At the same time, (iv) the gas neither reacts chemically with the solvent nor dissociates or
the temperature of water at lower associates in the solvent.
level is much less and therefore, it The solubility of most of the gases in a liquid decreases with increase in temperature
contains more amount of dissolved and therefore, Henry's law constants have smaller values at higher temperatures.
oxygen. Hence, marine life like Because of the decrease in solubility of gases with increase in temperature, the
fish prefers to stay at lower dissolved gases may be removed from liquids by heating. But this is not always the
level and stay away from the case. Some gases are more soluble at higher temperature than at lower temperature
upper layer of water. and hence these are not readily removed by heating.
SOLUTIONS

Applications of Henry’s law

Henry’s law finds many applications in industry and helps to explain
several biological phenomena. Some important applications are :
1. In the production of carbonated beverages. To increase the
solubility of CO, in soft drinks, soda water, beer or champagne, the bottles
are sealed under high pressure. When the bottle is opened under normal
atmospheric conditions, the pressure inside the bottle falls to atmospheric
pressure and the excess CO, bubbles out of the solution causing effervescence.
2. In deep sea diving (Scuba diving). Deep sea divers depend upon
compressed air for breathing at high pressure under water. The compressed
air contains N, in addition to O,, which are not very soluble in blood at normal
pressure. However, at great depths when the diver breathes in compressed air
from the supply tank, more N, dissolves in the blood and other body fluids
because the pressure at that depth is far greater than the surface atmospheric
pressure. When the diver comes towards the surface, the pressure decreases,
N, comes out of the body quickly forming bubbles in the blood stream. These
bubbles restrict blood flow, affect the transmission of nerve impulses. The
bubbles can even burst the capillaries or block them and starve the tissues
of O,. This condition is called “the bends,” which are painful and dangerous
to life. To avoid this condition, most professional divers these days use air
diluted with helium gas (about 11.7% He, 56.2% N, and 32.1% O,), because
of lower solubility of He in the blood than nitrogen. Moreover, because of
small size of He atoms (unlike nitrogen molecules), they can pass through cell
walls without damaging them. The excess O, dissolved in the blood is used
in metabolism and does not cause the condition of bends.
3. At high altitudes. At high altitudes, the partial pressure of O, is less than
that at the ground level. This results in low concentration of oxygen in the blood
and tissues of the people living at high altitudes or climbers. The low blood oxygen
causes climbers to become weak and unable to think clearly known as anoxia.
4. In the function of lungs. To minimise the painful effects of deep sea
divers during the decompression, oxygen diluted with less soluble helium gas
is used as breathing gas.

SOLVED EXAMPLES

0 Example 23. OU EKxample 24.

If Ng gas is bubbled through water at 293 K, how The Henry’s law constant for oxygen dissolved itn water
many millimoles of N, gas would dissolve in 1 litre is 4.384 x 107 atm at 25°C. If the partial pressure of
of water. Assume that N, exerts a partial pressure of oxygen in air is 0.2 atm, under atomspheric conditions,
0.987 bar. The K,, for N, at 293 K is 76.48 R bar. calculate the concentration (in moles per litre) of
dissolved oxygen in water in equilibrium with air
Solution : The solubility of gas is related to its mole ai 25°C.
fraction in aqueous solution. Solution : According to Henry’s law :
The mole fraction of the gas in solution, p = Ky
K,, = 4.34 x 10* atm,
Po. = 0.2 atm
If n is the number of moles of N in solution and 1 litre
of water contains 655.5 mol, then Pog = K, XO.

n n
iN, =
n+55.5 55.5 =1.29x10° AH
(2 in the denominator is neglected because it is << 55.5)
= a - 46x 106
n = 66.6 x 1.29 x 10° 4.34 x10
= 7.16 x 10+ mol Changing mole fraction into molarity
1000
or = 7.16 x 10°!m mol Moles of water = eT! =55.5 mol
= 0.716 m mol. Since "o, is very small in comparison to /H,0
| 120° MODERN'S abe + OF CHEMISTRY-AXIl

No, + "H,0 = nyo Lx 79

= = 0.79 at
No, Pu, ~ “100 ii
“0, * 4.0
_ a. = 2*lastam
100
Xo, x "HO = "Og 0,
46x10°x 65.5 = %o, Applying Henry’ law
No, = 2.65 x 10+ mol Bey oi
Since 2.66 x 10+ mol are present in 1000 mL of solution, 2
Molarity = 2.55 x 10+ M. — Pr, _ 0.79
OQ Example 25. > Ky, 8.54 x 10*
Dry air contains 79% N, and 21% O,. Determine the = 9.25 x 10°
proportion of N, and O, (in terms of mole fractions) x f Po, 0.21
dissolved in water at 1 atm pressure. Henry’s law 2 «Ko, 4.56 x 104
constant for N, and O, in H,O are 8.54 x 10* atm = 4.60x 10°
and 4.56 x 107 atm respectively. Proportion of N, and O,
Solution : Total pressure of air over water = 1 atm = fh x 10°: 46x 10°
Partial pressure of N, and O, are : = =

errs
=Prreact :
Answers to Practice Problems 26. What concentration of nitrogen should be present in a glass of water at room
26. 499 x 104M temperature ? Assume a temperature of 26°C, a total pressure of 1 atmosphere
27. 7.75 x 104atm and mole fraction of nitrogen in air of 0.78.
28. 5.86 g (K,, for nitrogen = 8.42 x 10°’ M/mm Hg). (A.[.S.B. 2009)
29. 1.58 bar 27. One litre of water under a nitrogen pressure 1 atm dissolves 0.02¢ of nitrogen
30. 0.181 bar at 293 K. Calculate Henry’s law constant.
28. Calculate the amount of CO, dissolved at 4 atm in 1 dm* of water at 298 K.
The Henry's law constant for CO, at 298 K is 1.67 & bar.
29. At what partial pressure, oxygen will have a solubility of 0.06 gL in water
at 293 K? Henry’s law constant (K,,) of O, in water at 303 K is 46.82 k bar.
(Assume the density of the solution to be the same as that of water).
30. The mole fraction of He gas in a saturated solution at 20°C is 1.25 x 10°.
Calculate the pressure of He gas above the solution. (K,, of He at
20°C = 144.98 k bar).

SOLID SOLUTIONS
@ Solvent C) Solute As we have already learnt, solid solutions are those solutions in which
both the components (i.e., solute and the solvent) are solids.
(a) Substitutional solid solution ;
Solid solutions are of two types :

(1) Substitutional solid solutions and

(11) Interstitial solid solutions.

(1) Substitutional solid solutions are those in which atoms, molecules

or ions of one substance take the place of particles of another substance in a
crystal lattice as shown in Fig. 5 (a). Brass is acommon example of substitutional
C) ecient @ Solute solid solution of copper and zinc. Bronze, monel and steel are other familiar
examples of this type of solid solution. Zinc sulphide and cadmium sulphide
op iorete) cone Souen also form such solid solutions in which cadmium ions randomly replace zinc
ions in the ZnS lattice.
Fig. 5 Solid solutions
SOLUTIONS 2/21 —
(it) Interstitial solid solutions are those which are formed by placing
atoms of one kind into voids or interstices in the lattice of atoms of other
substance. This is shown in Fig. 5(6) in which solute particles are shown in
the interstices present in the atoms of solvent lattice. The common example of
interstitial solid solution is tungsten carbide (WC). In this case, tungsten atoms
are arranged in a face centred cubic pattern with carbon atoms in octahedral
holes i.e., spaces within the crystal where carbon atoms are surrounded by six
tungsten atoms at the vertices of an octahedron. Tungsten carbide is extremely
hard substance and has many uses in making of cutting and grinding tools.
Even, some metals have a tendency to dissolve large quantities of gases and
form solid solutions of gases in metals. For example, palladium and platinum
are capable of taking up hydrogen at room temperature to form solid solutions
of the hydrogen in the metal.

add on
Q.1. Which aqueous solution has higher concentration : 1 molar or 1 molal solution of the same solute?
Give reason. (C.B.S.E. Sample Paper 2007)
Ans. 1 Molar solution has higher concentration than 1 molal solution. A molar solution contains one mole of solute
in one litre of solution while a one molal solution contains one mole of solute in 1000 g of solvent. If density of
water is one, then one mole of solute is present in 1000 ml of water in 1 molal solution while one mole of solute
is present in less than 1000 mL of water in 1 molar solution (1000 mL solution = amount of solute + amount
of solvent). Thus, 1 molar solution is more concentrated.
. Ethanol is an organic compound, yet it is freeely miscible with water, Explain.
. The miscibility of ethanol in water is due to hydrogen bonding between the molecules.
. What is the normality of
(a) 1.5 M H,SO, (b) 1.2 M CH,COOH (c) 1.00 M NaOH ?
. (a2) Normality = 1.5 x2=3N (65)12x1=12N (c)1.0x1=10N
» Which out of molarity or molality will change with change in temperature and why ?
» Molarity changes with rise in temperature. Volume of a solution increases with rise in temperature and this
causes change in molarity because it is related as moles of solute in a given volume of solution.
. Will the molarity of a solution at 50°C be same, less or more than molarity at 25°C ?
» Molarity at 50°C of a solution will be less than that at 26°C because molarity decreases with temperature. This
is because volume of the solution increases with increase in temperature but number of moles of solute remains
the same.
. What is the sum of the mole fractions of all the components in a three component system ?
- i. Fi +%)+%x%,= 1
. How is the molality of a solution different from its molarity ?
» Molarity is the number of moles of solute per litre of the solution while molality is the number of moles of solute
per kilogram of the solvent.
Q.8. State the formula relating pressure of a gas with its mole fraction in liquid solution in contact with
it. (D.S.B. 20065)
Ans. The pressure of a gas over a solution in which the gas is dissolved is proportional to the mole fraction of the
gas dissolved in the solutioni.e., p « x
or p = K,,.« (where K,, is Henry's law constant)
Q.9. At a same temperature, hydrogen is more soluble in water than helium. Which of them will have a
higher value of K,, and why ? (A.LS.B. 2005)
Ans. Helium will have higher value of K,, because if gas has more solubility, its K,, value is lower.
Q.10. What is the relation between normality and molarity of a given solution of sulphuric acid ?
Ans. Normality = 2 x Molarity.
 MODERN’S abc + OF CHEMISTRY-XII

Q.11. What 1s the effect of temperature on the solubility of sodium sulphate decahydrate (Na,SO,.10 H,O) ?
Ans. The solubility first increases upto 32.8°C (called transition temperature) and then decreases.
Q.12. The dissolution of ammonium chloride in water is endothermic process. What is the effect of
temperature on its solubility ?
Ans. since dissolution of NH,Cl in water is endothermic process, its solubility increases with rise in temperature
(Le-Chatelier principle).
Q.13. Give reasons, at higher altitudes, people suffer from a disease called anoxia. In this disease, they
become weak and cannot think clearly. (C.B.S.E. Sample Paper 2007)
Ans. At high altitudes, the partial pressure of oxygen is less than that at the ground level. This leads to low
concentration of oxygen in the blood and the tissues of the people living at high altitudes. As a result of low
oxygen in the blood, the people become weak and unable to think clearly. These are the symptoms of a condition
known as anoxia.

VAPOUR PRESSURE OF LIQUID SOLUTIONS

Vapour Pressure of Liquid
When a liquid is allowed to evaporate in a closed vessel, a part of the liquid
evaporates and fills the available space with the vapours. Since the vapours
donot leave the container, these get collected in the vapour state above the
surface of the liquid. Due to vaporisation, liquid changes into vapours and
level of liquid decreases. As the evaporation proceeds, the number of gaseous
molecules in the vapour phase increases gradually. These molecules move about
at random in a limited space and during their random movement, some of these
strike the surface of liquid and get condensed. The process of condensation acts
in opposite direction to the process of evaporation. Thus, both evaporation and
condensation processes go on simultaneously. Ultimately, a stage is reached
Fig. 6. Vapour pressure of a liquid.
when the rate of evaporation becomes equal to rate of condensation and an
equilibrium gets established between liquid and vapour phases. The pressure
exerted by the vapours at the equilibrium is called vapour pressure. Thus,
the pressure exerted by the vapours above the liquid surface in
equilibrium with the liquid at a given temperature is called vapour
pressure.
Factors on which vapour pressure of a liquid depends
de catntig Plus The vapour pressure of a liquid depends upon :
Quantitatively, the effect of (i) Nature of the liquid. Each liquid has a characteristic vapour pressure
temperature on vapour pressure because each liquid has different magnitude of intermolecular forces.
of a liquid is given by Clausius- The liquids, which have weaker intermolecular forces, tend to escape
Clapeyron equation as: readily into vapour phase and therefore, have greater vapour pressure.
For example, dimethyl ether and alcohol have higher vapour pressure
= Avapll T; i
: | Te | than water at a given temperature because of weaker intermolecular
forces in them as compared to water.
where p, and p, are the vapour (it) Temperature. The vapour pressure of a liquid increases with increase
pressure at temperatures T, and in temperature. This is due to the fact that with increase in tempera-
T, respectively and Avaplt 18 the ture, more molecules will have larger kinetic energies. Therefore, larger
enthalpy of vaporisation of the number of molecules will escape from the surface of the liquid to the
liquid. vapour phase resulting in higher vapour presssure.
Vapour Pressure of Liquid Solutions
Liquid solutions are formed when solvent is a liquid and the solute may be
a gas, a liquid or a solid. We have already learnt about solutions of gases in
liquids. Let us learn about the solutions of liquids and solids in a liquid. Such
solutions may contain one or more volatile components. Generally, the liquid
solvent is volatile. The solute may or may not be volatile.
(a) Vapour Pressure of Liquid-liquid Solutions and Raoult's Law
(Raoult's Law for Volatile Solutes)
When a binary solution of two volatile liquids is placed in a closed vessel,
both the components would evaporate and eventually an equilibrium would be
established between vapour phase and the liquid phase. In the case of binary
solution of volatile liquids, the vapour phase consists of vapours of both the
components.
SOLUTIONS

The French chemist Francois Marie Raoult (1886) gave a quantitative

relationship between the partial pressures and the mole fractions of two
components. This relationship is known as Raoult’s law which states that
at a given temperature, for a solution of volatile liquids, the
partial vapour pressure of each component in solution is equal to
the product of the vapour pressure of the pure component and its
mole fraction.
Let us consider a binary solution of two volatile liquids and denote the
components as A and B having the mole fraction x, and xp, respectively. If
p, and pp are the vapour pressures of the components in the solution, then
according to Raoult’s law
Pa =PaXg
and Pp =Dp Xp
where p,° is the vapour pressure of the pure component A and p,° is the
vapour pressure of pure component B at the same temperature.
According to Dalton’s law of partial pressures, the total pressure p will
be the sum of the partial pressure of the components of the solution. This is
given as:
P =PatPp
Substituting the values of p, and pp, we get
Pp =PyX,+ Pp Xp tl )

As we know, “a+ “p= lorx,=1-x,

: P =p,° (1—xXp) + DpXp
or P =P,° —Pa Xpt+ Dp Xp

p = Pa t+ (pp - Pax at 12)

From equation 12, the following conclusions can be drawn :
(4) Total vapour pressure over the solution can be related to the mole
fraction of any one component [x, or x, as x, = (1 — xp).
(it) Total vapour pressure of the solution varies linearly with the mole
fraction of component B because p,° and p,°
are constant.
(iit) Depending on the vapour pressure of the pure
components A and B, total vapour pressure over
the solution decreases or increases with the
increase of the mole fraction of the component
A. 2
=
a
ia
The equation 12 shows that the total vapour pressure o
b=]
a.
(p) is a linear function of the mole fraction x, (or x, as Xx, :
=
=
= 1—x,) because p,° and p,° are constant at a particular S
> Vapour
———>
pressure
temperature. This is shown in Fig 7. The dotted lines
give the partial pressures of the two components versus
composition and the solid line gives the total vapour
Mole Fraction —-—
pressure versus composition. The graph can be easily tp=0
understood as: Fig. 7. Vapour pressure behaviour of liquid-liquid solution of
According to Raoult’s law, the partial vapour pressures | two volatile compounds obeying Raoult’s law. The dashed line I
of two components A and B of a solution are given as: _| andl represent the partial vapour pressure of the components.
The total pressure 1s given by the line III (solid line).
Pa=Pa°X, and Pp = Pp’Xp
Therefore, the vapour pressures of the components
are linear functions of their mole fractions. Now,
(i) when x, 1, i.e., the liquid is pure A
Pa = Pa X¥1=DA"
(iz) when x, 0, z.e., the liquid is pure B
Px = Px XO0=0
lan MODERN'S abe + OF CHEMISTRY

Thus, the plot of p, against x, should give a straight line passing through
-AXIl

Ppa? (when x, = 1) and 0 (when x, = 0). This is shown by line I in Fig. 7. It is

clear from the curve that when the liquid is pure (x, = 1), its vapour pressure
is equal to p,°. As component B is added to component A (x, decreases), the
vapour pressure decreases along the line I till it becomes zero (x, = 0).
Similarly, the variation of partial pressure of component B (p,) with its
mole fraction (x,) is represented by the plot from x, = 0 (.e., Dp = Pp°® X O = 0)
to xp = 1 (.e., Dp = Pp° X 1 = pp’). It is shown by line II.
The total vapour pressure p, exerted by the solution as a whole at any
composition is given by the sum of partial vapour pressures according to
Dalton’s law of partial pressures. Thus,
P= PratPp
= Pax, t Ppxp
This is shown by line II in Fig. 7, obtained by joining the points p,° and
Pp’: It is clear from the figures that the vapour pressure of solutions of different
compositions, lies between the vapour pressure of the pure components (p,°
and p,°) and they lie on the straight line joining p,° and p,°. The minimum
value of p (total vapour pressure) is p,°and the maximum value is p,° assuming
that the component A is less volatile than component B i.e., p,°< pp’.

Composition in vapour phase

The composition of vapour phase in equilibrium with the solution is
determined by the partial pressure of the components. If y, and y, are the
mole fractions of the two components 1 and 2 respectively in the vapour
phase, then according to Dalton’s law of partial pressures :
Partial pressure of a component = Mole fraction of the component
x Total pressure in vapour phase
a Pie = er
or Po YoP
In general, D: = ¥. Pyta

Mole fraction of component 1 in vapour phase, y,

Mole fraction of component 2 in vapour phase, y, = —

In general, mole fraction of a component in vapour phase
_ Partial vapour pressure of component
Total vapour pressure

(6) Vapour Pressure of Solutions of Solids in Liquids

(Raoult's Law for Non-Volatile Solutes)
This is a most common class of solutions formed
by the dissolution of solids in liquids such as sodium
chloride, glucose, urea, sugar in water and iodine
and sulphur in carbon disulphide. Some physical
properties such as vapour pressure are quite different
from those of pure solvents.
Let us add a small amount of a non-volatile solute
to the solvent (e.g., sugar in water) to form the solution
(Fig. 8). When evaporation of this solution takes
place, the vapour phase again consists of vapours
of the solvent (i.e., of water) because the solute is
non-volatile. However, the vapour pressure of the
solution is found to be less than that of the
Pure Solvent Solvent and Solute pure solvent. This can be explained as follows :
Fig. 8. Vapour pressure of (a) pure liquid and of(6) solution. We know that evaporation is a surface
phenomenon. The vapour pressure depends on the
SOLUTIONS

escape of solvent molecules from the surface of the liquid. In the case of
solution, the non-volatile sugar molecules [as shown by small black spheres in
Fig. 8(5)] also occupy a certain surface area. Therefore, the surface has both
solute and solvent molecules; and the fraction of surface covered by solvent
molecules gets reduced. As a result, lesser number of solvent molecules will
escape into vapours. In other words, vapour pressure of the solution will
be less than that of the pure solvent or there will be a lowering in vapour
pressure. The increase in the concentration of sugar in the solution will
further lower the vapour pressure of the solution. Vapour pressure of
Raoult’s law for liquid solutions containing non-volatile solutes. pure solvent (p*°)
According to Raoult’s law, the partial vapour pressure of volatile
component in the solution is directly proportional to the mole fraction in it. =
When the solute is non-volatile, only the solvent molecules are present in a
the vapour phase. Therefore, the vapour pressure of the solution will be the
=o
oo
vapour pressure due to solvent only. 3
Vapour pressure of the solution = Vapour pressure of the solvent in the
solution. :
oo
oo

If p, 1s the vapour pressure of the solvent over a solution containing ar

cy
=P
non- volatile solute and x, is its mole fraction, then according to Raoult’s
law, the vapour pressure of the solvent in the solution, 3
3S
PaX*a =

Pa =PaXg 0 o2 o4 06 og LO
or p =p, "%, (.p = Dy) Mole fraction of solvent ———>
LCs, p (solution) =p (pure solvent) x mole fraction of solvent.
Fig. 9. Plot of vapour pressure of
This relationship is known as Raoult’s law. solution containing non-volatile solute
Thus, for solutions containing non-volatile solutes, the Raoult’s law versus mole fraction of the solvent.
may be stated as
at a given temperature, the vapour pressure of a solution containing
non-volatile solute is directly proportional to the mole fraction
of the solvent.
The above expression also implies that p « x, KEY NOTE
1.e., Vapour pressure of solution is directly proportional to the mole fraction of the According to latest convention, pressure
solvent in the solution. The proportionality constant is equal to vapour pressure is represented as p instead of P. de both
abbreviations are commonly used. But in
of pure solvent (p,°). Thus, if vapour pressure of the solution containing a non-
the present text, p 1s used for pressure.
volatile solute is plotted against the mole fraction of the solvent, a straight line
plot will be obtained as shown in Fig. 9.
The above relationship may also be expressed in different ways as:
Rearranging the above equation,
P = Feet A
Poo=%x
ey fo
Pa
Subtracting each side of the equation from 1, we have
1- Fe ree
Pa
a —

or Ly = Xp Cx, +Xp=lorl—x,
=Xx,)
Pa
or P* BO solvent
es ~ Psolution
SO1UTLOn —
= a

P solvent

Here, p,° —p, (difference in vapour pressure of pure solvent and solution)
represents the lowering in vapour pressure on the formation of solution. Now,
by dividing the lowering in vapour pressure with the vapour pressure of the
pure solvent, 7.e.,(0,° — ps) /p,° we get the relative lowering in vapour
pressure. The above relation also gives an alternative statement of Raoult’s
law. Thus, the Raoult’s law in its modified form may be stated as
the relative lowering in vapour pressure of an ideal solution
containing the non-volatile solute is equal to the mole fraction
of the solute at a given temperature.
ane MODERN'S abe + OF CHEMISTRY
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Raoult’s law as a special case of Henry’s law

KEY NOTE Raoult’s law may be regarded as a special case of Henry’s law. According
The difference and similarity to Raoult’s law, the vapour pressure of a volatile component in given
between Raoult’s law and Henry’s solution is given by the relation :
law must be noted carefully.
Pa=Py Xg
Similarities where p,° is the vapour pressure of the pure component, p, is the vapour
e Both Raoult’s law and Henry’s
pressure in the solution having mole fraction x,. In the case of solution of a
law apply to volatile component
in solution. gas in a liquid, the gaseous component is volatile component. Its solubility
e Both laws state that the vapour is governed by Henry law which gives the relation :
pressure of one component is p=K yx
proportional to the mole fraction where p is the pressure of the gas above the solution and x is its mole
of that component. fraction. K,, is a proportionality constant known as Henry’s constant.
Differences
e Raoult’s law defines the The comparison of equations for Raoult’s law and Henry’s law shows that
proportionality constant as the the partial pressure of the volatile component or gas is directly proportional
vapour pressure of the pure to its mole fraction in solution. The only difference in the two expressions is
component, whereas Henry’s the proportionality constant p,° (in Raoult’s law) and K,, (in Henry’s law).
law defines the proportionality
constant as some experimentally Therefore, Raoult’s law becomes a special case of Henry’s law in
determined value (Henry’s which K,, becomes equal to vapour pressure of the pure component
constant, K,,). (p,°). Even in the liquid solutions, one of the components may sometimes
obey Henry’s law over a range of mole fraction.
In that case K,, becomes equal to p,°. In practice, in solutions in which
solute behaves ideally according to Henry’s law, the solvent also behaves
ideally according to Raoult’s law. However, the reverse is not necessarily
true and the Raoult’s law ideality of the solvent does not mean that the
solute must obey Henry’s law.
As the solution becomes more and more dilute, and approaches a limit
of infinite dilution (x, ———+ 0) its components behave more ideally. The
solvent behaves Raoult’s law whereas the solute (minor component) obeys
Henry’s law for dilute solutions.

IDEAL AND NON-IDEAL SOLUTIONS

The binary liquid-liquid solutions may be classified into two types :
(1) Ideal solutions
(2) Non-ideal solutions
These may be described as follows:
1. Ideal solutions
An ideal solution may be defined as the solution which obeys Raoult’s
law exactly over the entire range of concentration.
Such solutions are formed by mixing the two components
which are identical in molecular size, in structure and have almost
identical intermolecular forces. In these solutions, the intermolecular
interactions between the components (A — B attractions) are of same
magnitude as the intermolecular interactions in pure components
(A — A and B — B attractions). According to Raoult’s law, the partial vapour
pressure of two components of the solution may be given as:
Pa =PaX,
and Pp =DPp Xp
Total pressure p is given by
P =Pat Pp =PaXa + Pp Xp
The ideal solutions have also the following characteristics:
(4) Heat change on mixing its zero. Since there is no change in magni-
tude of the attractive forces in the two components present, the heat
change on mixing i.e. A nixing! in such solutions must be zero.
SOLUTIONS

(77) Volume change on mixing is zero. In ideal solutions, the volume

of the solution is the sum of the volumes of the components before
mixing 1.e., there is no change in volume on mixing or A... V 1s zero.
For example, when we mix 100 cm? of benzene with 100 cm? of toluene,
the volume of the solution is found to be exactly 200 cm*. Therefore, there is
no change in volume on mixing i.e. A nixing’ = 0. It has been noticed that the
solutions generally tend to become ideal when they are dilute.
The characteristics of an ideal solution may be summed up as follows :
(z) It must obey Raoult’s law. (iz) A nizing should be zero.
(zzz) A MLM V should be zero.

Examples of ideal solutions. In fact, ideal solutions are quite rare but
some solutions are nearly ideal in behaviour at least when they are very
dilute. A few examples of ideal solutions are:
(1) Benzene and toluene (it) n-hexane and n-heptane
(111) Bromoethane and iodoethane (iv) Chlorobenzene and bromobenzene.
The graphical behaviour of ideal solution has already been discussed in
Fig. 7. Such solutions which obey Raoult’s law are called ideal liquid solutions.
2. Non-ideal solutions
The solutions which do not obey Raoult’s law over the entire range
of concentration are called non-ideal solutions.
Therefore, for such solutions
Pa # PaXa and = Pp # Pp Xp
Thus, the vapour pressure of such solutions is either higher or lower than
that predicted by Raoult’s law. In non-ideal solutions, there is a noticeable
change in volume and heat energy when the two components are mixed. Most
of the solutions are non-ideal because they deviate from ideal behaviour to
more or less extent. Thus, for non-ideal solutions,
(4) none of the components obey Raoult’s law over the entire composi-
tion range, 1.€., Dx # Da°X, and Pp # Pp°Xp
(it) A. -ving¥ 18 not equal to zero.
(tit) A not 18 not equal to zero.
Thus, non-ideal solutions do not obey Raoult’s law and are accompanied
by change in enthalpy and change in volume during their formation.
Differences between ideal and non-ideal solutions
The main points of differences between ideal and non-ideal solutions are
summed up below:

Ideal solution Non-ideal solution

1. The interactions between the The interaction between the
components are similar to those components are different from those
in the pure components. of the pure components.
2. There is no enthalpy change on | There is enthalpy change on mixing.
mixing. (eel # (0)
(A PYLEanes a
3. There is no volume change on _ | There is volume change on mixing.
mixing. (Ae oe 0)
(AmixingV = 0) hu
4, Each component obeys Raoult’s Their components do not obey
law at all temperatures and Raoult’s law. They show positive and
concentrations, negative deviations from Raoult’s law
L€., Py =P,°X xX, and 1.C., Pa #PxyX, and
— oO

Pe Pp #Dp Xp
 MODERN'S abe + OF CHEMISTRY
-AXIl

Types of Non-ideal Solutions

Non-ideal solutions show positive and negative deviations from the ideal
behaviour depending upon their nature.
(4) Non-ideal solutions showing positive deviations from Raoult’s
law. Consider a binary solution of two components A and B. If the A—B
interactions in the solutions are weaker than the A—A and B-B interactions
in the two liquids forming the solution, then the escaping tendency of A and
B types of molecules from the solution becomes more than from pure liquids.
As a result, each component of solution has a partial vapour pressure greater
than expected on the basis of Raoult’s law. The total vapour pressure will be
greater than corresponding vapour pressure expected in case of ideal solution
of the same composition. This type of behaviour of solution is described as
positive deviations from Raoult’s law. Mathematically, it may be expressed as:
Px > Pax, and Pp > Dp'Xp
The total vapour pressure,
2 P = Py + Ppis always greater than (p,°x, + Pp°Xp)
=
uf
ne) The positive deviations have been shown in Fig. 10, in which dotted lines
o
oO show the ideal behaviour upon mixing while the thick lines exhibit the actual
= behaviour. A few examples of solutions showing positive deviations are :
o
S
_
(1) Ethyl alcohol and cyclohexane
(it) Acetone and carbon disulphide
Mole Fraction ——» (111) Benzene and acetone
Xpj=1 x,=0
(tv) Carbon tetrachloride and choloroform
Xp_=0 Xp=l
(v) Acetone and ethyl alcohol
Fig. 10. Positive deviations from (vi) Ethyl alcohol and water.
ideal behaviour. The dotted lines
(------) represent ideal behaviour and Explanation for positive deviations. Let us explain by considering a
solid lines ( ) represent actual solution of ethyl alcohol and cyclohexane. In ethyl alcohol, the molecules are
behaviour. held together due to hydrogen bonding as shown below :

When cyclohexane is added to ethyl alcohol, the molecules of cyclohexane

tend to occupy the spaces between ethyl alcohol molecules. Consequently, some
hydrogen bonds in alcohol molecules break and the attractive forces in alcohol
molecules are weakened. The escaping tendency of alcohol and cyclohexane
molecules from the solution increases. Consequently, the vapour pressure
of the solution is greater than the vapour pressure as expected according to
Raoult’s law.
In such solutions, Aske and ae are also not equal to zero as
explained below :
(1) A wagti 18 positive because energy is required to break A—A or B—B
attractive forces. Therefore, dissolution process is endothermic.
(it) Because of the decrease in the magnitude of intermolecular forces
in solutions, the molecules will be loosely held and, therefore, there will be
increase in volume on mixing. Thus, Dita will be +ve.
Since the dissolution process in endothermic, heating will increase the
solubility of such a solution.
(11) Non-ideal solutions showing negative deviations from Raoult’s
law. In such solutions, the A—-B interactions are stronger than the A—A and
B-—B interactions present in the two liquids forming the solution. Due to stronger
A-—B interactions, the escaping tendency of A and B types of molecules from the
solution becomes less than from pure liquids. Consequently, each component
of the solution has a partial vapour pressure less than expected on the basis
of Raoult’s law. As a result, the total vapour pressure becomes less than
SOLUTIONS

the corresponding vapour pressure expected in case of ideal solution. The

solutions are said to have negative deviations from Raoult’s law.
Mathematically,
Pa < Pa°X, and Pp < Pp’Xp
Thus, the total vapour pressure,
P =P, + Ppis always less than (p,°x, + DpXp)
The negative deviations have been shown in Fig. 11, in which dotted lines
show the ideal behaviour upon mixing while the thick lines show the actual
behaviour. A few examples of the solutions showing negative deviations are:
Vapour
———+
pressure
(1) Acetone and chloroform
(it) Chloroform and diethyl ether A
re Mole Fraction —e x a=0
(iit) Chloroform and nitric acid
(iv) Acetone and aniline
(v) Water and nitric acid Fig. 11. Negative deviations from
(vi) Diethyl ether and chloroform. ‘ideal behaviour. The dotted lines
Explanation for negative deviations. Let us illustrate by considering a ) represent ideal behaviour and
‘solid lines ( ) represent actual
solution of acetone and chloroform. When acetone and chloroform are mixed,
behaviour.
there are new attractive forces due to intermolecular hydrogen bonding. Thus,
the attractive forces become stronger and the escaping tendency of each liquid
from the solution decreases.
Therefore, the vapour pressure of the solution is less than that expected
for an ideal solution.
In these solutions also, A = H and A MAXI V are not equal to zero as
explained below : Acetone Chloroform
) Asin is negative because energy is released due to increase in
attractive forces. Therefore, dissolution process is exothermic and heating the
solution will decrease solubility.
(it) Because of the increase in forces of attraction in the solution, the
molecules will be held more tightly. Therefore, there will be decrease in volume
on Mixing i.e. A nixing® will be negative.
The main properties of two types of non-ideal solutions are summed up
below :
Solutions having +ve Solutions having —ve
deviation from ideal deviation from ideal
behaviour behaviour
. The interactions between the components| The interactions between the components
are less than in the pure components. are more than in the pure components.
ee eee eee i> FP.X, and Das pi, te
aM use H = +ve Mfxing H = -ve
Dissolution is endothermic. Dissolution is exothermic
. Heating increases solubility.
ee = +ve
Heating decreases solubility.
el = —ve
iO Competition Plus
Azeotropes are liquid mixtures which
Azeotropes or Constant Boiling Mixtures distil over as if these are pure liquids.
There are some mixtures of liquids (solutions) which on boiling produce For details, refer Competition File
vapour with the same composition as the liquid and boil at a constant temperature. (Page 98).
Therefore, such liquid mixtures distil over as if these are pure liquids. In such
cases, it is not possible to separate the components by fractional distillation.
The solutions (liquid mixtures) which boil at constant temperature
and can distil unchanged in composition are called azeotropes or
azeotropic mixtures (Greek meaning boiling without change).
There are two types of azeotropes depending upon the type of deviations
from Raoult’s law. These are:
(4) Minimum boiling azeotropes
(it) Maximum boiling azeotropes.
| 2180° MODERN'S abe + OF CHEMISTRY
-AIl

REMEMBER
(4) Minium boiling azeotropes: The solutions which show a
@ Solutions showing positive deviations
large positive deviation from Raoult's law form minimum boiling
from ideal behaviour form minimum : _
boiling azeotropes. azeotrope at a specific composition. For example, ethanol-water
@ Solutions showing negative deviations mixtures (obtained by fermentation of sugars) are rich in water.
from ideal behaviour form maximum The fractional distillation gives a solution containing approximately
boiling azeotropes. 95% by volume of ethanol. Once the composition has been obtained
a, the liquid and vapour have the same composition and therefore, it
© cannot be further distilled to separate water from ethanol. Other
j 1 R U Curious...% i; methods of separation.
have to be used to prepare 100% ethanol.
| oO Pure ethyl alcohol cannot be obtained from (it) Maximum boiling azeotropes: The solutions which show
rectified spirit (95.6% of alcohol) even by negative deviation from Raoult's law form maximum boiling azeotrope
fractional distillation!
at a specific composition. For example, nitric acid (HNO,) and water
>» This is because a mixture of 95.6% alcohol form maximum boiling azeotrope. The azeotrope has the approximate
and 4.4% water forms an azeotropic
composition 68% nitric acid and 32% water by mass with a boiling
i.e., constant boiling mixture. At this
stage liquid and vapour have the same point of 393.5 K.
composition and therefore, it cannot be Some common azeotropic mixtures are given below :
further distilled to separate water from
ethanol.

Components Composition Boiling Point (K)

(mass % B) B Azeotrope

Minimum Boiling Azeotropes

C,H,OH 95.6 373
n-C,H,OH 72.0 373
C,H,OH 6.8 334.2
Maximum Boiling Azeotropes
HCl 20.2 Sis)
HNO, 68.0 373
HCOOH 1A .O Sis)
CH,COCH, 20.0 334.2
It is clear from the above table that in case of minimum boiling azeotrope,
the boiling point of the azeotrope is less than the boiling point of either of
the pure components. Similarly, in case of maximum boiling azeotrope, the
boiling point of azeotrope is more than the boiling point of either of the pure
components.

Soltucug Numerical Probleme

FORMULAE AND UNITS
According to Raoult’s law, for a binary solution of components A and B
Pa =PaXa
Pp =Pp%,a
where Pa and Pa are the vapour pressure of pure component A and its vapour pressure in solution respectively
and x, is its mole fraction in solution. Pp’ and Pp are the vapour pressure of pure component B and its vapour
pressure in solution respectively and x, is its mole fraction.
For a solution containing a non-volatile solute,
Vapour pressure of solution = Vapour pressure of solvent in solution, p, = p,°. x,
where p,° 1s the vapour pressure of pure component and x, 1s its mole fraction in solution.
SOLUTIONS

SOLVED EXAMPLES

LU) Example 26. Phenzene = 0-256 x 0.40 = 0.1024 bar

The vapour pressure of ethyl alcohol at 298 K is 40 Mole fraction of toluene, x,,,.,. = 1 — 0.40 = 0.60
mm of Hg. Its mole fraction in a solution with methyl Vapour pressure of pure toluene,
alcohol is 0.80. What ts its vapour pressure in solution
P° tuene = 9:0925 bar
if the mixture obeys Raoult’s law?
Partial vapour pressure of toluene,
Solution : According to Raoult’s law, Protrene = 0-0925 x 0.60 = 0.0555 bar
Pa = Pars Total vapour pressure of solution,
Vapour pressure of pure ethyl
Ptotal = Prenzone +P toluene = 0: 1024 + 0.0555 = 0.158 bar.
alcohol (p,°) = 40 mm of Hg
(71) Calculation of composition of vapour phase
Mole fraction of ethyl alcohol (x,)= 0.80
Mole fraction of benzene in vapour phase
Phenzene _ 0.1024
Vapour pressure of ethyl alcohol benzene 7 Dens 0.158 = 0.648
in solution (p,) = 40 x 0.80 Mole fraction of toluene in vapour phase
= 32 mm of Hg.
_ 0.0555 = 0.351
LU) Example 27. toluene ~ “9158
An aqueous solution of glucose is made by dissolving Example 29
10 g of glucose (C,H,,O,) in 90 g of water at 303 K. Vapour pressure of chloroform (CHCI,) and
If the vapour pressure of pure water at 303 K be dichloromethane (CH,Cl,) at 298 K are 200 mm Hg
32.8 mm Hg, what would be the vapour pressure of and 415 mm Hg respectively.
the solution? (A.LLS.B. 2000) (t) Calculate the vapour pressure of the solution
Solution : According to Raoult’s law, vapour pressure prepared by mixing 25.5 g of CHCl, and 40 g of
of the solution, CH,Cl, at 290 K and
Pa =PaX%a (it) Mole fraction of each component in solution.
where p,°= vapour pressure of pure water and x, is the mole (Pb.S.B. 2009, 2010, Kerala S.B. 2012)
fraction of water. Solution : (i) Molar mass of CHCl, = 1x 124+1x1+3x 35.6
Since solute is non-volatile = 119.6 g mol?
Vapour pressure of solution = p, = P,°X, Molar mass of CH,Cl, =~ 1x 1234+2x1+4+2x 36.5
= 86 g mol?
Px = 32.8 mm Hg

Moles of water = 90 = 5.0 Moles of CHCl, = —2°8— ~ 0.213 mol

18 119.5g mol

Moles of glucose = oe
180
0.0556 Molesoles of
o CH,CL,
gol = ———-8—
55g mol ~
= 0.470
0). mo mol
Mole fraction of water,x, = _ {iia > = 0.989 Total number of moles = 0.213 + 0.470 = 0.683 mol
°“A 5.0 + 0.0556
Vapour pressure of solution = 32.8 x 0.989 *CHCly = rans = 0.312
a on 44 mm.
*CH2Clo = 1.0 — 0.312 = 0.688
LI Example 28.
At 298 K, the vapour pressure of pure benzene, C,H, Poucls = p°CHCl, x xCHCl,
is 0.256 bar and the vapour pressure of pure toluene = 200 x 0.312 = 62.4 mm Hg
C,H,CH, is 0.0925 bar. If the mole fraction of benzene
in solution ts 0.40 (1) what ts the total vapour pressure Pcu,cl, = p°CH,Cl, x xCH,Cl,
of the solution? (it) Calculate the composition of the 4.15 x 0.688 = 288.6
vapour in terms of mole fraction. Prot] = 82-4 + 288.5
(Pb.S.B. 2009, 2010) = 347.9 mm Hg
Solution : (4) Calculation of total vapour pressure (iz) Mole fraction in vapour phase
According to Raoult’s law, YCHCl; _ PCHCl; _ 6 2.4 _ 0.18
Vapour pressure of a component = Vapour pressure of pure P 347.9
liquid x Mole fraction
Mole fraction of benzene, x,. one = 0-40 VoueCl, — PCH2Cl2_ 288.5
Pp 347.9
Vapour pressure of pure benzene, p®, ane — 0.256 bar
Partial vapour pressure of benzene,
= 0.82.
cz MODERN'S abe + OF CHEMISTRY
-AXIl

It may be noted that since CH,Cl, is a more volatile a& Ms 0.80, x» = 2+ _2999
component than CHCl, [p® (CH,Cl,) = 416 mm Hg and : 4+1 441
p° (CHC1,) = 200 mmHg] and therefore, the vapour phase “. p,° x 0.80 + p,° x 0.20 = 560 mm Att?
is also richer in CH,Cl,. Thus, it may be concluded that Multiply eq. (i) by 4 and eq. (ii) by 5, we get
at equilibrium, os as phase will Be always rich in 3p,°+ p,° = 2200 mm (ii)
the component which is more volatile. .
4p,° +p, = 2800 mm ALU)
Subtracting —p,° =— 600 mm
LU) Example 30.
oe p, =600 mm of Hg
Two liquidsX and Y on mixing form an ideal solution.
Substituting in eq. (iii) we get
The vapour pressure of the solution containing 3 mol
of X and 1 mol of Y is 550 mm of Hg. But when 4 mol 3 x 600 + p,°= 2200 or p,°= 2200 — 1800 = 400 mm Hg
of X and 1 mol of Y are mixed, the vapour pressure Vapour pressure of pure component X = 600 mm Hg
of the solution, thus, formed ts 560 mm of Hg. What Vapour pressure of pure component Y = 400 mm Hg
will be the vapour pressure of the pure X and pure
Y at this temperature ? KEY NOTE
Solution : Let the vapour pressure of X be p,°and of
Mole fraction of a component in vapour phase may
Y be p,° and x, and x, be their mole fractions.
be calculated as :
Then according to Raoult’s law, the total pressure, p is Mole fraction of component A in vapour phase
Pp =p,°.X, + py. X, _ Partial vapour pressure of A in solution
In the first solution, Total vapour pressure
3 1
= 0.75, x5 = ona” 0.25
|
Mole fraction of component B in vapour phase
1 = 341
*. p,° x 0.75 + p,°x 0.25 = 550 mm w(L) : Partial vapour pressure of B in solution
In the second solution, 7 Total vapour pressure

ol. The vapour pressure of pure liquid A at 310°C is 0.158 bar. The vapour pressure
of this liquid in solution with liquid 5 is 0.095 bar. Calculate the mole fraction
of A in the solution if the mixture obeys Raoult’s law.
om. At 293 K, ethyl acetate has vapour pressure of 72.8 torr of Hg and ethyl
propionate has vapour pressure of 27.7 torr of Hg. Assuming their mixtures to
obey Raoult’s law, determine the vapour pressure of a mixture containing 25 g
of ethyl acetate and 50 g of ethyl propionate.
oo. An aqueous solution containing 28% by weight of a liquid. A (molecular
mass = 140) has a vapour pressure of 0.210 bar at 37°C. Calculate the vapour
pressure of pure liquid (vapour pressure of water at 37°C = 0.198 bar).
34. Benzene and toluene form nearly ideal solution. At a certain temperature, the
vapour pressure of the pure benzene is 150 torr and of pure toluene is 50 torr.
= Answers to Practice Problems. = Calculate the vapour pressure of the solution containing equal weights of two
substances at this temperature.
31. 0.601 35
The vapour pressure of ethanol and methanol are 44.5 and 88.7 mm Hg
32. 44.26 torr ofHg respectively. An ideal solution is formed at the same temperature by mixing
33. 0.448 bar 60 g of ethanol and 40 g of methanol. Calculate the total vapour pressure of
the solution and the mole fraction of methanol in the vapour phase.
34, 104.1 torr
(Pb.S_B.E. 2009, 2010)
35. 66.15 mm Hg, 0.657 36. Methanol and ethanol forms nearly ideal solution at 300 K. A solution is
36. p(CH,OH) = 60.3 mm Hg, made by mixing 32 g methanol and 23 g ethanol. Calculate the partial
PG ba) = 166 mo hie: pressure of its constituents and the total pressure of the solution. (at 300 K;
p° (CH,OH) = 90 mm Hg, p°(C,H.OH) = 61 mm Hg).
p (Total) = 77.1 mm Hg 37
At 20°C, the vapour pressure of pure liquid A is 22 mm Hg and that of pure
ode Ae aay Teheked sini lier cab liquid B is 756 mm Hg. What is the composition of the solution of these two
A and B. components that has a vapour pressure of 48.5 mm Hg at this temperature
(assume ideal behaviour) ?
SOLUTIONS

o8. Two liquids A and B have vapour pressure of 0.658 bar and 0.264 bar respectively. — Answers to Practice Problems
In an ideal solution of the two, calculate the mole fraction of A at which the
two liquids have equal partial pressures.
38. 0.286
o9. The liquids X and Y form ideal solution having vapour pressures 200 and 39. 0.67
100 mm Hg respectively. Calculate the mole fraction of component X in vapour 40. p(CH,OH) = 264 mm Hg
phase in equilibrium with an equimolar solution of the two. p(C,H.OH) = 1386 mm Hg
40. Atacertain temperature, the vapour pressure (in mm Hg) of CH,OH and C,H.OH
solution is represented by P = 119 x + 136 where x is the mole fraction of CH,OH. Hints & Solutions on page 66
What are the vapour pressures of pure components at this temperature ?

Accelerate Your Potential

td 540) 3) BA (for JEE Advance)
The mole fraction of X in the vapours in For equimolar binary solution of liquids A and B
equilibrium with homogeneous mixture of liquids X and Poel = 0.6 and p,” = 20 torr
Y is 0.42. The vapour pressure of liquids X and Y at the
Protal = “a Pa + Xp Pp
same temperature are 406.5 and 140 torr respectively. 45 = 0.6 x 20 + 0.6 x p,”
Calculate the mole fraction of X in the solution. 0.6.p,° = 45-10 = 35
According to Raoult’s law, he Pp - 3b x 2 = 70 torr
If mole fractions are x, and x, for the new solution,
Px = Py” x My ete)
22.5 = 20x, + 70 x,
ee ee _..(2)
apes er SE TIN! hea 5
In vapour state, mole fractions of X and Y are:
BO ee ie
oe Px
47.5
© Peotan oe eee POR
A 50
0.42 = "* orp, = 0.42p (iii) X_ = 1-0.96 = 0.05
Dean 7 Aer came gecy X%, _ 9.95 _ 4900
Xp 0.05
Similarly, yy = Bs a
Preotat) re A solution of A and B with 30 mol %
A is in equilibrium with its vapour which contains
| or Dy = 0.58 Dustan Atv) 40 mol % B. Assuming that the solution and the vapour
Pr(eotat) behave ideally, calculate the ratio of vapour pressure
Dividing eq. (111) by eq. (zv), of pure A and pure B.

7 In solution, mol % of A is 30, so that

ig ae WE ea ...(V)
Py 0.58 eee
In vapour phase, mol % of B is 40, so that
From eq. (1), (iz) and eq. (v), y, = 0.60, ¥, = 0.40

Py __ **x
Px JQ Now, ae = Pa an Xa Da

Py py X(1- xy) total vapour pressure x,4pa°+<xpDp°

406.5 xy 0.30p,°
=a or 2.
0.50 p,4° + 0.70 pp°
= 0.60 lt)

or 406.6 x, = 101.36 — 101.36 x, Similarly,

607.86 x, = 101.36 SS <pPp-
xy = 0.20 a
total
ae
vapource tepressure oe
x,Da°+XpPp
a a

i Liquids A and B form ideal solution Pen LL): ner mes

over the entire range of composition. At temperature 0.30 py° + 0.70pp°
T, equimolar binary solution of liquids A and B has
Dividing eq. (z) by eq. (zz):
vapour pressure 45 torr. At the same temperature,
a new solution of A and B having mole fractions X, Usd yie ue
and X, respectively has vapour pressure of 22.5 torr. 0.70pp° _—«0.40
What is the value of x,/x, in the new solution? (Given = Pao _ 0.60 | 0.70
that the vapour pressure of pure liquid A is 20 torr at
pee 0.40 ~ 0.30
temperature T). (JEE Advance 2018)
 MODERN'S abe + OF CHEMISTRY
-AIl

. What happens to vapour pressure of water if a tablespoon of sugar is added to it ?

. Addition of non-volatile solute lowers the vapour pressure of solvent (water).
. Why is the time saved when cooking is done in a pressure cooker ? (J.K.S.B. 2013)
. At higher pressure over the hquid (due to weight of the pressure cooker lid), the liquid boils at higher temperature.
Therefore, cooking occurs faster.
. Why is the vapour pressure of a liquid constant at a constant temperature ?
. Vapour pressure is the pressure of the vapour at equilibrium state when rate of evaporation becomes equal to
rate of condensation. Equilibrium constant does not change at a particular temperature and, therefore, vapour
pressure remains constant.
. Two liquids A and B are mixed and the resulting solution is found to be cooler. What do you conclude
about deviation from ideal behaviour ?
. The solution shows positive deviation from ideal behaviour.
. Can we separate the components of azeotropic mixture by distillation ?
. No, we cannot separate the components of an azeotropic mixture by distillation because at a particular composition,
both the components boil at the same temperature.
Q.6. Mixing of acetone with chloroform takes place with reduction in volume. What type of deviation
from Raoult’s law is shown in this case ?
Ans. The solution has negative deviation from Raoult’s law because decrease in volume indicates strong forces of
interaction between the molecules in solution.
Q.7. Why is liquid ammonia bottle first cooled in ice before opening it ?
Ans. At room temperature, the vapour pressure of liquid ammonia is very high. On cooling vapour pressure decreases.
Therefore, the liquid ammonia will not splash out.
Q.8. Two liquid A and B boil at 145°C and 190°C respectively. Which of them has higher vapour pressure
at 80°C ? (D.S.B. 2006)
Ans. Lower the boiling point, more volatile it is. Therefore, liquid A will have higher vapour pressure at 80°C.
Q. 9. A and B liquids on mixing produce a warm solution. Which type of deviation from Raoult’s law is
there? (C.B.S.E. Sample Paper 2011)
Ans. Negative deviation.
Q. 10. A solution of chloroform and acetone is an example of maximum boiling azeotrope. Why ?
(CLB.S.E. Sample Paper 2012)
Ans. The solution of chloroform and acetone has lower vapour pressure than ideal solution because of stronger
interactions between chloroform and acetone molecules. As a result, total vapour pressure becomes less than
the corresponding ideal solution of same composition (i.e., negative deviations). Therefore, the boiling points of
solutions are increased and form maximum boiling azeotropes.
. The dissolution of ammonium chloride in water is an endothermic process. What is the effect of
temperature on its solubility?
Ans. The solubility increases with rise in temperature (Le Chatelier's principle).

COLLIGATIVE PROPERTIES
The dilute solutions of non-volatile solutes exhibit certain characteristic
properties which do not depend upon the nature of the solute but depend
only on the number of particles (molecules or ions) of the solute i.e., on the
molar concentration of the solute. These are called colligative properties
(colligative, from Latin : co means together, ligare means to bind). Thus,
the properties of the solutions which depend only on the number
of solute particles but not on the nature of the solute are called
colligative properties.
The four important colligative properties are :
(i) Relative lowering in vapour pressure
(i) Klevation in boiling point
(iit) Depression in freezing point
(iv) Osmotic pressure.
RELATIVE LOWERING IN VAPOUR PRESSURE
We have already studied that when a non-volatile solute is added to a
solvent, the vapour pressure of the solution decreases. Let x, be the mole
fraction of the solvent, x, be the mole fraction of the solute and p,° be the
vapour pressure of the pure solvent and p be the vapour pressure of solution.
SOLUTIONS

Since solute is non-volatile, there will be no contribution of solute to the KEY NOTE
vapour pressure and the vapour pressure of the solution will be only due to
the solvent. Therefore, the vapour pressure of the solution (p) will be equal Colligative properties of dilute
to the vapour pressure of the solvent (p,), over the solution, i.e., solutions are also called
Pp =p democrative properties. This is
But, according to Raoult’s law, the vapolir pressure of solvent is equal to because just as in democracy, it is
the product of its vapour pressure in pure state and its mole fraction,
only the number of persons which
Pa = ParXa count. In the same way, it is the
or P =Pr=PaxXs sd 1)
Since x, 1s always less than one, the vapour pressure of the solidion is number of particles (irrespective
always less than Pa i.e., vapour pressure of the pure solvent. of their nature) which counts.
The lowering in vapour pecan 1s: This means that if two solutions
contain equal number of solute
=p pie, particles of A and B (i.e., molar
or = pa° (1 — X,)
concentration is same) then the
But = X, = Xp 80 that
two solutions will have same
ADy = PaXp
colligative properties irrespective
or APA = Xp of the nature of A and B. In
Pa”
other words, the relative lowering
in vapour pressure, elevation
Thus, Pa, = Pa Pa _y, (14)
Ps Pa in boiling point, etc. will be
same for the two solutions. The
where, p,° — p, (difference in vapour pressure of pure solvent and colligative properties are very
solution) represents the lowering in vapour pressure on the formation of solution useful to determine the molar
and (p,° — p,)/ p,° gives the relative lowering in vapour pressure. Thus, the
mass, commonly called molecular
relative lowering in vapour pressure of an ideal solution containing
weight of the non-volatile solutes.
the non-volatile solute is equal to the mole fraction of the solute at a
given temperature.

It may be noted that in a solution containing several non-volatile solutes, WATCH OUT !
the lowering in vapour pressure depends on the sum of the mole fractions It must be remembered that only
of different solutes. relative lowering in vapour
pressure is a colligative
property. Vapour pressure or
Relative lowering of vapour pressure — a colligative property.
lowering in vapour pressure are
According to Eq. 14, the relative lowering in vapour pressure depends only on
not colligative properties.
the molar ene atest of the solute (mole fraction) and is independent of its
nature. Therefore, relative lowering in vapour pressure ts a colligative property.
Determination of Molar Mass of a Solute from Relative Lowering
in Vapour Pressure WD Competition Plus
Molar mass of a non-volatile solute can be calculated from relative lowering Relative lowering in vapour pressure
in vapour pressure. A known mass of the solute is dissolved in a known is measured by Ostwald Walker
quantity of solution and relative lowering in vapour pressure is measured dynamic method. For detail, refer
experimentally. According to Raoult’s law, the relative lowering in vapour Competition File (Page 98).
pressure on the addition of a non-volatile solute to the solvent is:
Pa'=Psx_,
Pa”
Suppose w, and wy, are the weights of the solvent and solute respectively
and M, and M, are their corresponding molar masses. Then,
Mole fraction of solute, x, = "B
ha + ip

where 7, and n, are the moles of the solvent and the solute respectively and
Ws Wp
nlA — > np 1B =— :
Ma Ms

Wp

Xp = Mp
lane Therefore, relative lowering in vapour pressure is
MODERN'S abe + OF CHEMISTRY
-AXIl

Pa’—Px __ &p/Mp

For dilute solutions, n, 1s very small in comparison to n, (np << n,)

so that np, can be neglected in the denominator,
Ny + ip = Ny
Thus,

Pa’—Pa = bia} = Wp / Mp
Pa° ny Ws/My
Pa’-Pa _ UpXMa (15)
Pa? Wy x Mp

or sc)

Thus, the molar mass of the solute can be determined if the other quantities,
Py"
— Py
W,, Wp, M, and relative lowering in vapour pressure Pae are known.

Selutug Namerteat Probleme

FORMULAE AND UNITS
According to Raoult’s law,
relative lowering in vapour pressure,

(2s
°— Dal |y A
Oy i)
Np np
Ny tnhg Ny
and molecular mass of non-volatile solute,

Wp X My
\ Pion a
Ps”

LU) Example 31. (zz) Calculation of vapour pressure of solution

Vapour pressure of water at 20°C is 17.5 mm of Hg p = Vapour pressure of solvent — Lowering in vapour
and lowering of vapour pressure of a sugar solution pressure
= 17.5 — 0.061 = 17.439 mm of Hg
is 0.061 mm of Hg. Calculate
(zit) Calculation of mole fraction of sugar and water
(1) relative lowering of vapour pressure
Mole fraction of sugar, x, (solute)
(it) vapour pressure of the solution
(iit) mole fraction of sugar and water. Pa — PA = xX,
Solution : (i) Calculation of relative lowering of Pa
vapour pressure
Vapour pressure of water (p,°) = 17.6 mm of Hg Here Pa ~Pa _ 0.00348
Lowering of vapour pressure (p,° — p,) = 0.061 Pa
.. Relative lowering of vapour pressure,
.. Mole fraction of sugar, x, = 0.00348
Pa ~Pa _ 0.061 ~ 0.00348 Mole fraction of water, x, = 1-—x, = 1- 0.00348
Pr’ 17.5 0.9965.
SOLUTIONS

LU) Example 32. Solution : A 5% aqueous solution of urea means that out
The vapour pressure of pure benzene at a certain of 100 g of solution, urea is 5 g and water is 965 g.
temperature ts 0.850 bar. A non-volatile, non-electrolyte Weight of solute (urea), i. = bg
Weight of solvent (water), w, = 95g
solid weighing 0.50 g is added to 39.0 g of benzene
Molar mass of urea Me = OO,
(molar mass 78 g mol). The vapour pressure of the
Molar mass of water M, = 18
solution, then 1s 0.845 bar. What is the molar mass
Vapour pressure of water, p,° = 23.75 mm Hg;
of the solid substance?
Vapour pressure of solution, p, = ?
IN.C.E.R.T) (Meghalaya S.B. 2014, H.P.S.B. 2014, According to Raoult’s law,
Kerala S.B. 2016)
Pa’-Py — WaMa
Solution : According to Raoult’s law Px w,Ms,

ca
ae See Wp XMy (for dilute solution) es 23.75 -— pa 5 x 18
Pa* * Mg X wa 23.75 ~ 95x60
Wp = 0.50 g, w, = 39.0 g, p, = 0.845 bar, py = 0.850 bar
5 x 18 x 23.75
or 23.76 — Pa = 95x60. = 0.375
0.850 —0.845 _ 0.5 x 78
0.850 39.0 x Mp or p, = 23.75 — 0.3976 = 23.376
.. Vapour pressure of solution = 23.375 mm Hg.
0.005 0.5 x 78
0.850 39.0xM, Example 35.
A solution containing 30 g of a non-volatile solute in
_ 0.5 x 78 x 0.850
or Mz, = 170 g mol". 90 g water has a vapour pressure of 2.8 kPa at 298
0.005 x 39.0
K. Further 18 g of water ts added to solution, the new
LU) Example 33.
vapour pressure becomes 2.9 kPa at 298 K. Calculate
Calculate the mass of a non-volatile solute (molecular
(1) Molecular mass of solute.
mass = 40), which should be dissolved in 114 g octane
to reduce its vapour pressure to 80%. (ii) Vapour pressure of water at 298 K. |\N.C.E.R.T.
(Pb.S.B. 2008, Assam S.B. 2017) Solution : w, = 30 g, w, = 90 g, p, = 2.8 kPa
Solution : The vapour pressure is reduced to 80% on the According to Raoult’s law,
addition of a non-volatile solute so that WE
Pac-Px = —
100-80 =
1
—=0.2 Pa°—Pa _xy = _ Mp = wp XMa
ra B Wa iia! : Mp XWp
Pao 100 5
Now, according to Raoult’s law My, Mz
Pa TPA _, Pa®-2.8 _ 80 18
Pa” . Pi” Mp 90
Let mass of non-volatile solute to be added = x g
< 1_ = _ 6
Pa’-Pa _ _ 40 Pa Mz
Pa” il4 4%, 6
114 40 or = = ]— —
(Molar mass of octane = 114) Pa Mp

aD x / 40 2.8 M, — 6
or - = —B__ At)
“ “ 14+x/40 Pa Mp
0.21+—] 4 = Similarly, w, = 30 g, w, = 90 + 18 = 108 g, p, = 2.9 kPa
| 40) AQ)

or 0.2 -~— FE — — x —

40. 40
02 0.8x
“40g
(29 _ 55
Pa° Mz
or x = 1l)g
.. Mass of solute to be added = 10 g. .. 29 4 3
LU) Example 34. Pa° Mp
Calculate the vapour pressure of an aqueous solution
containing 5% by mass of urea (NH,CONH,) at 298K. or = ——— .. (LE)
The vapour pressure of water at 298K ts 23.75 mm Hg.
(Assam S.B. 2015)
 MODERN'S abe + OF CHEMISTRY
-AXIl

Dividing eq. (z) by eq. (11) we get M, = 34g mol"

2.8 _ Mg-6 Substituting the value of M, in eqn. (z) we get

2.8 34-6 28
0 34 34
28M... 14 — 20M, — ya Pa
2.9M, —2.8M, = 17.4-14 28p, = 2.8 x d4
0.1M, = 3.4 Pa = oA kPa.

=Pue
Deal iio
41. 30 ¢ of urea (M = 60 g mol") is dissolved in 846 g of water. Calculate the vapour
pressure of water for this solution if vapour pressure of pure water at 298 K
is 23.8 mm Hg. (A.L.S.B. 2017)
42. The vapour pressure of water is 12.5 kPa at 300 K. Calculate vapour pressure
of 1 molar solution of a solute in it.
45. The vapour pressure of water at 20°C is 17.5 mm Hg. A solution of sucrose (molar
mass = 342) is prepared by dissolving 68.4 g in 1000 g of water. Calculate
(t) relative lowering of vapour pressure
(it) vapour pressure of solution. (Pb.S.B. 2004)
44, The vapour pressure of pure benzene at a certain temperature is 262 bar.
At the same temperature the vapour pressure of a solution containing 2 g of
non-volatile, non-electrolytic solid in 100 g of benzene is 256 bar. What is the
molecular mass of the solid ? (A.P.S.B. 2011)
45. The vapour pressures of pure liquids A and B are 450 mm and 700 mm of Hg
respectively at 350 K. Calculate the composition of liquid mixture if total vapour
pressure is 600 mm of Hg. Also find the composition of the mixture in vapour
phase. (CBSE Sample Paper 2010, Assam S.B. 2015)
46. The vapour pressure of a 5% aqueous solution of a non-volatile organic substance
Answers to Practice Problems at 373 Kis 745 mm. Calculate the molar mass of the solute. (Vapour pressure
of water at 373 K = 760 mm Hg). (Jharkhand S.B. 2012, Manipur S.B. 2017)
41. 23.55 mm Hg
47. At 26°C, the vapour pressure of pure water is 23.76 mm of Hg and that of an
42. 12.08 kPa aqueous dilute solution of urea is 22.98 mm of Hg. Calculate the molality of
43. (2) 0.0036 (iz) 17.487 mm of Hg the solution.
4A, 68.12 g mol? 48. What mass of a non-volatile solute, urea (NH,CONH,) need to be dissolved in
45. 0 ees a 0s 100 ¢g of water in order to decrease the vapour pressure of water by 25% ? What
46. 48 g mol? will be the molality of the solution ?
AZ. 1.85 m 49. Urea forms an ideal solution in water. Determine the vapour pressure of an
aqueous solution containing 10% by mass of urea at 40°C. (Vapour pressure of
48. 111 g, 18.6 m water at 40°C = 55.3 mm of Hg) (A.LS.5. 2006, Nagaland S.B. 2015)
49. 53.46 mm Hg 50. The vapour pressure of water at 293 K is 0.0231 bar and the vapour pressure of
50. 1560.0. a solution of 108.24 ¢g of a compound in 1000 g of water at the same temperature
Hints & Solutions on page 66 is 0.0228 bar. Calculate the molar mass of the solute.

ELEVATION IN BOILING POINT

The boiling point of a liquid is the temperature at which its vapour
pressure becomes equal to the atmospheric pressure. We have learnt that
the vapour pressure of the solution containing non-volatile solute is less than that
of the solvent. Therefore, the solution has to be heated to a higher temperature
so that its vapour pressure becomes equal to the atmospheric pressure. Thus,
the boiling point of the solution is always higher than that of the pure solvent.
For example, vapour pressure of water is 1.013 bar (or 1 atm) at 373 K.
Therefore, water boils at 373 K because its vapour pressure at this temperature
becomes equal to one atmospheric pressure which is 1.013 bar. The vapour
pressure of an aqueous solution of sucrose is less than 1.013 bar at 373 K and
therefore, the solution will not boil at 373 K. In order to make the solution to
boil, its temperature must be increased so that its vapour pressure becomes
SOLUTIONS

equal to 1.018 bar (1 atm). Thus, boiling point of a solution is

always higher than the boiling point of the pure solvent in which
the solution is prepared.
1.0 atm (1.013 bar)
The elevation in boiling point on the addition of a non-
volatile solute to a solvent can be easily illustrated graphically.
The vapour pressure of the pure solvent or solution increases
with rise in temperature. The variation of vapour pressure
of the solvent and solution at different temperatures is Boiling Point
shown in Fig. 12. The curve AB gives the vapour pressure for the Elevation
pure solvent and the curve CD gives the vapour pressure for the
solution at different temperatures. The curve CD representing the Vapour
pressure
———>
vapour pressure of the solution at different temperatures lies below
the curve AB which corresponds to the vapour pressure of the pure Temperature (KK)
solvent. This is because of the fact that the vapour pressure of the ———_

solution is less than that of the pure solvent at all temperatures. Fig. 12. Elevation in boiling point.
It is clear from the figure that the vapour pressure of the
pure solvent becomes equal to atmospheric pressure at X (corresponding to
temperature T; °) while the vapour pressure of the solution becomes equal
to a iasphen: pressure at Y (corresponding to temperature T,). Thus,
the boiling point of the pure solvent is T, while that of the Aimer
is T,. Since T, is greater than je there ‘f an elevation or increase in
boiling temperature of the salto as compared to that of the solvent.
Mathematically, elevation in boiling point, AT, may be expressed as:
AT, = T, — T,°
It has been found out experimentally that the elevation in the boiling point
(AT) of a solution is proportional to the molal concentration of the solution, .e.,
AT, «xm
or AT, = K,m eG be
where m is the molality of the solution and represents moles of solute in 1 The units of K, are degree/
kg of solvent and K, is called molal boiling point elevation constant or molality, i.e. K m or
molal boiling point constant or ebullioscopic constant. °C m|! or K kg mol"!
If nm: = 1.
then AT, =
Thus, molal boiling point elevation constant, K,, is defined as
the elevation in boiling point for 1 molal solution 1.e., a solution
containing 1 gram mole of solute dissolved in 1000 g of the solvent.
K, can be calculated from molar
Elevation in boiling point — a colligative property. From Eq. (17), enthalpy of vaporisation as :
as K, is constant, so that
AT, b cm fe MRT,”
Thus, elevation in botling point ts directly proportional to the molal A
vapH x 1000
concentration of the solute (t.e., number of molecules) and therefore, it is a where M is a molar mass of solvent,
colligative property. T, 1s the boiling point of the solvent,
The K, values for some common solvents are given in Table 3. RK. is gas constant and A,apit is the
Table 3. Molal boiling point elevation constants (K,) for some solvents. molar enthalpy of vaporisation of
the solvent.
Solvent
For example, latent heat of
Water (H,O) vaporisation is 2.257 kJ g! for
Ethanol (C,H,OH) water. Its molal elevation constant
Benzene (C,H,) can be calculated as :
Chloroform (CHC1,) koe MRT,”
Kther (C,H,,0O) A yap Hx1000
Carbon tetrachloride (CC1,) R = 8.814 J K-! mol?
Carbon disulphide (CS,)
M = 18 g mol!
Acetic acid (CH,COOH)
T, = 373 K
Cyclohexane (C 6 H,)
H = 2.267 x 18 x 10° J mol“!
Determination of Molar Mass of Solute from Elevation in Boiling - 18x 8.314x(373)?
Point Temperature Bir; 2.257x18x10" x1000
Let wy gram of a non-volatile solute is dissolved in w, grams of the solvent 0.612 K kg mol
and M, is the molar mass of the solute.
 MODERN'S abe + OF CHEMISTRY
-AXII

WATCH OUT ! Therefore, the molality, m of the solution is :

Moles of solute x 1000
It must be remembered that n=
Wt. of solvent in grams
elevation in boiling point is a
colligative property, but boiling Wp
where moles of solute = ——
point is not a colligative property. M,
_ wp X 1000
Mp ~*~ Wa

Substituting the value of m in the relation (Eq. 17)

AT, = Kym
_ K, xwz, x 1000 |
we get, AT, = —
M,xw, A ..(18)
Thus, molar mass of solute,
M. = K;, X wp X 1000
BO AT, X wa
From the above relation, molar
mass of the solute can be calculated
knowing the values of other quantities.

Seluiug Numerical Prebleme

FORMULAE AND UNITS
Elevation in boiling point
AT, = K, ™* FTL

m = molality of solution, K, = Molal elevation in boiling point

or AT, =
Ws x Mp

where Ma, = Molecular mass of solute

w, = Weight of solvent
Wp, = Weight of solute
and molecular mass of solute,
1000 x K, Xwg
M, =
Ws x AT,

=e) 0)B= oe ee Le
LU) Example 36. Solution : Molar mass of a substance can be calculated as
Molal elevation constant for benzene is 2.52 K/m. A
solution of some organic substance in benzene boils M, = —
at 0.126°C higher than benzene. What is the molality
of the solution ?
K, = 2.63 K kg mol’, w, = 1.80 g,w, = 90g
Solution : The elevation in boiling point on dissolving
a solute is: AT, — $64.11 — 363.23 = 0.88 K
AT, = K,.m
AT, = 0.126°, K, = 2.62 K/m =m, —2:58 x 1.80 x 1000 _ 575 ops
BT 90 x 0.88
7 AT, _ 0.126
m = K, = ORG 7 = 0.05
LJ Kxample 38.
*. Molality of solution = 0.05 m. A solution containing 0.730 g of camphor (molar mass
LU) Example 37. = 152) in 36.8 g of acetone (b.p. 56.30°C) boils at
The boiling point of benzene ts 353.23 K. When 56.55° C. A solution of 0.564 g ofan unknown compound
1.80 g of a non-volatile solute was dissolved in 90 g in the same weight of solvent boils at 56.46°C. Calculate
of benzene, the boiling point is raised to 354.11 K.
the molar mass of the unknown compound.
Calculate the molar mass of the solute.
(K, for benzene is 2.53 K kg mol) Solution : In this problem, the value of K, is not given.
(Kerala S.B. 2013, Mizoram S.B. 2018, The first data is used to calculate K, which is used to calculate
Pb. S.B. 2017, Karnataka S.B. 2018) the molar mass from the second data.
SOLUTIONS

(¢) Calculation of K, for acetone Example 41.

A solution of glycerol (C,H,O,) in water was prepared
K, = Wp X 1000 by dissolving some glycerol in 500 g of water. This
solution has a boiling point of 100.42°C while pure
AT, = 56.56 — 66.30 = 0.26°C, M, = 162 water boils at 100°C. What mass of glycerol was
WwW, B = 0.730 g,w, = 36.8 g
dissolved to make the solution ?
0.25 x 152 x 36.8 (K, for water = 0.512 K kg mol)
- 1.92 Km?
=. = 0.736 x 1000 (D.S.B. 2012, ALS.B. 2012, Pb.S.B. 2013)
(74) Calculation of molar mass of unknown compound Solution : Elevation in boiling point
K, x 1000 X we
M, = AT, X Wa T; =>
K, x 1000 x wy
—$_— .. ~

Ww» +4 Ma,
K, = 1.92 Km", AT, = 66.46 — 66.30 AT, =100.42—100=0.42°, w,—500g,w,,=?, K, =0.512Kkg mot
= 0.16°C
M,=3x12+8x1+3x16=92
WwW, = 0.664 g,w, = 36.8 g,
0.512 x 1000 X wp,
M ee NE A eee a 7 500 x 92
BS 016x368 ~~ 8™mo-
Example 39. 0.42 x 500 x 92
On dissolving 3.24 g of sulphur in 40 g of benzene, or w, = ———_____—
0.512 x 1000
boiling point of solution was higher than that of
benzene by 0.81 K. K, value for benzene is 2.53 K kg = 37.73 ¢
molt. What is the molecular formula of sulphur ? Mass of glycerol to be added = 37.73 g
(Atomic mass of sulphur = 32 g mol-). (D.S.B. 2000) Example 42.
Solution : Let us first calculate the molar mass of sulphur, A solution prepared by dissolving 1.25 g of oil of winter
K, x 1000 X wp, green (methyl salicylate) in 99.0 g of benzene has a
M, = boiling point of 80.31 °C. Determine the molar mass
AT, X Wy
of this compound. (B.P. of pure benzene = 80.10 °C
K, = 2.63 K kg mol", w, = 3.24 g, w, = 40 g, AT, = 0.81 K and K, for benzene = 2.53 °C kg mol)
2.53 X 1000 x 3.24 (D.S.B. 2010)
Mz =~ 081 x 40 - -< Solution : AT. = biseae!
Mp Xw,
|
Let the molecular formula of sulphur = 5,
Atomic mass of sulphur = 32 K, x 1000
xw
Molecular mass = 32 x x 7 ar Tr
bX Wy
or g2x = 2560
K, = 2.53 °C kg mol",
or x = 7.91 = 8
: Molecular formula of sulphur = §,. W, = 99.0 g, Wp = 1.25 g

Example 40.
AT, = 80.31 — 80.10 = 0.21 °C
2.53x1000x1.25
What would be the molar mass of a compound if 6.21 g
of it dissolved tn 24.0 g of chloroform form a solution
M,; =
0.21x99.0
that has a boiling point of 68.04°C. The boiling point 152.1 g mol"!
of pure chloroform is 61.7°C and the boiling point Example 438.
elevation constant, K, for chloroform is 3.63°C/m. 18 g of glucose, C,H,,O0, (molar mass = 180 g molt)
(D.S.B. 2011) is dissolved in 1 kg of water in a sauce pan. At what
Solution : Elevation in boiling point, temperature will this solution boil?
AT, = 68.04 — 61.7 = 6.34°C (K, for water = 0.52 K kg molt, boiling point of pure
Mass of substance, w, = 6.21g,
water = 373.15 K).
Mass of chloroform, w, = 24.0g
K, = 3.63°C/m (D.S.B. 2013, Pb.S.B. 2016)
K, x 1000 x u
Solution : AT, = a
Wp, X LOOO w, xMp
K, XW, X 1000 Wp = 18 g,w, = 1000 g, M, = 180,
or M, =
AT, XW K, = 0.52 Km”
7 5.63
x 6.211000 0.52 x 1000 x 18
7 6.34x 24 ATs = ~“q000x180 = 9-002 IS
Boiling point of solution = 373.15 + 0.052 = 873.202 K.
 MODERN'S abe + OF CHEMISTRY-AXIl

- Answers to Practice Problems

51. 128.26 g mol?

52. 146.6 g mol? 61. A solution containing 8 g of a substance in 100 g of diethyl ether boils at 36.86°C,
53. 373.202 K whereas pure ether boils at 35.60°C. Determine molecular mass of the solute (For
54. 150 gmol? ether K, = 2.02 Kkg mol”). (A.L.S.B. 2008)
55. 96.64 g mol? 52. The boiling point of a solution containing 1.5 g of dichlorobenzene in 100 g of
benzene was higher by 0.268°C. Calculate the molar mass of dichlorobenzene
56. 263 g mol?
(K, for benzene = 2.62 degree/molal).
57. 1.28°C
53. 18 g of glucose, C,H,,O,, is dissolved in 1 kg of water in a sauce pan. At what
58. 53.06 g mol? temperature will the water boil. K, for water is 0.62 K kg mol™ and boiling point of
Hints & Solutions on page 66 water is 373.15 K. N.C.E.R.T) P.S.B. 2008)
54. The boiling point of water (100°C) becomes 100.52°C if 3 g of anon-volatile solute is
dissolved in 20 ml of it. Calculate the molar mass of the solute (K, for water = 0.62 Km”).
55. Asolution containing 0.613 g of naphthalene (molar mass = 128) 1n 60 g of CCl, gives
a boiling point elevation of 0.402°C, while a solution of 0.625 g of an unknown solute
gives a boiling point elevation of 0.650°C. Find the molar mass of the unknown solute.
56. 10 gram of a non-volatile solute when dissolved in 100 gram of benzene raises its
boiling point by 1°. What is the molecular mass of the solute? (K, for benzene = 2.63
K mol). (Pb.S.B. 2016, Meghalaya S.B. 2016)
57. What elevation in boiling point of alcohol is to be expected when 5 g of urea (molar
mass = 60) are dissolved in 75 g of it? The molal elevation constant for alcohol is
1.156°C.
58. A solution containing 12.6 g of a non-electrolyte substance in 175 g of water gave
boiling point elevation of 0.70 K. Calculate the molar mass of the substance.
(K, for water = 0.62 Kkg mol). (7. P.S.B. 2010, 2013, Pb.S_B. 2012)

DEPRESSION IN FREEZING POINT

We know that at the freezing point of a solvent, the solid and the liquid
Freezing point are in equilibrium. This is only possible if they have the same vapour pressure
Vapour
pressure depression Thus, the freezing point is the temperature at which the solid and the liquid
states of the substance have the same vapour pressure. It has been observed
that when a non-volatile solute is added to a solvent, the freezing point of the
solution is always lower than that of the pure solvent. This may be illustrated
Temperature (K) ——— graphically as shown in Fig. 18.
Fig. 18. Depression in freezing point. In the figure, the curve BC gives vapour pressure of the pure solvent. We
know that the addition of a non-volatile solute lowers the vapour pressure
and the curve DE gives the vapour pressure curve for the solution at different
temperatures. The curve AB corresponds to the vapour pressure of the solid
at different temperatures.
K, can be calculated from molar
enthalpy of fusion by the relation :
The temperature corresponding to the point B where the solid and liquid
solvent meet (i.e., solid and liquid states have the same vapour pressure)
Kk. 2 ee
MRT;
ae represents the freezing point temperature of pure solvent (T/). The temperature
A p,5H x 1000 corresponding to the point D where the solid solvent and liquid solution meet
where M is the molar mass of the (z.e., solid and liquid states have the same vapour pressure) represents the
solvent. Tis the freezing point and freezing point temperature of the solution (T,.
A,,,41 18 the molar enthalpy of fusion Since T, is less than T,/, this shows that the freezing temperature of
of the solvent. the solution is less than that of pure solvent and the depression in freezing
For example, latent heat of fusion of temperature (AT,) is given as:
ice is 6.0 kJ mol". Its molal depression
AT, = TP —T
constant can be calculated as :
It has been determined experimentally that the depression in freezing
K. = MRT,” point of a solution is proportional the molal concentration of the solution i.e.,
Ar Hx1000 AT, “am
A,,, H=6.0 x 10° J mol, T, = 273 K = m (19)
The units of K,are degree/molality i.e. Km, °C m-! or K kg mol where
_ 18x 8.314 x (273)* is the molal freezing point depression constant. It is also called mola
6.0 x 10° x 1000 eryoscopic constant.
~186Km. If m=1
AT, = K;
SOLUTIONS

Thus, molal freezing point depression constant is defined as the The units of Kare degree/
depression in freezing point for 1 molal solution i.e., a solution containing molality z.e., K m™ or °C m=? or
1 gram mole of solute dissolved in 1000 g of solvent.
K kg mol.
Depression in freezing point—a colligative property. From Eq. (18)
as Kk; constant,
AT, om
Thus, the depression in freezing point temperature is directly proportional
to the molal concentration of the solute (1.e., number of molecules) and therefore,
it 1s a colligative property.
The K, values of some common solvents are given in Table 4.
Table 4. Molal freezing point depression constant
(K,) for some solvents. KEY NOTE

Solvent Freezing Molal elevation constant (K,) and

point (K) molal freezing point depression
constant (K,) have characteristic
Water (H,0) values for different solvents. These
Ethanol (C,H.OH)
are expressed as degree/molal 1.e.,
Benzene (C,H,)
K/m. For example, for water a -
Chloroform (CHCI,)
1.86 degree/molal. It means that
Carbon tetrachloride (CC1,)
for 1 molal solution of a substance
Carbon disulphide (CS,)
Ether (C,H,,O) in water, the freezing point will be
Cyclohexane (C,H,,) lowered by 1.86°. Thus, stands
Acetic acid (CH,COOH) for 1 molal solution. Similarly for
water, K, = 0.62 K/m. However,
Determination of Molar Mass of Solute from Depression in Freezing sometimes and K, are also
Point Temperature expressed as mol per 100 ¢g ; z.e.,
The depression in freezing point termperature (AT) is usefulin determining K/mol per 100 g. The values in latter
case are 10 times the value expressed
the molar mass of the solute (M,). To calculate the molar mass of an unkown
as K/m. For example, K, for water
non-volatile compound, a known mass of it is dissolved in a known mass of a
= 0.52 K/m or 5.2 K/mol per 100 g.
solvent and depression in its freezing point (AT) is determined. For using the relations given in
Let wt. of the solute =wpg Eqs. 3.16 to 3.19, 1t should be used
Wt. of solvent =w, g as K/m only.
Molar mass of the solute = M,
wp, X 1000 e Anti-freeze solutions. Water
Molality of solution m = is used in radiators of vehicles.
Mp X Wa
If the vehicle is to be used in
By substituting the value of m in the relation AT,= K,m, we have
places where the temperature is
_ Ky Xwp x1000
AT, less than zero then water would
w, <Mp, freeze in the radiators. To avoid
M K; Wp x 1000 (20) this problem, certain substances
are used in radiators so that water
BY AT, XW, ~ does not freeze at low temperature
All other values being given, the molar mass of the solute can be calculated. in radiators. These are called
anti-freeze solutions. Ethylene
Solucug Numerical Probleme glycol in water is commonly used
in car radiators which lowers the
freezing point of water. Freezing
FORMULAE AND UNITS
point can be lowered to the desired
Depression in freezing point
extent by changing the amount of
AT, = hyxfn
ethylene glycol.
m= molality of solution and K- = molal depression in freezing point
se AT, K ¢ X Wp x 1000
e In cold countries, common salt
w, *Mp,
(NaCl) or calcium chloride (CaCl,)
where M, = molecular mass of solute are used to clear snow on the
w, = weight of solvent roads. This is because they depress
We weight of solute
the freezing point of water to such
and molecular mass of solute
an extent that water cannot freeze
M, = K ¢ x 1000
x wp to form ice. Hence, it melts off easily
at the prevailing temperature.
 MODERN'S abe + OF CHEMISTRY-AIl

—= = SOLVED =>
EXAMPLES
NV |) |= 3

L] Example 44. 4.90 x 3.26 x 1000

45 g of ethylene glycol (C,H,O,) is mixed with 600 g M, = 226 x 0.112
of water. Calculate 632 g mol?
(i) the freezing point depression Now, molecular mass of Se, = x x 78.8
(it) the freezing point of the solution 632 =x x 78.8
(K, for water = 1.86 K kg mi) 632
78.8
N.C.E.R.T. (H.P.S.B 2014, 2015, Pb.S.B. 2017)
“. Molecular formula of selenium = Se,.
Ky XW X 1000 Example 47.
Solution : (i) AT, =
w, X Mp 1.02 g of urea when dissolved in 98.5 g of certain
w, = 600 g,w, = 45g, K, = 1.86 K kg mol solvent decreases its freezing point by 0.211 K. 1.60 g
M, =2x 12+6x1+2-x 16 = 62 mol” of unknown compound when dissolved in 86.0 g of the
same solvent depresses the freezing point by 0.34 K.
AT, _ 1.86 x 45 x 1000
Calculate the molar mass of the unknown compound.
600 x 62
(Molar mass of urea = 60 g mol).
= 2.256 K
Solution ;: Let us first calculate K,.
= Freezing point depression = 2.25 K
AT, - Ky X wp X 1000
(ii) Freezing point of aqueous solution = 273.156 — 2.26
= 270.90 K
ws, X Mp
For urea solution,
Example 45. Wy = 1.02 g, wy = 98.6 g, AT,= 0.211 K
Addition of 0.648 g of a compound to 50 mL of
0.211 — K, *1.02 x 1000
benzene (density 0.879 g/mL) lowers the freezing point
98.5 x 60
from 5.51°C to 5.03°C. If K,for benzene is 5.12 K kg
mol —1, calculate the molar mass of the compound. K, _ 0.211 98.5
x 60 =~ 122 Km-"
(P0.S.B. 2014, 2016, Meghalaya S.B. 2015) 1.02* 1000
Now, molar mass of unknown compound can be calculated as:
Solution : The molar mass, M, is calculated as :
K, Xwp 1000
M. - Ky X Wp x 1000
AT, = ie tla Bettie
w, XM,
zs Ww a x AT
K, xX wp, x 1000
or Ms _ paar elie © each’
WwW, = 0.645 g, Ws x AT;
w, = (60 mL) x (0.879 g/mL) w, = 1.60 g, w, = 86.0 g, AT, = 0.34 K, K- —~ 1.22 Km?
= 43.95 g
M 1.22 X 1.60
x 1000
K- = 6.12 Kmr+,
_ 86.0
x 0.34
AT, = 5.61 -—6.038 = 0.48°C
= 66.76 g mol"
M 5.120.643 x 1000 Example 48.
Bo 43.95 x0.48 Ethylene glycol (molar mass = 62 g mol") is a common
_ 156.06. automobile antifreeze. Calculate the freezing point
Example 46. of a solution containing 12.4 g of this substance in
The molal freezing point depression constant of 100 g of water. Would it be advisable to keep this
benzene (C,H,) ts 4.90.K kg mol, Selenium exists as substance in car radiator during summer ?
a polymer of the type Se,. When 3.26 g of selenium is (K,for water = 1.86 Km and K, for water = 0.512 Km)
dissolved in 226 g of benzene, the observed freezing (CL.B.S.E. Sample Paper 2007)
point ts 0.112°C lower than for pure benzene. Deduce Solution :
the molecular formula of selenium. (Atomic mass of Moles of ethylene glycol
Se = 78.8 g mol) (A.I.S.B. 2002, D.S.B. 2002) 12.4
= — =(0.2 mol
Solution : The molar mass M,, is calculated as : 62
0.2
M, = K; X Wg x 1000 Molality = ioo * 1000 = 2m
wy x ATy Freezing point depression
AT, = 0.112", AT, = K, x m
w, = 226 g, = 186 x 2=3.72 K
Ww, = 3.26 g, Freezing point of aqueous solution
K, = 4.90 Km} = 273.16 — 3.72 = 269.43 K
Boiling point elevation of solution
SOLUTIONS

AT, = K, x m K, = 6.1K kg mol!

Co
= (62% 3 = 1.04K 5.11.0 x 1000
= TIT
Boiling point of solution ABs
20.0x 2.3
= 373.15 + 1.04 = 374.19 K Maz, = 110.87
Since boiling point is higher than room temperature in
For AB, compound
summer, it is advisable to keep this substance in the car
AT; = Lo K, wy 1:0 gw, = 20.0 ¢
radiator during summer.
5.1 x 1.0 x 1000
LJ Example 49. M,, 4 = —————— = 196.5
20.0 «1.3
Two elements A and B form compounds having Man, = 196.165
“4
molecular formula AB, and AB, When dissolved in iect a is the atomic mass of A and 5b is the atomic mass
20 g of benzene, 1 g of AB, lowers the freezing point of B, then
by 2.3 K, whereas 1.0 g of AB, lowers it by 1.3 K. Mag, See if2b — 110.87 A(t)
The molar depression constant for benzene ts 5.1 K Map, = @+ 4b = 196.15 salt)
kg mol, Calculate the atomic mass of A andB.
N.C.E.R.T, (A.1.S.B. 2004, Uttarakhand S.B. 2012) Subtracting eqn. (zi) from eqn. (z)
Solution : Let us first calculate molar masses of AB, —~2b = — 85.28
56 = 42.64
and AB,.
Subsite the value of 6 in egn (z)
For AB, compound
a+2x4264 = 110.87
K; XWz x 1000 a = 110.87 — 85.28 = 25.59
° Wy x AT, Atomic mass of A = 25.59
AT, = 2.3K, w, =10g,w, = 200g Atomic mass of B = 42.64.

69. A 10% solution (by mass) of sucrose in water has freezing point of 269.15 K.
Calculate the freezing point of 10% glucose in water, if freezing point of pure
water is 273.15 K.
Given : (Molar mass of sucrose = 342 g mol)
(Molar mass of glucose = 180 g mol) (A.LS.B. 2017, D.S_B. 2017)

. Calculate the mass of a compound (molar mass = 256 g mol") to be dissolved in

75 g of benzene to lower its freezing point by 0.48 K (K- = 6.12 K kg mol)
(D.S.B. 2014)
61. A solution containing 18 g of a non-volatile solute in 200g of H,O freezes at
272.07 K. Find the molecular mass of the solute. (K, - 1.86 K m})
(Meghalaya S.B. 2018)
62. 1.00 g of non-electrolyte solute dissolved in 60 g of benzene lowered the freezing
point of benzene by 0.40 K. Find the molar mass of the solute.
(K- for benzene = 6.12 K kg mol”). (Mizoram.S.B. 2013, A.L.S.B. 2013)
63. When 2.56 g of sulphur was dissolved in 100 g of CS,, the freezing point lowered
by 0.3883 K. Calculate the formula of sulphur (5,).
(K, for CS, = 3.83 K kg mol, Atomic mass of sulphur = 32 g mol")
(D.S.B. 2016) — Answers to Practice Problems
64. What mass of ethylene glycol (molar mass = 62.0 g mol) must be added to 59. 2656.55 K
5.60 kg of water to lower the freezing point of water from 0°C to —10.0°C ? 60. 18¢
(K, for water = 1.86 K kg mol). (A.LS.B. 2010) 61. 155 g mol +
65. Two aqueous solutions containing respectively 7.5 g urea (molar mass = 60) 62. 256 g mol?
and 42.75 g substance X in 100 g of water freeze at the same temperature. 63. S,
Calculate the molecular weight of X. 64. 1.833 kg
65. 342 g mol}
66. When 30.0 g of a non-volatile solute having the empirical formula CH,O are
66. C,H,O,
dissolved in 800 g of water, the solution freezes at —1.16°C. What is the molecular
formula of the solute ? (K, for water = 1.86 K m?). Hints & Solutions on page 66
 MODERN'S abe + OF CHEMISTRY
-AXIl

67. In winter, the normal temperature in a Himalayan’s valley was found to be

—10°C. Is a 30% by mass of aqueous solution of ethylene glycol (molar
mass = 62) suitable for car radiator 2(K, for water = 1.86 K/m) (Pd.S.6. 20171)
68. An aqueous solution freezes at 272.07 K, while pure water freezes at 275 K.
Determine the molality and boiling point of the solution.
(Given K, for water = 1.86 K/m, K, = 0.512 K/m).
(Ar. S.B. 2006, Mizoram S.B. 2015)
Answers to Practice Problems 69. A solution of urea in water has a boiling point 101.128°C. Calculate the freezing
67. It is suitable because water point of the same solution. Molal constant for water, K, and K, are 1.86°C and
freezes at — 12.86°C 0.612°C respectively. (Pb.S.B. 2006)
68. 0.5 m, 373.256 K
70. Ethylene glycol (molar mass = 62 g mol”) is used as an antifreeze for water
58. A Te
to be used in car radiators in cold places. How much ethylene glycol should
70. 333.3 ¢
be added to 1kg of water to prevent it from freezing at —10°C? [K, for water =
Hints & Solutions on page 66 1.86 K kg mol*] (Nagaland S.B. 2018)

OSMOSIS AND OSMOTIC PRESSURE

Osmotic pressure is another colligative property. Before
we discuss osmotic pressure let us try to understand osmosis
and its difference from diffusion.
Osmosis. The phenomenon of osmosis was studied for
the first time by Abbe Nollet in 1748. Let us consider an
aqueous solution of sugar placed in an inverted thistle funnel
Sugar having a semipermeable membrance (SPM) such as animal
solution
bladder or parchment paper, attached to its bottom. The
thistle funnel is lowered into a beaker containing water.
The membrane is such that it allows only the molecules
semipermeable of the solvent and not of the solute to pass through it. In
(Initial state) membrane (Final state}
other words, the membrane is permeable only to solvent
Fig. 14. Process of osmosis and measurement of osmotic molecules. Thus, there will be movement of water molecules
pressure in a thistle funnel. from pure solvent into the solution. As a result, water
passes into the thistle funnel and level of solution in the
thistle funnel rises gradually (Fig. 14). This process is called osmosis. Thus,
the phenomenon of the flow of solvent through a semipermeable
membrane from pure solvent to the solution is called osmosis.

Osmosis can also take place between the solutions of different concentrations.
In such cases, the solvent molecules move from the less concentrated
solution (low solute concentration) to a more concentrated solution
(higher solute concentration) through a semipermeable membrane.
Difference between osmosis and diffusion. Although both diffusion
and osmosis involve the movement of the molecules, still they differ in the
following respects:

KEY NOTE
Osmosis 18 very common pheno- 1. The process of osmosis takes place No semi-permeable membrane is
menon which we observe in nature through a semi-permeable membrane. needed for the diffusion process.
or at home. For example, raw =. The osmosis involves the movement of In diffusion, both the solute and the
mangoes shrivel when pickled in the solvent molecules only. solvent molecules can move.
brine (salt water), wilted flowers
a In osmosis, molecules of solvent move from In diffusion, the molecules move from
revive when placed in fresh water,
a region of lower concentration of solution a region of higher concentration into
blood cells collapse when suspended
into a region of higher concentration. the region of lower concentration.
in saline water. If we look into
these processes carefully, we notice » Osmosis is limited to solutions only. Diffusion is common in gases as well
one thing common in all. All these as in liquids.
substances are bound by membranes . Osmosis can be stopped or reversed by It cannot be stopped or reversed.
which occur in nature in plants and applying additional pressure on the
animals. higher concentration side.
SOLUTIONS

Semipermeable membrane. We have pointed out that a semipermeable

membrane is one which allows only the solvent and not the solute to pass
through it. Nature has provided many such membranes both in plants and
animals for specific functions e.g., pig’s bladder or parchment. These can also be
synthetic such as cellophane membrane, etc. But these are rather not particularly
useful in the laboratory due to their imperfect nature. Consequently, they can
be even artificially prepared. One such membrane is the film of gelatinous
precipitates of cupric ferrocyanide, Cu,[Fe(CN),]. These membranes appear to (a) Normal size of egg
be continuous sheets or films, yet they contain a network of submicroscopic
holes or pores. Small solvent molecules like water can pass through these holes
but bigger molecules like solute cannot pass through these holes. These types
of membranes are called semipermeable membranes (SPM).
Demonstration of osmosis
Take two eggs. Remove the outer hard shell of the eggs by dissolving in
dilute HCl. Place one egg in distilled water [Fig. 15 (a@)] and the other egg
in a saturated sodium chloride solution [Fig. 15 (6)]. After a few minutes, it (b) Egg swells in water
will be observed that the egg placed in water swells [Fig. 15 (56)] whereas the
other placed in salt solution shrinks [Fig. 15 (c)]. This curious observation Water enters into the
can be explained on the basis of process of osmosis. The skin of the egg acts egg because of higher
as a semipermeable membrane. In the first case, the concentration of water concentration of water
outside the egg.
(solvent) is higher outside the egg. Therefore, pure water enters into egg due
to osmosis and the egg swells. On the other hand, the water comes out of egg
material when placed in a saturated solution of sodium chloride due to higher
concentration of water (solvent) inside the egg. Therefore, the egg shrinks.
NaCl
Osmotic pressure
Solution
We have studied that when an aqueous solution of sugar is placed in an
inverted thistle funnel and separated from pure water with the help of a semi-
permeable membrane, there will be osmosis of water molecules into the solution
of sugar. As a result, the level of solution in the stem of the funnel will rise (c) Egg shrinks in salt solution
and an additional hydrostatic pressure will be exerted on the solution. This Water comes out of the egg because
hydrostatic pressure will tend to oppose the inflow of solvent into the funnel. of higher concentration of water
The level of solution will continue rising till a particular height. At this stage, inside the egg
equilibrium is reached and the hydrostatic pressure of the liquid exactly balances
the tendency of the liquid to pass inward through the semipermeable membrane. Fig. 15. Demonstration of osmosis.
Thus, there will be no more osmosis taking place.
The equilibrium hydrostatic pressure on the solution due to osmosis
ofthe pure solvent into it is a measure of osmotic pressure.
Alternatively, to understand the concept of osmotic pressure, m = Pressure required
to stop osmosis
consider an apparatus shown in Fig. 16. It consists of two vessels
connected by a semipermeable membrane. These two compartments
are fitted with water-tight frictionless pistons. Let us take solution
semipermeable
in one compartment and pure solvent in the other compartment. membrane (SPM
Due to osmosis, there will be flow of solvent into the solution
compartment through the semipermeable membrane. As a result,
the piston on the solution side will tend to move outwards. To
stop this movement of piston outwards, we have to apply pressure
on the solution side. This pressure just sufficient to stop osmosis
will be equal to the osmotic pressure. Thus, osmotic pressure
may be defined as
the minimum excess pressure which must be applied
fo a solution to prevent the passage of solvent into it
through a semipermeable membrane.
Thus, osmotic pressure is the pressure applied to the solution Fig. 16. Demonstration of concept of osmotic
to prevent osmosis. It is generally denoted by 7. pressures.
7 2/48 MODERN'S abe + OF CHEMISTRY
-AXIl

Osmotic pressure — a Colligative Property

Van’t Hoff (1887) observed that for dilute solutions, the osmotic pressure
(1) is given as:
mt =cRT
where c is the molar concentration of the solution (molarity), Tis the temperature
and R is the gas constant.
For a solution, at a given temperature, both R and T are constant
“. Tac
Since osmotic pressure depends upon the molar concentration of solution,
therefore, it ts a colligative property.
Experimental Measurement of Osmotic Pressure
Berkeley and Hartley’s Method. The principle of
Pressure Gauge
oO a = this method is to apply external pressure on the solution
sS Water Rasorvor 1h) by putting weight on the piston just sufficient to prevent
o the osmosis of the solvent into it. The apparatus consists
aS)
oo of a porous pot containing copper ferrocyanide deposited on
a]
O its walls which acts as a semipermeable membrane. It is
fitted into a bronze cylinder to which is fitted a piston and
a pressure gauge (Fig. 17). The porous pot is fitted with a
water reservoir on one side and a capillary indicator on the
other side. Water is put in the porous cell while the bronze
cylinder is filled with the solution, the osmotic pressure of
which is to be measured. Water placed in the porous pot
tends to pass into the solution through the semipermeable
Porous pot with Gun metal vessel
semipermeable membrane membrane with the result that the level in the capillary
indicator moves downwards. External pressure is now
Fig. 17. Berkely and Hartley apparatus for measuring applied on the piston so that the water level in the capillary
ee indicator tube remains constant. This pressure which is
equal to the osmotic pressure is read from the pressure gauge.

Determination of Molar Mass from Osmotic Pressure

According to Van’t Hoff equation,
m = cRT

But c= .

where nis the number of moles of solute dissolved in V litre of the solution.
a _ v RT

or TV =nRT ..A(21)
This equation is called Van’t Hoff equation for dilute solutions.

The number of moles of solute n may be givn as a Here wy, is the

B
weight of the solute and M, is its molar mass.
Substituting the value of n in the above expression,
wp RT wpRT

VM, 2B Vn
t= M.-=

Thus, the molar mass of the solute, Mj, can be calculated.

Conditions for Getting Accurate Value of Molar Mass
(i) The solute must be non-volatile.
(it) The solution must be dilute, i.e., concentration of the solution in the
solution should not be more than 5%.
(iit) The solute should not undergo either dissociation or association in
the solution.
SOLUTIONS

Biological significance of osmosis Water moves from low conc.

Osmosis plays a significant role in the absorption of water by the plants ai it) toae cone.— =)
which is taken in by the roots. The absorption of water by plants from the
soil through the roots and its movement to different parts of plants is due to
the process of osmosis. Plants and animal bodies are composed of very large
number of cells. The cells contain a fluid (called cell sap) and the walls of the
cells are made up of living cytoplasmic membrane which acts as a semipermeable
membrane.
If the cell comes in contact with water or some dilute solution whose (a) Swelling or rapture Pa
osmotic pressure is less than that of cell sap present in the cell, there will be cell wall Hemolysis.
a tendency of water to enter into the cell through the cell wall. This causes
swelling or rupture of the cell, a process known as hemolysis. On the other
hand, if the cell comes in contact with a solution of higher osmotic pressure
than that of cell sap present in the cell, the water from the cell will go out
resulting shrinkage of the cell. This shrinking of the cells is called plasmolysis.
The membranes of plants and animal bodies allow water to pass through
but block the passage of the enzymes and proteins that have been synthesised
in the cell. The cell saps have generally higher osmotic pressure and, therefore, ‘(b) Shrinkage of cell wall
when the cells come in contact with water, there is tendency of water to enter Plasmolysis.
into the cell due to osmosis. Therefore, the osmosis process helps the plants
to absorb soil water and push it up to the stem and other parts of the plants
and trees. Plants which grow in marshy lands have more concentrated saps Learmiug Plus
which develop an osmotic pressure of the order of twenty five atmospheres.
Thus, the plant may absorb excess of water from the soil which might cause The osmotic pressure method
bursting of root hair. Ultimately the plant decays. The addition of fertilizer is widely used for measuring the
may raise the osmotic pressure of the soil water. Consequently, the cell sap molecular masses of proteins,
is not in a position to absorb excessive water and the decay of the plant is polymers and other macro-
thus, checked. molecules. It is regarded as one
The use of salt and sugar as preservatives in pickles and jams has its of the most suitable methods. The
other methods such as depression
basis in preventing growth of fungi and bacteria by osmosis.
in freezing point or elevation
Isotonic solutions
in boiling point cannot be used
We know that different solutions have different vapour pressures.
because of the following reasons:
Consequently their osmotic pressures must also be different. When two such
(1) The changes (AT, or AT,)
solutions are separated by a semipermeable membrane, the solvent molecules observed in other amethode based
flow from the solution of lower osmotic pressure towards solution of higher on colligative properties are very
osmotic pressure. This continues till both the solutions attain the same osmotic small (e.g., for substances having
pressure. At this stage, there is no further osmosis. molar mass of 10° g mol-}, the AT
The solutions having same osmotic pressure at the same temperature or AT, are only 0.0001K). These
are called isotonic solutions or isosmotic solutions. cannot be easily measured. On the
From the equation, m = cRT, it is clear that if two solutions have same other hand, osmotic pressure of
concentrations, they must have same osmotic pressure at the same temperature. the order of 10-° atm can be easily
Thus, solutions of equimolar concentrations at the same temperature measured in terms of mm of Hg.
have same osmotic pressure, i.e., are isotonic. (it) Elevation in boiling point
method for these biological
Hypertonic and hypotonie solutions
molecules such as proteins is not
If a solution has more osmotic pressure than some other solution, suitable because these molecules are
it is called hypertonic. For example, 0.1 M urea solution exerts higher not stable at higher temperatures.
osmotic pressure than 0.05 M sucrose solution. Hence, 0.1 M urea solution is The osmotic pressure method has
hypertonic to 0.05 M sucrose solution. the advantage because it can be
On the other hand, a solution having less osmotic pressure than the measured at room temperature.
other solution is called hypotonic. For example, 0.05 M sucrose solution LU) Thus, osmotic pressure
exerts lower osmotic pressure than 0.1 M urea solution. Therefore, 0.05 M method is used for measuring
sucrose solution is hypotonic to 0.1 M urea solution. molecular masses of proteins,
Thus, a hypertonic solution will be more concentrated with respect polymers and other macro-
to other solution and a hypotonic solution will be less concentrated molecules because
with respect to other solution. (1) it can be measured around
room temperature
It is quite interesting to note that a 0.91% (mass/volume) solution of (it) osmotic pressure values are
sodium chloride (known as saline water) is isotonic with fluids inside human larger and measurable even
red blood cells (RBC). In this solution, the corpuscles neither swell nor shrink. for dilute solutions.
Therefore, the medicines are mixed with saline water before being injected into (iit) Molarity of the solution is used
the veins. Therefore, normal saline water is quite safe to inject intravenously. instead of molality.
aso MODERN'S abe + OF CHEMISTRY-AXIl

However, the solutions having concentration more or less than 0.91% (mass/
R U Curious....
volume) are not safe as explained below:
= Salt water fish die when they are (4) A pure sodium chloride solution with salt concentration less than
suddenly transferred to a fresh 0.91% (mass/volume) is said to be hypotonic solution. When red blood cells
water aquarium! are placed in this solution, water flows into the cells and they swell or burst.
Osmosis tries to equalise the (iz) A pure sodium chloride solution with salt concentration more than
concentration of water in the 0.91% (mass/volume) is said to be hypertonic solution. When red blood cells
solution; bothin the cells of the fish are placed in this solution, water flows out of the cells and they shrink or
and the surrounding water. Water collapse due to loss of water by osmosis.
from aquarium passes through the People taking a lot of salt or salty food experience water retension in tissue
cell membranes causing them to
cells and intercellular spaces because of osmosis. The swelling or puffiness is
expand and get ruptured.
called edema. When red blood cells are placed in this solution, water comes
out of the cells and they shrink.
Osmosis can also explain some other commonly occurring processes :
(4) Carrots which have become limp because of water loss into the atmosphere
R U Curious....
can be placed into the water which makes them firm again. Water will move
= A person suffering from high into them through osmosis.
blood pressure is advised to take (iz) A raw mango placed in concentrated salt solution (brine) loses water
minimum quantity of common salt! due to osmosis and shrivel into pickle.
> The osmotic pressure increases (iit) Wilted flowers revive when placed in fresh water due to osmosis.
with the amount of solute. Since (iv) The preservation of meat by salting and fruits by adding sugar protects
the body fluid contains Na* and
against bacterial action. A bacterium on salted meat or candid fruit loses water
Cl ions and if we take more
due to osmosis, shrivels and ultimately dies.
salt, the concentration of these
ions will increase leading to high Reverse osmosis and desalination of sea water. The process of osmosis
osmotic pressure. The high osmotic can be reversed if a pressure larger than the osmotic pressure is applied on the
pressure may cause rupture of solution side. As a result, the solvent starts moving from solution towards the
the cells. Therefore, the patients pure solvent through the semipermeable membrane. This process of movement
suffering from high blood pressure of solvent through a semipermeable membrane from the solution to the pure
are advised to take less of common solvent by applying excess pressure on solution side is called reverse osmosis.
salt. A variety of polymer membranes are available these days for desalination of
sea water. The pressure needed for reverse osmosis are generally quite high and
workable porous membrane is a film of cellulose acetate placed over a suitable
support. Cellulose acetate membrane is permeable to water but impermeable
to impurities and other ions present in sea water. These days many countries
meet their water requirement from desalination plants.

Desalination of sea water. The reverse osmosis process can be used for desalination of sea water for
getting drinking water. A schematic set up for the process is shown in Fig. 18. If no pressure were applied to
the salt water solution, osmosis would transfer water into the solution as shown in Fig. 18 (a). When a pressure
greater than osmotic pressure is applied on the salt water side of a semipermeable membrane the pure water
flows from the salt water side to pure water side through the semipermeable membrane. As a result, water is
squeezed out of sea water as shown in Fig. 18 (0). Thus, the pure water is obtained which does not contain
dissolved undesirable salts.
Pressure>nt

semipermeable Semipermeable
membrane (SPM) membrane (SPM)

tN)

Water
outlet

‘Water moves to
Reverse osmosis
(b)
Fig. 18. Desalination of water (a) Osmosis and (5) Reverse osmosis.
SOLUTIONS

Colligative Properties of Solutions Selucug Namertcalt Probleme

Containing Mixture of Solutes
Since colligative properties depend on the FORMULAE AND UNITS
total number of particles, therefore, these Van’t Hoff equation
will depend on the number of molecules from = Ch
different solutes present. These become : nRT
| Pe
e Relative lowering in vapour pressure ey
Ap — =m;xM, Osmotic pressure (in atmospheres)
Dp 1000 number of moles,
where m, is the molality of each solute volume (in litres)
and M. is its molar mass. concentration in moles per unit volume
absolute temperature,
e Elevation in boiling point
= 0.082 L atm mol? K-1
Alpe be
and molecular mass of solute
e Depression in freezing point = WpkT
AT, = K, =m, BB VsX<er
e Osmotic pressure Wp, = Weight of solute,
© ieee M, molecular mass of solute
where c. is the molarity of each solute. For isotonic solutions, osmotic pressures are equal. Since
tm = eRT so at the same temperature, concentration are equal
for isotonic solutions.

= — | SOLVED EXAMPLES & =

LU) Example 50. T = 300KandR = 0.083 L bar K-! mol
200 cm? of an aqueous solution of a protein contains 1.71 x 0.083 x 300
tT = = 0.249 bar.
1.26 g of the protein. The osmotic pressure of such 342 x 0.5
a solution at 3800 K is found to be 2.57 x 10°
bar. Calculate the molar mass of the protein. LU) EKxample 52.
(R = 0.083 L bar molt -1) N.C.E.R.T, Calculate the osmotic pressure of a solution obtained
(Hr. S.B. 2012, Pb.S.B. 2012, 2014, H.P.S.B. 2015) by mixing 100 mL of 3.4 percent solution of urea
(mol. mass = 60) and 100 mL of 1.6 percent solution
Solution : According to Van’t Hoff equation,
of cane sugar (mol. mass = 342) at 293 K.
7 fh _ WpRT
m=cRT = vy kr = M,V (R = 0.088 L bar K+ mol-))
Solution : After mixing the volume of the solution =
200 mL.
W_RT
(4) Osmotic pressure of urea
M, ~
w, = 3.4 g, V = 200 mL = 0.2 L, T = 203 K,
V = 200 em® = 0.20 L, iw, = 426 oy T = 300 K
M, = 60, R = 0.083 L bar mol? K+
R = 0.083 L bar K! mol, m1 = 2.67 x 10° bar
WpRT

M BRB;
1.26 g x0.083 L bar K7!mol™! x 300 K ~ MpV
2.57% 10-* bar
x0.20 L
3.4 x 0.083 x 293
61039 g mol. or ~ = 60 x 02 = 6.89 bar

LU) Example 51.

(71) Osmotic pressure of cane sugar
If 1.71 g of sugar (molar mass = 342) are dissolved W, = 1.6 g, V = 200 mL = 0.2 L, T = 298 K, M, = 342,
in 500 cm? of a solution at 300 K, what will be its R = 0.083 L bar moltK"?
osmotic pressure? WpRT
(R = 0.083 L bar K+ mol) (Mizoram S.B. 2014) M,V
Solution : According to Van’t Hoff equation, 1.6 x 0.083 x 293
or tc = — 0.57 bar
n WRT 342 x 0.2
mt = chRT = Vv RT = M,V
Since the dilute solution behave like ideal gases, the total
osmotic pressure will be equal to the sum of the partial osmotic
500 pressure (similar to Dalton’s law of partial pressure of gases).
m = 6.89 + 0.57 = 7.46 bar.
as MODERN'S abe + OF CHEMISTRY
-AIl

N —— nRT _— 6.8
nen = Say? "997.45
This problem can be solved by first calculating the total
number of moles of urea and sugar because the colligative = 100¢ = 100 ml = 0.1L,
properties are independent of the nature of the solute.
II 0.082 L atm mol K-}
4
Moles of urea = 0.0667, =<
Hm = 908 K

Moles of sucrose 16
342
= 0.00472 al
6.8 x 0.082 x 298
321.45 x 0.1
Total moles 0.0667 + 0.0047 5.17 atm.
0.0614
Vv 200 mL = 02 Lb
LJ EKxample 55.
TU A solution prepared by dissolving 8.95 mg of a gene
fragment in 35.0 mL of water has an osmotic pressure
of 0.835 torr at 25°C. Assuming the gene fragment ts
a non-electrolyte, determine its molar mass.
LU) Example 53. (D.S.B. 2011, ALLS.B. 2011)
36 g of glucose dissolved per litre of the solution Solution : Mass of gene fragment = 8.95 mg
has an osmotic pressure of 4.98 bar at 300 K. If the = 8.95 x 10°¢
osmotic pressure of the solution ts 1.52 bar at the same Volume of water = 35.0 mL = 36.0 x 10° L
temperature, what would be its concentration ? Osmotic pressure, 7 = 0.335 torr = 0.335/760 atm
N.C.E.R.T. Temperature = 256°C = 273 + 26 = 298 K
Solution : According to Van’t Hoff equation,
m =cRT a =

M,xV
36
Cc, = 180 M, t, = 4.98 bar
0.335 8.95 x 107 x 0.0821 x 298
and ey = T, = 1.62 bar 760 Mz x 35.0 x 10°
4.98 bar = © RT _)
180 8.95 x 10°? x 0.0821 x 298 x 760
M, A OrAGAnS!”
ROE eS
1.62 bar =c,RT =F 0.335 x 35.0 x 10

Dividing eqn. (iz) by eqn. (z), = 14193.3 g mol? or

1.42 x 10* g mol".
Co
—=— x« 180 —~
Lb
36 4.98
Example 56.
c oes x 36 0.061 M A solution containing 15 g urea (molar mass = 60
4.98 180
g mol) per litre of solution in water has the same
Concentration of second solution = 0.061 M. osmotic pressure (isotonic) as a solution of glucose
Example 54. (molar mass = 180 g mol-!) in water. Calculate the
A solution of an organic compound was prepared by mass of glucose present in one litre of tts solution.
dissolving 6.8 gin 100g of water. Calculate the osmotic (A.LS.B. 2014, Kerala S.B. 2018)
pressure of this solution at 298 K when boiling point Solution : For isotonic solutions,
of solution is 100.11°C. Given K, for water = 0.52 T (urea) = m (glucose)
Km and R = 0.082 litre atm K+ mol. n(urea) . 2RE_15 RT
(Ar.S.B. 2005) Vv 60 1
Solution : Molecular mass can be calculated from boiling
point data as : 1 (glucose) = nRT_w , RT
K, X wp, X 1000 & — “vy 180° 1
M, B =
AT, XW,
w, = 6.8 g, w, = 100 g, K, = 100.11 — 100 = 0.11 Now DY er iy *oj
60 180
K, = 0.62 Km?
“ 15x180
BT 0.11 x 100
60 al
= 321.465
SOLUTIONS 253)

=Dira
Drv tic ea
71. A solution of sucrose (molar mass = 342 g mol”) is prepared by dissolving
68.4 g of it per litre of solution. What is the osmotic pressure at 300 K ?
72. Osmotic pressure of a solution containing 3.5g of dissolved protein per 50cc of
a solution is 25 mm (Hg) at 37°C. Calculate the molar mass of protein.
(Mantpur S.B. 2014)
73. The osmotic pressure of a solution containing 9.2 g of a substance (moar mass =
176) in 302 ml of solution was found to be 4.1 atomsphere at 15.65°C. Calculate
the value of solution constant.
74, Calculate the osmotic pressure of a solution obtained by mixing 100 ml of 1.5%
solution of urea (molar mass = 60) and 100 ml of 3.42% of cane sugar (molar
mass = 342) at 20°C. (R = 0.82 litre atm K+ mol"*).
75. Three grams of non-volatile solute when dissolved in a litre of water shows an
osmotic pressure of 2 bar at 300 K. Calculate the molar mass of the solute.
(R = 0.083 L bar K+ mol-*).
76. Calculate the osmotic pressure of a solution containing 10 gram each of glucose
(C,H,,0,) and sucrose (C,,H,.O,,) in 1000 cm? of the solution at 25°C. (R =
0.083 L bar K+ mol-*)
77. A solution containing 10.2 g of glycerine per litre is found to be isotonic with
a 2% solution of glucose. Calculate the molar mass of glycerine (molar mass of
glucose = 180). (Mizoram 8.5. 2016)
78. A 5% solution of cane sugar (molar mass = 342) is isotonic with 0.877% solution
of urea. Calculate the molar mass of urea.
(Uttarakhand 8.5. 2014, Nagaland 8.B. 2016)
79. What is the concentration of solution of sucrose (molar mass = 342) which is
isotonic with a solution containing 6 g of urea per litre ? —= Answers to Practice Problems
80. Osmotic pressure of a solution containing 7 g of a protein per 100 cm® of solution A a? ait
is 3.3 x 10° bar at 37°C. Calculate the molar mass of protein. gee
81. A solution of an organic compound is prepared by dissolving 68.4 gin 1000 g of oe Pee,
water. Calculate the molecular mass of the compound and osmotic pressure of 73. 0.0821 litre atm/mol/degree
the solution at 293 K when elevation in boiling point is 0.104 and K, for water 74, 4.20 atm.
is 0.62 Knrt. (AHr.S.B. 2005) 75. 37.36 g molt
82. A solution of an organic compound is prepared by dissolving 34.2 g in 500 g of 76. 2.10 bar
water. Calculate the molecular mass of the compound and freezing point of the 77.918
solution. Given that K, for water = 0.52 K m“”, b.pt. of solution = 100.14°C, toe ay
for water = 1.87 Km}. (Ar.S.B. 2005 78. 69.99 g mol
83. The average osmotic pressure of human blood is 7.7 atm at 40°C. 79. 34.2 gL”
(a) What would be the total concentration of various solutes in the blood ? 80. 545679
(6) Assuming the concentration to be essentially the same as the molality, 81. 342, 4.80 atm
calculate the freezing point of blood (K. for water = 1.86°C m°). 82. 342, — 0.374°C
84, The osmotic pressure of blood is 8.21 atm at 37°C. How much glucose should 82 . 0.30 mol Lt, — 0.658 °C
be used per litre for an intravenous injection that is isotonic with blood ?
: -. 84, 58.06 g
85. 600 mL of aqueous solution containing 2.5 g of a protein shows an osmotic pressure 85. 31198 =
of 25 mm Hg at 27°C. Determine the relative molecular mass of protein. ; si cama
(Tripura S.B. 2016) Hints & Solutions on page 66

Accelerate Your Potential

PROBLEM S (for JEE Advance)

i) How many grams of sucrose (molecular AT = K,- m.

mass 342) should be dissolved in 100 g water in order Freezing point of solution, T; = 0 — AT,
to produce a solution having difference between the or T, = K, x m1 _..(it)
boiling point and freezing point equal to 105°? Subtracting eq. (ii) from eq. (2)
| (K, == 0.512 Km",
-1
K, == 1.86 Km)
-1
T,-T, = 100 +K, x m-(0-K-xm)
Cy T
ee
T Sane 0° ay 1065 = 100+ K,xm+ K; x m
Rese age!ea eee ee Sen
105 = | 100+ 0.612 x m+1.86xm
eae
Boiling point of solution,T,= 100 + AT, 2.572 m =6
or T, = 100+K,m _...i) or m = —2_ = 2.108
2.372
asa MODERN'S abe + OF CHEMISTRY

Xp x L000
-AIl

Now nae Weucrose X L000 or = ee

M4
M,sucrose x Weolvent
_ 2:0112X1000
_91456
2108 — Wsucrose * 1000 78
342 x 100 AT = K-x 11
Bete 2.108 x 342 x 100 ~ 72.09 g
aes! oe
AT 0.73 _ Km
1000 sie Ke = Tn 7 0.1436 ~ 98
Problem If boiling points of an aqueous
solution Problem $35 Calculate the amount of ice that will
containing a non-volatile solute is 100.15°C. What is separate out on cooling a solution containing 50 g of
its freezing point? Given latent heat of fusion and ethylene glycol in 200 g of water to -9.3°C. (K-for water
vaporisation of water are 80 cal g‘ and 540 cal g1 = 1.86 K m")
respectively. Let us calculate the amount of water present
For a given aqueous solution in the solution.
oe Kx m ala)
Mz x Wy
de ee ...{tt)

K, =
RT?
, and patter)
ie os ”
* pel
fA K, x 1000 x wp,
f Wi,x AT;
1000 /, AT, = 0-(-9.3) =9.3°

= 4
RT, (EU
| We 1.86 x 1000 x 50 = 161.29 g
K, 1000 /, ae
Dividing eq. (iii) by eq. (iv) 62x 9.3
Amount of ice separated from 200 g of water
Ky T, xb,
i = 200 — 161.29 = 38.71 g.
K, Ty Xe
iP At 10°C, the osmotic pressure of urea
AT,
; ry
* to
|
solution is 500 mm Hg. The solution is diluted and the
temperature is raised to 25°C, when the osmotic pressure is
AT, T; x lp found to be 105.3 mm Hg. Calculate the extent of dilution.
T, = 0 + 273 = 273 K, For initial solution,
T, = 100 + 273 = 373 K 500
x
—— atm, T = 273 =
+ 10 = 2838K
l, = 80 cal g*, 1,= 640 cal g* 760
Let volume of solution is V,
AT, = 100.15 — 100 = 0.15
AT; 273x273 x540 ro ORT
V
0.15 § 373x373x80
BUUE es UE eR ons i)
273 x 273 x 540 760 Vi
or AT ==
oaeaeae Uo = 0.558
f ~ 373x373x80 After dilution, let the volume becomes V, and temperature
, = 0-0.642 = -0. 542°C. is raised to 26°C.
{ Avery small amount of non-volatile SOUUS 105.3 ™ = “ atm, T = 273 + 26 = 298 K
Problemdoes not dissociate) is dissolved in 56.8 cm? of the
benzene (density 0.889 g cm“). At room temperature,
vapour pressure of this solution is 98.88 mm Hg while 105.3 _ 4 yRx 208 ai)
760 V;
that of benzene is 100 mm Hg. Find the molality of this Dividing eq. (z) by eq. (zz)
solution. If the freezing temperature of this solution is 500 _ Ve . 283
0.73 degree lower than that of benzene, what is the value
105.3 VV, 298
of molal freezing point depression constant of benzene ?
V> 500 x 298
[ Solution | ber very dilute solutions, or + = —— =6
Vi 105.3 x 283
= X,(%,= mole fraction of substance) ' The solution was diluted 5 times.
pe
100
- 98.88 155 Hundred grams of a 5 m urea solution
100 eye are cooled to — 6°C. What amount of urea will separate
7 te Ae el2
out ? (K = 1.86 K nr’).
N itp = np : :
ow, a (for dilute solution) Molality of solution at — 6°C
Rath Ry
i ee K-m
_em—BxM
itp
% VL 9 LE) :
| AT, 6
or oo — = aaa = 3.23 molkg™
* 1000 -
Molality, ————— hte)
Dividing equation (z) by eq. (iz) 5 m solution of urea means that 5 moles or 65 x 60 g
of urea are present in 1000 g of solvent or
peice (1000 + 5 x 60) g of solution, so that
m 1000
SOLUTIONS

(1000 + 300) g of solution contain urea = 300 g

us calculate the amount of urea to make the molality
; 300 =
100 g of solution contain urea = ——— x 100 gars ae
1300 1000 g of water contain urea = 60 x 3.23 g
= 23.08 g 60 x 3.23 x 76.92
Mass of water in the solution = 100 — 23.08 76.92 g of water contain urea = 1000
= 76.92 g - 14.91¢g
When urea separates out, mass of water does not
change. At —6°C, the molality is 3.23 mol kg. Let Mass of urea separated = 23.08 — 14.91
-8.17 g

ABNORMAL MOLAR MASSES : ELECTROLYTIC SOLUTIONS

We have discussed in the previous sections that the colligative properties
help us to calculate the molar masses of solutes. But in some cases, the molar
masses determined by these methods do not agree with the expected or theoretical
values. The accurate values of molar masses can be obtained only if the following
two conditions are satisfied.
1. The solutions should be dilute
The solutions used for measuring colligative properties must not be too
concentrated. In the concentrated solutions, the particles begin to interact with
each other as well as with the solvent. As a result, the vapour pressure and
therefore, other colligative properties depend upon the nature of the solute and Colligative property of an
not just on the number of solute particles. electrolyte solution is always greater
than that of anon-electrolyte solution
2. The solute must not dissociate or associate in solution
of the same molar concentration
The equations derived for measuring the colligative properties are for because of the dissociation of the
non-electrolyte solutes which do not undergo any dissociation or association in electrolyte.
the solution. However, discrepancies in determination of molar mass arise when
the solutes dissociate or associate on dissolving in a solvent. This is because due
to the association or the dissociation of the solute molecules in the solution, the
number of molecules undergo a change. Therefore, abnormal molar masses
are obtained as discussed below:
1. Association of solute particles
In certain solvents, generally non-polar, the solute molecules undergo
association i.e., two, three or even more molecules exist in combination with
each other to form bigger molecules. For example, suppose n simple molecules
combine to form an associated molecule as :
nA == a
n single molecules one molecule
Therefore, the total number of molecules in solution become less than
the number of molecules of the substance added and, therefore, colligative
properties will be lower. Since the colligative properties are inversely
proportional to the molar mass of the solute, the molar masses tn such cases will
be greater than the theoretical values. For example, in benzene solvent, both
ethanoic acid (acetic acid) and benzoic acid exist as dimers as:
2CH,COOH = = (CH,COOH),
Ethanoic acid Dimer
2C,H.COOH —— (C,H-COOH),
Benzoic acid Dimer
The molar masses of ethanoic acid and benzoic acid have been found to be
nearly 120 and 244 which are about double than their normal values of 60 and
122 respectively. The association of solute molecules in a solution is generally
due to the hydrogen bonding between these molecules. For example, benzoic acid
and ethanoic acid (acetic acid) exist as dimers due to the formation of hydrogen
bonds as shown ahead:
ase. MODERN'S abe + OF CHEMISTRY-AXIl

CH,—C
/ onl
C—CH, C,H,—C
ON eo
Ethanoic acid Benzoic acid

2. Dissociation of solute molecules

Molecules of electrolytes (acids, bases and salts) dissociate or ionise in a
solvent to give two or more particles. For example, AB dissociates to give double
number of particles as
AB == A*t+B-
Consequently, the total number of particles increases in solution and,
therefore, the colligative properties of such solutions will be large. Since colligative
properties are inversely proportional to molar mass, the observed molar mass
will be less than the theoretical value. For example, KC] dissociates to give Kt
and CI ions.
KCl =—— Kr+cCh
This means that if we dissolve 1 mol of KCl (74.5 g) in water, we expect
1 mol of Kt and 1 mol of Cl ions to be produced in the solution. Therefore, there
would be 2 mol of particles in the solution instead of 1 mol. Consequently, the
colligative properties would also be about double than expected. For example, if
REMEMBER we ignore interionic attractions, 1 mol of KCl in 1 kg of water would be expected
to increase the boiling point by 2 x 0.52 K (K, = 0.52 Km™) = 1.04 K. Obviously,
The normal value of colligative
the molar mass of the salt must be about half of its normal value 1.e., 37.25.
property is the theoretically
calculated value assuming no Van’t Hoff Factor
association or dissociation and In 1886, Van’t Hoff introduced a factor called Van’t Hoff factor, ‘”’ to express the
abnormal value of colligative extent of association or dissociation of solutes in solution. Van’t Hoff factor is defined as
property is the experimentally the ratio of the normal molar mass to the observed molar mass
determined value. (or abnormal molar mass) of the solute, i.e.,
For solutes which donot undergo
association or dissociation, Normal molar mass
<= ar
eeere

p<) Observed (or abnormal) molar mass

For solutes undergoing e In ease of association, observed molar mass being more than the
association, normal, the factor ‘i’ has a value less than 1.
rie ae e Incase of dissociation, the Van’t Hoff factor is more than 1 because
For solutes undergoing the observed molar mass has a lesser value.
dissociation, e In case of solutes which do not undergo any association or
i> | dissociation in a solvent, the Van’t Hoff factor ‘i’ will be equal to
1 because the observed and normal molar masses will be same.
Since the molar masses are inversely proportional to the colligative property,
Van’t Hoff factor may also be defined as:
the ratio of the observed value of colligative property to the normal
value of the colligative property.
Observed value of colligative property
os ’ = “Normal value of colligative property

Inclusion of Van’t Hoff factor (z) modifies the equations for colligative
properties as follows:
: A
Relative lowering in vapour presure, =
Pp
Elevation in boiling point, AT,
Depression in freezing point, AT,
Osmotic pressure, TT
SOLUTIONS

The Van’t Hoff factor is given for some strong electrolytes in Table 5.
Table 5. Values of Van’t Hoff factor at various concentrations for
some common strong electrolytes.

Electrolyte Value of i ‘ for complete

0.1 m 0.01 m 0.001 m dissociation

NaCl Lay 1.94 1.97 2A)

KCl 1.85 1.94 1.98 2.0
Mgso, Berea | 1.538 1.82 2.)
K,SO, 2.32 2.70 2.84 3.0
It is clear from the table that values of ‘i’ for KCl, NaCl and Mgso,
approaches 2 (expected for complete dissociation) as the solution becomes
very dilute. Similarly, the ‘i? value approaches 3 (for complete dissociation)
for K,SO, as the solution becomes very dilute.
Van’t Hoff Factor and Extent of Dissociation or Association in an
Electrolytic Solution
Van’t Hoff factor can be used to calculate the extent of dissociation or
association in terms of degree of dissociation or association of a substance in
solution.
(4) Degree of dissociation. It is defined as the fraction of total substance
that undergoes dissociation into tons, 1.é.,
No. of moles of the substance dissociated
Degree of dissociaton =
Total number of moles of the substance taken
Suppose a molecule of an electrolyte gives m ions after dissociation. Then
if we start with 1 mole of the solute, and & is the degree of dissociation, then
at equilibrium :
Number of moles of solute left undissociated = 1 — o&
Number of moles of ions formed = mo
Total number of moles of particles = 1- @ + mo
Observed number of moles of solute
Van't Hoff factori =
Normal number of moles of solute
1-—-a+ma
.=
1—-a+ma=t1 ;
or ait
1) = p= 1
i-1
om Aol
Normal molar mass
But i=
Observed molar mass
Knowing the value of ‘i’? from observed molar mass and normal molar
mass, degree of dissociation, & can be calculated.
For the electrolytes of the type AB, such as KCl, NaCl, etc., the number
of particles in solution i.¢., m = 2
= os ee
For the electrolytes of the type AB, like CaCl,, Ba(NO,), etc., the value
ofm = 3, so that

(11) Degree of association. It is defined as the fraction of total number

of molecules which combine to form associated molecules, 1.e.

D f iaton
No. of moles of the substance associated
= See
ae Total number of moles of substance taken
ase MODERN'S abe + OF CHEMISTRY

For example, suppose nm simple molecules of the solute associate to form

-AXIl

the associated molecule A,.

nA = A,
If we start with 1 mole of A and @ is the degree of association, the
concentration of the species after association is :
[A] =o/n
[A] =(1-90)
Total number of moles after association = 1 — @ + o/n
Thus, the colligative properties will correspond to (1 — @ + Wn) mole
particles rather than one mole of particles.
Van’t Hoff factor, ‘7’ is
i Observed number of moles of solute particles
Number of moles of solute particles assuming no association
1 —a+a/n
1
1
t =1+a0(1/n—-1)
or a(Un-—-D=f 7
_ é-1
a ~ = in —A
Normal molar mass
But a
Observed molar mass
Thus, knowing ‘n’ the number of simple molecules which combine to give
associated molecule, observed molar mass, degree of association (@) can be
calculated.

Selucug Namerteat Probleme

FORMULAE AND UNITS
Van’'t Hoff factor
Observed colligative property Normal molecular mass No. of particles after dissociation or association
i —
Normal colligative property © Observed molecular mass No. of particles without dissociation or association
(z) If observed colligative property < normal colligative property or observed molecular mass > normal molecular mass
= the solute is associated.
(11) If observed colligative property > normal colligative property or observed molecular mass < normal molecular mass
= the solute is dissociated.
Calculation of degree of dissociation or association
® Calculate Van't Hoff factor using above relations.
® Write dissociation or association equation. Starting with 1 mole and assuming «@ to be degree of dissociation or
association, calculate the actual number of particles. Then
oe Actual number of particles
i:
Equate i from above two steps and calculate a; the degree of dissociation or association.

SOLVED EXAMPLES
LU) Example 57. Weight of solvent = 50 g
Calculate the boiling point of solution when 2 g of K, = 0.62 Km+
Na,SO, (M = 142 g mol) was dissolved in 50 g of Na,SO, undergoes complete ionization as:
Na,SO, ——= 2Nat + sor
water, assuming Na,SO, undergoes complete
One mole of Na,SO, gives 3 mole particles and therefore,
ionization. (K, for water = 0.52 K kg mol
i =<
(A. S.B. 2016)
3x 0.52 2x 1000
ixK, X wp x 1000 = ——_——__ = 0.439
Solution: AT, = AT, 142 50
Mp XW
Boiling point of solution = 373 + 0.4389
Weight of solute, w, = 2 g
= 373.489 K
Molar mass = 142 g mol!
SOLUTIONS

LU) Example 58. KC] ionizes as :

Calculate the amount of CaCl, (molar mass = 111 g If w is the degree of ionization, then
mol) which must be added to 500 g of water to lower KCl =~ Kr+ Cr
its freezing point by 2K, assuming CaCl, is completely Initial moles 1 0 0
dissociated. (K, for water = 1.86K kg mol") Moles after dissociation 1-—© oO Oo
(A.LS.B. 2015). Total number of moles after dissociation= 1—-Q@+a@+a0
Solution: CaCl, undergoes complete dissociation as: -1+@
CaCl, —> Ca** + 2CT . Observed moles ofsolute 1+a
One mole of CaCl, will give 3 mole particles and therefore, ~ Normal moles of solute — 1
the value of ‘“’ will be equal to 3. 1+a
= = £02 ars, 1+ a= 1.92
AT, = i K-x m or m= 1.92 —]1 = 0.92
_ Ux Ke x wp x 1000 Percentage ionization = 92%.
7 Mp XW, Example 61.
K, = 1.86 K kg mol", w, = 600 g, w, = ?, AT, = 2K, i = 3, 2 g of benzoic acid (C,H ,COOH) dissolved in 25 g of
M, = 111 g mol benzene shows a depression in freezing point equal
3x 1.86 X Wp x 1000 to 1.62 K. Molar depression constant for benzene ts
111 x 500 4.9 K kg mol. What is the percentage association of
acid if it forms double molecules (dimer) in solution?
2x111x 500
w
B ~ 3x1.86
x 1000
— 19.89 g N.C.E.R.T (Pb. S.B. 2009)
Solution : Let us first calculate observed molar mass,
LJ Example 59. Mk K; XWp x 1000
At 25°C, 3 g of a solute A in 100 mL of an aqueous . AT; X Wa
solution gave an osmotic pressure of 2.5 atmosphere. WwW, = 2g,w, = 26 g, AT, = 1.62 K
What is the nature of solute (associated or dissociated)
K, = 49 Kkg mol
if its normal molar mass ts 246? 49 x 2 x 1000 =<
Solution : Normal molar mass of solute = 246 M, = 462x25 = 2341.98 £ mol

The molar mass may be calculated as: Observed molar mass = 241.98 mol"!
Normal molar mass of C,H.COOH
m= chT = ——= M,V
=7x12+6x1+2x
16=122 ¢ mol?
Benzoic acid associates as :
_— waRT
or M, = xV 2C H.COOH —— (C,H,COOH),
If wis the degree of association
Wp = 3.0 g, V=100 ml = 0.1 L, 7 = 2.5 atm, Initial moles 1 0
Moles after association 1-a o/2
R = 0.082 L atm mol? K-}. Total moles after association = 1—-a@+o@j2=1-oa/2
M,, = 3 x 0.082 x 298 ~ 293. _ N ormal 1 molar
mol mass _ 122 _ 0504
20 * 0.1 Observed molar mass 241.98
This means that the solute has abnormal behaviour }-——
OL
in solution. Since observed molar mass is more than the
Now f= = — 0.504
normal value (246) the solute exists as associated in
solution. ot = (b0a4
2
LJ Example 60.
A solution containing 0.5 g of KCI dissolved in 100 g _ _ _ 0.496
2
of water freezes at — 0.24°C. Calculate the percentage ao = 0.496 x 2 = 0.992
tonization of the salt. (K, for water = 1.86 Km=). Thus, degree of association of benzoic acid in benzene
(C.B.S.E. Sample Paper 2007) = 99,2°%,

Solution : Let us first calculate the observed molar Example 62.

MASS AS:
A solution containing 3.100 g of BaCl, in 250 g
— Ky; X Wz X 1000 of water boils at 100.083°C. Calculate the Vant
= ATy X Wa Hoff factor and molality of BaCl, in this solution.
w, = 0.5 g, iw, = 100 g, AT; = 0 —(— 0.24) = 0.24°, K-= 1.86 (K, for water = 0.52 Km-1, molar mass of BaCl, =
208.3 g mol) (A.L.S.B. 2001)
1.86 x 0.5 x 1000 :
Mp =~ 924x100. °° Solution : Molality of the solution,
oy. eX 1000
Normal molar mass of KCl] = 39 + 35.5 = 74.6 Ms ~*~ Wa

Van't Hoff factor, w,, = 3.100 g, w, = 260 g, M, = 208.3

Normal molar mass 74.5 ee 5.100 x 1000 — 0.05952
~ Observed molar mass ‘38.75 208.0 250
ac Now, let us calculate normal elevation in boiling point,
MODERN'S abe + OF CHEMISTRY-AXIl

Observed freezing point depression = 0.0205 K

AT, = K,xm Gert tint ei Observed freezing point
= 0.05952 x 0.52 = 0.03096 Calculated freezing point
Observed elevation in boiling point, 0.0205 K
=1.041
AT, = 100.083 — 100 = 0.083°C ~ 0.0197 K
oe Observed AT, _ 0.083) _ Acetic acid dissociates as :
Normal AT, 0.03095 CH,OOH —— CH,COO- + Ht
Example 638. Initial conc. m 0 0
The freezing point of a solution containing 0.3 g of Cone. after m (1 — x mol) mx mol mx mol
acetic acid in 30.0 g of benzene is lowered by 0.45°. dissociation
Calculate Van't Hoff factor. (K, for benzene = 5.12 K Total moles of particles = m(1 —x +x +x) = m(1 +x)
kg mol). (A.I.S.B. 2001) = m+ x) —_ 1.0 Al

Solution : Let us first calculate observed molar mass IT

Kkf x wy X 1000 x = 0.041

on AT, x Ws .. Degree of dissociation = 0.041
Wy = 0.3 g, wy = 30.0 g, AT-= 0.46°, K-= 6.12 Kkg molt [CH,COOH] = m (1 — x) = 0.0106 x (1 — 0.041) = 0.0102
[CH,COO] = mx = 0.0106 x 0.041 = 4.35 x i=
5.12 x 0.3 x 1000 |
M. = 9 ——_ £1 3.
0.45 x 30 ee [H*] = mx = 4.35 x 10+
Normal molar mass = 60 |CH,;COO-
||H*|
Normal molar mass _ 60 _ 0.527.
oe _ Observed molar mass 113.8
(4.35x10-*) (4.35x10~*)
Example 64.
0.0102
A solution contains 0.8960 g of K,SO,in 500 mL
= 1.86 x 10°.
solution. Its osmotic pressure is found to be 0.690
atm at 27°C. Calculate the value of Van't Hoff factor. Example 66.
(At. mass K = 39.0, S = 32, O = 16, R = 0.082 atm Calculate the freezing point depression expected for
mol! K-1). (A.LS.B. 2001) 0.0711 m aqueous solution of Na,SO., If this solution
Solution : Let us first calculate observed molar mass, actually freezes at —-0.3820°C, what would be the value
M, _ Ve xKxT of Vant Hoff factor ? (K, for water is 1.86° C mol)
Tx V (D.S.B. 2009)
Ww, = 0.8960 g, V=600 ml=0.5L Solution: Freezing point depression,
R = 0.082 L atm mol"! K-, r = 0.690 atm, T = 300 K AT; = K- x ml
M, = 0.8960 x 0.082 x 300 _ 63.9 K, = 1.86°C mol , m = 0.0711
0.690 x 0.5 AT; = 1.86 x 0.0711 = 0.132°
Normal
molar mass = 2 x 39
+ 32 +4x 32-174 Observed freezing point 0 — (— 0.820) = 0.3820°
Normal molar mass Observed freezing point
Van't Hoff factor, i Van't Hoff factor
Observed molar mass Calculated freezing point
174 0.320
= —— = 2.72.
63.9 0.132
Example 65. Example 67.
0.6 mL of acetic acid (CH,COOH) having density What mass of NaCl (molar mass = 58.5 g mol-1) must
1.06 g mL-! is dissolved in 1 litre of water. The be dissolved in 65.0 g of water to lower the freezing
depression in freezing point observed for this strength point by 7.50 °C ? The freezing point depression
of acid was 0.0205°C. Calculate the Van't Hoff factor constant, K,, for water is 1.86 K kg mol-!. Assume
and dissociation constant of the acid. Vant Hoff factor for NaCl is 1.87. (AJ.S.B. 2011)

Solution : Moles of acetic acid =

0.6mL x 1,06 g mL
60 g mol
Solution: at, = ¢R*1000xup
K, x 1000
ws, XMp
= 0.016 mol i = 1.87
[M (CH,COOH = 60] K, = 1.86 K kg mol},
Mass of water = 1000 mL x 1gmL7+=1000¢2 w, = 65.0g,M,=68.5, AT,=7.50°C
1.86 x 1000 X wp,
Molality = TabO ex1000 = 0.0106 mol kg 7.60 = 187 x
65.0 x 58.5
Now, AT, = K, x m. _ 7.50 65.0x 58.5
Wy
= 1.86 K kg mol™ x 0.0106 mol kg? 1,871.86 x 1000
= 0.0197 K 8.2 g.
SOLUTIONS

LJ Example 68. Molality of solution = 1.00 m

Calculate the freezing point of solution when 1.9 g of Calculated boiling point elevation,
AT, (cale.) = K, x m
MgCl, (M = 95 g mol) was dissolved in 50 g of water,
assuming MgCl, undergoes complete ionization. (K, for = Dbl? s1.—. 0.512
water = 1.86 K kg mol") (D.S.B. 2016) Van't Hoff factor, i
Observed boiling point elevation
Solution: AT, = ixKy xwp x1000 ~ Calculated boiling point elevation
Ms * LW a

WwW, = 1.9 g, w, = 50 g, M, = 95 g mol’, K, = 1.86 Km"! |

=
0.512
DTS. = 0.c51.

MgCl, undergoes complete ionization as Example 71.

MgCl, —> Mg** + 2CIl Determine the osmotic pressure of a solution prepared
oe by dissolving 2.5 x 107 g of K,SO, in 2L of water
AT, = 31.86 1.9 «1000 at 25°C, assuming that tt ts completely dissociated.
95 x 50 (R = 0.0821 L atm K+ mol, Molar mass of K,SO,
= 2.2382 K = 174 g mol). (D.S.B. 2013)
Solution : Since K,SO, dissociates completely,
Freezing point of solution = 273 — 2.232 = 270.768 K
K,SO, —> 2Kt + 80,7"
Ll Example 69. One mole of K,5O, will give 3 mole particles and therefore,
Calculate the boiling point of a solution prepared by the value of % is 3.
adding 15.00 g of NaCl to 250.0 g of water. (K, for Osmotic pressure, 7 = icRT
water = 0.512 K kg mol-! and molar mass of NaCl = RT
58.44 g mol). (D.S.B. 2011) avea
W, = 26x 10%g,V=20L,M, =174
Solution : AT, = iK, x 1000 x wy R = 0.0821 L atm K-! mol}
NaCl dissociates as : w, x My
3 x2.5x107 x 0.0821 x 298
NaCl —+ Nat + Cl
174 x 2.0
i i= 2 = 5.27 x 10° atm.
Ww, = 16.0 g, w, = 260.0 g, M, = 568.44 g mol Example 72.
K, = 0.612 K kg mol™ 3.9 g of benzoic acid dissolved in 49 g of benzene shows
a depression in freezing point of 1.62 K. Calculate
2x 0.512 x 1000 x 15.0
AT, = the vant Hoff factor and predict the nature of solute
250.0 x 58.44
(associated or dissociated). [Given: Molar mass of
= 1.06°C benzoic acid = 122 g mol, K ,for benzene = 4.9 K kg
Boiling point of solution = 100 + 1.05 = 101.05°C mol] (D.S.B. 2015)
Solution: AT, = iK, x Mm
LJ Example 70.
_ txKy
xwp x 1000
A 1.00 molal solution of trichloroacetic acid
(CCL,COOH) ts heated to tts boiling point. The solution Mp .4 Wa

has the boiling point of 100.18°C. Determine the Vant 162 Lx 4.9 x 3.9 x 1000
Hoff factor for trichloroacetic acid (K, for water= . 7 122 x 49
0.512 K kg mol-). (D.S.B. 2012) 1.62 x 122 x 49
Solution : Observed boiling point elevation, or i = = 7.506
4.9 x 3.9 x 1000
AT, = 100.18 — 100.0 = 0.18°C
Since ‘2’ is less than one, the solute is associated.

=Drake
Dra Lee:

86. Decinormal solution of NaCl developed an osmotic pressure of 4.6 atm at 300 K.
Calculate the degree of dissociation. — Answers to Practice Problems
87. Calculate the freezing point of a one molar aqueous solution (density 1.04 g L“) of KC1. 86. 87%
(K-for water = 1.86 kg mol, atomic masses of K = 39, Cl = 35.5).
87. — 3.852°C
88. Calculate the boiling point of a one molar aqueous solution of KBr (density 1.06 gm L~*).
88. 101.106°C
(K, for water = 0.52 kg mol}, atomic masses : K = 39, Br = 80).
89. Calculate the amount of sodium chloride (electrolyte) which must be added to one 89. 47.161
kilogram of water so that the freezing point is depressed by 3K. Give K, for water = 90. 12%
1.86 K kg mol}. (Nagaland S.B. 2017). Hints & Solutions on page 66
» Phenol associates in benzene to form a dimer (C,H.OH),. The freezing point of a solution
containing 5 g of phenol in 250 g of benzene is lowered by 0.70°C. Calculate the degree
of association of phenol in benzene. (K-for benzene = 6.12 Km“) (Pb. S.B. 2009)
 MODERN'S abe + OF CHEMISTRY
-AXIl

91. 1.6 g of Ba(NO,), dissolved in 100 g of water shows a depression in freezing point
equal to 0.28°C. What is the percentage dissociation of the salt? (K,for water
= 1.86 K/m and molar mass of Ba(NO,), = 261). (Pb.S.B. 2004, 2009)
92. Calculate the difference between the boiling points of 0.2 m Na,SO, and 0.6 m
glucose assuming complete dissociation of Na,SO,. (K, for water = 0.62 Km)
95. The freezing point of a solution containing 0.2 g of acetic acid in 20.0 g of benzene is
lowered by 0.45°C. Calculate the degree of association of acetic acid in benzene.
(K, for benzene = 5.12 K mol kg) (Pb.S.B. 2004)
94. Calculate the normal freezing point of a sample of sea water containing 3.8% NaCl
and 0.12% MgCl, by mass. (K, forwater = 1.86 Km).
95. Calculate the molality of NaCl solution whose elevation in boiling point is equal
to the depression in freezing point of 0.25 m sodium carbonate solution in water
— Answers to Practice Problems assuming complete dissociation of salts. (K-= 1.86 Km™, K, = 0.62 Km™).
- 0.01 m aqueous solution of K, [Fe(CN),] freezes at — 0.062°C. What is the apparent
91. 81%
percentage of dissociation ? (K-for water = 1.86 K kg mol) (Pb. S.B. 2002)
92. 0.052
97. Calculate the amount of KC] which must be added to 1 kg of water so that the
93. 94.6% freezing point is depressed by 2K. (K-for water=1.86Kkgmol?) (D.S.B. 2012).
94, — 2.59°C . An aqueous solution containing 4.9 g of a solute dissolved in 500 mL of the solution
95. 1.34 m shows an osmotic pressure of 2.1 atmosphere at 27°C. What is the nature of the
96. 77.7 % solute (associated or dissociated, if the molar mass of the solute is 57 a.m.u.)?
97. 40.05 g (Hr. S.B. 2006)
98. Associated solute 99. 0.01 M solutions of KC] and BaCl, are prepared in water. The freezing point of KCl is
59,3 °C found to be —2°C. What freezing point would you expect for BaCl, solution assuming
both KCl and BaCl, to be completely ionized?
100. —1.59°C
100. Calculate the freezing point of an aqueous solution containing 10.60 g of MgBr, in 200 g
Hints & Solutions on page 66 of water. (Molar mass of MgBr, = 184, K-for water=186Kkgmol 4) (D.S.B. 2011)

de OhAG
al mev Accelerate Your Potential
els >» PROBLEMS (for JEE Advance)

IES A 1.2% solution (wt. /volume) of NaCl is NaCl dissociates as :

isotonic with 7.2% solution (wt./ volume) of glucose NaCl =— Nat + CL
(molar mass = 180). Calculate the degree of dissociation If w is the degree of dissociation
of NaCl solution. Initial moles 1 0 0
Moles after dissociation 1—- © Ct CO.
Let us first calculate observed molar mass of Total moles after dissociation = 1-—-@+4+@+a@=1+¢4
NaCl. Moles of solute after dissociation _1+a
For isotonic solutions. aa Normal moles of solute SOG |
m(NaCl) = mt (urea) 1+a@
Now, Peg os 1.95
wRT a® = 1965-1 = 0.95.
and Tt =
MV. 165 To 500 cm? of water, 3.0 x 10° kg of acetic
Osmotic pressure of NaCl, acid is added. If 23% of acetic acid is dissociated, what
aro 1.2 RT will be the depression in freezing point ? K, and density
Mx0.1 of water are 1.86 K kg mol" and 0.997 g cm respectively.
Osmotic pressure of urea, Volume of water = 500 cm®
Density of water = 0.997 g cm™®
7.2 RT
Tt (urea) = ———— Wt. of water = Volume x Density
180 x 0.1
= 600 x 0.997 = 408.5 g
N 12RT 7.2RT
3.0x10% x 1000
eM x01 ~~ «180x0.1 Moles of acetic acid =
60
Pe M — +01) mle (mol. wt. of CH,COOH = 60)
ti = 0.06
Moles of acetic acid
Normal molar mass of NaCl = 58.5 Molality = x 1000
Wt. of water
Normal molar mass = 58.5
ee
39 7 125re yf 0.05
ee x 1000 Ree age
Observed molar mass 498.5
SOLUTIONS

Acetic acid dissociates in water as: on LH" |[80,” |

CH,COOH =— CH,COO- + Ht HSO;
Initial moles 1 0 0 [H*] = 0.08 x 0.6 = .04, [HSO,-] = 0.08 (1 — 0.6) = .04,
If @ is the degree of dissociation, [S0,?"] = 0.08 x 0.6 = 0.04
1-@ O. C
K = eee = 4.0 x 10%.
Total moles after dissociation = 1-@+@+Q=-1+@4
iv A storage battery contains a solution of
Waite Elle coe Moles after dissociation H,SO, 38% by weight. At this concentration van’t Hoff
Normal moles factor is 2.50. At what temperature, will the battery
content freeze? (K. for water = 1.86 Km")
l+a@
il Weight of H,SO,(w,) = 38 g
a = 23% = 0.23 Weight of water (w,) = 100 — 38 = 62g
Calculated AT,,
f
i= a = 1.23 1000 x K, x w,
w, x Mp
Now, AT; =] K-m
1000 x 1.86 x 38 — 11.633°
= 1.25 x 1.86 x 0.1005 = 0.220 62 x 98
Depression in freezing point = 0.229°. Observed AT,
Vant Hoft factor, 1: = —____—"
The freezing point of a 0.08 molal Calculated AT,
Observed AT, = 1 x Calculated AT
solution of NaHSO, is —0.372°C. Calculate the
= 2.5 x 11.633 = 28.08"
dissociation constant for the reaction: .. Freezing point of battery contents = 273 — 29.08
HSO, = H* +SO,> — 243.92 K.
1k Acertain mass ofasubstance when dissolved
(K, for water = 1.86 Km‘)
in 100 g of benzene lowers the freezing point by 1.06°C.
NaHSO, dissociatesas: The same mass of solute dissolved in 100 g water lowers
the freezing point by 1.15°C. If the substance has normal
NaHsO, ————> Na* + HSO,”
molecular weight in benzene and is completely dissociated
Since the concentration of NaHsSO, is 0.08 m, in water, into how many ions does it dissociate in
water ? K, for water and benzene are 1.86 and 5.12 K kg
[Na*] = 0.8 m, HSO, = 0.08 m
mol!" respectively.
Now, HSO, also dissociates as: AT; is given as :
HSO, == Ht+ 80,7
K, x 1000 x wp
If «is the degree of dissociation, then after dissociation ee eee
f Mz x100
at equilibrum,
Since the given solute behaves as normal in C,H, and
[Hso,-] = 0.08 (1 — a), dissociates in water.
[H*] = 0.80,[S0,~] = 0.08 « M(normal) fe M(in benzene)

Total concentration of all ions (7.e., Na* H*,HSO, and M(observed) M(in water)

SO,”) 0.12 * 1000 X wp

= 0.084 0.08 (L— @) + 0.08 @ + 0.08 o fimteh 1.06 = ©i PA
ae M(in benzene)
x 100 ©)
= 0.16+ 0.08 a
1.86 x 1000
we,
“ 0.16+0.08 a I t oe tat
”. Van’t Hoff factor i = =-9+a se iiecaahs M(in water)
x100 sss
0.08
Now, AT; = I K; x m Dividing equation (iz) by eq. (2)

= 1x 1.86 x 0.08 = 0.1488 1 ea benzene) 7 L165 x5atl bet _9 99

M(in water) 1.06 1.86
AT f — 0 — (— 0.872) = 0.3872
or 1 = 2990=3
or 0.572 = 0.14881
Since the solute is completely dissociated, ~ = 1, the
0 i = 0.872 =9.5 solute is ionised into three ions in water. If solute is AB,.
0.1488
A,B, eee 2 vise
Thus, 24+o0 = 256o0ra=0.5
Dissociation constant for the reaction is x+y = 3.
| 264 MODERN'S abe + OF CHEMISTRY
-AIl

iL The plot given below shows P—T curves For solvent Y |

(where P is the pressure and T is the temperature) for ae i ey — 867 = 1Ks (from graph) Gi)
two solvents X and Y and isomolal solutions of NaCl in Pied Gb Gi) aI 7 de
these solvents. NaCl compeletely dissociates in both the . K ‘
solvents. —)X = 2
_ 1% 3,4 (Ky dy
z | Now for solute 8S, which dimerizes in both solvents
: 7 1. SoventX 25 =— 5&5,
3 2. Solution of NaCl in solvent X ectea | 1 0
- 3. Solvent Y Obs Sa 8 After association 1 — @ w/2
: A. Solution of NaCl in solventY Total no. of moles 1 ee 1 — ae

oO Oe 1=~1—a/2
ture (K) (AT,)¢ = (1—“WQAK,), x m ...(iit)
On addition of equal number of moles of a nonvolatile | , ies =
| AT), =(1-—-— = 0.66
solute S in equal amount (in kg) of these solvents, the Se 9 ee a Soy os
elevation of boiling point of solvent X is three times that
solvent Y. Solute S is known to undergo dimerization Elevation in boiling point in solvent X and Y
in these solvents. If the degree of dimerization is 0.7 (AT, x ~ 3 (Given)
in solvent Y, then what is the degree of dimerization (AT, )y
in solvent X ? Dividing eq. (1iz) by (iv) for same concentration,
(JEE Advance 2018) g _ i-@ /2 , (Kox
When NaCl is solute, 0.65 (Ky by
i 1l-a/2
rs
AT, =txK, xm 0.65 :
For solvent X 3x 0.65
a) ee Se
AT, = 362 — 360 = 2K (from graph) | 2
2 = 2x(K;)x m (2) -w2 = 0.976-1 = -0.025
or &® = 0.06

Q.1. (4) Out of 1 M glucose and 2 M glucose, which one has a higher boiling point and why?
(it) What happens when the external pressure applied becomes more than the osmotic pressure of
solution? (A.LS.B. 2016)
(z) The elevation in boiling point is a colligative property and depends upon the number of moles of solute
added. Higher the concentration of solute added, higher will be the elevation in boiling point. Thus, 2M
glucose solution has higher boiling point than 1M glucose solution.
(it) When the external pressure applied becomes more than the osmotic pressure of the solution, then the
solvent molecules from the solution pass through the semipermeable membrane to the solvent side. This
process is called reverse osmosis.
. Blood cells are isotonic with 0.9% sodium chloride solution. What happens if we place blood cells
in a solution containing
(4) 1.2% sodium chloride solution?
(it) 0.4% sodium chloride solution? (ALL S.B. 2016)
(z) 1.2% sodium chloride solution is hypertonic with respect to 0.9% sodium chloride solution or blood cells.
When blood cells are placed in this solution, water flows out of the cells and they shrink due to loss of
water by osmosis.
(it) 0.4% sodium chloride solution is hypotonic with respect to 0.9% sodium chloride solution or blood cells.
When blood cells are placed in this solution, water flows into the cells and they swell.
. What will happen if pressure greater than osmotic pressure is applied on the solution separated by
a semipermeable membrane from the solvent ?
. It will result into reverse osmosis i.e., there will be net flow of the solvent from the solution to the solvent.
. Will the elevation in boiling point be same if 0.1 mole of sodium chloride or 0.1 mole of sugar is
dissolved in 1 L of water ?
SOLUTIONS 9165 —
Ans. The elevation in boiling point of 0.1 mole of NaCl and 0.1 mole of sugar dissolved in water will not be same.
Elevation in boiling point is a colligative property and depends upon the number of solute particles. NaCl is
ionic and give more number of particles due to ionisation than sugar which consists of molecules.
Q.5. When dehydrated fruits and vegetables are placed in water, they slowly swell and return to original
form. Why ? Would a temperature increase accelerate the process ? Explain.
Ans. The cell walls of fruits and vegetables are semipermeable. The liquid inside the cells in the dried fruits and
vegetables is more concentrated. When these dried fruits and vegetables are placed in water, water enters the fruits
and vegetables due to osmosis and they swell and return to their original form. Since the increase in temperature
increases the osmotic pressure (1 ox T) , hence the process gets accelerated by increase in temperature.
Q.6. Why is great care taken in intravenous injection to have comparable concentration of solutions to
be injected to that of blood plasma ? (Pb. S.B. 2016)
Ans. During intravenous injections, the concentrations of the solution to be injected should be comparable to blood
plasma. If the solution is less concentrated, its osmotic pressure will be low. The water will try to move into the
red blood cells through the cell walls. As a result, cells will swell and burst. On the other hand, if the solution
1s more concentrated, the water in the cells will try to move outside the cell to the more concentrated solution
by osmosis. This causes cells to shrink and consequently cease to function.
Q.7. Which colligative property is prefered for the molar mass determination of macromolecules ?
Ans. Osmotic pressure measurement is preferred over all other colligative properties because
(z) even in dilute solutions, the osmotic pressure values are appreciably high and can be measured accurately.
(11) osmotic pressure can be measured at room temperature. On the other hand, elevation in boiling point
is measured at high temperature where the solute may decompose. The depression in freezing point is
measured at low temperatures.
Q.8. Will the depression in freezing point be same or different if 0.1 mole of sugar or 0.1 mole of glucose
is dissolved in one litre of water ?
Ans. The depression in freezing point will be same in both the solutions because both are non-electrolytes and give
same number of solute particles.
Q.9. Outer hard shells of two eggs are removed. One of the eggs is placed in pure water and the other
is placed in saturated solution of sodium chloride. What will be observed and why ? (Pb. S.B 2016)
Ans. The egg placed in water will swell due to osmosis of pure water into the egg. On the other hand, the egg placed
in saturated solution of NaCl will shrink due to osmosis of water out of the egg. This is because osmosis always
occurs from higher concentration of solvent to lower concentration of solvent.
Q.10. Are equimolar solutions of sodium chloride and urea isotonic? Why ? (J.K.S.B. 2013)
Ans. Sodium chloride gets dissociated to two ions (Na* and Cl) and exerts almost double osmotic pressure than
urea (which is non-electrolyte).
Q.11. Why is it advised to add ethylene glycol to water in a car radiator while driving in a hill station ?
Ans. Ethylene glycol lowers the freezing point of water and, therefore, it does not freeze in a hill station.
Q.12. Sodium chloride solution freezes at lower temperature than water but boils at higher temperature
than water, Explain.
Ans. Freezing point of a liquid depresses on the addition of a non-volatile solute and therefore, a solution of sodium
chloride freezes at lower temperature than freezing point of water. On the other hand, there is elevation in
boiling point on the addition of a non-volatile solute and consequently boiling point of sodium chloride solution
is more than that of water.
Q.13. What is de-icing agent? How does it function?
Ans. Common salt acts as a de-icing agent because it lowers the freezing point of water to such an extent that it
does not freeze to form ice. Hence, it is used to clear snow from roads.
Q.14. Why is camphor preferred as a solvent for measuring the molecular mass of naphthalene by Rast
method?
Ans. Camphor has a large K,value (39.8%) and therefore, causes large depression in melting point of solution with
very small amount of solute (naphthalene).
Q.15. When mercuric iodide is added to an aqueous solution of KI the freezing point is raised, Why ?
(CLB.S.E. Sample Paper 2007)
Ans. Hgl, forms a complex with KI and therefore, the number of particles in solution decreases.
Hgl, + 2KI —- K,[Hgl,]
As a result, the depression in freezing point is less and hence the freezing point increases.
Q.16. Arrange the following in increasing order of freezing point :
0.2 M NaOH, 0.2M Na,CO.,, 0.1M AgNO.,, 0.1M (NH,), 50,.FeSO,.6H,O.
Ans. 0.2M Na,CO, < 0.1M (NH,), 5O,.Fe50,.6H,O < 0.2M NaOH < 0.1M AgNO,
 MODERN'S abe + OF CHEMISTRY
-AXIl

Q.17. Why does an azeotropic mixture distils without any change in composition ?
Ans. Azeotropic mixture on boiling forms vapours in the same mole fraction of the two components as present in the
liquid mixture.
Q.18. Under what conditions Vant Hoff’s factor ‘7’ is
(4) equal to unity (77) less than 1 and (711) greater than 1 ?
Explain the answer
Ans. (1) When the solute does not undergo any dissociation or association in the solution i.e., for non-electrolyte
solutes.
(11) When the solute undergoes association in the solution.
(111) When the solute undergoes dissociation in the solution.
Q.19. What would be the value of Vant Hoff's factor for a dilute solution of K,SO, in water ? (A.[.S.B. 2005)
Ans. L= 3.
Q.20. State the condition resulting in reverse osmosis. (A.LS.B. 2007)
Ans. When pressure larger than osmotic pressure is applied on the solution.
Q.21. Given below is the sketch of a plant for carrying out a process.
P applied > x
—- Piston
N
Fresh water
container

SPM
(1) Name the process occurring in the above plant.
(ii) To which container does the net flow of solvent take place ?
(471) Name one SPM which can be used in this plant.
(iv) Give one practical use of the plant. (CLB.S.E. Sample Paper 2007)
Ans. (1) Reverse osmosis (it) To fresh water container
(111) Film of cellulose acetate (iv) This can be used as desalination plants to meet potable water requirements.
Q.22. Which of the following solutions has higher freezing point?
0.05 M AI,(SO,),, 0.1 M K,[Fe(CN),] Justify. (CLB.S.E. Sample Paper 2017-18)
Ans. 0.05 M Al1(SO,), has higher freezing point.
AT, “ix concentration
For 0.05 M AL(SO,),, 2 = 6
AT, oc 6 x 0.05 = 0.25 moles of ions
For 0.1 M K,[Fe(CN),], 1 = 4
AT o 4 x 0.1 = 0.40 moles of ions
.. Depression in freezing point for 0.06 M Al,(SO,), will be less and hence freezing point will be higher.

Hints & Solutions for |

Practice Problems
300 x 25 Density of solution is needed to calculate the molality
Lj 1. Mass of solute (1) = t00 =75¢g of the solution.
| 400 x 40 _j 3. 10% by weight means that 10 g of glucose is present
Mass of solute (2) = joo 160 g in 100 g of solution.
Total mass of solute = 75 + 160 = 235 g Mass of solvent = 100 — 10 = 90 g
Total mass of solution= 300 + 400 = 700 g Moles of glucose = — — 0.0656
% mass of solute = 222 x 100 = 33.57% 0.0556
100 Molality = — x1000 = 0.618 m.
% mass of solvent = 100 — 33.5 = 66.43%
— 18 Lj 4. 10% Na,CO, (w/v) means 10 g of Na,CO, are present
_j 2. Moles of glucose = 1807 0.1 mol = dia ar ealacon:

Molarity = 01 x 1000 = 0.2 M. Molarity of Na,CO, solution = 10/106 x 1000 = 0.94 M

500 100
SOLUTIONS

Wt. of HCl left after heating = 18.25 — 3.25 = 15.0 g

Molarity of HCl solution = ee x 1000 =1M
00 15.0 x 1000 |
Normality = 0.685 N.
Na,CO, + 2HCl ——> 2NaCl + CO, + H,O 36.5 x600 —

oy = 8)
_j9. 99% H,SO, means that 99 g of H,SO, is present in
100 ¢g of solution.
1 JNagC0, 2 Jue Moles of H,5O, = —=1.01 mol
0.94xV, | 1x100
1 7 2 Vol. of solution = ——
ae sa ee
2x 0.94 Molarity =
_) 5. 965% H,SO, means that 965 g of H,SO, is present in
100 g of solution.
Vol. of solution = 100 = 54.05
1.85
_j 10.
_—e
95 x 1000 | Moles of urea = 60 0.05
, _ oo =17.93M
Molarity = 9854.05 0.05 x 1000 ei
Similarly, 15% H,SO, means 16 g of H,SO, is present Molality = 350 = 0.2 m
in 100 g of solution.
250
100 Moles of water ——=18.
18 3.89
Vol. of solution = ——=90.91
1.10 0.05
; 15 x 1000 .
Moles fraction of solute = = 0.0036.
Molarity - ———"""—-
= 1.68 M 13.89 + 0.05
orerny = 98 x 90.91 | ah 1 kg of water contains ethyl alcohol = 1.55 mol
Applying molarity equation,
2 kg of water contain ethyl alcohol = 155 x 2
M,V, — M.V, 3.10 mol
(96% H,SO,) (15%H,SO,) Mass of ethyl alcohol 3.10 x 46
17.93 x V, = 1.68 x 100 142.6 g
V, = eX
17.93
_ 9.37 ems = 9.4 ein
1.68 x 1
_j 12. Moles of HC] =
38
36.5
.. Volume of 95% H,SO, required = 9.4 cm?
Mass of 100 cm? of 15% H,SO, to be prepared Volume of solution = 100 = 84.03 mL
1.19
= 100 x 1.10 =110¢g
38 /36.5
Mass of 9.4 cm® of 95% H,SO, = 9.4 x 185 =17.4 g Molarity = x 1000 = 12.89 M
84.03
.. Mass of water to be taken = 110 - 17.4 = 92.6 g. 1.24 /248
_j 6. If 100 g is the total mass, _j 13. Formality = x 1000 = 0.05 F
100
Mass of ethanol = 95 g
_j 14. Moles of NaOH = *2
AO
= 0.1
Moles of ethanol = 25, _ 2.065
46 Volume of solution = 100 mL
Moles of water = 8 = (0,278 Mass of solution = 100 x 1.088 = 1038.8 g
Mass of water = 108.8 — 4.0 = 99.8 g
| 2.065 |
Mole fraction of ethanol = 706540278 0.88
Moles of water = “7 = §.54

Mole fraction of water = __

0.278 0.12.
? 065 + 0.278 (1) Mole fraction of NaQH = _ OL = 0.018
0.1+ 5.54
_] 7. Moles of water = = = 0.67
(it) Molarity = a x 1000 = 1M
Moles of acetic acid = =1.8
Molality = we x 1000 = 1.002 m -
Moles of ethanol = 2 = 2.0
_j 15. Suppose 100 mL of each solution is mixed.
Mole fraction of water = __ 0.67 = 0.15. Total volume of the solution = 200 mL
0.67 +1.8 + 2.0 .
_j] 8. 1L of N/2 HCl solution contains Wt. of H,SO, in 30% H,SO, = —_—_—
= 36.5/2 = 18.25 g of HCl
Wt. of HCl lost on heating = 3.25 g
— 36.54 g
lane MODERN'S abe + OF CHEMISTRY
-AXIl

_j 20. CaCl, == Ca** + 2Cr

Wt. of H,SO, in 70% H,SO, = Se
2 x 6.02 x 10% CI ions are obtained from 1 mol of
-112.7¢g CaCl, 1.606 x 107° Cl ions are obtained from CaCl,
Total wt. of H,SO, = 36.64 + 112.7 = 149.24 g = —— 5 1.505 x 10” = 0.126 mol
Wt. of water = (100 x 1.218 + 100 x 1.610) — 149.24 2x 6.02 x 10
= 1833.56 g re 0.125 x 1000 = 0.25 M.
Molarity = —— /98 500
x 1000 = 7.61 M

Molality = 149.24/98 x
Mass/Molar mass
1000 =11.4 m.
O 21. Molarity = x 1000
Vol. of solution
_} 16. 18 M H,SO, means 18 mole of H,5O, are present in 1 _ Mass of NaQH/40
x 1000
1000 mL of solution. 5 200
Mass of solution = 1000 x 1.84 = 1840 ¢ 1 3 200 x 40
Mass of NaOH = =16g
Mass of H,SO, = 18 x 98 = 1746 g 5 1000
Mass of water = 1840 — 1764 = 76 g
Amount of NaOH in 100 mL of solution = 5 g
76 4,22
Moles of water = 18 Total mass of NADH = 1.6+5=6.6¢
Total volume = 100 + 200 = 300 mL
Mole fraction of H,SO,= ae = 0.81 6.6/40
Molarity = x 1000 = 0.55 M.
Mass % H,SO, = 7755 100 = 95.87%. 300
Lj 22. 2.05 M acetic acid solution means 2.05 moles of acetic
[_j17. Gram equivalents of oxalic acid = —— = 0.02 acid are present in 100 mL of solution.
Mass of solution = 1000 x 1.02 = 1020 g
Mass of oxalic acid = 0.02 x 63 = 1.26 g Mass of 2.05 moles of CH,COOH
126 g of oxalic acid contain = 6.02 x 10*° molecules - 60 x 2.05 = 123 ¢g
6.02 x 107° x 1.26 Mass of water = 1020 — 123 = 897 g
1.26 ¢g of oxalic acid contain =
126 : 2.05 aang — 9 on.
Molality = =— x1000=2.29m
= 6.02 x 107! molecules Y= 897
_j18. Mole fraction of benzene = 0.46
_j 23. 69% HNO, means 69 g of HNO, is present in 100 g of
Mole fraction of chloroform = 1 — 0.45 = 0.556
solution.
| 0.45 x 78
Wt % benzene = 975 576+0.554119.5° Vol. of solution = 100 _ 70.92 mL
1.41
= 34.8
Lj 19. Mol. mass of Glauber’s salt (Na,5O,.10H,O) = 322 69 g of HNO, is present in solution= 70.92 mL

Mol. mass of Na,SO, = 142 23 g of HNO, is present in solution = on x 23 = 23.64 mL

— s
_j 24. 4.27 M H,SO,
"4 (aq) solution means that 4.27 mol of
Wt. of Na,SO, - PSO XO
oon H,SO, is present in 1000 cm? of solution.
= 35.533 g Mass of solution = 1000 x 1.25 = 12560 ¢g

Moles of Na,SO, = 39-933 - 9.95 M Mass of 4.27 mol of H,SO, = 4.27 x 98 = 418.46 g
142 Mass of water present = 1250 — 418.46 = 831.54 g
(i) Molarity = 9° - 0.25 M Molality —_ 4.27 x 1000 =§,135 , m
—————
83154
(ii) Density - 1077.2kg _ 1077.2 x 10°¢ = 1.0772 gcm™ -
7 3 = 6 3 100 |
m 10° cm LJ 25. Moles of AI(NO,), = TT a 0.469 mol.
Mass of 1 dm? of solution = 1000 x 1.0772 = 1077.2 g
Mass of water = 1000 x 0.9982 = 998.2 g
Mass of Na,SO, = 0.25 x 142 = 35.6 a 0.469
Mass of water = 1077.2 — 35.6 = 1041.7 g Molality = 90892 * 1000 = 0.470 m

Mass of solution = 998.2 gH,O+ 100g AI(NO,),

Molality = —2:75_ 1900 = 0.24 m
1041.7 = 1098.2 ¢

(1it) Moles of water = et = 51.87 Volume of solution = wee 1099.3 em?

0.9990
Mole fraction of Na,SO, = 9.25 4.3 x 10° 0.469
x 1000 = 0.427 M.
0.25 + 57.87
Molarity = 3999.3
SOLUTIONS

_j 26. Partial pressure of N, in atmosphere & mole fraction

_j 31. Mole fraction of A in solution = aaes= 0.601
of N, in air
Py, = 0.78 atm = 0.78 x 760 mm Hg C 82. Moles of ethyl acetate (CH,COOC,H,) = 2 = 0.284
= 692.8 mm Hg
Now, according to Henry's law, solubility of a gas : a0
Moles of ethyl propionate (CH,COOC,H_) = Ton" 0.490
dissolved is proportional to pressure of gas
Solubility of N, = K,, x PN, Mole fraction of ethyl acetate = __0.284
0,284 + 0.490
8.42 x 10-’ M/mm Hg x 592.8 mm Hg 0.367
= 4,99 x 10-4 M. Mole fraction of ethyl propionate 1 — 0.367 = 0.633
_j 27. > Baek Vap. pressure of ethyl acetate = 72.8 x 0.367
= 26.72 torr
= Moles of N,
Vap. pressure of ethyl propionate = 27.7 x 0.633 = 17.53 torr
Moles of N, + Moles of H,O
Total vap. pressure = 26.72 +17.53 = 44.25 torr.
0.02
_ 28
_ _4 s
C) 838. Moles of liquid A = 28 _ 99
~ o02, 1000179 *10 140

28 18 Moles of water = = =4.0

p = latm

kK == =- Mole fraction of liquid A, x, = —°2 0.048

Mole fraction of water, x,, = 1.0 — 0.048 = 0.952
= —_ > = 7.75 x 10*atm.
1.129 x 10 0.210 = Py %+ PyX,
p 0.210 Py x 0.048 + 0.198 x 0.952
a 25. x 9 = K,
——

0 0.210 — 0.198 x 0.952 _

K,, = 1.67 k bar = 1.67 x 10° bar 0.048 aaa nee,
p = 4atm = 4 bar 34. Let the weight of benzene and toluene in the solution
4 bar = Ww gram.
“2 = 176x10°bar Moles of benzene = =a (Molar mass = 78)
= 2.395 x 10°
Moles of toluene = oo (Molar mass = 92)
Xy = —2— = 2.39510
m+ Ny i
——2__ = 2.395 x 10° Mole fraction of benzene, x, = _Lv (8 Ltt = 0541
1000 |.
—— + Ne
18
n, = 0.183 + 2.396 x 10-°n,
78" 92
0.998 n, = 0.133 Mole fraction of toluene, x, = 1 — 0.641 = 0.459
or n, = 0.133 mol Partial vapour pressure of benzene,
Amount of CO, dissolved = 0.133 x 44 = 5.85 g P, = Po x x, = 160 x 0.641 = 81.16 torr
_j 29. Mass of 1L of solution = 1000 g
Partial vapour pressure of toluene, p,= P;” x x,=60 x 0.459
Mass of water = 1000 — 0.06 = 999.94 g
= 22.95 torr
Moles of water = ati = 66.566 Total vapour pressure of solution = 81.15 + 22.95
= 104.1 torr.
0.06
Moles of O, = ag 1.875 x 10°
535. Moles of ethanol = 7 = 1,304
-—3
. Mole fraction of O,, x, = ee
§65.65+1.875 x 107 Moles of methanol=
40 = 1,250
—2 2
a POON Were i0” Mole fraction of ethanol = __ 1504 = 0.51
55.55
1.304 + 1.250
Now, Po, = Ky x Xo, = (46.82 x 10° bar) x (8.37 x 10°)
Mole fraction of methanol = 1 — 0.51 = 0.49
= 1.58 bar.
plethanol) = 44.6 x 0.651 = 22.69 mm Hg
Lj} 30. p,,. = Ky x x4, = (144.98 x 10° bar) x (1.25 x 10°)
p(methanol) = 88.7 x 0.49 = 438.46 mm Hg
= 0.181 bar
 MODERN'S abe + OF CHEMISTRY
-AXIl

Total vapour pressure = 22.69 + 43.46

25.8 — Pa =
_ 80x18x
3
23.8= 0.2532
=
66.15 mm Hg 60 x 846
Mole fraction methanol in vapour phase Pa = 23.8 — 0.25632 = 23.55 mm Hg
p (methanol) _j 42. Mole fraction of solute = sik = 0.0177
Total vapour pressure
43,46 12.3 — py
= 0.657. 123 = 0.0177... ; p, = 12.08 kPa
66.15
32 68.4
LJ 43. Moles
oles ofof sucrose
sucr — ——_=().2
IG)
_]j 36. Moles of methanol = —=1
32
Moles of ethanol = - =0.5
Moles of water = a“ = 55.56

Mole fraction of sucrose = __ 02 _ 0.0036

Mole fraction of methanol = _1_ . 0.67 0.2+ 55.56
140.5

0.5 (1) Relative lowering of vapour press. = Mole fraction of

Mole fraction of ethanol = : = 0.33 solute — 0.0036
+0.5
Partial vapour pressure of methanol = 90 x 0.67 - = 0.0036 or = 0.0036
= 60.38 mm Hg Pa
Partial vapour pressure of ethanol = 61 x 0.33 Pp, = 17.4387 mm Hg
= 16.8 mm Hg 262 — 256 2 78
44, —————_ = == A
p (total) = 60.3 + 16.8 = 77.1 mm Hg. 4 262 Mp, 100
_j 37. Let x, and x, are the mole fractions of liquids A and (Mol. wt. of benzene = 78)
B in the solution, then 2 x 78 x 262 |
_ ——— =68,.12
Pa = Pa X, = 22%, Ma= ~q00x6 ~**'? s mol”.-1
Pp = PaeXt,=P, (1-%,) =T6(1-xg | j 45. Let mole fraction of liquid A in solution = x A
Pyt+Pyp = 22x, + 76 (1—-x,) = 48.5 Mole fraction of liquid B in solution, x, = 1-—x,
x, = 0.5 p =p,°x,+P, *,0T=p,° x, +P, (1—-x,)
Thus, the solution contains equal moles of both
p = 600 mm Hg
liquids A and B.
600 = 460 x, + 700 (1 —x,)
_j 38. Let the mole fraction of A = x
100
Mole fraction of B =1—-x
0.658 x =0.264 (1 — x)
Solving
“A =~ ——=(0,4
950
Mole fraction of liquid A = 0.4
or x =0.286
Mole fraction of liquid B = 1— 0.4 = 0.6
_j 39. Since solution is equimolar, Calculation of composition of vapour phase
Mole fraction of X =0.6, Mole fraction of Y = 0.5 ri =p, X, = 4650 mm x 0.4= 180 mm
Prota = Ps + Joe 200 x 0.6 + 100 x 0.5 Pz =f, XL, = 700 x 0.6 = 420 mm

= 160 Piotal = Pa + Pp = 180 + 420 = 600 mm

Mole fraction of X in vapour phase = iso= 0.67 Pa 180
Ya = Ras a = 0.3
_j 40. For CH,OH, x =1
P=119 + 136 = 254
mm Hg fe Oe
Prtotal 600
For C,H.OH, x = 0
a AG. Pa — Pa = wp XMa
-. P=119x0+138656 = 1385
mm Hg.
D. w, XMp
Pa~Pa _WpXMy w, = 60¢,w,
= 100—-50=95¢
_j 41.
PA Mp XW, Px, = 160 mm, p, = 746 mm
Pa = 23.8 mm, w, = 30 g,w, = 846g 760 — 745 5.0 x18
M, = 60 g mol’, M, = 18g mol? 760 95xMp,
23.8-p, 30x18 Solving
23.8
60x 846 M, = 48g mol".
SOLUTIONS

23.76 — 22.98 Boiling point of solution

| 47. 23.56 = 373.165 + 0.062 = 373.202 K
or Xp = 0.0383
Now for the dilute solution, _j 54. AT, = 100.62 — 100 = 0.52, w, = 20 ml = 20 g

np
(assuming density = 1 g ml“)
¥

B
_-

na
——s
sicht)
0.52 x 3x 1000
_ — — = 150
Maj 0.52 x 20 "
Molality, m = “B. x 1000 saaltz)
Wa _j 55. Calculation of K, :
Dividing eq. (ii) by eq. (2), _» AT, Xw, x Mp
m _ 1000, i.e 1000 | Wa in 1000 x wp
Xp Ws Ws 18 _ 0.402 x 50 x 128 — 5.02 K m7
x, x 1000 _ 0.033 x 1000 1000 x 0.513
18 18 5.02 x 0.625 x 1000
_— ——___——_ = 96.54
= 1.83 mm. M, 0.650 x 50
_j 48. Let the initial pressure of solvent, p,° = p
2.53 x 10 x 1000
7 25 3 _j 56.
M, = 1 =x 1000 ae
Pressure of solution = p 100? = 4P
AT, = K, x wp x 1000
_j 57.
wp Mp XW,
p-3/4p © 60
p — Mp, 100 1.15 x5 x 1000 ae
= 60 x75 = 1.28
60 18
or w,=lllg M, = 0.52 x 12.5 x 1000 _ 53.06
_} 58.
: 111/60 x 1000 0.70 x 175
Now, molality, m = a = 18.5 m. _j 59. For sucrose solution,

Lj 49. w,=90¢g.w,=10¢8
Wp X 1000
Pa’- Pa — WpxMy
AT, = 273.15 — 269.15 = 4.0, w, = 10, w, = 100-10 = 90
P,° 7 LW 4 * Ms,

55.3 — Ds 10x18 |
—§_— = = 0.0333 10100
55.3 90 x 60
For glucose solution,
66.3—p, = 1.84
w,=10,w, =100—-10=90g
P, = 53.46 mm Hg.
_j 50. Lowering in vapour pressure, M, = 180
AT, = 12.31x10x1000
Pa®—p, = 0.0231 — 0.0228
90 x180
= 0.0003 bar
= 7.6K
e w,M
Pa Pa _ a (For dilute solutions) Freezing point of glucose solution = 273.15 — 7.6
Pa WaMp = 265.55 K
0,0003 108,24 x 18
0.0231 1000 x My _j 60. A T,
K,x1000 x
bela dietetic bas fl
108.24 x 0.0231x18 Wa ¥ 4 Msp

“ Ms = ~~ 09,0003 x 1000 ~ 10% 0.48

5.121000 X wp

Lj 51. AT, = 36.86 — 36.60 = 1.26°C, K, = 2.02 Km? 75x 256

M. = 2.02 x 8 x 1000 0.45 x 75 x 256

= 128.25. =18¢
B 1.26 x 100 B 5.121000
K, X wp x 1000
- on: M, 7 AT, * Wy _j 61. ag. . Be*1000Xu5
K, *1000 w.

_ 2.62 x a x 1000 = 146.6.

0.268 x 100
aa 1.86 Kkg molt, w, = 18g, w, = 200 g,
K,, X wp x 1000
AT, AT,= 273.15—-272.07 = 1.08°
Mp 4 La
1.86 x 1000 x18
0.52 x18 x 1000 Mac ee _ 155 ¢ mol
180 x 1000
= 0.052 B 1.08 x 200 —
 MODERN'S abe + OF CHEMISTRY
-AIl

Ky X Wp X 1000 68.4 x 0.082 x 300

_j 62. 71. c= —
g42x1l.. = 4.92 atm.
B AT; x Wa

M = WRRT _ 3.5x0.0821*310
_ 5.12 x 1.0 x 1000 = 256 g mol" _j 72.
TV 25 /'760 x 50/1000
0.40 x 50
3.83 x 2.56 x 1000 = §4159.7
M, = ——————— = 256 M,rV
= 1000 x 0.383 ris Solution constant, R =
Wp x T
If formula of sulphur is 8,
= 0.082 L atm mol? K+.
oa XX = 266 ee ees
7A, Total volume after mixing = 100 + 100 = 200 em®
Molecular formula = 8,.
= 0.2L
a AT, xw, X Mp 1” ,, \ 1.5 x 0.082 x 293 _ 9G ate
B K, x 1000 60 x 0.2
: 3.42 x 0.082 x 293
10 x5500 x 62 | : — = 1,20 | .
Se euauest) 342 x 0.2 os
1.86 x 1000
t (solution) = 3.0 + 1.2 = 4.2 atm.
or = 1.833 kg.

M, = WpRT
: ni Ky x 7.5 x 1000 75.
. For urea, a AT, x 100 = mxV
_ 3.0 x 0.083 x 300 - 27.95.
, K, x 42.75 x 1000 2x1
For X, M, = ——_____
AT, x 100 _ 10. ~—=«10
76. Total
otal moles = ——_+4+——=0O,
moles 180 * 349 0.085
Dividing, 89 - 15 om,’ =342.
M, 42.75 ae 0.085 x oes x 298 — 2.10 bar.
a Ky Xwg X1000 1,86 x 30.0 x 1000
BT wax AT, = 800 X 1.16 77. nr ok
V
M, =80.1
,
1(glycerine) 10.2. RT
_ Me,
n— __Mol.formulamass _ 60 _ 9 tT = x ;
Empirical formula mass 30
2 RT
Molecular formula = (CH,O), = C,H,O, Tt (glucose)
(eI = Sy
180 x= 1
. Ww, = 30 g, w, = 70 g, K, = 1.86 Km’, M, = 62
1.86 x 30 x 1000
10.2,RT _ 2 RT
AT, = = 12.86. M | 180 0.1
62 x 70
M — 10.2 x — x O.1
The solution will freeze at —12.86° C and therefore, it
will be suitable.
= 91.8 ¢ mol!
AT, = 273 — 272.07 = 0.93°
5 x RT 0.877 x RT
AT, 0.93 78.

K, "186 7
iti = 0.5 m 342 x 0.1 M x 0.1

M = 59.99 g mol.
AT, = K, xm =0.512 x 0.5 = 0.256
79. Let wt. of sugar = w g per litre
Boiling point of solution = 373 + 0.256 = 373.256 K.
wxR T _ 6 ’ RT
AT,.= 101.128 — 100 = 1.128°
342x1 ~ 6° 1
AT, 1.128 __9903 m
= So.) w = 34.2 g/litre.
mK, 0.512
_ WpkT
AT, = K,x m = 1.86 x 2.203 = 4.1 80.
M, = mx V
Freezing point of solution = 0 — 4.1 = - 4.1°C.
—— AT; x Wa x Ma
7 x 0.083 x 310
_j 70.
B K, x 1000
= 33x10?x01
0.52 x 68.4 x 1000 |
AT, = 0—(— 10) = 10° Sl.
Mp =~ 9104x1000.”
10 x 1 x 10° x 62
wy = 68.4 x 0.082 x 293
1.86 x 1000 T™ = 3421 (V = 1000 g = 1 L)
= ebabead g.
— A.80 atm.
SOLUTIONS

_} 82. AT, = 100.104 — 100 = 0.104° AT, =i1 x K, xm

ug, - DABEEIOO aug 2 x 0.62 x 1.063 = 1.106°

Boiling point of solution = 100 + 1.106 = 101.106°C.
__J 89. Since NaCl undergoes complete dissociation as:
AT, = see = 0.374
NaCl————> Na*® + Cl
.. Freezing point = — 0.3874°C. One mole of NaCl will give 2 mole particles and the value
of ‘“’ will be equal to 2.
O 83. c= = if __.930mol 17
~ RT 0.0821 313 AT. = i Kem
Assuming molar concentration as equal to molality K, = 1.86 Km} AT, = 3K,i=2
m = 0.30, K, =~ 186°C m? so = 2x 1.86 xm

AT; = K- x m = 1.86 x 0.30 = 0.558° 3

Freezing point of blood = 0 — 0.558 rar "nm =70— Beas

—W =(.806
OU mol/k
Se
= - 0.558 °C. Grams of NaCl = 0.806 x 58.5 = 47.151 g per kg
| j 84. 2x (blood) = x (glucose solution) = 8.21 atm. 2.121000 x5
_j 90. M,(observed) = = 146.3
nV 250 x 0.70
Now, mV
= nkKT or n= RT
Molar mass of phenol (C,H,OH) = 94
8.21 x 1.0 10
z= OOS es —
|
0.0821 x 310 31 i = _7F | = 0.64
146.3
10
Weight of glucose= = X 180 = 58.06 g. 2C,H.OH == (C,H,OH),
31
| 7 _ We _ WRT Initial 1 0
L}) 85. m=cRT= aa or M, = V
After association 1 — «a a/2
w, = 2.6 g, R= 0.0821 L atm mol’ K+ _— 1l-a+a/2 = 1l-a/2 — 0.64
T = 273 + 27 = 300 K 1 1
a = 0.36
Tt = on atm, V = 600 7, a = 72%
760 1000
M, - (2.5 g x 0.0821 L atm mol 'K™')x(300 K) Lj 91. M, (observed) =
1.86 x 1000 x 1.5
0280x100. = 99.64
(73 atm} x(SL)
. 760 1000 ; 261
3119.8 ¢ molt. ’ = 99.64
_]} 86. m= 0.1 x 0.082 x 300 = 2.46 Ba(NO,), —— Ba** + 2NO,
4. | Initial 1 0 0
= ——=1.87
‘= 946° °° After dissociation 1-a@ Ol ples
1.87 = — or & = 87%. _ eee ~ 2.62

_} 87. 1 molar solution means that 1 mole of KCl is dissolved a = 81%

in 1000 mL of solution.
_j 92. AT, (glucose) = 0.62 x 0.6 = 0.26
Mass of solution = 1000 x 1.04 = 1040 g T, = 100.26
Mass of KCl = 74.5 g AT,(Na,5O,) = 3 x 0.62 x 0.2 = 0.312
Mass of water = 1040 — 74.5 = 966.5 g T, = 100.3812
Difference in boiling point = 100.312 — 100.26
Molality of solution = — = x 1000 = 1.0357 m
= 0.052".

Since KCl is strong electrolyte, 1=2

5.12 x 0.2 x 1000
AT; =1 K, x m Lj} 93 M, (observed) —_ =
———20 x 0.45 rs1138.78
|

= 2x 1.86 x 1.0357 = 3.852° 60 |

— — =(0 527
Freezing point of solution = 0 — 3.862 = -— 3.852°C, i= 773.78°°°
_j] 88. Molar mass of KBr = 39 + 80 = 119
2CH,COOH =~ (CH,COOH),
Amount of KBr = 119 g
Initial 1 0
Mass of solution = 1000 x 1.06 = 1060 g
After dissociation 1 — o o/2
Mass of water = 1060 — 119 = 941 g
ee sates = 1 =o — 0.527
Molality of solution = oH x 1000 = 1.068°

Since KBr is a strong electrolyte, 1 = 2

= 94,6°%.
 MODERN'S abe + OF CHEMISTRY
-AIl

L} 94. Moles of NaCl = 3.8/68.5 = 0.065 AE ss of K-m

Moles of MgCl, = 0.12/95 = 0.00126
K- = 1.86 K kg mol", AT, =2h t= 2
NaCl ——+; }# Na+ Cr (2 particles) 42 = 2x1860xm
MgCl, ——> Mg** + 2CI (3 particles) 2
or a = SS pap 0.5376 mol/kg
Total moles of all species = 2 x 0.065 + 3 x 0.00126
= 0.1338 mol Grams of KCl = 0.5376 x 74.6 = 40.05 g per kg
Mass of water in 100 g of sea water = 100 — (38.8 + 0.12)
WpRT
— 96.08 g Lj] 98. Nf ,

Molality. 0.1338
olality = 96.08 ~ 1000000 == 1. 1.39m _ 4.9 0.082 x 300 _ 114.8
2.10.5
AT; = 1.86 x 1.39 = 2.59
Since, observed molar massis more than the theoretical
Freezing point = -— 2.59° C molar mass, the solute is associated in nature.
Lj 95. NaCl ——+ Nat + CI (i = 2) Lj 99. z for KCl = 2,7 for BaCl, = 3

Na,CO, ——> 2Na** + CO,” (@ = 3) AT; (KCl) = 2 x K, x 0.01

AT,(NaCl) = AT,(Na,CQ,) AT, (BaCl,) = 3 x K-x 0.01

ix K,xm=1ix K, x m AT, (KCl) 2
2x 0.62 x m= 3 x 1.86 x 0.25 AT, (BaCl,) 3
m = 1.54 m. 3 AT, (KCl) =>x2=
AT, (BaCl,) = 5x 3 3P
_]} 96. (AT) cal = 1.86 x 0.01 = 0.0186
_ 0.062 _ ”.Freezing point of BaCl,= - 3°C.
~ 0.0186 awe
Lj 100. For MgBr,,
K,[Fe(CN),] == 38K* + [Fe(CN),]*
MgBr, —~> Mg*t + 2Br-
Initial 1 0 0
After dissociation 1 — a 30 o/2
1=3
Lx Kp X wp X 1000
j= 83.33 fr ws, XMp
7 a = 77.7%
_ 31.86 10.50 x 1000
_J 97. Since KCl undergoes complete dissociation as:
7 200 x184
KCl K* +Cl — 1.59
One mole of KCl will give 2 mole particles and the value Freezing point = 0 — 1.59°C
of ‘x’ will be equal to 2. = — 1.59°C.

® Vapour pressure. It is the pressure exerted by the vapours above the liquid surface in equilibrium with the liquid at a
given temperature.
® Henry’s law. The mass of a gas dissolved in a given volume of the liquid at a given temperature is directly proportional
to the pressure of the gas in equilibrium with the solution.
® Raoult’s law. At a given temperature, for a solution of volatile liquids, the partial vapour pressure of each component in
solution is equal to the product of the vapour pressure of the pure component and its mole fraction.
® Ideal solution. The solution which obeys Raoult’s law exactly over the entire range of concentration.
® Non-ideal solution. The solution which does not obey Raoult’s law.
® Azeotropes. The solutions (liquid mixtures) which boil at constant temperature and can distil unchanged in composition
are called azeotropes.
SOLUTIONS 2/75 —

Colligative properties. These are the properties of the solutions which depend only on the number of solute particles
but not on the nature of the solute.
Osmosis. It is the phenomenon of the flow of solvent through a semipermeable membrane from pure solvent to the
solution.
Osmotic pressure. It is the excess pressure which must be applied to a solution to prevent the passage of solvent into
it through a semipermeable membrane.
Isotonic solutions. The solutions having the same osmotic pressure at the same temperature are isotonic solutions.
Van’'t Hoff factor. It is the ratio of the normal molar mass to the observed molar mass of solute or it is the ratio of the
observed colligative property to the normal colligative property.

QUICK CHAPTER ROUND UP)

CONCENTRATION OF SOLUTIONS Molality and mole

amount of solute present in a given quantity of solution fraction are independent
of temperature

Molarity (M) Molality (m) Mole fraction (x) Normality (N)

Moles of solute Moles of solute Moles of solute Equiv. of solute
x 1000 —_—__————_ * 1000 * 1000
Vol of solution (mL) Wt. of solvent (g) Total moles of solution Vol. of solution (mL)

Henry's law Henry's law gives relationship Raoult's law

im = p orm — Kp between solubility of gas ina
1 Pa =PaX, andPy = Dg Xp
Koc p or p= Fr X liquid and pressure.
and p = Py + Pp =P, + (Dp—DPalkg

IDEAL SOLUTIONS
e
e
Se aoe NON-IDEAL SOLUTIONS
Bee ee . mis er e donot obey Raoult's law
e
Anixing V = 0 avi e interm © Avixing H # 0
» benzene + toluene ee on
» n-hexane + n-heptane

AZEOTROPES
Liquid mixture boiling without Positive deviations from Raoult's Negative deviations from Raoult's law
change in composition law p, <p. sand po, < po.
Solutions with +ve deviations “pp, > px, and p> pe, A isng = —Ve
~ ha Ree sate hanes ease
from ideal behaviour form
minimum boiling azeotropes. © Avixing V= +ve Acetone + Chloroform
Li = , * Li 1iZing

Solutions with -ve deviation from » Ethyl alcohol + Cyclohexane Water + Nitric acid
ideal behaviour form maximum > Benzene + Acetone
boiling azeotropes.
 MODERN'S abe + OF CHEMISTRY-AIl

it eee x M

Relative lowering in vapour pressure ; Ree =x, and M, = ~B =

Pa W, Pa Pa
Pa

Elevation in boiling point : AT, =K,xm,ei M, — Po

mieexto00
AT), X Wy
d K, MRT,
AH.4p * 1000

= : i : K; x Wy * 1000
Depression in freezing point : AT, = K, xm, Vig= a
gf a
4 K, MRT;
an SST a Sey
AH ¢ cion * L000

Osmotic pressure : i — {ai RI and M, = “B _ :

| 1
_ Observed colligative property
Normal colligative property

® In osmosis, there is net flow of solvent from solvent ® Thesolutions having same osmotic pressure
to the solution or from less concentrated solution are called isotonic solutions.
to more concentrated solution through the semi-
® Ifasolution has more osmotic pressure than
permeable membrane.
some other solution, itis called hypertonic.
® Asolution having less osmotic pressure than
the other is called hypotonic solution.

@ The reverse osmosis process can be

used for desalination of sea water.

Van't Hoff factor

i Normal molar mass — Observed colligative property

- Observed molar mass Normal colligative property
If observed colligative property < normal colligative property
or observed molar mass > normal molar mass.
= the solute is associated.
If observed colligative property > normal colligative property
or observed molar mass < normal molar mass
=> the solute ts dissociated.

e For solutes which donot undergo Colligative Properties for solutes undergoing
association or dissociation, association or dissociation
t=1 PA-PA ix
e For solutes undergoing association, Po E
Sed o ee AT, = iK,m
e For solutes undergoing dissociation, iK,m
i>I _- icRT
SOLUTIONS
27)
herteleymrtebehmesast ear

ed
—-*
pressure
Vapour >
Vapour
pressure
Vapour
—-*
pressure

X,=1 Mole x,=0 x,=1 Mole

Mole aAa=

xg=0 Fraction Xp=l X_g=0 Fraction X_=1 X_=0 Fraction Xg=1

> Ideal behaviour » Positive deviation from » Negative deviation from

ideal behaviour ideal behaviour

1.0 atm (1,013 bar)

Boiling point
elevation Freezing point
—*
Vapour
pressure depression
Vapour
—-®
pressure
solution

Temperature (K) Ty Tye

——> Temperature (K) ———->

» Elevation in boiling point > Depression in freezing point

\ (So aa Solved
o

In-text Questions //
Q.1. Calculate the mass percentage of benzene (C,H,) Ans. Mass of benzene = 30 ¢g
and carbon tetrachloride (CCL,) if 22 g of benzene
Moles of benzene = = = 0.385
is dissolved in 122 g of carbon tetrachloride.
Ans. Total mass of solution = 22 + 122 —- 144 ¢ (Mol. mass of C,H, = 78)
Mass of CCl, = 70 g
Mass % benzene = x 100 = 15.28%
Moles of CCl, = —2
154
= 0.454
122
Mass % CCI, = qa x 100 = 84.72% (Mol. mass of CCl, = 164)

Q.2. Calculate the mole fraction of benzene in solution

containing 30% by mass in carbon tetrachloride. Xoo
_ __0.385__ _ 9.459
0.385 + 0.454
| 278 MODERN’S abe + OF CHEMISTRY-XII

Q.3. Calculate the molarity of each of the following Moles of H,S = 0.195
solutions :
Moles of water = _ = 55.55
(a) 30 g of Co(NOQ,),.6H,O in 4.3 L of solution.

(b) 30 mL of 0.56 M H,SO, diluted to 500 mL. Mole fraction of H,S = __9.195____ = 0.0035
55.554+ 0.195
Ans. (a) Molar mass of Co(NO,),.6H,O
Now, p = K,x, Pressure = 0.987 bar
= 68.98 +2 x144+6x16+6x18

= 290.93 or K,, = 2 0287 har _ 259 bar.

X5 0.0035
30
= eee .
Moles of Co(NO,), = (),105
6H,O 290.93
Q.7. Henry’s law constant for CO, in water is
1.67 x 10° Pa at 298 K. Calculate the quantity of
Molarity = — = 0.024 M CO, in 500 mL of soda water when packed under
2.5 atm CO, pressure at 298 K.
(d) M,V, = MV, Ans. K. =d@ee 5/10" Pa
p = 2.6 atm = 2.6 x 101.325 x 10° Pa
0.6
x 30 mL = M, x 500mL
= 2.583 x 10° Pa
0.5
x 30 Now, p $i, X,
M, : = ——
=p = 0.03 M
or, vy = x = 2.588<10"Pa =1.517x10°
Q.4. Calculate the mass of urea (NH,CONH,) required
in making 2.5 kg of 0.25 molal aqueous solution.
Ans. 0.26 molal solution means 0.25 moles of urea in 1000 g Moles of water = ~ = 27.78
of water
Mass of urea = 0.256 x 60-15 ¢
Total mass of solution = 1000 + 15 = 1015 ¢ ty = —2—
Ny + No ~
= sp — =1517x10
27.784 Ty
or = 1.015 kg
1.015 kg of solution contain urea = 15 g n, = 0.0419 + 0.0015 n,
or 0.9985 n, = 0.0419
2.6 kg of solution will require urea = 1015 x 2.5
N, = 0.0420
= 36.94 ¢g Amount of CO, dissolved = 0.0420 x 44 = 1.85 g.
Q.8. The vapour pressure of pure liquids A and B are
Q.5. Calculate (a) molality (6) molarity and (c) mole
450 and 700 mm Hg at 350 K respectively. Find
fraction of KI if density of 20% (mass/mass) aqueous out the composition of the liquid mixture if total
solution of KI is 1.202 g mL1. (Hr. S.B. 2013)
pressure is 600 mm Hg. Also find the composition
Ans. 20% solution of KI means 20 ¢g of KI are present in of vapour phase.
100 g of solution or 80 g of water.
Ans. Let mole fraction of liquid A in solution = x,
Mass of KI = 20 g
Mole fraction of liquid B is solution = x, = (1 — x,)
Molar mass of KI = 39 + 127 = 166

Moles of KI = 20 = 0.120 Pp = Pat Pp=*,PA

+ XpPp
166

(a) Molality = a x 1000= 1.5 m. X,Pa+1-— x4) pp = X,~PA + PR —XaPB

600 = x, x ABO + 700 —X, x 700

: 100
(6) Volume of solution = —
1,202
-=83.19 mL 250 x, = 100
Molarity =
4 0.120 _
34.19 x 1000 = 1.44 M
, x, = 10 0.4
250
(c) Moles of KI = 0.120 x, = 1-04=0.6
Composition in vapour phase
Moles of H,O = -.= 4.44
Pa = X, pa = 0.4 x 4560 = 1860 mm
| 0.120
“KI ~ 4.44 + 0.120 Pp =XpPp = 0.6 x 700 = 420 mm
Q.6. H,S a toxic gas with rotten egg like smell is used
Total pressure = 180 + 420 = 600 mm
for qualitative analysis. If the solubility of H,S
in water at STP is 0.195 m, calculate Henry’s law
constant.
Mole fraction of A in vapour phase, y, = awe= 0.3

Ans. 0.195 m solution means that 0.195 moles of H,5 is

| ; . 420
dissolved in 1 kg of water. Mole fraction of B in vapour phase, y, = a0" 0.7
SOLUTIONS
279
Q.9. Vapour pressure of pure water at 298 K is 23.8 mm Q.11. Calculate the mass of ascorbic acid (Vitamin
Hg. 50 g of urea (NH,CONH,) is dissolved in 850 ¢g C, C,H,O,) to be dissolved in 75 g of acetic
of water. Calculate the vapour pressure of water acid to lower its melting point by 1.5°C.
for this solution and its relative lowering. K, = 3.9 K kg mol",
Ans. AT, Hee
Ans. Moles of urea = — = 0.833 M =6x12+1x8&+6x
16=176

Moles of water = = = 47,099 M K, x 1000 x wz

0.833
Mole fraction of urea = = 0.0173
0.833 + 47,222 3.9 x 1000 x wp
176 =
75X15
PaPA _ x, = 0.0173
Pa 176.x 75x 1.5
i) = 5.08 £

23.8 - Pa 0.0173 B~ 3.91000

23.5 : Q.12. Calculate the osmotic pressure in Pascals exerted by
oe oo Py = 0.412 a solution prepared by dissolving 1.0 g of polymer
Px = 23.39 of molar mass 185, 000 in 450 mL of water at 37°C.
Relative lowering of vapour pressure = 0.0173.
Ans. m = cRT = Rt
Q.10. Boiling point of water at 750 mm Hg is 99.63°C.
How much sugar is to be added to 500 g of water fl =
1.0
such that it boils at 100°C. 185000

Ans. AT, =100 — 99.63 = 0.37° V = 450 mL

M. - K, x 100 x wp T = 273 + 37 =310 K
: w, x AT,
R = 8.314 x 10° Pa L mol! K-}
0.522 x 1000 x wp 1.0 x 8.31410" x 310
342 = ——__—_—— ——
500 x 0.37 185,000 x 450/1000
5342 x 500 x 0.37
Ww = =121.7 30.96 Pa.
5 0.522 x 1000 =

Textbook Exercises //
Q.1. Define the term solution. How many types of
solutions are formed ? Write briefly about each Volume of solution = 1000 _ 66.49
1.504
type with an example.
Ans. A solution is a homogeneous mixture of two or more 1.08
Molarity = x 1000 = 16.24 M
substances whose composition can be varied. There are 66.49
nine types of solutions. Q.5. A solution of glucose in water is labelled as 10%
For details refer Text Page 1 — 2. w/w, what would be the molality and mole fraction
Q.2. Suppose a solid solution is formed between two of each component in the solution ? If the density
substances, one whose particles are very large and of solution is 1.2 g mL“, then what shall be the
the other whose particles are very small. What kind molarity of the solution ?
of solid solution is this likely to be ? Ans. Refer Solved Example 12 (Page 9).
Ans. Interstitial solid solution. Q.6. How many mL of 0.1 M HCl are required to react
completely with 1 g mixture of Na,CO, and NaHCO,
Q.3. Define the following terms : (i) Mole fraction, containing equimolar amounts of two ?
(74) Molality, (777) Molarity, (iv) Mass percentage.
Ans. Refer Solved Example 21 (Page 12).
Ans. Refer Text Page 2 — 5. Q.7. Asolution is obtained by mixing 300 g of 25% solution
Q.4. Concentrated nitric acid used in the laboratory and 400 g of 40% solution by mass. Calculate the
work is 68% nitric acid by mass in aqueous solution. mass percentage of the resulting solution.
What should be molarity of such sample of the acid
if the density of solution is 1.504 g mL! ? Ans. 300 g of 26% solution contains solute = a =75¢
Ans. 68% HNO, means that 68 g HNO, is present in
100 g of solution. 400 x 40
400 g of 40% solution contains solute = — =160¢
68
Moles of HNO, = 63 =1.08
Total solute = 75 + 160 = 236 g
Density of solution = 1.504 g mL"! Total solution = 300 + 400 = 700 g
ono MODERN'S abe + OF CHEMISTRY

Ans. Vapour pressure of pure water at the boiling point = 1

-AIl

% of solute in the final solution = ~~ x 100 = 33.5% atm = 1.013 bar

Vapour pressure of solution = 1.004 bar
% of water in the final solution = 100 — 33.6 = 65.5%. Mass of solute = 2 g
Q.8 An antifreeze solution is prepared from 222.6 g Mass of solution = 100 g
of ethylene glycol (C,H,O,) and 200 g of water. Mass of solvent = 100-2 =98 g
Calculate the molality of the solution. If the density Applying Raoult’s law
of the solution is 1.072 g mL“, then what shall be
the molarity of the solution ?
p M, x M,
Ans. Refer Solved Example 15 (Page 10).
Q.9. Asample of drinking water was found to be severely 1.013 — 1.004 y, 2x18
contaminated with chloroform (CHCI,), supposed
1.013 ~ Ms, x98
to be a carcinogen. The level of contamination was
15 ppm (by mass) : (1) express this in percent by
mass, (11) determine the molality of chloroform in ) — ——>—__—_
2x18 x 1.013 = 41.35 -1
the water sample. M; = ~0.009 x 98 a
Ans. Refer Solved Example 19 (Page 10). Q16. Heptane and octane form ideal solution. At
Q.10. What role does the molecular interactions play in 373 K, the vapour pressures of the two liquid
solution of alcohol and water ? components are 105.2 kPa and 46.8 kPa respectively.
Ans. There are strong hydrogen bonding in alcohol molecules What will be the vapour pressure of a mixture of
as well as water molecules. On mixing alcohol and water, 26.0 g of heptane and 35 g of octane ?
the molecular interactions become weak. Therefore, they 26.0
show positive deviation from ideal behaviour. As a result, Ans. Moles of heptane = ——=(0.26
100
the solution will have higher vapour pressure and lower
boiling point than that of alcohol and water. Moles of octane = 32-0 _ 0.31
Q.11. Why do gases always tend to be less soluble in 114
liquids as the temperature is raised ?
Ans. The dissolution of a gas in a liquid is exothermic process. x(heptane) = __9.26 __ 9 ang
Therefore, in accordance with Le-Chatelier’s principle, 0.26 + 0.31
with increase in temperature, the equilibrium shifts in
the backward direction. x(octane) = —0-31_ _ 0.544
0.26 + 0.31
Liquid + Gas — Dissolved gas AH =—ve
Therefore, the solubility of gas in solution decreases with Total pressure = 105.2 x 0.456 + 46.8 x 0.544
rise in temperature. A7.97 + 25.46
Q.12. State Henry’s law and mention some important
— 73.43 kPa.
applications.
Q.17. The vapour presure of water is 12.3 kPa at
Ans. Refer Text Page 17 — 19.
300 K. Calculate vapour pressure of 1 molal solution
Q.13. The partial pressure of ethane over a solution of a non-volatile solute in it.
containing 6.56 x 10° g of ethane is 1 bar. If the
solution contains 5.00 x 107° g of the ethane, then Ans. ———
1
Mole fraction of solute = =0.0177
what shall be the partial pressure of the gas ? 1+1000/18
Ans. According to Henry’s law
m=kxp fee, 0d
6.56 x 10° ¢ =k x Lbar p
or k = 6.56 x 10° g bar! 12.5 - Pa
Now, when m = 6.00 x 10% g,p =? = 0.0177
12.5
Applying m =k xp’
5.00 x 10-7 g = 6.56 x 107° g bar! x p
Q.18. Calculate the mass of a non-volatile solute (molar
5.00 x 10 mass 40 g mol") which should be dissolved in
P= 656X102 7.62 bar
114 g octane to reduce its vapour pressure to 80%.
Ans. Refer Solved Example 35 (Page 37).
Q.14. What is meant by positive and negative deviations
Q.19. A solution containing 30 g of non-volatile solute
from Raoult’s law and how is the sign of A_,.H
exactly in 90 g of water has a vapour pressure of
related to positive and negative deviations from
2.8 kPa at 298 K. Further, 18 g of water is then
Raoult’s law ?
added to the solution, the new vapour pressure
Ans. Refer text ; Page 28. becomes 2.9 kPa at 298 K. Calculate (7) molar mass
For positive deviation A_...,H = +ve of the solute, (71) vapour pressure of water at 298 K.
For negative deviation A_....H =—ve Ans. Refer Solved Example 35 (Page 37).
Q.15. An aqueous solution of 2% non-volatile solute exerts Q.20. A 5% solution (by mass) of cane sugar in water has
a pressure of 1.004 bar at the normal boiling point freezing point of 271 K. Calculate the freezing point
of the solvent. What is the molar mass of of the of 5% glucose in water if freezing point of pure
solute? water is 273.15 K.
SOLUTIONS

Ans. For cane sugar, AT; = 273.15 — 271.0 = 2.15° CuS = Cu” + S*
2.15 x 100 x 342
Ke = 7000 x5 fa. =. ies
= 14.706 K m+ Kk. = [Ca (81
For glucose solution, = §x*5=57
14.706 x 1000 = 5
AT, = = 4.085 K Solubility, s = K,, ~ ./6 x 10718
100 « 180
*. Freezing point = 273.15 — 4.085 = 269.07 K. = 2.45 x 10M
Q.21. Two elements A and B form compounds having ..Highest molarity = 2.45 x 10° M
formula AB, and AB,. When dissolved in 20 g of Q.28. Calculate the mass percentage of aspirin (C,H,O,)
benzene (C,H,), 1 g of AB, lowers the freezing point in acetonitrile (CH,CN) when 6.5 g of C,H,O, is
by 2.3 K, whereas 1.0 g of AB, lowers it by 1.3 K. The dissolved in 450 g of CH,CN.
molar depression constant for benzene is 5.1 K kg Ans. Refer Solved Example 11 (Page 9).
mol-!, Calculate atomic masses of A and B. Q.29. Nalorphene (C,,H,,NO,), similar to morphine, is
Ans. Refer Solved Example 49 (Page 45). used to combat withdrawal symptoms in narcotic
Q.22. At 300K, 36 g of glucose present per litre in its users. Dose of nalorphene generally given is 1.5
solution has an osmotic pressure of 4.98 bar. If mg. Calculate the mass of 1.5 x 10° m aqueous
solution required for the above dose.
the osmotic pressure of the solution is 1.52 bar
at the same temperature. What would be its Moles of solute
Ans. Molality = ——___—_————. x 1000
concentration? Mass of solvent (in g)
Ans. Refer Solved Example 55 (Page 52).
Molecular mass of nalorphene
Q.23. Suggest the most important type of intermolecular =19x12+21x1+1x14+3s3x16
attractive interaction in the following pairs.
= 311
(z) n-hexane and n-octane (it) I, and CCI, (it) 1.5 x10°
NaClO, and water (#v) methanol and acetone (v) Moles of nalorphene = 311. 4.82 x 10 °mol
acetonitrile (CH,CN) and acetone (C,H,O).
Ans. (4) van der Waals interactions, (11) van der Waals 4.82 x 10°
156x10% = x 1000
interactions (111) i1on-dipole (iv) hydrogen bonding Mass of water

(v) dipole-dipole interactions.

Q.24. Based on solute-solvent interactions, arrange 4.82 x 10° x 1000
Mass of water = 15x10
the following in order of increasing solubility in
n-octane and explain. Cyclohexane, KCl, CH,OH, = 3.21 g.
CH,CN. Q.30. Calculate the amount of benzoic acid (C,H.COOH)
Ans. KCl < CH,OH < CH,CN < cyclohexane. required for preparing 250 mL of 0.15 M solution
Q.25. Amongst the following compounds, identify which in methanol.
are insoluble, partially soluble and highly soluble Moles of solute
in water ? (7) phenol, (7) toluene, (711) formic acid, Ans. Molarity = — —_
eee Vol. of solution (in mL)
(7) ethylene glycol, (v) chloroform, (vi) pentanol.
0.15 — Moles of benzoic acid x 1000
Ans. (t) partially soluble (zz) insoluble (zzz) soluble (1v) soluble
250
(v) insoluble (vz) partially soluble. 0.15 x 250
Q.26. If the density of some lake water is 1.25 g mL“! and Moles of benzoic acid = 4000. 0.0375
contains 92 g of Nat ions per kg of water. Calculate
the molality of Na* ions in the lake. Molecular mass of benzoic acid (C,H,COOH)
Ans. Mass of Nat ions = 92 g =7x12+6x1+2x16
— 122
Moles of Nat ions = = =4 Amount of benzoic acid = 0.08765 x 122 = 4.575 g.
Mass of water = 1 kg Q.31. The depression in the freezing point of water
observed for the same amount of acetic acid,
Moles of solute
Molahty = ————_ trichloroacetic acid and trifluoroacetic acid
ey = Mass of solvent in kg
increases in the order given above. Explain briefly.
— a oe
Ans. The acids can be arranged in the following order of
1
Q.27. If the solubility product of CuS is 6 x 10", Calculate depression in freezing point :
the maximum molarity of CuS in aqueous solution. acetic acid < trichloroacetic acid < trifluroacetic acid
Ans. K,, of CuS = 6 x 10° This can be explained on the basis of degree of
If s is the solubility, then ionization which depends upon the strength of the acid.
lone Trifluoroacetic acid is more acidic than trichloroacetic Total number
MODERN'S abe + OF CHEMISTRY

of moles = m(1 — &) + ma@ + mo = m(1 + @)

-AXIl

acid which is more acidic than acetic acid. Therefore,

degree of ionization of these will decrease as : = Mato) _ 14a0= 10763
if
trifluoroacetic acid > trichloroacetic acid > acetic acid o = 1.0753 — 1 = 0.0753
Greater the degree of ionization, greater will be ‘“’ and [CH,FCOO-] = mo. = 0.60 x 0.0753 = 0.03765
hence depression of freezing point.
[H*] = ma = 0.50 x 0.0753 = 0.03765
Q.32. Calculate the depression in the freezing point of
[CH,COOH] = m (1 — @)
water when 10 g of CH,CH,CHCICOOH is added to
250 g of water. K, = 1.4 x 10°, K,= 1.86 K kg mol, 0.50 (1 — 0.07538) = 0.462
Molar mass of CH,CH,CHCICOOH
K, # [CH,FCOO ][H*]
Ans.
= 4x12+7x1+35.6+2
x 16 = 122.5 g mol! [(CH,FCOOH]
Moles of CH,CH,CHCICOOH = oe = 8.16 x 10 mol (0.03765) x (0.03765)
0462—~«~”W
8.16 x 10° x 1000 = 3.07 x 10°.
Molality of solution =
250 Q.34. Vapour pressure of water at 293 K is 17.535 mm Hg.
= 0.3265 m Calculate the vapour pressure of water at 293 K
If wis the degree of dissociation of CH,CH,CHCICOOH, when 25 g of glucose is dissolved in 450 g of water.

CH,CH,CHCICOOH = CH,CH,CICOO- + Ht om PP gee

Initial cone. c 0 0 Pp Mg Wa
Cone. after dissociation 17.535-p _25x18
ce(1— a) co col 17.535 180x450
K - COCO — 17.535 — p
= c(1—a@) —5.56 x 10°
17.535
114x107 17.535 — p =0.0975
or a= AK. = 0.065
0.3265 p =17.438 mm Hg.
To calculate Van't Hoff factor, Q.35. Henry’s law constant for the molality of methane
in benzene at 298 K is 4.27 x 10° mm Hg. Calculate
CH,CH,CHCICOOH ~— CH,CH,CHCICOO™ + H* the solubility of methane in benzene at 298 K under
At equi. 1-7 WA Oo 760 mm Hg.
_ 1 Ans. p=kxC
i seen 7 — = 1 + 0.065
= 1.065
760 mm —-4.256 x 10°mmxC
AT, =iK,m = 1.065 x 1.86 x 0.3265 CK 760 :
-178x10°
= 0.647° 4,25 x10

Q.33. 19.5 g of CH,FCOOH is dissolved in 500 g of water. or 1.78 x 10°

The depression in the freezing point of water Q.36. 100 g of liquid A (molar mass 140 g mol") was
observed is 1.0°C. Calculate the Van’t Hoff factor dissolved in 1000 g of liquid B (molar mass
and dissociation constant of fluoroacetic acid. 180 g mol"). The vapour pressure of pure liquid
(C.B.S.E. Sample Paper 2010) B was found to be 500 torr. Calculate the vapour
pressure of pure liquid A and its vapour pressure
Ans. Molecular mass of CH,FCOOH
in the solution if the total vapour pressure of the
—-~2x124+3x14+1*1942x16= T7T5 solution is 475 torr.
Moles of CH,FCOOH= a2.= 0.25 Ans. Moles of A = = (0,714

Molahty = = 0.50 m 1000 5 556

Moles of B =
500 180
AT, =K. x m1 0.714
Mole fraction of A = = 0.114
= 1.86 x 0.50 = 0.93 K 0.714 + 5.556
Van't Hoff factor
Mole fraction of B =1 — 0.114 = 0.886
_ Observed freezing point depression
Protal ~Pa + PR = Paxa + PpXp
~ Calculated freezing point depression
476 = Px x 0.114 + 500 x 0.886
= aa = 1.0753
0.93 A756 =0.114Px + 443
CH,FCOOH dissociates as : 0.114PA =32
CH,FCOOH = CH,FCOO- + H* Px =280.7 torr
Initial cone. m. 0 0
.. Vap. press. of pure A = 280.7 torr
After dissociation m(1 — a) 7.0L m7.CL
Vap pressure of Ain solution = 280.7 x 0.114 = 32 torr
(ais degree of dissociation)
SOLUTIONS 2/83 —

Q.37. Vapour pressure of pure acetone and chloroform at 328 K are 632.8 mm Hg and 741.8 mm Hg respectively.
Assuming that they form ideal solution over the entire range of composition, plot D,..015 Penioroform 224 P acetone
as a function of x_..,,,.- [he experimental data observed for different compositions of mixture is :
100 x yn 0 11.8 23.4 36.0 50.8 58.2 64.5 72.1
Paccton/mmHg 0 54.9 110.1 2024 322.7 4059 454.1 521.1
Pebloroforn/m™m Hg 632.8 548.1 469.4 359.7 257.7 193.6 161.2 120.7
Plot this data also on the same graph paper. Indicate whether it has positive deviation or negative deviation
from the ideal solution.
Ans.
a 0.00 0.118 0.645 0.721
Pa-ct,,/mm Hg 0 54.9 454.1 / 621.1
Perioroforn’mm Hg 632.8 648.1 161.2 120.7
p (total) 632.8 603.0 616.3 641.8

700

ieo _

300

200
(mm
Vap.
Hg)
pressure
100

0
01 02 03 04 05 06 O07 O08

Mole fraction of acetone (x,_...,.)

The plot of p(total) dips downwards and therefore, the solution shows negative deviation from ideal behaviour.

Q.38. Benzene and toluene form ideal solution over the Total vapour pressure
entire range of composition. The vapour pressure — 94.65 + 16.48
of pure benzene and toluene at 300 K are 50.71 = 41.13 mm Hg
mm Hg and 32.06 mm Hg respectively. Calculate Mole fraction of benzene in vapour phase
the mole fraction of benzene in vapour phase if 80
24.65
g of benzene is mixed with 100 g of toluene. PE “anaa 0.60

Ans Moles of benzene = = —~ 1.026 Q.39. The air is a mixture of number of gases. The
major components are oxygen and nitrogen with
(Molecular mass of C,H, = 78) approximate proportion of 20% is to 79% by volume
Moles of toluene 44s 1.087 at 298 K. The water is in equilibrium with air at
92 a pressure of 10 atm. Henry’s law constants for
(Molecular mass of C,H, = 92) oxygen and nitrogen at 298 K are 3.30 x 107 mm and
6.51 x 10mm respectively. Calculate the composition
Mole fraction of benzene,
of these gases in water.
1.026 , |
= To096+1.087 486 Ans. The vapour pressure of air over water = 10 atm. The
Mole fraction of toluene, , partial pressures of N, and O, are:
x, = ]1-—0.486 = 0.614
= Pro = #9 X10 = 7.9 atm
Ph, = Pr, * Xz 100
= 60.71 x 0.486 = 24.65 mm Hg = 7.9 x 760 mm = 6004 mm Hg

Be, x 0.614 = 16.48

apa= 32.06 x10
20
Pog = 7 2.0 atm.
2 = 2.0 x 760 mm Hg = 1520 mm Hg
MODERN'S abc + OF CHEMISTRY-XIl

Z 0.75 x 2.5
Applying Henry’s law "Rn = 947 x 0.082 x 300
Pug = K,(N,) x Xn, = 0.0308 mol.

Amount of CaCl, dissolved = 0.0308 x 111 = 3.42 g

or ~d9? = Ky(N,
=) 6.5110! Q.41. Determine the osmotic pressure of a solution
—9,22 x 10° prepared by dissolving 25 mg of K,SO, in 2 litre
= of water at 25° C, assuming that it is completely
Pc 1520
Similarly, dissociated.
. ~ Ky(O,)
( 3.3010"
Ans. If K,50O, is completely dissociated,
-4.6 x 10° oie 2h7+ 50,7
Q.40. Determine the amount of CaCl, (i = 2.47) dissolved b- 3
in 2.5 litre of water such that its osmotic pressure
Mol. mass of K,5O, = 2 x 39+ 32+4x 16=174
is 0.75 atm at 27°C,
tw = i cRT
Ans. For CaCl,, 1 =2.47
m =i cRT _ ; Wp x RT
_;"8yxRT
M,x V
=" = xR
_ 3x 25x 10 x0,082 x 298
2.47 X np X 0.082 x 300 174 x 2.0
0.75 =
2.5 =5.27 x 10° atm.

Exemplar Problems //
Subjective Questions

example, polar solutes dissolve in polar solvents and

non polar solutes in non polar solvents. Thus, we can
Q@.1. Components of a binary mixture of two liquids A say “like dissolves like’.
and B were being separated by distillation. After Q.4. Concentration terms such as mass percentage,
some time separation of components stopped and ppm, mole fraction and molality are independent
composition of vapour phase became same as that of of temperature, however molarity is a function of
liquid phase. Both the components started coming temperature. Explain.
in the distillate. Explain why this happened.
Ans. Molarity of a solution is defined as the number of moles
Ans. Since both the components are coming in the distillate of solute dissolved per litre of solution. Since volume
and composition of liquid and vapour phase become depends on temperature and changes with change in
same, this shows that hquids have formed azeotropic temperature, therefore, the molarity will also change
mixture. Therefore, these components cannot be with change in temperature. On the other hand, mass
separated at this stage by distillation. does not change with change in temperature, and
Explain why on addition of 1 mol of NaCl to 1 therefore, concentration terms such as mass percentage,
litre of water, the boiling point of water increases, mole fraction and molality which do not involve volume
while addition of 1 mol of methyl alcohol to one are independent of temperature.
litre of water decreases its boiling point. Q.5. What is the significance of Henry’s Law constant
Ans. NaCl is a non volatile solute, therefore, addition of K,,?
NaCl to water lowers the vapour pressure of water. Ans. Higher the value of Henry's law constant K,,, the lower
As a result, boiling point of water increases. On the is the solubility of the gas in the liquid.
other hand, methyl alcohol is more volatile than
water, therefore its addition increases the total vapour
Q.6. Why are aquatic species more comfortable in cold
water in comparison to warm water?
pressure over the solution. As a result, boiling point of
(A.LS.B. 2018)
water decreases.
Ans. At a given pressure, the solubility of oxygen in water
Q.3. Explain the solubility rule “like dissolves like”
increases with decrease in temperature. Therefore, the
in terms of intermolecular forces that exist in
concentration of oxygen in sea is more in cold water
solutions.
and thus presence of more oxygen at lower temperature
Ans. A substance dissolves in a solvent if the intermolecular makes the aquatic species more comfortable in cold
interactions are similar in both the components. For water.
SOLUTIONS

Q.7. (a) Explain the following phenomena with the help When the bottle is opened at room temperature
of Henry’s law. under normal atmosphere conditions, the pressure
(4) Painful condition known as bends. inside the bottle decreases to atmospheric pressure
(71) Feeling of weakness and discomfort in and excess CO, fizzes out.
breathing at high altitude. Q.8. Why is the vapour pressure of an aqueous solution
(6) Why soda water bottle kept at room temperature of glucose lower than that of water?
fizzes on opening ? Ans. In pure liquid water, the entire surface of liquid is
Ans. (a) (t) Deep sea divers depends upon compressed air occupied by the molecules of water. When a non volatile
for breathing at high pressure under water. The solute, such as glucose is dissolved in water some of the
compressed air contains N, in addition to O,, surface is covered by non volatile glucose molecules.
which are not very soluble in blood at normal Therefore, the fraction of surface covered by the solvent
pressure. However, at great depths when the molecules decreases. As a result number of solvent
diver breathes in compressed air from the molecules escaping from the surface also gets reduced
supply tank, more N, dissolves in the blood and consequently the vapour pressure of aqueous solution
and other body fluids because the pressure of glucose is reduced.
at that depth is far greater than the surface Q.9. How does sprinkling of salt help in clearing the
atmospheric pressure. When the diver comes snow covered roads in hilly areas? Explain the
towards the surface, the pressure decreases, phenomenon involved in the process.
N, comes out of the body quickly forming Ans. When salt is spread over snow covered roads, it lowers
bubbles in the blood stream. These bubbles the freezing point of water to such an extent that water
restrict blood flow, affect the transmission of does not freeze to form ice. As a result, the snow starts
nerve impulses. The bubbles can even burst melting from the surface and therefore, it helps in
the capillaries or block them and starve the clearing the roads. Hence, common salt acts as de-icing
tissues of O,. This condition is called “the agent.
bends,” which are painful and dangerous to Q.10. What is “semi permeable membrane”?
life.
Ans. The continuous sheets or films (natural or synthetic)
(iz) At high altitudes the partial pressure of O, is which contain a network of submicroscopic pores or holes
less than that at the ground level. This results through which small solvent molecules like water can
in low concentration of oxygen in the blood and pass; but the bigger molecules of solute cannot pass are
tissues of the people living at high altitudes or known as semi permeable membrane.
climbers. The low blood oxygen causes climbers to
become weak and unable to think clearly known
Q.11. Give an example of a material used for making
semipermeable membrane for carrying out reverse
as anoxia.
osmosis.
(6) To increase the solubility of CO, 1n soft drinks, the
soda water bottles are sealed under high pressure. Ans. Cellulose acetate.

Memory TEST W

Two liquids A and 5 boil at 125°C and 146°C respectively.

“a Say True or False
Liquid A will have higher vapour pressure.
1. Both molality and mole fraction are independent of Elevation in boiling point of 0.1 m NaCl solution will be
temperature. nearly twice that of 0.1 m glucose solution.
2. The solubilities of all ionic substances increase with 10 Solution of ethanol and cyclohexane shows positive
increase of temperature. deviation from Raoult’s law.
oe The depression in freezing point for 1 m solution of a 11 Colligative properties depend only upon the moles of
solute in water and benzene is same. solute and are independent of the nature of solute and
A, If observed value of the colligative property 1s more than solvent.
the normal value of same property then Van’t Hoff factor 12. The more concentrated solution is said to be hypertonic
is more than one. with respect to less concentrated solution.
5. Van't Hoff factor, : < 1if there is association of the solute 15. Minimum boiling azeotropes are obtained in liquid solution
in the solution. showing negative deviation from Raoult’s law.
6. The freezing point of 0.1 m solution of acetic acid in 14, For solution showing positive deviation from Raoult’s law
benzene is more than freezing point of 0.01 m solution. AV mixing = —Ve and AH, ig = +ve.
be Lowering in vapour pressure is a colligative property. 15. Molality of 1 M aqueous solution is less than 1 m.
Ts MODERN'S abe + OF CHEMISTRY

15. The variation of solubility of Na,SO,. 10H,O is a

-AXIl

i: Complete the missing links

discontinuous curve. With increase in temperature, it
1. At the same temperature, nitrogen gas is .............. first . . and then.
soluble in water than oxygen. 16. Beanies. of 1a eERSRaNER UESoxygen in the blood
2. For a non-ideal solution showing positive deviation and tissues, ae living at high altitude suffer from a
from Raoult’s law, A: ee IB wicccaciecees PON eae disease called.
16 ceceeeeseee = 17. People taking a Rit,of sate develop swelling or puffiness
3. The solubility of a solute decreases with increase in of their tissues. This disease is called ...............
temperature if dissolution process is .............. and 18. The solution having same osmotic pressure are called
increases with increase in temperature if dissolution is .. and they have same .............. .
(03) Choose the correct alternative
For 100% diesouauen of K,[Fe(CN),], Van't Hoff factor
- = .
1. The concentration term independent of temperature is
5. If Geena caslae mass of a solute is more than calculated molarity /molality -
molar mass, then the solute undergoes .............. in the 3. For acetone + ethyl alcohol non-ideal solution, DM is is
solvent. +ve/—ve-
6. The sum of mole fractions of all the components in a oe Chloroform + Benzene form non-ideal solution showing
three component system is equal to .............. positive/negative deviations.
7. If 0.1 m solution of NaCl freezes at — 4.2°C, then 0.1 m A pure NaCl solution with concentration more than 0.91%
solution of glucose will freeze at .............. in the same is called /rypertonic/ hypotonic.
solvent. A 0.01 m solution of cane sugar has less/more osmotic
8. The molarity of pure water is .............. pressure than 0.001 m solution.
9. The freezing point of 0.1 M NaCl slain GE ed eeeetacwcde _ A non-ideal solution showing positive deviation forms
than that of 0.1 M MgCl, solution. an azeotrope with lowest/highest boiling point.
10. A solution which has lower osmotic pressure compared The freezing of aqueous 0.1 M Na,CO, solution is
to that of other solution is called ................ less/more than 0.2 M NaOH solution.
11. AH_..;,, for solutionanne positive deviations from When the solute undergoes association in solution, the
value of Van't Hoff factor is less/more than 1.
Raoult’s law is. ;
In the reverse osmosis pressure larger/smailler than
12 A solution of some organic substance in benzene boils at
osmotic pressure is applied on the solution.
0.126°C higher than benzene. The molality of the solution
0 ee oie 2 a 10. Normality of 1.6 M CH,COOH solution is 1.5N/3.0N .
13. The most suitable colligative property to measure 11 Solubility of most of the gases in A liquid increases with
molecular mass of polymers is ........... decrease /increase in temperature.
14 Desalination of sea water is based on i phenomenon 12 Elevation in boiling point of 0.1 m CaCl, solution less /more
+)ee than 0.1 m NaCl solution.

elie’ Memory Test WW

Say True or False |B. | Complete the missing links
1. True less 2. +ve, —ve
2. False. Solubility increases or decreases with temperature
exothermic, endothermic
depending upon whether solubility process is endothermic
5 5. association 6. 1 7. — 2.1°C
or exothermic.
3. False. It depends upon nature of solvent. 56.6 M 9, more 10. hypotonic 11. +ve
4, True 5. True 0.06 m 13. osmotic pressure
6. False. The depression in 0.1 m solution of acetic acid is reverse osmosis 15. increases, decreases
more than 0.01 m solution of benzene so that f.p. of first anoxia 17. edema
solution is less. isotonic, molar concentration.
7. False. Relative lowering in vapour pressure is colligative
property and not lowering in vapour pressure. Choose the correct alternative
8. True 9. True 10. True
1. molahty 2. +ve 3. negative 4. hypertonic
11. False. Colligative properties depend upon the nature of
solvent. 5. more 6. lowest 7. more 8. less
12. True 13. False 9. larger 10. 1.5N 11. decrease
14, False. AH_.. =+ve, AV... =+4+ve 15. False. 12. more
mixing mixing
SOLUTIONS

Higher Order Thinking Skills

or Advanced Level
QUESTIONS WITH ANSWERS
I, Il, or Ill represent pure liquids and which represents
HOTS
the solution ?
1. Why is a person suffering from high blood pressure
is advised to take minimum quantity of common salt ?
Ans. Osmotic pressure is directly proportional to the
concentration of the solutes. Our body fluids contain a number
of solutes. If a person takes more salt, the concentration of Nat
and Cl ions entering into the body fluid, raises the concentration
of the solutes. As a result, osmotic pressure increases which
may rupture the blood cells.
2. Why water cannot be separated completely from
ethanol by fractional distillation ?
Ans. Ethanol and water (95.4% ethanol and 4.6% H,O) Ans. The vapour pressure of a mixture of two volatile
form a constant boiling mixture (azeotrope) boiling at 351.5 K. liquids is always intermediate between the vapour pressures
Hence, further water cannot be removed by fractional distillation. of the two liquids. Thus, the curves I and III represent pure
3. Why is melting point of a substance used as a liquids and the middle curve II represents the solution.
criterion for testing the purity of a substance ? 8. If vapour pressure of liquid A is greater than
the vapour pressure of liquid B, then boiling point of
Ans. A pure compound has a sharp melting point. Impurities
A is lower than that of liquid B. Do you agree with the
present, if any, lowers the melting point of the compound
statement? Explain.
(similar to depression in freezing point).
Ans. This statement is true. If vapour pressure of a liquid
4. Ifglycerine, C,H.(OH), and methyl alcohol, CH,0H is high, lesser heating is needed to make its vapour pressure
are sold at the same price per kg, which would be cheaper equal to the external pressure (atmospheric pressure). Therefore,
for preparing an anti-freeze solution for the radiator of its boiling point is lower.
a car?
9. Pure benzene has vapour pressure three times
Ans. Methyl alcohol, CH,OH is cheaper because it has that of pure toluene. They form nearly ideal solution.
lower molecular mass and a given mass of CH,OH contains What would be the ratio of their mole fractions in the
more moles than the same mass of glycerine. More moles of vapour phase of a solution having equal mole fractions
solute means higher molality and therefore, it causes lower of benzene and toluene.
freezing point (because AT, will be more). In other words, it Ans. Since benzene and toluene have equal mole fractions
would take less methyl alcohol to protect a radiator to a given in the solution,
freezing point.
Py — Po (" X, = x,)
5. If K, for water is 1.86° C/m, explain why 1 m NaCl P; P;
in water does not have a freezing point equal to =o
(7) -1.86°C and (it) -3.72°C. Since the vapour pressures 1n the vapour phase are in the
Ans. (1) There are two moles of ions per mol of NaCl. ratio of their mole fractions, then
Therefore, AT, cannot be equal to 1.86 and freezing point cannot 2= 3
be equal to 0 — 1.86 = -1.86°C.
y
(iz) AT, cannot be equal to 2 x 1.86 = 3.72 and freezing
Advanced Level Problems
point = —3.72 because there are strong interionic attractions
for 1m solution so that the degree of ionization is not 100%
at the freezing point. The value of i is some what less than 2. 10. 0.052 g of glucose (C,H,,0,) has been dissolved
in 80.2 g of water. Calculate (7) the boiling point
6. Why is camphor preferred as a solvent in finding
and (ii) freezing point of the solution (K = 186 K m1,
the molecular mass of naphthalene by Rast method ? K, = 5.2 K mm").
Ans. Camphor has a large value of K, (39.7° C m-}) Ans. Elevation in boiling point may be calculated from
so the depression in freezing point is large for solution of the relation,
naphthalene in camphor. This can be measured by even ordinary K, x wp, x 1000
thermometer. AT, =
Mz Xwy,
7. The following figure shows vapour pressure curves Ww, = 0.052 g, w, = 80.2 g, K, = 5.2 K m™, M, = 180
of two pure liquids and solution of the two. Which curves
| ar88 MODERN'S abc + OF CHEMISTRY-Aill

AT, = 0.2% 0.052 x 1000 ~ 0.0187 . . = 11.625

180 x 80.2 Freezing point = 0 — 11.625
Boiling point of water = 373 K = —11.625°C
Boiling point of solution = 373 + 0.0187 = 373.0187 .. Vehicle may be parked outdoor not below —11.625°C
= 373.02 K temperature.
Now, de ion in freezi int |
OEE Serer eran aia 13. The mole fraction of toluene in a solution in
AT. = Ky x Wp x 1000 benzene is 0.50. Calculate the weight percent of toluene
fo My x Ww, in solution.
wW, = 0.052 g,w, = 80.2 g, K-=186 K m+, M, = 180 Ans. Let the weight percent oftoluene in solution 1s x. This
: | means x g of toluene are present in 100 g of solution.
1.86% 0.052 1000 _
AT; = ——Jaoxs02 0.067 Wt. of toluene = xg

Freezing point of water = 273 K Wt. of benzene = (100 —-x)g

Freezing point of solution = 273 — 0.067 = 272.933 K. Mol. wt. of benzene (C,H,) = 78
11. The degree of dissociation of Ca (NO,), in dilute Mol. wt. of toluene (C,H.CH,) = 92
aqueous solution containing 7.0 g of the salt per 100 g of
water at 100°C is 70 percent. If the vapour pressure of Now, de: 2 5
water at 100°C is 760 mm, calculate the vapour pressure Nz +My
of the solution.
Ans. Calcium nitrate dissociates as : 55
4s Oy = hr 0.5
= ; Ca(NO,), —— Ca + 2NO, 7 (100 — x)

ti me e . 1 0 0 92° 73
After dissociation 1-x x rl |
Total no. of moles after dissociation = 1—x +x + 2x au
=] + 2x —_
92 =
Here x = 70% =0.7 78x +92(100 -x)
No. of moles after dissociation = 1 + 2 x 0.7 = 2.4 92x78
. Moles of solute after dissociation = 2.4 _ 04 ae 92x 78 _ = 05
= Normal moles of solute 1 92 78 x + 92(100
—x)
0 78x = 39x + 4600-46x
Now, “4 —"4 = ix
oe ' 85 x = 4600

Xp = —“B__ ,, “B = —- (For dilute solution) x * = 541

je ea | pee = Wt% of toluene = 54.1.
W,=7.0g, wy, = 100g, M,= 164, M,= 18 14. The freezing point of a solution containing
70x18 50 cm? of ethylene glycol in 50 g of water is found to be
We = 164x100 Fie - 34°C. Assuming ideal behaviour, calculate the density
aos of ethylene glycol.
ee = 2.4 x 0.00768 Ans. Depression in freezing point,
A
Pa’ —-Pax = 2.4 x 0.00768 x 760 = 14.0 mm Hg AT. = K,; x Wg x 1000
P, = 760—14.0 = 746 mm Hg. f My X Wa
12. A motor vehicle radiator was filled with 8 L of 4 |
water to which 2 L of methyl alcohol (density 0.8 g/mL) K, = 1.86 Km”, AT; = 0 — (-34) = 34
were added. What is the lowest temperature at which w, = ?,w, = 50g, M,= 62
the vehicle can be parked outdoors without a danger :
that water in the radiator will freeze ? K, of water 1.86 x w, x 1000
= 1.86 K m) ‘ of = 62 x 50
Ans. Let us calculate the depression caused by the addition
of methyl alcohol. 34 x 62 x 50 ee

ae f = ee . “B ~ 186x 1000
w, xMp,
w, = 8000 x 1.0 = 8000 g (Density of water = 1 g/ml) as a Yee
w, = 2000 x 0.8 = 1600 ¢ 56.67 = 50 xd

Me ==
AT. 2186x1000
x1600 or pe= “=,oa2 cm
f 8000 x32
SOLUTIONS

y- Revision Exercises
»»> Very Short Answer Questions <4 26. State the condition resulting in Reverse Osmosis.
(A..S.B. 2007)
1. Give one example of each of solid in gas and liquid in gas 27. Define osmotic pressure. (A..S.B. 2007)
solution. 28. What is meant by reverse osmosis ? (A.S.B. 2011)
2. Why does the molality of a solution remain unchanged with
temperature? (Assam S.B. 2013) MCQs from State Boards’ Examinations
3. What will be mole fraction of water in methanol solution 29. Which of the following solution shows maximum depression
containing equal number of moles of water and methanol ? in freezing point?
4. Define molal depression constant. How is it related to (a) 0.6 M Li,S80, (6) 1M NaCl
enthalpy of fusion ? (c) 0.6 M AL(SO,), (d) 0.5 M BaCl,
5. The boiling point increases and freezing point decreases (Maharashtra S.B. 2013)
when sodium chloride is added to water. Explain.
30. The molality of pure water is
(H.P.S.B. 2002)
(a) 55.5 (6) 50.5
6. Sodium chloride is used to clear snow from roads. Explain.
(c) 18 (d) 60.5
(H.P.S.B. 2002)
(Hr. S.B. 2018, 2015, 2018)
7. What is the general effect of temperature on the solubility
31. Constant boiling mixtures are called
of a gas 1n a liquid ?
(a) ideal solutions (6) azeotropes
8. When is the value of Vant Hoffs factor more than one ? (c) isotonic (d) None of these
9. Why does water from the soil rise to the top of a tall tree? (Hr. S.B. 2013)
10. What is the effect of temperature on molality of solution ? 32. The colligative properties of a dilute solution depend on
(Ar. S.B. 2005, H.P.S.B. 2005) (a) the nature of the solute
11. Calculate the normality of 1.6 MH,SO,. (Hr. S.B. 2006) (6) the nature of the solvent
12. How is AT, and AT, related to molecular mass of a solute ? (c) the number of particles of solute
(dq) the molecular mass of solute. (Mizoram S.B. 2014)
(Pb. S.B. 2006)
13. What is the normality of 0.5 M aqueous solution of tribasic 3a. The concentration term independent of temperature is :
acid ? (Pb. S.B. 2006) (a) Normality (6) Mass-volume per cent
14. Two liquids A and B boil at 145° C and 190°C respectively. (c) Molality (d) Molarity
Which of them has a higher vapour pressure at 80° C ? (Manipur S.B. 2014, Hr. S.B. 2015,
Meghalaya S.B. 2015, Mizoram S.B. 2018)
(D. S.B. 2006)
34. The number of moles of NaCl in 3 litres of 3 M solution
15. Under what condition Van’t Hoff factor ‘7 is less than one?
18:
(Pb. S.B. 2007)
(a) 1 (6b) 3
16. Under what condition Van’t Hoff factor ‘i’ is equal to
(c) 9 (dq) 271.Mizoram S.B. 2014)
unity ? (Pb.S.B. 2007)
17. Define Raoult’s law. (.P.S.B. 2012)
35. In countries nearer to polar region, the roads are sprinkled
with CaCl,. This is
18. Why does rubbing of isopropy] alcohol give a cooling sensation
to the skin ? (a) to minimise the effect of snow on roads
19. Define azeotropic mixture. (A.P.S.B. 2013, 2015) (6) to minimise pollution
20. Why is molality preferred for expressing concentration than (c) to minimise the accummulation of dust on the road
molarity? (J.K.S.B. 2013, H.P.S.B 2013) (ad) to minimise the wear and tear of the roads
21. Mention the enthalpy of mixing (A, ..H) value to form an (H.P. S.B. 2015)
ideal solution. (Karnataka S.B. 2014) 36. For solutes which do not undergo any association or
22. Define Henry’s law. (H.P.S.56. 2012, Karnataka S.B 2018, dissociation in a solute, van’t Hoff factor (z) will be
Manipur S.B. 2018) (a) less than 1 (6) more than 1
(c) equal to 1 (dq) zero (Mizoram S.B. 2015)
»> CBSE QUESTIONS <q 37. Which of the following 0.1 M aqueous solution is likely to
have the highest boiling point?
23. What is the sum of the mole fractions of all the components (a) Na,SO, (6b) KCl
in a three component system ? (A.L.S.B. 2004) (c) Glucose (dq) Urea (Tripura S.B. 2016)
24, How is the molality of a solution different from its molarity? 38. Which of the following solutions will have the minimum
(A..S.B. 2004) freezing point?
25. What would be the value of van’t Hoff factor for a dilute (a) 0.1M FeCl, (6) 0.1M BaCl,
solution of K,SO, in water ? (c) 0.1M NaCl (2) 0.1M Urea
(A.L.S.B. 2005, Uttarakhand S.B. 2012) (Mizoram S.B. 2016)
| 200
39. Isotonic solutions have
MODERN'S abc + OF CHEMISTRY-All

(c) intermolecular hydrogen bonding in ether

(a) same boiling point (6) same vapour pressure (ad) intermolecular hydrogen boonding in alcohol
(c) same melting point (d) same osmotic pressure (Nagaland S.B. 2018)
(Meghalaya S.B. 2016)
40. The value of Henry’s constant Aj, >> Short Answer Questions <4
(a) increases with increase in temperature 1. Define the following terms:
(6) decreases with increase in temperature
(a) Molality (6) Osmotic pressure
(c) remains constant
(c) Van’t Hoff factor (d) Molarity (Hr. S.B. 2018)
(d) first increases, then decreases (Meghalaya S.B. 2016)
41. Mole fraction of a solute in 2.5 molal aqueous solution is 2. (a) Establish a relationship between mole fraction of solute
(a) 0.48 (6b) 0.048
and molality of a binary dilute solution.
(c) 4.3 (d) 43 (Hr. S.B. 2017) (Manipur S.B. 2014)
42, Which of the following concentration of solution depends (6) Molality is preferred over molarity. Why?
on temperature ? (c) Which has higher boiling point 0.1M NaCl or 0.1M
(a) molality (6) molarity glucose? (A. P.S.B. 2018)
(c) mass % (d) mole fraction 3. (a) Define Raoult’s law and derive it.(Uttarakhand S.B. 2014)
(Assam S.B. 2017) (6) Why is osmotic pressure considered to be a colligative
43. Two solutions A and B are separated by a semipermeable property ? (Maghalaya S.B. 2013)
membrane. If the solvent flows from A to B, then
4. (a) How isthe colligative property changed when the solute
(a) Ais more concentrated than B undergoes association in solution ?
(6) Ais less concentrated than B
(6) Describe a method to determine the osmotic pressure of a
(c) both A and B are of same concentration
solution. How does it help in calculating the molar mass
(d) both A and B get diluted (Meghalaya S.B. 2017) of the solute ?
44, The van’t Hoff factor : for a compound which undergoes
5. Why do we get abnormal molecular masses from colligative
dissociation in one solvent and association in another solvent
properties? What is Van’t Hoff factor? How will you explain
is respectively
cases of association and dissociation of solute in such cases?
(a) less than one and greater than one
(Hr. S.B. 20183)
(6) less than one and less than one
(c) greater than one and less than one
6. (a) What is meant by positive and negative deviations
from Raoult’s law and how is the sign of A,_,H related to
(d) greater than one and greater than one
positive and negative deviations from Raoult’s law ?
(Meghalaya. S.B. 2017)
(6) Mixing acetone and chloroform occurs with reduction
45. At higher altitudes, the boiling point of water decreases
in volume and is endothermic process. What type of
because
deviation from Raoult’s law is shown in this case and
(a) the atmospheric pressure is low
why ?
(6) the atmospheric pressure is high
7. Explain :
(c) the temperature is low
(d) the temperature is high (Mizoram S.B. 2017) (i) A person suffering from high blood pressure is advised
to take minimum quantity of common salt. Explain.
46. Maximum amount of a solid solute that can be dissolved in
a given amount of a liquid solvent does not depend upon (11) A peeled egg when dipped in water swells while in
(a) pressure (6) temperature saturated brine solution it shrinks.
(c) nature of solute (d) nature of solvent (111) The bottle of liquid ammonia is cooled before opening
(Hr. S.B. 2017) the seal.
47. Low concentration of O, in the blood of people living at (iv) Semipermeable membrane of Cu,[Fe(CN),] is not used
high altitude is due to for studying osmosis in non-aqueous solutions.
(a) low temperature 8. (a) What is osmotic pressure and how is it related to the
(6) low atmospheric pressure molecular mass of the non-volatile substance ?
(c) high atmospheric pressure (6) What advantage the osmotic pressure has over the
(d) none of the above (Hr. S.B. 2017) elevation in boiling point method for determining the
48. The units of ebullioscopic constant is molecular masses ?
(a) K kg mol? (6) mol kg K"} 9. Define azeotropes and explain briefly minimum boiling
(c) K mol kg (d) none of these azeotropes by taking suitable example.
(Hr. S.B. 2017)
49, Molar solution means 1 mole of solute present in (CBSE Sample Paper 2011)
(a) 1000 g of solvent (6) 1000 g of solution 10. State Raoult’s law for a solution containing volatile liquids.
(c) 1 litre of solvent (d) 1 litre of solution Explain with suitable example the concept of maximum
(Mizoram S.B. 2018) boiling azeotropes ? (CBSE Sample Paper 2011)
50. An ether is more volatile than an alcohol having the same 11. (a) When dehydrated fruits and vegetables are placed in water,
molecular formula due to they slowly swell and return to original form. Why ? What
(a) dipolar character of ether is the effect of temperature on the process ? Explain.
(6) aleohols having resonance structure (Pb. S.B. 2016)
SOLUTIONS

(6) Prove that relative lowering in vapour pressure of a liquid 22. (a) CaCl, is used to clear snow in cold countries. Explain.
on addition of non volatile solute is a colligative property. (Hr. S.B. 2015)
(H.P.S.B. 2012) (6) Define the following and write their units:
12 (a) Sodium chloride solution freezes at lower temperature (a) Molarity (6) Molality (c) Normality
than water but boils at higher temperature than water. Or
Explain. What are colligative properties? Show that relative
(6) What are hypertonic solutions? Explain with the help of lowering in vapour pressure is a colligative property.
example. (H.P.S.B. 2012) (Hr. S.B. 2015)
135. (a) Define osmotic pressure. How can molar mass of a Zo. Define the following:
substance be determined from the measurement of (t) Boiling point
osmotic pressure of a solution? (Assam S.B. 2013) (it) Molal depression constant (Hr. S.B. 2015)
(6) What is osmotic pressure ? Show that it 1s a colligative 24. (a) Why is boiling point of water increased on addition of a
property. (Hr. S.B. 2017) non-volatile solute in it?
(c) What will happen ifa patient is given hypertonic solution (b) Why does NaCl solution freeze at lower temperature than
of glucose ? (Meghalaya S.B. 2018) water but boils at higher temperature than water?
14. (a) Prove that relative lowering in the vapour pressure Is a (Pb. S.B. 2015)
colligative property. 20. (a) Define hypertonic solution.
(6) Differentiate between ideal and non-ideal solutions. (Db) Explain that the depression in freezing point is a
(c) Define colligative properties and give its types. colligative property. Calculate the molar mass of a solute
(H.P.S.B. 2018) with it. (H.P.S.B 2017)
15. (a) Define the following : 26. State Henry’s law.
(1) Henry’s law At the same temperature, CO, gas is more soluble in water
(tt) Raoult’s law (Hr. S.B. 2018) than O, gas. Which one of them will have higher value of
(6) Give two applications of Henry's law. (Hr. S.B. 2018) Hiei? (Assam S.B. 2017)
16. (a) When Hgl, is added to aqueous solution of KI, why is 27. (a) State Henry’s law and mention its important applications.
there an increase in osmotic pressure of solution? (b) What would be the value of van’t Hoff factor for a dilute
(b) Out of 1M urea solution and 1M KC] solution, which one solution of K,SO Py (Uttarakhand S.B. 2015)
has higher freezing point?
28. (a) What are the characteristics of ideal solution?
(Pb. S.B 2018, H.P.S.B. 2018)
(c) Commerically available HC] contains 38% HCl by mass. (6) Why does vapour pressure of a liquid decrease when a
Calculate molality of the solution. (Pb. S.B. 2018) non-volatile solute is added into it?
17. Define freezing point. Explain why the freezing point of a (Manipur S.B. 2017)
solvent is lowered on dissolving a non-volatile solute into 29. (a) Define molarity and mole fraction giving examples.
it. (6) How is the molecular mass of a solute related to the
Or depression in freezing point of the solution?
What do you mean by abnormal molecular mass? Show (Manipur S.B. 2017)
that relative lowering of vapour pressure is a colligative (c) What is reverse osmosis? Mention one of its application.
property. (Jammu S.Z. 2018)
(Meghalaya S.B. 2018)
18. (a) Define : oO. What is meant by positive deviations from Raoult’s law? Give

(i) Molality of a solution an example. What is the sign of A_..H for positive deviation?
(iz) Isotonie solutions. (Karnataka S.B. 2018) Or
Define azeotropes. What type of azeotropeis formed by positive
(6) Van’t Hoff’s factor for a solution is less than 1, what is
deviation from Raoult’s law? Give an example.
the conclusion drawn from it? (Karnataka S.B. 2018)
(D.S.B. 2015)
(c) Why dosome non-ideal solutions show positive deviation
ol. (i) Two solutions are isotonic. What is meant by the
from ideal behaviour? Give suitable diagram.
statement.
(Nagaland 8.B. 2018) (zt) When a little amount of common salt is added in water,
19. What are the colligative properties ? Name the colligative the boiling point increases. Explain why?
property which is widely used to determine the molecular (Kolkata S.B. 2016)
mass of macromolecules. (Meghalaya S.B. 2017)
ode What are colligative properties? Prove that relative lowering
20. (a) Define an ideal solution and write one of its in vapour pressure is a colligative property. (H.P. S.B. 2016)
characteristics.
oo- State Raoult’s law for an ideal solution containing non-volatile
(6) Some liquids on mixing form ‘azeotropes’. What are solute. Why do non-ideal solutions show positive deviation
‘azeotropes ? (D.S.B. 2014)
from Raoult’s law? (H.P.S.B. 2016, Tripura S.B. 2016)
21. (a) State Henry’s law. What is the effect of temperature
oA, Define boiling point. What is elevation in boiling point? How
on the solubility of a gas in a liquid ?
will you find the molecular mass of a solute by using this
(6) State Raoult’s law for the solution containing volatile property? (H.P.S.B. 2016)
components. What is the similarity between Raoult’s
oe (a) What is osmotic pressure? How is it related to the
law and Henry’s law ? (D.S.B. 2014)
concentration of a solute in a solution?
[202 Or
MODERN'S abc + OF CHEMISTRY-All

mass 185000 in 500 ml of water at 37°C. [R = 0.0821

(6) State and explain Raoult’s law for a solution containing L atm K7? mol“4]. (Kerala S.B. 2014)
non-volatile solute. (Meghalaya S.B. 2016) 5. Either
36. Define the following terms: (a) A solution of NaOH is made by dissolving 0.8 g of it
(1) Ideal solution in 100 ml] of its solution. Calculate the molarity of the
(it) Molarity (M) (D.S.B. 2017) solution.
(6) What is the effect of addition of non-volatile solute to the
37. Define the following terms:
vapour pressure of a pure liquid ? Give reasons for your
(z) Abnormal molar mass
answer.
(11) Van’t-Hoff factor (D.S.B. 2017) (c) Calculate the molar mass of a substance 1.3 g of which
when dissolved in 169 ¢ of water gave the solution which
»> of=F Re SSeS <4 will boil at 100.025 °C at 1 atm. (K, = 0.52 Km).
Or
38. State Raoult’s law for solutions of volatile liquids. Taking
(d) Calculate the molarity and molality of a 15% solution
suitable examples explain the meaning of positive and
(by wright) of H,SO, of density 1.020 g. cm.
negative deviations from Raoult’s law.
(e) State Henry’s law of solubility of gases in liquid. Why do
(A.I.S.B. 2008; D.S.B. 2008) we see effervescence when a cold drink bottle is opened ?
39. Define the terms, ‘osmosis’ and ‘osmotic pressure’. What is () Molar mass of CH,COOH in aqueous solution as
the advantage of using osmotic pressure as compared to determined by the use of colligative properties is
other colligative properties for the determination of molar approximately double of the expected value. Why ?
masses of solutes in solutions? (A..S.B. 2010) (Meghalaya S.B. 2014)
40. State the following: 6. (a) Among the following, which is not a colligative property?
(t) Raoult’s law in its general form in reference to solutions. (1) Osmotic pressure
(it) Henry’s law about partial pressure of a gas in a mixture. (it) Elevation of boiling point
(A..S.B. 2011) (111) Vapour pressure
41, State Henry's law. Why do gases always tend to be less soluble (tv) Depression of freezing point
in liquids as the temperature is raised?
(6) 200 cm? of an aqueous solution of a protein contains
Or
1.26 g of protein. The osmotic pressure of solution at
State Raoult’s law for the solution containing volatile
300 K is found to be 8.3 x 10 bar. Calculate the molar
components. Write two differences between an ideal solution
mass of protein (R = 0.083 L bar K™ mol).
and a non-ideal solution. (A.L.S.B. 2015)
(c) What is the significance of van’t Hoff factor?
42, (i) Write the colligative property which is used to find the
(Kerala S.B. 2015)
molecular mass of macromolecules.
(tt) In non-ideal solution, what type of deviation shows the 7. (a) Mention a method used for desalination of sea water.
formation of minimum boiling azeotropes? (b) Define the term ‘osmotic pressure’. How does osmotic
pressure of a solution vary with temperature?
(A.I.S.B. 2016)
43, Give reasons for the following: (c) Calculate molarity of a solution containing 11.7 g NaCl
(a) Measurement of osmotic pressure method is preferred in 2.0 L solution. (M,.,, = 58.5 g mol)
for the determination of molar masses of macromolecules (Assam S.B. 2016)
such as proteins and polymers. 8. (a) Number of moles of the solute per kilogram of the solvent is
(6) Aquatic animals are more comfortable in cold water than (t) Mole fraction (it) Molality
in warm water. (iit) Molarity (tv) Molar mass
(c) Elevation of boiling point of 1 M KC] solution is nearly
double than that of 1 M sugar solution. (A.J.S.B. 2018) (b) “The extent to which a solute is dissociated or associated
can be expressed by Van't Hoff factor.’ Substantiate the

D> Longfinswer Questions

1. What are ideal and non-ideal solutions? What type of
XC statement.
(c) The vapour pressure of pure benzene at a certain
temperature is 0.850 bar. Anon-volatile, non-electrolyte
non-idealities are exhibited by cyclohexane ethanol and solid weighing 0.5 g when added to 39 g of benzene (molar
mass 78 g mol), vapour pressure becomes 0.845 bar.
acetone chloroform mixtures. Give reasons for your answer.
What is the molar mass of the solid substance?
2. What is Van't Hoff’s factor? What possible values can (Kerala S.B. 2016)
it have if the solute molecules undergo (i) association 9. (i) Prove that elevation in boiling point is a colligative
(it) dissociation in solution. Prove that osmotic pressure property.
is a colligative property. (11) The boiling point of benzene 1s 353.23 K. When 1.80 g of
3. (a) What is elevation in boiling point? How can you calculate a non-volatile solute was dissolved in 90 g of benzene, the
molecular mass of a solute using it ? Show that it is a boiling point is raised to 354.11 K. Calculate the molar
colligative property. mass of solute. (K, for benzene = 2.53 K kg mol")
(6b) Calculate molality and molarity of KI if density of 20% (Pb. S.B. 2017)
(mass/mass) aqueous KI is 1.202 g/mL. (Hr. S.B. 2013) 10. (i) Prove that depression in freezing point is a colligative
4, Osmotic pressure is a colligative property and it is property.
proportional to the molarity of solution. (ii) 45 g of ethylene glycol (C,H,O,) is mixed with 600 g of
(a) What is osmotic pressue ? water. Calculate the freezing point depression. (K, for
(6) Molecular mass of NaCl determined by osmotic water = 1.86 K kg mol!) (Pb. S.B. 2017)
pressure measurement is found to be halfof the actual 11. (i) Prove that osmotic pressure is a colligative property.
value. Account for it. (11) Calculate the molar concentration of urea solution if it
(c) Calculate the osmotic pressure exerted by a solution exerts an osmotic pressure of 2.45 atmosphere at 300 K.
prepared by dissolving 1.5 g of a polymer of molar (R = 0.0821 L atm.mol ?K%) (Pb. S.B. 2017)
SOLUTIONS

12. (a) Give the definition of solubility of a substance. (a) Define the following terms :
(6) Show that total vapour pressure over the solution of two (1) Ideal solution (11) Azeotrope (111) Osmotic pressure
liquids 1 and 2 at a particular temperature varies linearly (6) A solution of glucose (C,H,,O,) in water is labelled as
with the mole fraction of a component. 10% by weight. What would be molality of the solution?
(Assam S.B. 2018) (Molar mass of glucose = 180 g mol). (A.I.S.B. 2013)
13. (a) Asolution containing 15 g urea (molar mass = 60 g mol?) 18. (a) Define the following terms:
per litre of solutionin water has the same osmotic pressure (¢) Molarity
as a solution of glucose (molar mass = 180 g mol!) in (it) Molal elevation constant (K,).
water. Calculate the mass of glucose present in one litre
(6) A solution containing 15 g urea (molar mass = 60 g
of its solution.
mol!) per litre of solution in water has the same osmotic
(6) Define minimum boiling azeotropes with example.
pressure (isotonic) as a solution of glucose (molar mass
(Kerala S.B. 2018)
= 180 g mol!) in water. Calculate the mass of glucose
»> CBSE QUESTIONS rq present in one litre of its solution.
Or
14, (a) Why is meant by (a) What type of deviation is shown by a mixture of ethanol
(t) colligative properties and acetone ? Give reason.
(it) molality of a solution ? (6) Asolution of glucose (molar mass = 180 g mol) in water
(6) What concentration of nitrogen should be present is labelled as 10% (by mass). What would be the molality
in a glass of water at room temperature ? Assume a and molarity of the solution ? (Density of solution =
temperature of 25°C, a total pressure of 1 atmosphere and 1.2 ¢mL +). (A.LS.B. 2014)
mole fraction of nitrogen in air is 0.78 [K,, for nitrogen = 19. (a) A10%solution (by mass) ofsucrose in water has afreezing
8.42 x 10-‘ M/min Hg] (A..S.B. 2010) point of 269.15 K. Calculate the freezing point of 10%
15. (a) State the following : elucose in water if the freezing point of pure water is
(t) Henry’s law about partial pressure of a gas in a 203.155,
mixture. Given: (Molar mass of sucrose = 342 g mol)
(zt) Raoult’s law in its general form in reference to (Molar mass of glucose = 180 g mol)
solutions. (6b) Define the following terms:
(6) Asolution prepared by dissolving 8.95 mg ofa gene fragment (t) Molality (m)
in 35.0 mL of water has an osmotic pressure of 0.335 torr
(11) Abnormal molar mass
at 25°C. Assuming the gene fragment is a non-electrolyte,
Or
determine its molar mass.
(a) 30 g of urea (M = 60 g mol") is dissolved in 846 g of
Or
water. Calculate the vapour pressure of water for this
(a) Differentiate between molarity and molalityin asolution.
solution if vapour pressure of pure water at 298 K is
What is the effect of temperature change on molarity and
23.8 mm Hg.
molality in a solution ?
(b) Write two differences between ideal solutions and non-
(6) What would be the molar mass of a compound if 6.21
ideal solutions. (A..S.B. 2017)
g of it dissolved in 24.0 g of chloroform form a solution
that has a boiling point of 68.04°C. The boiling poimt
of pure chloroform is 61.7°C and the boiling point >> NUMERICALPROBLEMS <<
elevation constant, K, for chloroform is 3.63°C/m. 1. The density ofa 3 M sodium thiosulphate (Na,5,O,) solution
(A.ILS.B. 2011) is 1.25 g mL. Calculate
16. (a) Define the following terms : (t) the % by weight of sodium thiosulphate.
(1) Mole fraction
(11) the mole fraction of sodium thiosulphate.
(it) Ideal solution
(iii) the molalities of Na* and 8,0,” ions.
(6) 15.0 g of an unknown molecular material 1s dissolved in
450 g ofwater. The resulting solution freezes at —0.34°C. [Ans. (1) 37.92% (11) 0.065 (111) 7.730 m, 3.865 m]
What is the molar mass of the material ? (K- for water 2. Calculate the freezing point of an aqueous solution of a
= 1.83 K kg mol"). non-electrolyte having an osmotic pressure of 2 atm at
Or 300 K (K,= 1.86 K m!, R = 0.082 L atm K"! mo!"!)
(a) Explain the following : [Ans. — 0.151]
(t) Henry’s law about dissolution of a gas in a liquid 3. 0.01 m aqueous solution of sodium sulphate depresses the
(it) Boiling point elevation constant for a solvent. freezing point of water by 0.0284°C. Calculate the degree
(6) Asolution of glycerol (C gll,O, )in water was prepared by of dissociation of the salt. (K-for water = 1.86 K m*).
dissolving some glycerol in 500 g of water. This solution [Ans. 26.5%]
has a boiling point of 100.42°C. What mass of glycerol 4. Ice begins to separate at —0.744°C from a solution containing
was dissolved to make this solution ? (K, for water = 2.4 g of anon-electrolyte solute in 100 g of water. Calculate
0.512 K kg mol?) (A.L.S.B. 2012) the molecular weight of non-electrolyte and osmotic pressure
17. (a) State Raoult’s law for a solution containing volatile which the solution would exert at 20°C.
components. How does Raoult’s law become a special [Ans. 60, 9.622 atm.]
case of Henry's law ? 5. A solution of glycerol (C,H,O, ; molar mass = 92 g mol”) in
(6b) 1.00gofnon-electrolyte solute dissolved in 50 g ofbenzene water was prepared by dissolving some glycerol in 500 g of
lowered the freezing point of benezene by 0.40 K. Find water. This solution has a boiling point of 100.42°C. What
the molar mass of the solute. (K, for benzene = 5.12 K mass of glycerol was dissolved to make this solution? (K, for
kg mol). water = 0.512 K ke mol"). (D.S.B. 2010)
Or [Ans. 37.73 g]
_|a0 0.52 g of glucose (C,H,,O,) is dissolved in 80.2 g of water.
MODERN'S abc + OF CHEMISTRY-Aill

>a CBSE QUESTIONS <q

6.

Calculate the boiling point of the solution.

(K, for water is 0.52 K kg mol”). (Assam S.B. 2013) 17. A 0.1539 molal aqueous solution of cane sugar (molar
[Ans. 100.019°C] mass = 342 g mol) has a freezing point of 271 K while
. 9 g of a non-volatile solute when dissolved in 100 g of the freezing point of pure water is 273.15 K. What will be
water causes lowering of freeing point by 0.93 K. Calculate the freezing point of an aqueous solution containing 5 g of
the molecular weight of the solute when K, for water is glucose (mol. mass = 180 g mol") per 100 g of solution.
1.86 K/m. (Mizoram S.B. 2017) (A.I.S.B. 2007)
. (a) 7.45 g KCl is dissolved in 100 g of water. What will be [Ans. 269.07 K]
the mole fraction of KC] in solution. [Ans. 0.0177] 18. Calculate the temperature at which a solution contaiming
(6) On dissolving 9.0 g of glucose in 100 g of water, its 54 g of glucose (C,H,,O,) m 250 g of water will freeze.
freezing point is lowered by 0.93 °C. Calculate the molal (K,for water = 1.86 K kg mol*). (A.LS.B. 2008, D.S.B. 2008)
depression constant of water. (Uttarakhand S.B. 2013) [Ans, —2.23°C]
[Ans. 3.53 K m4] 19. A solution containing 8 g of a substance in 100 g of diethyl
. Calculate the boiling point of one molar aqueous solution ether boils at 36.86°C, whereas pure ether boils at 35.60°C.
(density 1.03 g mL) of NaCl. K, for water = 0.52 Km™. Determine the molecular mass of the solute (For ether
(Nagaland S.B5. 2016) = 2.02 K kg mol”) (A.I.S.B. 2008)
10. Calculate the osmotic pressure at 273 K of a 5% solution of [Ans. 128.25]
compound A. (molecular mass = 60) (Given that R = 0.0821 20. 100 mg of a protein is dissoved in just enough water to
L atm K* mol") (Mizoram S.B. 2016) make 10.0 mL of solution. If this solution has an osmotic
11. Calculate the molar mass of a substance 1.3 g of which pressure of 13.3 mm Hg at 25°C, what is the molar mass
when dissolved in 169 g of H,O gave the solution which of the protein ? (R = 0.0821 L atm mol K" and 760 mm
will boil at 100.025 °C at 1 atm. (K, = 0.52 K m“) Hg = 1 atm) (A...S.B. 2009, D.S.B. 2009)
(Meghalaya S.B. 2017) [Ans. 13980.4]
12. A solution containing 4.2 g of an organic compound in 50 g 21. What mass of ethylene glycol (molar mass = 62.0 g mol)
of acetone shows an elevation of boiling point by 1.8 K. must be added to 5.50 kg of water to lower the freezing
Determine the molar mass of the organic compound. K, of point of water from 0 to — 10.0°C (K, for water = 1.86 K
acetone = 1.71 K kg mol". (Nagaland S.B. 2017) kg mol). (A.I.S.B. 2010)
[Ans. 1.83 kg]
15. The boiling point of water is 100°C. Calculate the boiling 22. 15 g of unknown molecular substance was dissolved in
point of an aqueous solution containing 0.6 g of urea (molar
450 g of water. The resulting solution freezes at —0.34°C.
mass = 60) is 100 g of water. (K, for water = 0.52 Km)
What is the molar mass of the substance (K, for water =
(Mizoram S.B. 2018)
1.86 K kg mol?) ? (A.I.S.B. 2010)
14. The vapour pressure of a compound A of molar mass
[Ans. 182.35]
80 g mol at 20°C is 2.0 bar. When 4g of a non-volatile solid
is added to 40 g of compound A in a beaker, the resulting 23. What mass of NaCl must be dissolved in 65.0 g of water to
vapour pressure is 1.5 bar. Calculate molar mass of the lower the freezing point of water by 7.50°C? The freezing
non-volatile solid. (Mizoram S.B. 2018) point depression constant (K,) for water is 1.86°C/m.
Assume Van’'t Hoff factor for NaCl is 1.87. (Molar mass of
15. 1.8 g of glucose (C,H,,O,) is dissolved in 100 g of water in NaCl=58.5g). (A.I.S.B. 2011)
a beaker. At what temperature will water in the solution [Ans. 8.20 g]
boil at 1.013 bar? Given boiling point of pure water at 1.013
24, The freezing point of benzene decreases by 2.12 K when
bar is 373.15 K and K, for water is 0.052 K kg mol.
2.5 g of benzoic acid (C,H,COOH) is dissolved in 25 g of
(Assam 5S.B. 2018)
benzene. If benzoic acid forms a dimer in benzene, calculate
16. The freezing point of 0.1 molal solution of CH,COOH in the van’t Hoff factor and the percentage association of
benzene is 0.256 K (K,= 5.12 K m“'). What conclusion will benzoic acid. (K, for benzene = 5.12 K kg mol*)
you draw about molecular state of CH,COOH in C,H,? (CBSE Sample Paper 2017-18)
(Meghalaya S.B. 2018) [Ans. i = 0.505, « = 99.0%]

\
$8
RT7M
f ~ AH, x1000
1. Dust, water vapour in air (humidity)
where M is the molar mass and T, is the freezing point.
2. This is because molality involves masses which do not
5. When sodium chloride is added to water, there is elevation
change with temperature.
in boiling point and depression in freezing point.
o 0.5
6. Because it depresses the freezing point to such an extent
4, Molal depression constant K, is related to the enthalpy
that it cannot freeze to form ice.
of fusion, AH, as:
7. Solubility decreases
SOLUTIONS

8. i > 1 when the solute undergoes dissociation in the

4, (c) t= wp RT
solution. M, V
9. Due to osmosis.
_ 1.5 0.0821 «310
10. Remains unchanged.
~ 185000 5600/1000
11. 3.0N
12. AT, and AT, are inversely proportional to molecular = 4.13 x 10* atm
mass of solute. | | ee
13. 15N 7. (c) Moles of NaCl = 585
35

14. A
: hi
15. When solute undergoes association. Molarity = =().
ee 58.5x2
16. Solute behaves as non-electrolyte and does not undergo
8. (c) Refer Solved Example 32 (Page 37)
association or dissociation.
9. Refer Solved Example 387 (Page 40)
18. Being volatile in nature, isopropyl alcohol absorbs certain
10. Refer Solved Example 44 (Page 44)
energy from the skin which becomes cold.
20. Because molality does not change with temperature. 11. m=cRT
21. Zero
2.45 =c x 0.0821 x 300
23. One
24. Molarity changes with temperature but molality does _ 2.45
not change with temperature. = 0.099 mol Lt
0.0821 x 300
25. K,SO,—> 2K* +SO? ;i=3 12. (a) Refer Solved Example 56 (Page 52)
26. When pressure higher than osmotic pressure is applied
14, (6) Refer Solution to Practice Problem 26 (Page 69)
to the solution to get pure solvent.
15. (6) Refer Solved Example 55 (Page 52).
29. (c) 30. (a) 3l. (bd) a2. (c) 3a. (c)
34, (c) 35. (a) 36. (c) a7. (a) 38. (a) Or
39. (d) 40. (a) Al, (db) 42. (b) 43. (5) Refer Solved Example 40 (Page 41).
44, (c) 45. (a) 46. (a) 47. (b) 48. (a) 16. (6) Kefer Solution to Practice Problem, 61. (Page 71)
49. (d) 50. (d) Or
Short Answer Questions Refer Solved Example 41 (Page 41).
17. Refer Solution to Practice Problem 62 (Page 72)
4. (a) The association causes a decrease in the number of
particles and the colligative property also decreases. 18. Refer Solution to Practice Problem 57 (Page 71)
7. (i) The osmotic pressure increases with the amount of Or
solute. Since the body fluid contains Nat and CI ions Refer Solved Example 12 (Page 9)
and if we take more salt, the concentration of these
19. (a) Refer Solution to Practice Problem 59 (Page 71)
ions will increase leading to high osmotic pressure.
Or
The high osmotic pressure may cause rupture of the
cells. Therefore, the patients suffering from high blood (6) Refer Solution to Practice Problem 41 (Page 70)
pressure are advised to take less of common salt.
Numerical Problems
(iit) To lower the vapour pressure of NH, otherwise the
# 1. (c) Wt. of 1000 mL of Na,S,O, solution = 1.25 x 1000
gas will bump out of the bottle.
= 1250¢
(tv) Because Cu,[Fe(CN),] is soluble in non-aqueous Molar mass of Na,5S,O, = 238 x 2+32x2+16x3
solutions. = 155
42. (i) Osmotic pressure Wt. of Na,S,O, in 1000 mL of M solution
(it) Positive deviation from Raoult’s law. =3x 158 = 474 ¢
Now, 1250 g of solution contain = 474 g Na,5,O,
Long Answer Questions | 474
% by weight of sod. thiosulphate = [250 x 1000
3. (b) 20% (mass/mass) means that 20 g of KI is present
in 100g of solution or 80 g of water. = 37.92%.
Molar mass of KI = 39 + 127 = 166 (zi) Wt. of Na,5,O, present in 100 g of solution
, 20/166 | = 37.92 g
Molality = x1000 = 1.51 m Wt. of water present = 100 — 37.92 = 62.08 ¢g

Moles of Na,5,0, = 21.94 _ 94

Volume of solution = 100 _ 83.19 mL 158
~ 1202 ——
Moles of water = — = 3.45
Molarity = 20/166 | 1000 = 1.45 M |
83.19
[200 Now, osmotic pressure
MODERN'S abc + OF CHEMISTRY-A&All

Mole fraction of Na,S,O, = __0.24__ _ 9,065.

0.24 + 3.45
2 ip TRT
(vii) 62.08 g of water contain = 0.24 moles of Na,S,O, M,V
0.24
Molality of solution = x1000 = 3.865 m. 2.4 82.1x293
t= —@@_———_ = 9.622 atm.
Since 1 mole of Na,S,O, contains 2 moles of Na* and 60 «1000
1 mole of 5,0,7— K, x 1000 xw.
© 5. AT, = —2——_-8
Molality of Na* =2 x 3.865 = 7.730
Similarly, Molality of S,0,7 = 1 x 3.865 = 3.865 AT, = 100.42 -— 100.= 0.42, WwW, = 5900 g,

# 2. Osmotic pressure, x = cRT orc = — K, = 0.512 K kg molt, M, = 92, wp=?

2.0 7 0.42 = 0.512 1000 x w,
C= 0 0891x300 = 09-0812 molL
500 x 92
Since density of water is 1.0 g em”, the molarity of
aqueous solution may be taken equal to molality. b, = 0.42 x500 x92 = 37.73 g.
Molality of solution = 0.0812 m 0.512 x 1000
Now, AT, = K; x m
= 1.86 x 0.0812 = 0.151 e6. AT _K, Xwp X1000 — 0.52 x 0.52 x 1000
Freezing point of solution a 2 w, XMz 80.2 x 180
= 0-0.151 =- 0.151.
@ 3. The observed molecular mass can be calculated from = 0.019.
the reaction : Boiling point of solution = 100 + 0.019 = 100.019 °C.
K, x 1000 x wy
M, =
w, X AT,
A § w= Ke soca
0.01 m aquous solution means 0.01 mole or 0.01 w , x AT,
x 142 (mol. wt. of Na,SO, = 142) g of sodium sulphate
are dissolved in 1000 g of water. K, = 1.86 Km“, wg=9g, w,=100g
W, = 142 g,w, = 1000 g, AT, = 0.0264
AT,= 0.93 K
1.86 x 1000 x 1.42 |
M, (observed)
1000 x 0.0284 yu.= = x10
1.86x1000x9
LEG xd
Normal mol. mass 100 x 0.93
Vant’ Hoff factor, 1
Observed mol. mass = 180 g mol"

i= ee
93
1.53 @ 8. (a) Moles of KCl = ““2 014
74.5
Degree of dissociation can be calculated as : (Molar mass of KC] = 39 + 35.5 = 74.5)
Na,SO, —— 2N* + 40%
Moles of water = — = 5.56
Initial moles 1 0 0
After dissociation 1 — a 2a a4 0.1
= 0.0177.
Mole fraction of KCl = 012556
Total number of moles after dissociation
=l-a@+2%a+a0=1+
2a
(6) wy =9.0g, w,= 100g, AT,=0.93° M, = 342
a Moles after dissociation
‘7 Normal moles K, x 1000 x wy
{ 1+20 =153 oe ~ w, x Mz
1
or K, = AT, XW, X Mp _ 0. 100 x 342
x93
14+20 = 153
1000 x Wp
/ 1000 x 9.0
i
= 3.53 Km
or 9a = 1.53-1= 0.53
a = 0.53/2 = 0.256 #9. NaCl——+ Na* + Cl
.. Degree of dissociation = 26.5%.
i= 2
Ky X Wp x 1000
@ 4, M, = ——+~—_—_ AT, = ix K, x m7
wa x AT
2 x (0.52 Km!) x (1 m)
K- = 186,w, =2.4g,w, =100¢
1.04 K
AT; = 0 —(-— 0.744) = 0.744

_ 1.80x2.4x1000 _ Boiling point of solution = 373 + 1.04 = 374.04 K

= 100 x 0.744
SOLUTIONS

: : Dg Observed freezing point depression

¢ 10. C oncentration
trat of f solution
solut er100 mL
ame Van't
See Hoff fact
yeceniereeeds =
Se pene pzerse freezing point depression

MV,
5x 0.0821 273
60 x 100 /1000
Since ‘’ is less than one, this means that CH,COOH
undergoes association in benzene. The value 0.5 indicates
18.68 atm
that the number of particles become half and therefore,
11. M.
_ K,x1000xw, CH,COOH dimerises in benzene.
° . w, XAT,
@ 17. Refer Solved Example 47 (page 44)
K, = 0.52 Km", w,=138g, w, =169¢
¢ 18. AT,- K,
1000
x x wp
AT, 100.025 — 100 = 0.025 K w, XM,
M. So= 0.52 x 1000 x1.3 1.86 x1000x54) , 5.
169 x 0.025 250x180
= 160 g mol!
Freezing point of solution = 0 — 2.23
¢ 12. K, oie
M, = i X1000xw, 8
= — 2,23°C

W,p=42¢, w,=50g, AT, =18K K, x 1000 x w,

Ke = 7 hoa
¢ 19/41,
M. ee
= 1-71x1000 x4.2 is 2.02 x 1000 x8 = 128.25 g mol"
50 x 1.8 100 x 1.26
= 79.8 g mol"
m= =f RT==7Wy2 RTT or My —= —2
WRT
) 20.

¢ 13. a ee
K, xw, x 1000
mol™ K?
Mp * Wa w, = 100 x 10° g, R = 0.0821 L atm
0.52 x 0.6 x 1000 T = 298 K

60 =x 100
yaa atm, V = 107
= 0.052° 760 1000
Boiling point of solution = 100 + 0.052 = 100.052°C
or 273.15 + 100.052 = 373.202 K ™g)
(0.0821 L——atm
uy,= = 100x10 | x
mol "K™)x (298K.
13.3 | fees 10 L
— Wp XM 760 1000
# 14. FA
Fa ox = 3
Pa Mg Xwa = 13980.45 g mol.
@ 21. Refer Solution to Practice Problem 63 (page 72).
20-1. _ 4x80
2.0 Mp x 40) @ 22. Refer Solution to Practice Problem 60 (page 71).
@ 23. Lowering in freezing point, AT, = 7.50°C
05 _ 4x80
K- 1.86°C/m
20 Mp x 40
Mass of water, w, = 65.0 g
4x80
x 2.0
_ = ———_= 39 g mol Molar mass of NaCl, M, = 58.5
Mp 0.5 x40 s
Van't Hoff factor, : = 1.87, Mass of NaCl, w, =?
K, XwWp *1000
@ 15. AT, = —>
EP
Mz XW, iK ,x 1000 x wp
AT,
W, * Ms
0.52 x1.8x1000
180 x 100
AT, xwa X Mp
= 0.052° or Ww, =
Boiling point of solution = 373.15 + 0.052 = 373.202 K. tx Ky x 1000
# 16. AT; = K, x m1
= 5.12 x 0.1=0.512 K _ 7.50 x 65.0 x 98.5 = 8.20 g.
1.87 x 1.86 x 1000
Observed AT; = 0.256 K
[200 MODERN'S abc + OF CHEMISTRY-All

Competition Flo Additional Useful Information and Objective Questions

_————————— eee

ADDITIONAL USEFUL INFORMATION

Relation between molarity (M) and molality (m) MM,

Molarity (M) means that M moles of the solute are
present in 1000 mL of the solution. If density of the solution
(1000 p-MM,)+MM,
is p g cm, then MM,
Mass of solution = 1000 p M(M, —M,)+ 1000 p
Mass of solute = MM, (M,isthemolar mass of solute) MM,
Mass of solvent = 1000 p - MM, a “2 ~ M(M, —M,)+ 1000 p
Molali
Rearranging
ol’ = 7000p ” -MM, 1000 ded
1000p
- MM,
= — _., & — oo. ken
M(M, — M,)x,+ 1000 px, = MM,
_ M or MM, —-MM,x, + MM.x, = 1000 px,
or m= "MM,
MM, (1-x,) + MM,x, = 1000 px,
P 1000 MM,x, + MM.x, = 1000 px,
MM.
M(M,x, + M,x,) = 1000 px,
or —ni a 1000
m. M A eae
M, +*,M,
i _ MM,
mM 1000 Note : If molarity (M) is in mol/litre and density, p is in
kg/L and molality m is in mol/kg of solvent then 1000 will be
P = 1, MM,
replaced by 1 in the above relations.
M m 1000
Relation between molality (7m) and mole fraction(+,) AZEOTROPES - BOILING POINT DIAGRAMS
Molality means moles of solute in 1000 g of the solvent.
Some liquids on mixing form azeotropes which are
Moles of solvent = ee (M, is molar mass of solvent) binary mixtures having same composition in liquid and
1 vapour phase and boil at constant temperature. In such
Moles of solute =m
cases, it is not possible to separate the components by
Mole fraction (x,) = i fractional distillation. There are two types of azeotropes
1000
m+ called minimum boiling azeotropes and maximum boiling
l azeotropes.
— mM,
(7) Minium boiling azeotropes: In case of solutions
2 mM, +1000
showing very large positive deviations from Raoult’s
= a. mM, + 1000 _ xX 1000
law, there is a maximum in the vapour pressure curve
Xe mM, mM,
which is above the vapour pressure of either of the pure
1000 1-
or = IX Se Ae components. For one of the intermediate composition,
mM, Xyg ag —
the total vapour pressure of such a solution will be the
y- 1000 x, highest and the boiling point will be the lowest (because
My higher the vapour pressure, lower is the boiling point). At
Relation between molarity (M) and mole fraction(x,)
this point, the composition of liquid and vapour phase is
Molarity (M) means that M moles of solute are present in
1000 mL of solution. If p is the density of the solution, then same and the liquid mixture boils at constant temperature
mass of solution is 1000 p. Mass of solute = MM, (M, is the and remains unchanged in composition. Therefore, this
molar mass of solute). liquid mixture distils over as if it is a pure liquid. The
Mass of solvent = 1000 p - MM,
solution acquires the the property of boiling at constant
1000 p—-MM
Moles of solvent = tithe oAAD mest temperature and remains unchanged in composition.
M, These types of solutions are called minimum boiling
(M, is molar mass of solvent)
azeotropes.
Mole fraction,
x, = 1000 p-MM
, | yy
For example, ethanol and water form minimum
1
SOLUTIONS

boiling azeotrope. In this boiling point diagram (Fig. 1), For example, hydrochloric acid and water form
we indicate the composition of the vapour phase by the maximum boiling point azeotrope at the composition
upper curve and composition of the liquid phase by the x (HO) = 0.889 and x (HCI) = 0.111 (or 20.2% HCl) which
lower curve. As shown in Fig. 1, the boiling point diagram boils at 381.6 K (or 108.6°C) which has higher value than
shows an azeotropic composition at x(H,O) = 0.056 and that of pure water and HCl as shown in Fig. 2.
x(C,H.OH) = 0.944 at a temperature of 351 K (or 78°C)
MEASUREMENT OF RELATIVE LOWERING IN
which is lower than that of pure ethanol 351.5 K (or VAPOUR PRESSURE
78.5°C) and water 373 K (or 100°C). In this method, a stream of dry and pure air is passed
through bulbs containing solution and then through bulbs
containing pure solvent and finally through U-tubes containing
calcium chloride (if solvent is water).
As the dry air passes through the solution, it becomes
saturated upto the vapour pressure of the solution or the solvent.
The actual loss of vapours from the bulbs is obtained by weighing
them before and after the air has been passed through them.
Dry air

\ oto
(K)
Temperature
‘ ff Xy,0 = 0.056
(or 95% ethanol)

Ethanol XH,0 Water

SOLUTION
Fig. 1. Boiling point diagram for ethanol-water
The loss of water from the solution and the solvent is noted.
mixtures showing azeotrope.
These are proportional to p, and p,’ — p, respectively. .e.,
(iz) Maximum boiling azeotropes: In the case Loss in weight of solution bulb « vap. pressure of the solution
of solutions showing negative deviations, total vapour 4).
pressure becomes less than the corresponding ideal Loss in weight of solvent bulb « vap. pressure of solvent —vap.
solution of same composition (because lower the vapour pressure of solution (p,° — p,).
pressure, higher is the boiling point). The boiling points From this relative lowering in vapour pressure can be
of such solutions are increased because lower the vapour calculated. This method is known as Ostwald Walker
pressure, higher is the boiling point). For one of the dynamic method.
intermediate composition, the total vapour pressure will Illustration: A current of dry air was passed through a solution
be the least and the boiling point will be the highest of 13.4 g of non-volatile substance ‘S’ in 100 g of water and
(Fig. 2). At this composition, the solution also boils at then through water alone. The loss in weight of the former

constant temperature without a change in composition. was 1.02 g and that of the latter was 0.05 g. Calculate

These types of solution are called maximum boiling (1) mole fraction of the solute in the solution
(it) molecular mass of the solute.
azeotropes.
Solution: Loss in weight of solution « p, = 1.02 g
Loss in weight of solvent (water) < p,° — py
= 0.05 g
pe = (pe —ps) + Py = 0.05 + 1.02
= 107¢
= 0.05
<
ie)~ woa
Pa7Pa = —— = 0.0467
F:
a 1.07
X») = 0.0467
A

SoD
o — Azeotrope Now Px —Pa = Ng _ We/Mz,

-
5 cee nm w,/M,
(or 20,2% HCl) = 0.0467
13.4/M2 _ 9 0467
Water Xucy— HCl 100/18
13.4 x18
or M, = —
Fig. 2. Boiling point diagram for HC] water mixture. : 100 x 0.0467
51.65 g mol.
 MODERN'S abc + OF CHEMISTRY-All

e Q |
uestions |
Mult i p l e C h o i c C. Q. HEH
(c) 250, 750 (d) 400, 600
Al10. The volume of 80% sulphuric acid (H,SO,) by weight
A xo with only one correct answer (density = 1.80 g mL“) required to prepare 1L of 0.2 M
H,50, is
Types of Solutions and Expressing their
(a) 14.7 mL (6) 29.4 mL
Concentrations
(c) 6.8 mL (d) 13.60 mL
Al. An aqueous solution containing 6 g of urea in 500 mL of
solution has a density equal to 1.05. If the molar mass Solubility, Vapour Pressure of Liquid Solutions,
of urea is 60, then the molality of solution 1s : Ideal and Non-ideal Solutions
(a) 0.20 (6) 0.19 (c) 0.10 (d) 1.2. A11. The vapour pressure pure liquid ‘A’ is 70 torr at 27°C. It
A2, 2.5 litre of 1 M NaOH solution are mixed with another forms an ideal solution with another liquid B. The mole
3 litre of 0.5 M NaOH solution. Then the molarity of the fraction of B in the solution is 0.2 and total pressure of
resulting solution is solution is 84 torr at 27°C. The vapour pressure of pure
(a) 0.80 M (6) 0.1 M liquid B at 27°C is:
(c) 0.73 M (d) 0.50M (a) 14 torr (6) 56torr (ce) 140 torr (d) 70 torr.
A3. The volume of 4N HCl and 10 N HCl required to make Al2. Which of the following plots represents the behaviour of
1 litre of 6N HCl are an ideal binary liquid solution?
(a) 0.75 litre of 4 N HCl and 0.25 litre of 10 N HCl (a) plot of 1/p,,,., VS y, 1s linear (mol fraction of A in
(6b) 0.25 litre of 4N HCl and 0.75 litre of 10 N HCl vapour phase)
(c) 0.67 litre of 4 N HCl and 0.33 litre of 10 N HCl (b) plot of p,..., VS Yg 1s linear
(d) 0.50 litre of 4 N HCl and 0.20 litre of 10 N HCl (c) plot of p,.,., VS y, 1s linear
Ad, The mole fraction of methanol in its 4.5 molal aqueous (d) plot of 1/p,.,., VS Yp 1S non-linear
solution is A13. The vapour pressure of a solution prepared by dissolving
(a) 0.250 (6) 0.125 1 mol of liquid A and 2 mol of liquid B has been found to
(c) 0.100 (d) 0.075 be 38 torr. The vapour pressure of pure A and pure B are
A5. Density of 3M NaCl solution is 1.28 g/ce. The molality of 45 and 36 torr respectively. The solution
the solution is
(a) shows negative deviation
(a) 2.79 molal (6) 0.279 molal
(6) 1s a minimum boiling azeotrope
(c) 1.279 molal (d) 3.85 molal
(c) 1s an ideal solution
A6. The mole fraction of solute in 2.5 m aqueous solution is
(d) has A Hing positive
(a) 0.045 (6) 0.043
(c) 0.86 (d) 0.25
A114. Which pair will not form an ideal solution ?
(a) C,H,Br and C,H,1 (6) C,H.Br and C,H,1
AZ. Battery acid is 4.27M H,SO, (aq) and has the density of
1.25 g mL?. The molality of H,SO, in the solution is (c) C,H, and C,H,CH, (d) C,H,I and C,H,OH
(a) 3.416 m (6) 3.342 m Al5. When a gas is bubbled through water at 298 K, a very
(c) 5.1385 m (d) 2.1385 m
dilute solution of the gas is obtained. Henry’s law constant
for the gas at 298 K is 100 kbar. If the gas exerts a
A8. A 7M solution of potassium hydroxide (KOH) in water
partial pressure of 1 bar, the number of millimoles of
contains 40% by weight of KOH. The density of the solution
the gas dissolved in one litre of water is
1S
(a) 0.555 (6) 5.55
(a) 1.96 (6) 1.28
(c) 0.0555 (d) 565.5
(c) 0.49 (d) 0.98 A16. The partial pressure of oxygen in air is 0.2 atm. What
A9. What volume of 12M and 4M HCl must be mixed to is the concentration of dissolved oxygen in water in
prepare 1000 mL of 6M HCl? equilibrium with air at 25°C? (K,, for oxygen at 25°C is
(a) 200, 800 (6) 700, 300 4.34 x 10* atm)
(a) 2.56 x 10*M
Answers
(6) 3.68 x 10° M
(c) 4.26 x 10+ M (d) 2.96 x 10°M

Al. (b) A. (c) A8s. (c) AA. (d) AS5. (a) A6. (0) AS. (c) ~=Al10. (d)
All, (e) Al12,. (a) A183. (a) Al4, (d) Al15. (a) Al6. (a)
SOLUTIONS

A17. The vapour pressure of pure components X and Y are (a) 100.75°C (6) 100.5°C
200 torr and 100 torr respectively. Assuming a solution (c) 100°C (d) 100.25°C.
of these components obeys Raoult’s law, the mole fraction A25. An aqueous solution of sucrose boils at 100.01°C. The
of component X in the vapour phase in equilibrium with number of dextrose molecules in 100 g solution are
a solution containing equimoles of X and Y is (K, of water = 0.50°K kg mol)
(a) 0.22 (b) 0.33
(a) 1.2 x 107! (b) 2.0 x 1074
(c) 0.50 (d) 0.67
(c) 3.0 x 1078 (dq) 6.0 x 104
A18. If the ratio of vapour pressure of pure liquids A and B
A26. The vapour pressure of the solvent decreased by 10 mm of
is 1 : 2 and their mole fraction in solution is 1:2, then
Hg when a non-volatile solute was added to the solvent.
mole fraction of B in vapours is
The mole fraction of the solute in the solution is 0.2. What
(a) 0.25 (b) 0.80
(c) 0.56 (d) 0.20 should be the mole fraction of the solvent if a decrease in
A19. Two completely miscible liquids A and B form an azeotropic vapour pressure of 20 mm of Hg is desired :
mixture having maximum vapour pressure. If the liquid (a) 0.6 (b) 0.8 (c) 04 (d) 0.2
Ais more volatile, then which of the following respresents A27. Which of the following colligative property can provide
the boiling point-composition graph? molar mass of proteins (or polymers or colloids) with
iigB :
ereater precision ?
T :
(a) Relative lowering of vapour pressure ?
(6) Elevation of boiling point
(a) Ts (6) TA (c) Depression in freezing point
(d) Osmotic pressure
A28. An aqueous solution of a substance X boils at 100. 512°C.
Aaa 1 Ma | Xa= 1 Xg= 1 The freezing point of the solution is (K, = 1.86 Km“™ and
K, = 0.512 Km“)
i
T°

A
(a) 0.93°C (b) —0.93°C
rs (c) 1.86°C (d) -1.86°C
; . i
i A29. When a non-volatile solute (A) is added to solvent (B), its
(c) (d) y vapour pressure is reduced by 10%. If molar mass of B is
30% of molar mass of A, the mass ratio of B and Ais
X= 1 X,=1 X,=1 X,= 1
(a) 0.33 (b) 6.0
(c) 3.0 (d) 0.66
A20. Two liquids P and Q have vapour pressures 450 and
200 torr respectively at certain temperature. In an ideal A30. When 0.6 g of urea is dissolved in 100 g water, the solution
solution of the two, the mole fraction of P at which two
will boil at (K, for water = 0.52 K m™ and normal boiling
liquids have equal partial pressures is point of water = 100°C):
(a) 0.80 (6) 0.3808 (a) 372.48 K (6) 273.52 K
(c) 0.444 (d) 0.154 (c) 373.052 K (d) 273.052 K.
Colligative Properties
Colligative Properties of Electrolytic Solutions :
A21. A solution of solute X in benzene boils at 0.126°C higher Abnormal Molar Masses
than benzene. What is the molality of the solution ?
(K, for benzene = 2.52 K/m) A31. The osmotic pressure of equimolar solutions of glucose,
(a) 0.05 (b) 2 (c) 1 (d) 20. sodium chloride and barium chloride will be in the order :
A22. The osmotic pressure of 0.2 molar solution of urea at 27°C (a) BaCl, > NaCl > glucose (6) BaCl, >glucose> NaCl
(R = 0.082 litre atm mol K+) is: (c) Glucose > BaCl, > NaCl (d) NaCl>BaCl, > glucose.
(a) 492 atm (6) latm (c)0.2 atm (d) 27 atm. A32. Equal weights of m gram of the following substances were
A23. A 5% solution of glucose (molar mass = 180) 1s isotonic dissolved in equal amount of water. Which of these will
with a 2.5% solution of a substance X at the same have highest boiling points ?
temperature. The molar mass of X is (a) Urea (NH,CONH,)
(a) 360 (6) 180 (6) Glucose (C,H,,0,)
(c) 90 (d) 45 (c) Sodium chloride (NaCl)
A24, An aqueous solution containing 1 g of urea boils at 100.25°C.
(d) Calcium chloride (CaCl,)
The aqueous solution containing 3 g of glucose in the same
volume will boil at

nmswiets
Al7. (d) A18. (5) Al19. (a) A20. (d) A21. (a) A22. (a) A23. (c) A24. (d) A225. (a) A226. (a)
A27. (d) A28. (d) A29. (c) A30. (c) A381. (a) A382. (c)
 MODERN'S abc + OF CHEMISTRY-All

A33. Which one of the following pairs of solutions can be expected Select the correct answer using the codes given below :
to be isotonic at the same temperature ? (a) land 4 (6) 2and3
(a) 0.1 M urea and 0.1 M NaCl (c) 1,2 and 4 (dq) 2,3 and 4
(6) 0.1 M urea and 0.1 M MgCl,
(c) 0.1 M NaCl and 0.1 M Na,sO, Advanced Level
(d) 0.1 M Ca(NO,), and 0.1 M Na,SO, A41. Two volatile liquids A and B having vapour pressures p,°
A34, The Van’t Hoff factor for 0.1 M Ba(NO,), solution is 2.74. and p*,, respectively form an ideal solution. Ifx, and x, are
The degree of dissociation 1s the mole fractons in the solution andy, and y, are the mole
(a) 91.3% (6b) 87% (c) 100% (d) 74% fractions in vapour phase of A and B respectively, then a
A35. A 0.2 molal aqueous solution of weak acid (HX) is 20% plot of 1/y, along y-axis against 1/x, along x-axis gives a
ionized. The freezing point of this solution 1s : straight line. The slope of the straight line is
(K.= 1.86 K kg mol for water) (a) palp,” (b) pp lp.°
(a) — 0.45°C (b) —0.90°C (c) pao -—Dee (dZ) p,” —p,°
(c) —0.31°C (d) —0.53°C A42, Which of the following graph represents correctly
A36. Electrolyte A gives 3 ions and B is a non-electrolyte. If 0.1 the variation in thermodynamic functions during the
molar solution of solute B produces an osmotic pressure formation of a binary solution showing positive deviations
p, then 0.05 molar solution of A will produce an osmotic from ideal behaviour?
pressure equal to
(a) p (6) 15p (ce) O5p (d) 0.75 p
A37. 0.01 M solution each of urea, common salt and sodium
sulphate are taken, the ratio of depression in freezing
point of these solutions is
(a) 1:1:1 (®) 1:2:1
fe) Le220 (ft)2r 2:3
A38. Which of the following 0.10 m aqueous solution will have
the lowest freezing point ?
(a) Al, (SO,), (b) C.H,,0,
(c) Cy 5H,.0,, (d) KI (c) J mol (d)
A39. In a 0.2 molal aqueous solution of a weak acid, HX, the
degree of dissociation is 0.3. Taking K,, for water as 1.86,
the freezing point of the solution will be nearest to
G mix
(a) — 0.3860°C (6) — 0.206°C T Shnix

(c) + 0.480°C (dq) — 0.480°C A483, Dry air was passed successively through a solution of 5 g
A40. Which of the following solutions are isotonic with one of a solute in 80 g of water and then through pure water.
another ? The loss in weight of the solution was 2.5 g and that of pure
(1) 0.15 M urea (2) 0.05 M CaCl, water 0.05 g. The molar mass of solute is
(3) 0.1M MgsoO, (4) 0.15 M glucose (a) 48 (b) 32
(c) 40 (d) 35
Waswicts
A33. (d) A384, (b) A35. (a) <As6. (bd) A387. (c) A38. (a) A39. (d) <A4O0. (c) AA. (0)
AA42. (c) A43. (a)

(a) 5.55 mL (6) 11.10 mL

(c) 16.65 mL (dq) 22.20 mL
B from Competitive Examinations
(C_.B.S.E. PMT. 2007)
AIPMT & Other State Boards’
B2. 0.5 molal aqueous solution of a weak acid is 20% ionized.
Medical Entrance
If K, for water is 1.86 K kg mol"!, the lowering in freezing
Bl. Concentrated aqueous sulphuric acid is 98% H,SO, by
point of the solution is
mass and has a density of 1.80 g mL“. Volume of acid
(a) —0.56 K (6) —1.12 K
required to make one litre of 0.1 M H,SO, is
(c) 0.56 K (dq) 1.12 K (C_B.S.E. PMT. 2007)

Areswels
Bl. (a) B2. (d)
SOLUTIONS

Bs. A 0.0020 m aqueous solution of an ionic compound B11. Ofthe following 0.10 m aqueous solutions, which one
Co(NH,), (NO,)Cl freezes at —0.00732°C. Number of moles
will exhibit the largest freezing point depression?
of ions which 1 mol of ionic compound produces on being
(a) KCl (6) C.H 0;
dissolved in water will be (K, = 1.86°C/m)
(c) AL(SO,), (d) K,SO,
(a) 3 (b) 4
(A..P.M.T. 2014)
ic of (d) 2 (C_B.S.E. PMT 2009)
B12. The boiling point of 0.2 mol kg™ solution of X in water
BA. 25.3 g of sodium carbonate, Na,CO, is dissolved in enough 1s greater than equimolal solution of Y in water. Which
water to make 250 ml of solution. If sodium carbonate one of the following statements is true in this case?
dissociates completely, molar concentration of sodium ion, (a) Molecular mass of X is less than the molecular mass
Na* and carbonate ions, COZ are respectively (Molar of Y.
mass of Na,CO, = 106 g mol): (6) Yis undergoing dissociation in water while
X undergoes
(a) 1.90 M and 1.910 M (b) 0.477 M and 0.0477 M no change.
(c) 0.955 M and 1.910 M_ (d) 1.910 M and 0.955 M (c) X is undergoing dissociation in water.
(C.B.S.E. Med 2010) (d@) Molecular mass of X is greater than the molecular
B5. An aqueous solution is 1.00 molal in KI. Which change will mass of Y. (A.LP.M.T. 2015)
cause the vapour pressure of the solution to increase ? B13. Which one of the following electrolytes has the same value
(a) addition of 1.00 molal KI (6) addition of water of van’t Hoff factor (z) as that of Al,(SO,), (if all are 100%
(c) addition of NaCl (d) addition of Na,SO, ionised)?
(C.B.S.E. Med 2010) (a) Al(NO,), (6) K,[Fe(CN),]
B6. A solution of sucrose (molar mass = 342 g mol") (c) K,SO, (dq) K,[Fe(CN),) (A.LP.M.T. 2015)
has been prepared by dissolving 68.5 g of sucrose in B14. What is the mole fraction of the solute in a 1.00 m aqueous
100 g of water. The freezing point of the solution obtained solution?
will be (K, for water = 1.86 K kg mol”). (a) 0.03854 (6) 0.0177
(a) + 0.3872°C (b) — 0.570°C
(c) 0.177 (d) 1.770 (A.LP.M.T. 2015)
(c) —0.3872°C (d) — 0.520°C
B15. Which of the following statement about the composition of
(C.B.S.E. Med. 2010) the vapour over an ideal 1: 1 molar mixture of benzene
B7. The van’t Hoff factor i for a compound which undergoes and toluene is correct? Assume that the temperature is
dissociation in one solvent and association in other solvent constant at 25°C. (Given, vapour pressure data at 25°C,
is respectively
benzene = 12.8 kPa, toluene = 3.85 kPa)
(a) less than one and greater than one
(a) The vapour will contain equal amounts of benzene
(6) less than one and less than one
and toluene.
(c) greater than one and less than one
(dq) greater than one and greater than one (6) Not enough information is given to make a prediction.
(C.B.S.E. P.M.T, 2011) (c) The vapour will contain a higher percentage of
B8. p, and p, are the vapour pressure of pure liquid benzene.
components, A and B, respectively of an ideal binary (d@) The vapour will contain a higher percentage of toluene.
solution. Ifx, represents the mole fraction of component (NEET 2016)
A, the total pressure of the solution will be B16. At 100°C the vapour pressure of a solution of 6.5 g of a
solute in 100 g water is 732 mm. If K, = 0.52 Km™ the
(a) Py + Xs (Pp - Py) (0) Dy + X, (Pa — Pp)
boiling point of this solution will be
(c) Py +X, (Py - Py) (d) Py +X, (Py — Py)
(A..P.M.T. 2012) (a) 102°C (6) 1038C°
B9. 6.02 x 107° molecules of urea are present in 100 mL of (c) 101°C (d) 100°C (NEET 2016)
its solution. The concentration of solution is B17. Which one of the following is incorrect for an ideal solution?
(a) 0.001 M (6) 0.1 M (a) AH. =0
(c) 0.02 M (d) 0.01 M (NEET 2013) (b) AV_.. = 0
B10. How many grams of concentrated nitric acid solution (c) AP = Pa. — Pralculated iy Ral
should be used to prepare 250 mL of 2.0 M HNO,? The (d) AG... = 0 (NEET 2016)
concentrated acid is 70% HNO,. B18. The van’t Hoff factor (2) for a dilute aqueous solution of
(a) 90.0 g cone. HNO, (6) 70.0 g cone. HNO, the strong electrolyte barium hydroxide is
(c) 54.0 g conc. HNO, (d) 45.0 g cone. HNO, (a) O (6) 1
(NEET 2013) (c) 2 (d) 3 (NEET 2016)

Answer
Bs. (7d) B4. (d) BS. (5) B66. (c) Bi. (c) B8. (d) B9. (d) B10. (d) Bll. (c) Bl2.(c) B18. (5)
B14. (5) B15. (c) B16. (c) B17. (d) B18. (d)
 MODERN'S abc + OF CHEMISTRY-Aill

B19. If molality of the dilute solution is doubled, the value of (c) The correct order of osmotic pressures of 0.01 M
molal depression constant (Ky) will be solution of each compound is BaCl, > KC] > CH,COOH
(a) halved (6) tripled > glucose.
(c) unchanged (d) doubled (NEET 2017)
(d) In the equation osmotic pressure p = MRT, M is the
B20. Consider the following aqueous solutions and assume molarity of the solution.
100% ionization of electrolytes (e) The molecular weight of NaCl determined by
(I) 0.1 m urea (II) 0.04 m AlL,(SO,), colligative property measurement is less than its
(IIT) 0.05 m CaCl, (IV) 0.005 m NaCl theoretical molecular weight. (Kerala P.M.T. 2011)
The correct statement regarding the above solutions is B26. Equimolal aqueous solutions of NaCl and BaCl, are
(a) freezing point will be lowest for solution I
prepared. Ifthe freezing point of NaC] is —2°C, the freezing
(6) freezing point will be highest for solution IV point of BaCl, solution is expected to be
(c) vapour pressure will be highest for solution II
(a) —2°C (6) -3°C
(d@) osmotic pressure will be highest for solution III
(Kerala P.M.T. 2007) (c) -—1.5°C (qd) —1.66°C (A.M.U. Med. 2013)
B21. The temperature at which 10% aqueous solution (w/v) of B27. The degree of ionization of HF in 0.100 m aqueous solution
glucose will exhibit the osmotic pressure of 16.4 atm is is (freezing point of the solution = — 0.197°C and K, for
(R = 0.082 dm? atm K™ mol). water = 1.86 °C)
(a) 360°C (6) 180 K (a) 6% (b) 12%
(c) 90K (d@) 300 K (c) 3% (d) 9%
(e) 360 K (Kerala P.M.T. 2008) B28. The partial pressure of nitrogen in air is 0.76 atm. and its
B22. At 300 K the vapour pressure of an ideal solution containing Henry’s law constant is 7.6 x 10* atm at 300 K. What is
1 mole of liquid A and 2 moles of liquid B is 500 mm of the mole fraction of N, in the solution obtained when air
Hg. The vapour pressure of the solution increases by 25 is bubbled through water at 300 K?
mm of Hg if one more mole of B is added to the above
(a) 1x 10+ (b) 2x10*
ideal solution at 300 K. Then vapour pressure of A in its
pure state is (c) 1x10° (d) 2x10°
(a) 300 mm of Hg (6) 40 mm of Hg (e) 1x 10° (Kerala PMT 2014)
(c) 500 mm of Hg (d) 600 mm of Hg B29. The experimental and calculated elevation in boiling
(e) 200 mm of Hg (Kerala PMT 2009) points of an electrolyte AB in its aqueous solution at a
B23. Henry’s law constant of oxygen is 1.4 x 10°? mol L-! atm given concentration are 0.81 K and 0.54 K respectively.
at 298 K. How much of oxygen 1s dissolved in 100 mL at The percentage ionization of the electrolyte at this
298 K when the partial pressure of oxygen is 0.5 atm ? concentration 1s
(a) 14¢ (b) 3.2¢ (a) 20 (b) 40
(c) 22.4 mg (d) 2.24 mg (c) 50 (d) 60
(e) 3.2 mg (Kerala PMT 2009) (e) 80 (Kerala PMT 2014)
B24, The solubility of a gas in water at 300 K under a pressure B30. An electrolyte (AB) is 100% ionized in 10% aqueous
of 100 atmospheres is 4 x 10°? kg L“+. Therefore, the mass solution. What is the osmotic pressure (atm) of a 10% solution
of the gas in kg dissolved in 250 mL of water under a of the electrolyte at 300 K, if molecular weight of AB is
pressure of 250 atmospheres at 300 K is 200 g mol ?
(a) 2.5 x 10° (6b) 2.0 x 10°
(a) 200 (6) 100
(c) 1.25 x 10° (d) 5.0 x 10-3
(c) 246 (d) 24.6
(e) 3x 10° (Kerala PMT 2010)
B25. Which one of the following statements is false? B31. The density of 2.0 M solution of a solute is 1.2 g mL”. If
(a) Raoult’s law states that the vapour pressure of a
the molecular mass of the solute is 100 g mol", then the
component over a binary solution of volatile liquids molality of the solution is
is directly proportional to its mole fraction. (a) 2.0m (6) 1.2m
(5) Two sucrose solutions of the same molality prepared (c) 1.0m (dq) 0.6m
in different solvents will have the same depression
of freezing point. (e) 2.4m (Kerala PMT 2015)

Arse
B19. (c) B20. (5) B21. (e B22. (a) B23. (d) B24. (a) B25. (6) B26. (6) B27. (a) B28. (c)
B29. (c) B30. (d) B3l. (a)
SOLUTIONS

B32. The correct equation for the degree of association ‘a’ of (a) 17.325 mm Hg (6) 17.675 mm Hg
an associating solute, ‘n’ molecules of which undergoes (c) 15.750 mm Hg (d) 16.500 mm Hg

aed Gy ga tad
association 1n solution, is (A.LE.E.E. 2008)
B39. Two liquids X and Y form an ideal solution. At 300 K,
vapour pressure of the solution containing 1 mole of X
(c) eee @ gin, tall and 3 mole of Y is 550 mm Hg. At the same temperature,
~ Jon ~~ n—l if 1 mole of Y is further added to this solution, vapour
pressure of the solution increases by 10 mm Hg. Vapour
@) we me=e) (Kerala PMT 2015) pressure (in mm Hg) of X and Y in their pure states will be,
— il

B33. The vapour pressure of a solvent at 293 Kis 100 mm Hg. respectively
Then the vapour pressure of a solution containing 1 mole (a) 200 and 300 (6) 300 and 400
of a strong electrolyte (AB,) in 99 moles of the solvent at
293 K is (assume complete dissociation of solute) (c) 400 and 600 (d) 500 and 300 (A.[.E.E_E. 2009)
(a) 103 mm Hg (b) 99mm Hg B40. Ifsodium sulphate is considered to be completely dissociated
(c) 97mm Hg (qd) 101 mm Hg into cations and anions in aqueous solution, the change
(ec) 98mm Hg (Kerala PMT 2015) in freezing point of water (AT,), when 0.01 mol of sodium
sulphate is dissolved in 1 kg of water is (K, = 1.86 K kg
B34. The correct order of osmotic pressure of 0.01 M aqueous
mol‘)
solution of the following is
(a) 0.0744 K (6) 0.0186 K
(a) Sucrose > CH,COOH > KCl
(6) CH,COOH > Sucrose > KCl (c) 0.03872 K (qd) 0.0558 K (ASJ.E.E.E. 2010)
(c) Sucrose > KC] > CH,COOH BAl. On mixing, heptane and octane form an ideal solution. At
(d) KCl > Sucrose > CH,COOH 373 K, the vapour pressures of the two liquid components
(e) KCl > CH,COOH > Sucrose (Kerala PMT 2015) (heptane and octane) are 105 kPa and 45 kPa respectively.
Vapour pressure of the solution obtained by mixing 25.0
JEE (Main) & Other State Boards’ ge of heptane and 35 g of octane will be (molar mass of
Engineering Entrance heptane = 100 g mol" and of octane = 114 g mol):
B35. A 5.25% solution of a substance is isotonic with a 1.5% (a) 96.2 kPa (6) 144.5 kPa
solution of urea (molar mass = 60 g mol”) in the same (c) 72.0 kPa (dq) 36.1 kPa (A.._EL ELE. 2010)
solvent. If the densities of both the solutions are assumed
to be equal to 1.0 g cm, molar mass of the substance B42. A 5.2 molal aqueous solution of methyl alcohol, CH,OH,
will be 1s supplied. What is the mole fraction of methyl alcohol
in the solution?
(a) 90.0 g mol (b) 115.0 g mol?
(a) 0.086 (6) 0.050
(c) 105.0 g mol (d) 210.0 g mol
(A.LE.ELE. 2007) (c) 0.100 (d) 0.190 (A.LE.BE. 2011)
B36. The density (in g mL“) of a 3.60 M sulphuric acid solution B43. Ethylene glycol is used as an antifreeze 1n a cold climate.
that is 29% H,SO, (molar mass = 98 g mol’) by mass Mass of ethylene glycol which should be added to 4 kg
will be of water to prevent it from freezing at — 6 °C will be (K
(a) 1.64 (6b) 1.88 for water = 1.86 K kg mol“, and molar mass of ethylene
(c) 1223 (d) 1.95 (A.LLE.EE. 2007) glycol = 62 g mol)
(a) 400.00 g (6) 304.60 g
B37. At 80°C, the vapour pressure of pure liquid ‘A’ is 520 mm
Hg and that of pure liquid ‘B’ is 1000 mm Hg. If a mixture (c) 804.32 g (d) 204.30 g (A..LE.E.E. 2011)
of solution of ‘A’ and ‘B’ boils at 80° C and 1 atm pressure, B44, The degree of dissociation (a) of a weak electrolyte, aE.
the amount of ‘A’ in the mixture is (latm = 760 mm Hg): is related to Van’t Hoff factor (1) by the expression :
(a) 50 mol percent (6) 52 mol percent
(c) 34 mol percent (d) 48 mol percent on 8 ae
(A.LE.E.E. 2008) PS EL
B3s. The vapour pressure of pure water at 20°C 1s 17.5 mm Hg. i ge ee
If 18 g of glucose (C,H,,O,) is added to 178.2 g of water (x+ y-1) x+yt+1
at 20°C, the vapour pressure of resulting solution will be (A.LE.E.E. 2011)

Arswes
B32. (a) B33. (c) B34, (e) B35. (d) B36. (c) B37. (a) B38. (a) B39. (c) B40. (d) B41, (c)
B42. (a) B43. (c) B44, (ce)
 MODERN'S abc + OF CHEMISTRY-All

B45. The molality of a urea solution in which 0.0100 g of urea, B53. The freezing point of benzene decreases by 0.45°C when
((NH,),CO] is added to 0.3000 dm? of water at STP is : 0.2 g of acetic acid is added to 20 g of benzene. If acetic
acid associates to form a dimer in benzene, percentage
(a) 5.55 x 10+ m (6) 33.3 m association of acetic acid in benzene will be: (K, for
(c) 3.33x10%m (d) 0.555m (A LEE. 2011) benzene = 5.12 K kg mol")
(a) 64.6% (b) 80.4%
B46. A 5% solution of cane sugar (molar mass 342) is isotonic
(c) 74.6% (d) 94.6% (JEE Main 2017)
with 1% of a solution of an unknown solute. The molar
B54, For 1 molal aqueous solution of the following compounds,
mass of unknown solute in g/mol is which one will show the highest freezing point?
(a) 171.2 (6) 68.4 (a) [Co(H,O),]Cl,
(c) 34.2 (d) 136.2 (ALLELE. 2011) (6) [Co(H,O),CIC1,.H,O
(c) [Co(H,O),C1,]C1.2H,O
B47. The density of a solution prepared by dissolving
(d) [Co(H,O),Cl,.]3H,O (JEE Main 2018)
120 g of urea (mol. mass = 60 u) in 1000 g of water is
1.15 g/mL. The molarity of this solution is B55. Two liquids X and Y form an ideal solution. The mixture
has a vapour pressure of 400 mm at 300 K when mixed
(a) 1.78 M (b) 1.02 M in the molar ratio of 1:1 and a vapour pressure of
350 mm when mixed in the molar ratio of 1:2 at the
(c) 2.05 M (d) 0.50 M (A.LLE.E.E. 2012)
same temperature. The vapour pressures of the two pure
B48. for water 1s 1.86 K kg mol". If your automobile radiator liquids X and Y respectively are
holds 1.0 kg of water, how many grams of ethylene glycol (a) 250 mm, 550 mm
(C,H,O,) must you add to get the freezing point of the (6) 3850 mm, 450 mm
solution lowered to — 2.8°C ? (c¢) 350 mm, 700 mm
(a) 93g (6) 39¢ (@) 500 mm, 500 mm
(e) 550 mm, 250 mm (Kerala P.E.T. 2008)
(c) 27 ¢ (d) 72¢ (A.LE.E.E. 2012)
B49. The molarity of a solution obtained by mixing 750 mL of B56. A 6% solution of urea is isotonic with
0.5 M HCl with 250 mL of 2M HCl will be (a) 0.05 M solution of glucose
(6) 6% solution of glucose
(a) 0.875 M (6) 1.00 M
(c) 25% solution of glucose
(c) 1.75 M (d) 0.975 M (JEE Main 2013) (dq) 1M solution of glucose (Karnataka C.E.T. 2009)
B50. Consider separate solutions of 0.500M C,H,OH_.,..,; B57. The difference between the boiling point and freezing
0.100 M Mg,(PO,)oiaq, 0-250 M KBr,,,. and 0.125 M point of an aqueous solution containing sucrose (molecular
Na,PO sag) 8t 25 °C. Which statement is true about these wt. = 342 g mol) in 100 g of water is 105°C. If K, and
solutions, assuming all salts to be strong electrolytes ? K, of water are 1.86 and 0.51 K kg mol respectively,
(2) 0.500 MC,H,OH (aq)
has the highest osmotic pressure. the weight of sucrose in solution is about
(a) 34.2 2 (b) 342 ¢g
(6) They all have the same osmotic pressure.
fc) Y2¢ (dq) 72 ¢
(c) 0.100 M Mg,(PO,) 2(aq) has the highest osmotic (e) 68.4¢g (Kerala PET 2009)
pressure.
B58. The amount of solute (molar mass 60 g mol) that must
(d) 0.125 M Na,PO,.,,, has the highest osmotic
be added to 180 g of water so that the vapour pressure
pressure. (JEE Main 2014)
of water is lowered by 10% is
B51. The vapour pressure of acetone at 20°C is 185 torr. When
(a) 30g (6) 60¢g
1.2 g of a non-volatile substance was dissolved in 100 g
of acetone at 20°C, its vapour pressure was 188 torr. The
(c) 120g (d) 12¢
(e) 24 ¢ (Kerala PET 2010)
molar mass (g mol”) of the substance is
(a) 128 (b) 488 59. A solution containing 1.8 g of a compound (empirical
(c) 32 (d) 64 (JEE Main 2015) formula CH,O) in 40 g of water is observed to freeze
at — 0.465°C. The molecular formula of the compound is
B52. 18 g glucose (C,H,,O,) is added to 178.2 g water. The
(K, of water = 1.86 kg K mol)
vapour pressure of water (in torr) for this aqueous solution
1s (a) C,H,O, (6) C,H,O,
(a) 7.6 (6) 76.0 (c) C,H,O, (d) C5H1 05
(c) 752.4 (d) 759.0 (JEE Main 2016) (2) (H.,0- (Kerala P.E.T. 2011)

Answer
B45. (a) B46. (5) B47. (c) B48. (a) B49. (a) B50. (5) B51. (d) B52. (c) B53. (d) B54. (d)
B55. (e) B56. (d) B57. (d) B58. (56) B59. (e)
SOLUTIONS

B60. 58.5 g of NaCl and 180 g of glucose were separately 1.86 K kg molt. The degree of association of P if it forms
dissolved in 1000 mL of water. Identify the correct dimers in water is
statement regarding the elevation of boiling point (b.pt.) (a) 80% (b) 60%
of the resulting solutions. (c) 65% (d) 75%
(a) NaCl solution will show higher elevation of b.pt. (Karnataka CET 2014)
(6) Glucose solution will show higher elevation of b.pt.
B68. Van’'t Hoff factor of centimolal solution of K,[Fe(CN),] is
(c) Both the solutions will show equal elevation of b.pt.
(d) The b.pt. of elevation will be shown by neither of the 3.333. Calculate the per cent dissociation of K,[Fe(CN),].
solutions. (W.B.J.E.E. 2012) (a) 33.33 (6) 0.78
B61. Freezing point of an aqueous solution is — 0.186°C. If the (c) 78 (d) 23.33 (MH-CET 2015)
values of K, and K, of water are respectively 0.52 K kg B69. After adding non-volatile solute freezing point of water
mol? and 1.86 K kg mol“, then the elevation of boiling decreases to —0.186°C. Calculate AT, if K, = 1.66 K ke
point of the solution in K is mol and K, = 0.521 K kg mol?
(a) 0.52 (6b) 1.04 (a) 0.0521 K (b) 0.0186 K
(c) 1.34 (d) 0.134 (c) 0.521 K (d) 1.86 K
(e) 0.052 (Kerala P.E.T. 2012) (Karnataka CET 2015)
B62. The mass of a non-volatile solute of molar mass B70. 0.06% (w/v) aqueous solution of urea is isotonic with
40 g mol? that should be dissolved in 114 g of octane (a) 0.6% glucose solution (6) 0.1 M glucose solution
to lower its vapour pressure by 20% is (c) 0.06% glucose solution (d) 0.01 M glucose solution
(a) 8g (6) 114¢ (Karnataka CET 2015)
(c) 9.8 ¢g (d) 12.8g (Karnataka C.E.T. 2012) B71. Which of the following aqueous solutions has the highest
B63. The vapour pressures of two liquids A and B in their pure freezing point?
states are in ratio of 1 : 2. A binary solution of A and B (a) 0.01 m NaCl (6) 0.01 m Na,SO,
contains A and B in the mole proportion of 1 : 2. The mole (c) 0.1 m Sucrose (dq) 0.1m NaCl
fraction of A in the vapour phase of the solution will be (Karnataka CET 2015)
(a) 0.33 (6) 0.2 B72. A solution containing 2.44 g of solute dissolved in 75 g
of water boiled at 100.413°C. What will be the molar
(c) 0.25 (d) 0.52 (Karnataka C.E.T. 2012)
mass of the solute? (K, for water = 0.52 K kg mol)
B64. The measured freezing point depression for a 0.1 m aqueous (a) 40.96 gmol*? (6) 20.48 g mol
CH,COOH solution is 0.19°C. The acid dissociation
(c) 81.92 gmolt (d) None ofthese (A.M.U. 2015)
constant K, at this concentration will be (Given K,, the
B73. If P° and P are the vapour pressures of the pure solvent
molal cryoscopic constant = 1.86 K kg mol)
and solution and n, and n, are the moles of solute and
(a) 4.76 x 10° (6) 4x 10° solvent respectively in the solution, then the correct
(c) 8x 10° (dq) 2x 10° (W.B. JEE 2013) relation between P and P’ is
. The vapour pressure of pure benzene and toluene at a ny | Thy
particular temperature are 100 mm and 50mm respectively. (a) P*- =P a | (d)
(6) PP =P Fn
Then the mole fraction of benzene in vapour phase in contact
with equimolar solution of benzene and toluene is
(c) P =F |
ng || (@)
(d) P=P" |
74 |owe
| JEE 2016 )
(a) 0.67 (6) 0.75
(c) 0.33 (@) 0.50 B74, Calculate the molality of a solution that contains 51.2 g
(e) 0.20 (Kerala P.E.T. 2013) of naphthalene, (C,,H,) in 500 mL of carbon tetrachloride.
The density of CCl, is 1.60 g/mL.
B66. An aqueous solution containing 3 g of a solute of molar
mass 111.6 g molt in a certain mass of water freezes at (a) 0.250 m (6) 0.500 m
—0.125 °C. The mass of water in grams present in the (c) 0.750 m (d@) 0.840 m
solution is (K,= 1.86 K kg mol) (ge) 1.69 m (Kerala PET 2016)
(a) 300 (6) 600
B75. 31 g of ethylene glycol (C,H,O,) is mixed with 500 g of
(c) 500 (dz) 400 solvent (K, of the solvent is 2 K kg mol). What is the
(e) 250 (Kerala PET 2014) freezing point of the solution in K? (freezing point of
B67. A solution of 1.25 g of P in 50 g of water lowers freezing solvent = 273 K).
point by 0.3 °C. Molar mass of P is 94 and K, (water) = (a) 272 (6) 271

Arisuets
(c) 270 (dq) 274
(e) 275 (Kerala PET 2016)

B60. (a) B61. (e) B62. (a) B63. (5) B64. (5) B65. (a) B66. (d) B67. (a) B68. (bd) B69. (a)
B70. (d) B71. (a) B72. (a) B73. (c) B74. (5) B75. (5)
 MODERN'S abc + OF CHEMISTRY-Aill

B76. Osmotic pressure of the solution can be increased by (molecular wt. of CuCl, = 134.4, K, = 0.52 K molal”’).
(a) increasing the temperature of the solution (a) 0.16 (6) 0.05
(6) decreasing the temperature of the solution (c) 0.1 (d) 0.2 (1.7. 2005)
(c) increasing the volume of the vessel B87. When 20 g of naphthoic acid (C,,H,O,) is dissolved in
(d) diluting the solution. (Karnatka CLE.T. 2016) 50 ¢ of benzene (K = 1.72 K kg mol) a freezing point
B77. The molarity of 3 M solution of methanol if the density depression of 2 K is observed. The Van't Hoff factor ‘7’ is
of the solution is 0.9 g cm‘? is (a) 0.5 (6) 1
(a) 3.73 (6) 3.0
(c) 2 (d) 3 (LL.T. 2007)
(c) 3.33 (d) 3.1 B88. The Henry’s law constant for the solubility of N, gas in
(e) 3.2 (Kerala PET 2017)
water at 298 K is 1.0 x 10° atm. The mole fraction of N,
B78. The freezing point of equimolal aqueous solutions will be
in air is 0.8. The number of moles of N, from air dissolved
highest for
in 10 moles of water at 298 K and 5 atm pressure is
(a) C,H,NH,Cl (6) AgNO,
(a) 4.0 x 10+ (6b) 4.0 x 10°
(c) Ca(NO,), (d) La(NO,),
(e) D-fructose (Kerala PET 2017) (c) 5.0 x 10+ (d) 4.0 x 10° (IT-JEE 2009)
B79. Assuming the compounds to be completely dissociated in B89. Dissolving 120¢ of urea (mol. wt. 60) in 1000 g of water
aqueous solution, identify the pair of the solutions that gave a solution of density 1.15 g/mL. The molarity of the
can be expected to be isotonic at the same temperature. solution is
(a) 0.01 M Urea and 0.01 M NaCl (a) 1.78 M (6) 2.00 M
(6) 0.02 M NaCl and 0.01 M Na,SO, (c) 2.05 M (d) 2.22 M (L.T. 2011)
(c) 0.03 M NaCl and 0.02 M MgCl, B90. The freezing point (in °C) of a solution containing
(dq) 0.01 M Sucrose and 0.02 M glucose (WB JHE 2017) 0.1 g of K, [Fe(CN),] (mol. wt. 329) in 100 g of water
B80. The Van’t Hoff factor ‘*’ accounts for (K,= 1.86 K kg mol) is
(a) extent of dissolution of solute (a) —2.3 x 10° (b) —5.7 x 10°
(6b) extent of dissociation of solute (c) —5.7 x 10° (qd) —1.2 x 10° (LT. 2011)
(c) extent of mobility of solute B91. For a dilute solution containing 2.5 g of a non-volatile
(d) extent of solubility of solute (Karnataka CET 2017)
non-electrolyte solution in 100 g of water, the elevation
B81. What will be the percentage of dimerization of 61 g of
benzoic acid in 1000 g of a solvent and producing a in boiling point at 1 atm pressure is 2°C. Assuming
depression in freezing point of 2°C? Consider K, to be 6. concentration of solute is much lower than the
(a) 72% (6b) 67% concentration of solvent, the vapour pressure (mm of
(c) 438% (d) 28% (J.K. CET 2018) Hg) of the solution is (take K, = 0.76 K kg mol!-!)
B82. Calculate the molarity of a solution of 30 g of Co(NO,),.6H,O (a) 724 (6b) 740
in 4.3 L of solution. Consider atomic mass of Co = 59u, (c) 736 (d@) 718 (LLT. J.ELE. 2012)
N = 14u, O = 16u, H = lu B92. Pure water freezes at 273 K and 1 bar. The addition of
(a) 0.023 M (6) 0.238 M 34.5 g of ethanol to 500 g of water changes the freezing
(c) 0.046 M (d) 0.46 M (J.K. CET 2018) point of the solution. Use the freezing point depression
B83. Which of the following aqueous solution should have the constant of water as 2 K kg mol". The figures shown
highest boiling point? below represent plots of vapour pressure (V.P.) versus
(a) 1.0 M NaOH (6) 10M Na,SO, temperature (T).
(c) 10M NH,NO, (d) 1.0 M KNO, (Molecular weight of ethanol is 46 g mol?)
(Karnataka CET 2018) Among the following, the option representing change in
B84. Isotonic solutions are having the same the freezing point is
(a) surface tension (5b) vapour pressure
7
(c) osmotic pressure (d) viscosity.
(Karnataka CET 2018) fy

B85. If 1 mol of NaCl solute is dissolved into 1 kg of water, at (a)

ay
what temperature will water boil at 1.013 bar? (K, of =

water is 0.52 K ke mol).

(a) 373.15 K (6) 373.67 K
(c)
(e)
374.19 K
375 K
(d@) 373.19 K
(Kerala PET 2018)
(c) =
t
JEE (Advance) for ITT Entrance
i
B86. The elevation in boiling point of a solution of 13.44 g of 271 273 271 273
CuCl, in 1 kg of water using following information will be T/K —> TK —>

Answer
(JEE Advance 2017)

B76. (a) B77. (a) B78. (e) B79. (c) B80. (5) B8l. (5) B82. (a) B83. (b) B84. (c) B85. (c)
B86. (a) B87. (a) B88. (a) B89. (c) B90. (a) B91. (a) B92. (5)
SOLUTIONS

C7. Benzene and naphthalene form an ideal solution at room

temperature. For this process, the true statement (s) 1s (are)
(a) AGis positive (5) 2). ree 1s positive
Cl. Colligative properties of a solution are (c) AS surroundings
=0 (2) AH=0
(a) independent of the nature of solute (JEE Advance 2013)
(6) inversely proportional to molecular mass of solute C8. The solution which is isotonie with 6% (m/v) solution of
(c) proportional to concentration of solute urea is / are:
(d@) independent of the amount of solvent. (a) 18% (m/v) solution of glucose
C2. Non-ideal solutions showing negative deviations are: (6) 0.5 M solution of BaCl,
(a) acetone + ethyl alcohol (c) 1M solution of sucrose
(D) acetic acid + pyridine (d) 1M solution of acetic acid
(c) chloroform + benzene
C9. Mixture(s) showing positive deviation from Raoult’s law
(d) earbon tetrachloride + toluene at 35°C is (are)
C3. Which of the following form nearly ideal solution ?
(a) carbon tetrachloride + methanol
(a) Chlorobenzene + Bromobenzene
(6) carbon disulphide + acetone
(6) Hexane + Heptane (c) Ethanol + Cyclohexane
(c) benzene + toluene
(d) Acetic acid + Pyridine
(d) phenol + aniline. (JEK Advance 2016)
C4, In the depression in freezing point experiment, it is
C10. For a solution formed by mixing liquids L and M, the
observed that
vapour pressure of L plotted against the mole fraction of
(a) the vapour pressure of the solution is less than that
M in solution is shown in the following figure. Here x, and
of pure solvent.
Xy, represent mole fractions of L and M, respectively, in
(6) the vapour pressure of the solution is more than that
the solution. The correct statement (s) applicable to this
of pure solvent
system is (are)
(c) only solute molecules solidify at the freezing point.
(d) only solvent molecules solidify at the freezing point.
C5. For 0.5 m aqueous solution of KCl, the important physical
properties at 27°C are K,(water) = 1.86 K m“, K, (water) L

= 0.512 Km
(a) freezing point of solution = — 3.72°C
(6) boiling point of soution = 100.512°C
(c) osmotic pressure = 3.76 atm (a) attractive intermolecular interactions between L—Lin
(d) observed molecular mass = 37.25 (approx. assuming pure liquid L and M—M in pure liquid M are stronger
degree of dissociation = 1). than those between L—M when mixed in solution.
C6. Which of the following statements is/are wrong ? (6) the point Z represents vapour pressure of pure liquid
(a) The value of colligative property decreases when M and Raoult’s law is obeyed when x, ——> 0
solute undergoes dissociation. (c) the point Z represents vapour pressure of pure liquid
(6) For AICl,, the Van’t Hoff factor is 3. M and Raoult’s law is obeyed when x, = 0 tox, =1
(c) Solvent rises from soil to the top of a tall tree due (d) the point Z represents vapour pressure of pure liquid
to osmosis. L and Raoult’s law is obeyed when x, —> 1
(d@) Aqueous solution of NaCl freezes at lower temperature
th (JEE Advance 2017)
an water.

C1. (a), (0), (ec) C2. (5), (c) C3. (a), (b) C4, (a), (d) C5. (6), (2d) C6. (a), (6) C7. (6), (c), (ad) C8. (a), (c)
C9. (a), (5) C10. (a), (d)
 MODERN'S abc + OF CHEMISTRY-Aill

Answer the following questions :

D5. The freezing point of the solution at 298 K will be
based on the given passage/comprehension (a) —0.744 °C (6) —0.3872 °C
Passage I. (c) —0.186 °C (dq) —0.093 °C
Vapour pressure of a liquid or a solution is the pressure D6. The vapour pressure of the solution at 298 K will be
exerted by the vapour in equilibrium with the liquid or solution (a) 0.0220 atm (6) 0.238 atm
at a particular temperature. It depends upon the nature of (c) 0.0238 atm (dq) 0.220 atm
the liquid and temperature. According to Raoult’s law, in D7. The amount of sodium chloride that should be dissolved
a solution, the vapour pressure of a component at a given in the same amount of water to get the same freezing
temperature is equal to the mole fraction of that component in point will be
solution multiplied by the vapour pressure of that component
in the pure state. The solutions in which each component
(a) 11.79¢ (b) 1.179¢
obeys Raoult’s law are called ideal solutions. There are two (c) 2.34 ¢ (d) 23.4 ¢
types of non-ideal solutions, showing positive deviations and Ds. If on dissolving the above amount of sodium chloride in
negative deviations from ideal behaviour. same amount of water, the freezing point is found to be
— 0.698 °C, the percentage dissociation 1s
Answer the following questions :
(a) 72% (b) 80%
D1. The vapour pressure of a pure liquid A is 40 mm of Hg
(c) 92% (d) 88%
at 300 K. The vapour pressure of this liquid in solution
Passage III
with liquid B is 32 mm of Hg. The mole fraction of A in
The equations derived for colligative properties are
solution obeying Raoult’s law is
based on the assumption that solutions are dilute and
(a) 0.6 (6) 0.5 (c) 0.2 (d) 0.8
solute molecules do not dissociate or associate in solution.
D2. Which of the following statements is correct for non-ideal
solutions ? Discrepancies in determination of molar masses or measuring
colligative properties arise when the solute dissociates or
(a) For solutions showing —ve deviations, AV nixing 20d
AH ixing are +ve.
associates on dissolving in a solvent. This is because due to
(6) For solutions showing negative deviations, the association or dissociation of solute molecules in the solution,
interactions between the components are greater the number of molecules undergo a change. Van't Hoff
than the pure components. introduced a factor called Van't Hoff factor ‘i’ to express the
(c) For solutions showing +ve deviations, AV
nizing =+VE extent of association or dissociation of solute in solution as :
but AH... = +ve. Normal molar mass
(d) For solutions showing —ve deviations, AV
nixine = Ve Observed molar mass
but AH. = +ve.
Inclusion of %’ modifies the equations for colligative
D3. Vapour pressure of a solution of heptane and octane is properties as :
eiven by the equation:
p(sol.) (mm Hg) = 35 + 65x, where x is the mole fraction = ae AT, = i Kym
of heptane. Vapour pressure of pure octane is
p
(a2) 100 mm Hg (6) 35 mm Hg AT, = 1 K,m Ti che
(c) 30 mm Hg (dq) 1.86 mm Hg
D4. If liquid A and B form ideal solution, then Answer the following questions :
(a) AG. =0 (6) AH ing = 9
(c) AG... =). AS £ = 0 (d) AS) xing =(0 D9. Electrolyte A gives 4 ions and B is a non-electrolyte. If
0.1 molar solution of solute B produces an osmotic
Passage II
pressure p, then 0.02 molar solution of A will produce
A solution of glucose (molar mass = 180 g mol) has
been prepared at 298 K by dissolving 7.2 g of glucose in 100 osmotic pressure equal to
g of water. for water is 1.86 K m“! and vapour pressure (a) 0.02p (b) 0.8 p
of water at 298 K is 0.024 atm.
(c) 0.4p (d) 0.6 p

nswiets
Passage-lI. D1. (d) D2. (6) Ds. (5) D4, (b) Passage-II. D5. (a) D6. (c) D7. (5) D8. (d)
Passage-III. D9, (5)
SOLUTIONS

D10.0.2 m aqueous solution of a weak acid (HX) is 20% D12. The elevation in boiling point for 1 M urea, 1 M glucose,
dissociated. The boiling point of this solution is (K, for 1 M NaCl and 1 M K;SO, are in the ratio :
water = 0.52 Km‘) (joy Be 2231
iw 1s Lea
(a) 101.04°C (d) 100.104°C
iQ fi 22aea ti) Begeasa
(c) 100.1248°C (d) 100.52°C
D13. The average osmotic pressure of human blood is 7.8 bar
D11. Which of the folowing equimolar solution is expected to at 37° C. The concentration of aqueous NaCl solution
have lowest freezing point ? that could be used in the blood stream is
(a) 0.6 M H,PO, (6) 0.5 M Na,PO, (a2) 7.8 mol L- (b) 1.5 mol L-?
(c) 0.6 M NaCl (dq) 0.5 M Aniline (c) 0.075 mol L-} (7d) 0.15 mol L“

Auisuets
Passage-III. D10. (c) D11. (b) D12. (a) D13. (d)

4, Assertion : Cooking time in pressure cookers 1s reduced.

Assertion Reason Type Questions Reason : Boiling point inside the pressure cooker is raised.
The questions given below consist of an Assertion and 5. Assertion : The sum of mole fractions of all components
Reason. Use the following key to choose the appropriate answer. of a solution is unity.
(a) If both assertion and reason are CORRECT and reason Reason : Mole fraction is independent of temperature.
is the CORRECT explanation of the assertion. 6. Assertion : Sodium chloride is used to clear snow on the

(6) If both assertion and reason are CORRECT but, reason roads.

is NOT THE CORRECT explanation of the assertion. Reason : Sodium chloride depresses the freezing point
of water.
(c) If assertion is CORRECT but, reason is INCORRECT.
7. Assertion : Osmotic pressure of 0.1 M urea solution is
(d) If assertion is INCORRECT but, reason is CORRECT.
less than that of 0.1 M NaCl solution.
(e) If both assertion and reason are INCORRECT.
Reason : Osmotic pressure Is not a colligative property.

1. Assertion : AH... and AV... are zero for the ideal solution. 8. Assertion : Elevation in boiling point for two isotonic
solutions may not be same.
Reason : The interactions between the particles of the
err
: Boiling point depends upon the concentration
components ofa solution are almost identical
of the solute.
as between particles in the liquids.
9. Assertion : Iodine is more soluble in CCl than in water.
2. Assertion : Increasing pressure on water decreases its
: : Reason : Non-polar solutes are more soluble in non-
freezing point.
polar solvents
Re ason : Density
ensity of of water
water 1s
1 maximum a L272 -K. a eee
: Camphor is usually used in molecular mass
3. Assertion : 0.1 M glucose solution has higher increment
determination.
in the freezing point than 0.1 M urea solution. ican
: Camphor has low cryoscopic constant and
Reason : K, for both has different values.
therefore, causes greater depression in
freezing point.

Rod) Pe ee te) 3.(e) 4, (a) 5. (d) 6. (a) 7. (c) 8. (e) 9. (a) 10. (c)
 MODERN'S abc + OF CHEMISTRY-Aill

1. Match the behaviour of solutions in Column I with the

examples listed in Column II.
Matrix Match Type Questions
Column I Column IT
Each question contains statements given in two columns.
Match the statements in column I with statements in column II. (A) Show idealbehaviour | (p) Water + Nitric acid
Each question contains statements given in two columns, (B) Show -ve deviation | (qg) Benzene + Acetone
from ideal behaviour.
which have to be matched. Statements in Column I are labelled
as A, B, C and D whereas statements in Column II are labelled (C) Show +ve deviation | (”) 7-hexane + n-heptane
as p,q, r are s. Match the entries of Column I with appropriate from ideal behaviour
entries of Column II. Each entry in Column I may have one or (D) Non-ideal solution (s) Carbon tetrachloride +
more than one correct option from Column II. The answers to chloroform
these questions have to be appropritate bubbled as illustrated
in the following example. 2. Match the type of solutions in Column I with the
If the correct matches are A-g, A-r, B-p, B-s, C-r, C-s and
characteristic property mentioned in Column II.
D-g, then the correctly bubbled matrix will look like the following: Column I Column IT
p qr s (A) Solution in which (p) Van’t Hofffactor will be less
solute undergoes than 1 observed
association
(B) Solution in which (g) observed molecular
mass will
solute dissociation be more than normal value
(C) Solution containing (r) colligative property will be
non-electrolyte more than normal value
(D) 0.1M solution of (s) Van’t Hoff factor will be
benzoic acid in benzene equal to 1.

nmswicts
EP ay =} (B) -—(p) (C) —(q) (s) (D) —(p) (q) (s)
(2) : (A) -(p) (q) (B) -(r) (C) —(s) (D) — (p) (q)

Integer type or Numerical Value Type Questions where x is the mole fraction of CH,OH. The vapour of
solution containing equimoles of CH,OH and C,H,OH is
y + 200 mm Hg. The value of y is
Integer Type: The answer to each of the following
question is a single-digit-integer ranging from 0 to 9. . An electrolyte A,B, 1onizes in water upto 75%. The van’t
Hoff factor for it is
1. How many of the following solutions show negative . The depression in freezing point expected for 0.6 m
deviation from ideal behaviour ? Al,(SO,), solution will be ‘n’ times compared with 0.2 m
Chloroform + diethyl ether, acetone + aniline, water Na,SO, solution. The value of 7 is
+ nitric acid, acetone + ethyl alcohol, acetone + carbon . 29.2% (w/w) HCl stock solution has a density of 1.25
disulphide, chloroform + nitric acid. g mL!. The molecular weight of HCl is 36.5 g molt.
The volume (mL) of stock solution required to prepare
2. The depression in freezing point for 1 M urea, 0.5 M
200 mL of 0.4 M HCl is (.1.T. 2012)
glucose, 1 M NaCl, and 1M K,SO, are in the ratio x: 1:
. MX, dissociates into M** and X- ions in an aqueous
y : 2, The value of x +z 1s
solution, with a degree of dissociation (a) of 0.5. The ratio
3. At a certain temperature, the vapour pressure (in mm of the observed depression of freezing point of the aqueous
Hg) of CH,OH and C,H,OH solution is represented as: solution to the value of the depression of freezing point in
p = 126x+142 the absence of ionic dissociation is.
(JhE Advance 2014)

Answer
1. 4 2. 8 Oo. Oo 4,4 a 9
SOLUTIONS 213)

8. If the freezing point of a 0.01 molal aqueous solution of a and X, respectively has vapour pressure of 22.5 torr. The
cobalt (IIT) chloride-ammonia complex (which behaves as a value of x,/x, in the new solution is ........ .
strong electrolyte) is —0.0558°C, the number of chloride (s) (Given that the vapour pressure of pure liquid A is 20 torr
in the coordination sphere of the complex is [K, of water at temperature T.) (JEE Advance 2018)
= 1.86 K kg mol] 11. The plot given below shows P—T curves (where P is the
(JEE Advance 2015) pressure and T is the temperature) for two solvents X and
Y and isomolal solutions of NaC] in these solvents. NaCl
9. The mole fraction of a solute in a solution is 0.1. At 298 K, completely dissocigfas Tiath thé solvents.
molarity of this solution is the same as its molality. Density
of this solution at 298 K is 2.0 g cm™®. The ratio of the cy
molecular weights ofthe solute and solvent, MWoaptute_ is E 1. SolventX
| anluant = 2. Solution of NaCl in solvent X
5 3. Solvent Y
(JEE Advance 2016) 2 4, Solution of NaCl in solvent Y
ny
Numerical Value Type: Give the correct numerical SS ye
value (in decimal notation truncated/rounded off to the Temperature (K)
second decimal place). On addition of equal number of moles of a non-volatile
10. Liquids A and B form ideal solution over the solute S in equal amount (in kg) of these solvents, the
entire range of composition. At temperature T elevation of boiling point of solvent X is three times that
enquimolar binary solution of liquids A and B has of solvent Y. Solute 5 is known to undergo dimerization
vapour pressure 45 torr. At the same temperature, in these solvents. If the degree of dimerization is 0.7 in
a new solution of A and B having mole fractions x A solvent Y, the degree of dimerization in solvent X is ...... .
(JEE Advance 2018)

nswels
8. 1 9. 9 10. 19.00 11. 0.05

Exemplar Problems I!
Objective Questions
<a 3. At equilibrium the rate of dissolution of a solid solute in
1. Which of the following units is useful in relating a volatile liquid solvent is :
concentration of solution with its vapour pressure? (a) less than the rate of crystallisation
(a) mole fraction (0) parts fer million (6) greater than the rate of crystallisation
cc) MISS Percentapi a, Ne moflty (c) equal to the rate of crystallisation
2. On dissolving sugar in water at room temperature solution
(d) zero
feels cool to touch. Under which of the following cases a
dissolution of sugar will be most rapid? 4, A beaker contains a solution of substance ‘A’. Precipitation
(a) Sugar crystals in cold water. of substance ‘A’ takes place when small amount of ‘A’ is
(6) Sugar crystals in hot water. added to the solution. The solution is
(c) Powdered sugar in cold water. (a) saturated (6) supersaturated

Anse
(ad) Powdered sugar in hot water. (c) unsaturated (d) concentrated

1. (a) 2. (d) 3. (c) A, (5)

eri MODERN'S abc + OF CHEMISTRY-Aill

. Maximum amount of a solid solute that can be dissolved 14, Which of the following statements is false?
in a specified amount of a given liquid solvent does not (a) Two different solutions of sucrose of same molality
depend upon : prepared in different solvents will have the same
(a) Temperature (6) Nature of solute depression in freezing point.
(c) Pressure (d) Nature of solvent (6) The osmotic pressure of a solution is given by the
. Low concentration of oxygen in the blood and tissues of equation1=cRT (wherec is the molarity of the solution).
people living at high altitude is due to (c) Decreasing order of osmotic pressure for 0.01 M
aqueous solutions of barium chloride, potassium
(a) low temperature
chloride, acetic acid and sucrose is BaCl, > KCl >
(6) low atmospheric pressure
CH,COOH > sucrose.
(c) high atmospheric pressure
(d) According to Raoult’s law, the vapour pressure exerted
(d) both low temperature and high atmospheric pressure by a volatile component of a solution is directly
. Considering the formation, breaking and strength of proportional to its mole fraction in the solution.
hydrogen bond, predict which of the following mixtures 15. The values of Van't Hoff factors for KCl, NaCl and K,5O,,
will show a positive deviation from Raoult’s law? respectively, are :
(a) Methanol and acetone. (a) 2,2 and 2 (6) 2,2 and3
(6) Chloroform and acetone. (ec) 1, l and 2 (qd) 1,land1
(c) Nitric acid and water. 16. Which of the following statements is false?
(¢@) Phenol and aniline. (a) Units of atmospheric pressure and osmotic pressure
. Colligative properties depend on are the same.
(a) the nature of the solute particles dissolved in solution. (Dd) In reverse osmosis, solvent molecules move through
(6) the number of solute particles in solution. a semipermeable membrane from a region of
(c) the physical properties of the solute particles lower concentration of solute to a region of higher
dissolved in solution. concentration.
(d) the nature of solvent particles. (c) The value of molal depression constant depends on
» Which of the following aqueous solutions should have the nature of solvent.
highest boiling point? (d) Relative lowering of vapour pressure, is a
(a) 1.0 M NaOH (6) 1.0 M Na,SO, dimensionless quantity.
(c) 1.0 M NH,NO, (d) 1.0 M KNO, 17. Value of Henry’s constant A,, :
10. The unit of ebullioscopic constant is (a) increases with increase in temperature.
(a) K kg mol or K (molality) (6) decreases with increase in temperature.
(6) mol kg K* or K-“(molality) (c) remains constant.
(c) kg molt K* or K“\molality)* (d) first increases then decreases.
(d) K mol kg? or K (molality) 18. The value of Henry’s constant K,, is
11. In comparison to a 0.01 M solution of glucose, the (a) greater for gases with higher solubility.
depression in freezing point of a 0.01 M MgCl, solution (6) greater for gases with lower solubility.
is (c) constant for all gases.
(a) the same (b) about twice (d) not related to the solubility of gases.
(c) about three times (d) about six times 19. Consider the figure given below and mark the correct option.
12. An unripe mango placed in a concentrated salt solution Piston (A) Piston (B)
to prepare pickle, shrivels because
(a) it gains water due to osmosis.
(6) it loses water due to reverse osmosis.
(c) 1t gains water due to reverse osmosis.
(d) it loses water due to osmosis. Concentrated
13. At a given temperature, osmotic pressure of a concentrated Fresh water
sodium chloride
solution of a substance (A) solution in
(a) is higher than that of a dilute solution. water (B)
(6) is lower than that of a dilute solution.
(c) is same as that of a dilute solution.
(d) cannot be compared with osmotic pressure of dilute (a) water will move from side (A) to side (B) if a pressure

aswel
solution. lower than osmotic pressure 1s applied on piston (B).
(6) water will move from side (B) to side (A) if a pressure
ereater than osmotic pressure 1s applied on piston (B).

5. (c) 6. (5) 7. (a) 8. (b) 9. (bd) 10. (a) i te) 12. (d) 13. (a)
14. (a) 15. (5) 16. (5) 17. (a) 18. (5) 19. (5)
SOLUTIONS

(c) water will move from side (B) to side (A) if a pressure (c) vapour pressure is equal in both the containers.
equal to osmotic pressure is applied on piston (B). (dq) vapour pressure in container (B) is twice the vapour
(ad) water will move from side (A) to side (B) if pressure pressure in container (A).
equal to osmotic pressure is applied on piston (A). 23. If two liquids A and B form minimum boiling azeotrope at
20. We have three aqueous solutions of NaCl labelled as ‘A’, some specific composition then
‘B’ and ‘C’ with concentrations 0.1M, 0.01M and 0.001M,
(a) A-B interactions are stronger than those between
respectively. The value of van’t Hoff factor for these
A-A or B—-B.
solutions will be in the order
(6) vapour pressure of solution increases because more
(a) i, <1, <4, (b) i, > tp > tg
number of molecules of liquids A and B can escape
(c) , =tp =ig (2) 2. St from the solution.
21. On the basis of information given below mark the correct (c) vapour pressure of solution decreases because less
option. number of molecules of only one of the liquids escape
Information: from the solution.
(A) In bromoethane and chloroethane mixture, intermolecular (d) A—B interactions are weaker than those between
interactions of A-A and B-B type are nearly same as A-A or B-B.
A-B type interactions.
24. 4L of 0.02 M aqueous solution of NaCl was diluted by
(B) In ethanol and acetone mixture A—-A or B-B type adding one litre of water. The molality of the resultant
intermolecular interactions are stronger than A-B type
solution 1s
interactions.
(a) 0.004 (6) 0.008
(C) In chloroform and acetone mixture A—A or B-B type
intermolecular interactions are weaker than A-B type (c) 0.012 (d) 0.016
interactions. 25. On the basis of information given below mark the correct
(a) Solution (B) and (C) will follow Raoult’s law. option.
(6) Solution (A) will follow Raoult’s law. Information : On adding acetone to methanol some
(c) Solution (B) will show negative deviation from of the hydrogen bonds between methanol molecules
Raoult’s law. break.
(dq) Solution (C) will show positive deviation from (a) At specific composition, methanol-acetone mixture
Raoult’s law. will form minimum boiling azeotrope and will show
22. Two beakers of capacity 500 mL were taken. One of these positive deviation from Raoult’s law.
beakers, labelled as “A”, was filled with 400 mL water (6) At specific composition, methanol-acetone mixture
whereas the beaker labelled “B” was filled with 400 mL forms maximum boiling azeotrope and will show
of 2 M solution of NaCl. At the same temperature both positive deviation from Raoult’s law.
the beakers were placed in closed containers of same
(c) At specific composition, methanol-acetone mixture
material and same capacity as shown in figure given
below:
will form minimum boiling azeotrope and will show
negative deviation from Raoult’s law.
(d) At specific composition, methanol-acetone mixture
will form maximum boiling azeotrope and will show
negative deviation from Raoult’s law.
26. K,, value for Ar(g), CO,(g), HCHO (g) and CH, (g) are 40.39,
1.67, 1.83 x 10° and 0.413 respectively.
Arrange these gases in the order of their increasing
At a given temperature, which of the following statement solubility.
is correct about the vapour pressure of pure water and
that of NaCl solution. (a) HCHO < CH, < CO, < Ar
(a) vapour pressure in container (A) is more than that (6) HCHO < CO, < CH, < Ar
in container (B). (c) Ar < CO, < CH, < HCHO
(6) vapour pressure in container (A) is less than that in (d) Ar < CH, < CO, < HCHO
container (B).

nswels
20. (c) 21. (bd) 22. (a) 23. (d) 24. (d) 25. (dD) 26. (c)
 MODERN'S abc + OF CHEMISTRY-A&All

»
Note:
Multiple Choice Questions (Type-ll)

In the following questions two or more

o
options
31. Isotonic solutions must have the same
(a) solute
(6) density
may be correct.
(c) elevation in boiling point
27. Which of the following factor (s) affect the solubility of a (d) depression in freezing point
gaseous solute in the fixed volume of liquid solvent ?
32. Which of the following binary mixtures will have same
(1) nature of solute (z1) temperature (11) pressure
composition in liquid and vapour phase?
(a) (2) and (zzz) at constant T (a) Benzene — Toluene
(6) (z) and (zz) at constant P (6) Water — Nitric acid
(c) (iz) and (zz) only (c) Water — Ethanol
(d) (iit) only (dq) n-Hexane — n-Heptane
28. Intermolecular forces between two benzene molecules are 33. In isotonic solutions :
nearly of same strength as those between two toluene (a) solute and solvent both are same.
molecules. For a mixture of benzene and toluene, which (b) osmotic pressure is same.
of the following are not true? (c) solute and solvent may or may not be same.
(a) A... H = zero (b) A... V = zero (d) solute is always same solvent may be different.
(c) These will form minimum boiling azeotrope. 34. For a binary ideal liquid solution, the variation in total
(d) These will not form ideal solution. vapour pressure versus composition of solution is given
29. Relative lowering of vapour pressure is a colligative by which of the curves?
property because
(a) It depends on the concentration of a non electrolyte
solute in solution and does not depend on the nature
of the solute molecules.
p Pp
(6) It depends on number of particles of electrolyte solute
in solution and does not depend on the nature of the
solute particles.
(c) It depends on the concentration of a non electrolyte — X, xy — X) >
solute in solution as well as on the nature of the (a) (b)
solute molecules.
(d) It depends on the concentration of an electrolyte or
non electrolyte solute in solution as well as on the
nature of solute molecules. T tT
p p
30. Van't Hoff factor ‘:’ is given by the expression

Normal molar mass

(a) 2 = —____
Abnormal molar mass
<— xX, x3 < X, 4

(b) iz Abnormal molar mass

(c) (d)
~ Normal molar mass
35. Colligative properties are observed when
©) iz Observed colligative property (a) anon volatile solid is dissolved in a volatile liquid.
“’ * = ‘Calculated colligative property (6) anon volatile liquid is dissolved in another volatile
liquid.
ore Calculated colligative property (c) a gas is dissolved in non volatile liquid.
Observed colligative property (d@) a volatile liquid is dissolved in another volatile liquid.

Asset
27. (a), (6) 28. (ce), (d) 29. (a),(b) 30. (a),(c) 31. (c),(d) 32. (b)(c) 33. (6),(c) 34 (a)(d) 35. (a){d)
SOLUTIONS ani7]

D> a <
Pieter ae cn:

Note : In the following questions match the items given in Column I and Column II.
36. Match the items given in Column I and Column II.

(a) Saturated solution ') Solution having same osmotic pressure at a given temperature as that of given solution.
(6) Binary solution A solution whose osmotic pressure is less than that of another.
(c) Isotonic solution Solution with two components.
(d@) Hypotonic solution A solution which contains maximum amount of solute that can be dissolved in a given
amount of solvent at a given temperature.
(e) Solid solution A solution whose osmotic pressure is more than that of another.
(f) Hypertonic solution A solution in solid phase.

37. Match the items given in Column I with the type of solutions given in Column II.

(a) Soda water ') A solution of gas in solid

(6) Sugar solution - A solution of gas in gas
(c) German silver . A solution of solid in liquid
(d) Air _ A solution of solid in solid
(e) Hydrogen gas in palladium ' A solution of gas in liquid
A solution of liquid in solid
38. Match the laws given in Column I with expresions given in Column II.

(a) Raoult’s law ic AT, = Kan

(6) Henry’s law Tt =e
(c) Elevation of boiling point 7 =» 9) + X,pe
(d) Depression in freezing point AT, = K,m
(e) Osmotic pressure | py 4%

Number of moles of the

fina ; ep
ea Sle e
ee Melee eee w Volume of solution in litres
Number of moles of a component
(6) Volume percentage (it) Total number of moles of
all the components
Volume of the solute component
in solution
(c) Mole fraction (1it) a See eo x 100

Mass of the solute component

in solution
cls eH) Total mass of the solution eure

(eninolacty (v) Normal molar mass

Abnormal molar mass

Nnswets
36. (a)—(iv); (b)3(ii1); (c)3); (Do); (e)o(v1); (ov) 37. (a)—v); (b)(t12); (e)iv); (d)a1); (e) (2);
38. (a)—(111); (b)(v); (e)(iv); (d)(2); (e)—(21); 39. (a)—Aiv); (b)-0i1); (ea); (dol); (e)(0);
 MODERN'S abc + OF CHEMISTRY-Aill

Reason : The volume of a solution changes with change

in temperature.
41. Assertion : When methyl alcohol is added to water, boiling
In the following questions a statement of assertion
point of water increases.
followed by a statement of reason is given. Choose the
Reason: When a volatile solute is added to a volatile
correct answer out of the following choices.
solvent elevation in boiling point is observed.
(a) Assertion and reason both are correct statements and 42. Assertion : When NaCl is added to water a depression
reason 1s correct explanation for assertion. in freezing point is observed.
(b) Assertion and reason both are correct statements but Reason : The lowering of vapour pressure of a solution
reason is not correct explanation for assertion. causes depression in the freezing point.
(c) Assertion is correct statement but reason is wrong 43. Assertion : When a solution is separated from the pure
statement. solvent by a semipermeable membrane, the solvent
(d) Assertion and reason both are incorrect statements. molecules pass through it from pure solvent side to the
(e) Assertion 1s wrong statement but reason is correct solution side.
statement. Reason : Diffusion of solvent occurs from a region of high
40. Assertion : Molarity of a solution in liquid state changes concentration solution to a region of low concentration
with temperature. solution.

nswets
40. (a) Al. (d) 42. (a) 43. (c)

ons for
Hints & Explanati Difficult Objective Type Questions
Molality of solution
A. mcq with only one correct answer
= —“_ x1000 =4.5
bx18
A.1. (6) : Mass of solution = 500 x 1.05 = 525 g
mz 18 x 4.5
Mass of urea = 6¢ = 0.081
Mass of solvent = 525-6=519¢ aa 6 1000
6/60... Mole fraction of CH,0H
Molality = 519 *1000
a. - 1
= 0.1927 m
a+b 1+ b/a
A2. (c): M,V, + MLV, = MV,
1 x 2.56 + 0.5 x 3=M, x 5.5 (Total solution = 5.5 L)
ft ~~ ft = 0.075
14 i! 1+ 12.34
295+15 = M, x 5.5 0.081
Ad. (a): 3 Molar solution of NaCl means that 3 mol of NaCl
M, > = “Dae
-=0.73M
/ is dissolved in 1000 mL of solution.
AS. (e): Let volume of 4N HCI used = x mL Mass of 3 M NaCl solution = 1.25 x 1000 = 1250 g
Mass of 3 mole NaCl = 3 x 58.5 = 175.5 g
Volume of 10 N HCI used= (1000 — x) mL
Mass of solvent = 1250 — 175.5 = 1074.5 g
N,V, + N,V, = N,V,
Molality = —° — x 1000 = 2.79 m
4 xx+10 x (1000 —x) = 6 x 1000 1074.6
6x = 4000 AG. (b): Moles of solute = 2.5

: a = 666.7 mL Moles of water =

1000 _
18
Vol. of 4 N HCl used = 0.67 L Mole fraction of solute = ————
1 = 0.043
Vol. of 10 N HCl used = 1 — 0.67 2.5+ 55.6
AZ. (c): 4.27 M H,SO, (aq) means that 4.27 moles of H,50,
= 0.38 L
are present in 1000 mL of solution.
Ad, (d): Let a mole of CH,OH and 6 mole of water be present
in the solution. Mass of solution = 1000 x 1.25 = 1250g
Mass of water = bx 18 Mass of 4.27 moles of H,S5O, = 4.27 x 98 = 418.46 g
SOLUTIONS

Mass of water present = 1250 — 418.46 = 831.54 g Total pressure = 15 + 24 = 39 torr

4.27 x1000 The observed pressure is less than expected value
Molality = = §.135 m and hence it shows negative deviation.
31.64
A8. (d) - 7M solution of KOH means 7 moles of KOH in A115. (a) The mole fraction of the gas in the solution,
1000 mL of solution.
ee 1 — 10-5
Wt. of KOH = 7 x 56 = 392 gin 1000 mL K,, 1000 x 10°
Since the solution 1s 40% by weight, it means that 40g of If n is the number of moles of gas in a solution of
KOH is present in 100 g of solution. 1 L of water contains 55.5 mol, then
392 g of KOH is present in mand x 392 = 980 g
40) c= A = — = 100x10°
nm+55.5 bo.
; 980
Density = —— =0.98 gmL7?
1000 n = 55.5 x 10°=55.5 x 10°? millimoles.
AQ. (c) : Suppose x mL of 12M HCl to be mixed with or = 0.55 millimoles
(1000—x) mL of 4 M HCl.
Al6. (a) : os Ky%o,
M,V, + M.,V, = M,V,
12 x x + 4 (1000-x) 6 x 1000 Here Po, = 0.2 atm, K,, = 4.34 x 10* atm
12x + 4000 -— 4x = 6000 0.2 = 434 x 10*x x,
2
&x = 2000
Xp = ee = 461 x 10°
9 4
= 2000 _ 950 mL. 4.34 x10
Volume of 12 M HCl required 950 mL
"0, "0,
Volume of 4 M HCl required = 1000 — 250 = 750 mL Now i. = ae
2 No, tho y,0
A10. (d) : Moles of H,SO, = oe For 1 litre water, Myo = 55.55.
100
Volume of solution = re = 55.5 mL 1) ve
Xo = <= -—_ =4 61x 106
80 x 1000
Molarity of solution = = 14.7M
98 x 55.5 or ik o — 4.61 x 10° «x 55.55
2
Now MV, =M.V,
2.56 x 10+ M.
14.7 x ¥, = 0.2 x 1000
A17. (d) : For equimolar solution of X and Y
v, = 22> Fe eb mL. ty = 0.5, x, = 0.5
14,7
Px = 0.5 x 200 = 100 torr
All, (c) Mole fraction of A = 1-—0.2=0.8 Py = 0.5 x 100 = 50 torr
DaXX,t+D'pXxyp FB Proeat = 100 + 50 = 150 torr
p°, = 70 torr; p*,, =/?)p= 84 torr Mole fraction of component X in vapour phase,
70 x 0.8 + p°p x 0.2 = 84
Dp’, x 0.2 = §4 — 56 = 28 torr yx, = —. = 0.67
28
Ps: —=140torr A18. (6) : In solution,
0.2
ix, =%, Xp, = 2x
Dy XX,
Al2.(a) : yy = Px’ =P; Pa = 2P
Prceat

plot of y, vs 1/p,,,.) 1s near

Pa=X XP, Pp = 2x x 2p = Axp
Protal= XP + 4xp= Sxp
Al13. (a) : According to Raoult’s law
Mole fraction in vapour phase,
1
Ps = Xa Pp, = g X45= 15 torr
PB 4xp 0.8

i. =.,. po =x 86 = 24 torr YB Protal 7 5xp

 MODERN'S abc + OF CHEMISTRY-Aill

Ald. (a) : The vapour pressure of A is more than that of B. 20

Therefore, boiling point of A is less than that of B = *
DR .
1.6, PT.
0.2
(a) represents the azeotrope of minimum boiling 10 = —_ orx,= 0.4
20 Xo
point.
Mole fraction of solvent = 1 — 0.4 = 0.6
A20. (6) : Let the mole fraction of P be x
Mole fraction of Q =1-x A27. (d) : Molar mass of macro-molecules (proteins, colloids,
etc.) can be determined with greater accuracy by
450 x = 200(1 — x)
finding osmotic pressure because the magnitude
650 x = 200 of this colligative property 1s comparatively large
even in dilute solutions.
xc = ae = 0.308 ee
650 A28. (d) : AT, = 100.512 — 100 = 0.512°

A211. (a) : AT, = K,xm SATs

= K, yi
0.512"
or m= AT, = —— = 0.05 m
K, 2.52 AT, = K; xm = 1.86 x 1 = 1.86°
A22.(a) : nm = cRT Freezing point of solution = 0 — 1.86 = — 1.86° C
= 0.2x 0.082 x 300=4.92atm 29. (c) - A is solute and B is solvent.
A23.(c) : The two solutions have same osmotic pressure, 10
Pg B =PpB - 100
—— PpB = 0.9p,°
B
5 pT = 2° R'
RT
180 M M, = -” M, = 0.30 M,
2.) 100
orM = — 180 = 90 g mol?
Pg’ — Pp Sa, w, XM,
A24, (d) - AT, = K, x1000 xwp 2 “ M, xu,
Wa Xx Ms
Pp? -—0.9D,° _ Way 0.30 M,
Since K, and w, are same for two solutions,
Pg” Wy M,

AT, Wy Mp w
0.1 = “x03
AT, (urea) = 0.25°, wz = 1g, M, = 60 Wp,
AT,’ (glucose) = ?, wz = 3g, M, = 180 w
or —B = 0.3 = 3.0

0.25 _ 1x180 twa 0.1

AT, 3x60 AS0. (c) K, x1000 x

AT, = ey Metin cheese! |
Wa xMp

or AT, = 0.252 0.52 «1000 x 0.6 ~ 0.052

.. Boiling point of solution = 100 + 0.25 = 100.25°C 100 = 60
A25. (a) : AT, = 0.01°, w, = 100 g, K, = 0.50, M, = 342 .. Boiling point of solution : 373 + 0.052 = 373.052 K
AT /@ K, x 1000 xw, A31. (a) It depends upon the number of particles.
w, XM, NaCl (2 particles, Na*, Cl), BaCl, (3 particles,
Ba?*, 2Cl-) and glucose (non-electrolyte)
or Wp, = AT, X wy x Mg A832. (c) The simple inspection of the question shows that (d)
K, x 1000 should be the correct choice because CaCl, will give
3 mol of ions for 1 mol of CaCl, dissolved (assuming
_/ 0.01x100x342 _ 4 ge4 4 it to be completely dissociated). However, in the
0.50 x 1000 given question, the amounts are given in grams.
0.684 If we assume that m grams of all the substances
No. of molecules = 349 x 6.023
x10°
are dissolved in 1000 g of solvent then,
= 1.2 x 107!. Molal cone. of NaCl in solution
A26. (a) For first solution, = ——x2=0.034m
10
58.5
a = 0.2 Molal cone. of ions of CaCl, in solution
Pa
For second solution = “43=0.027m
ite|
Molal cone. of NaCl in solution is more than molal
conc. of CaCl, solution.
SOLUTIONS

A33. (d) : They give same number of ions

A34, (5) Ba(NO,), == Ba?* + 2NO, Pa’
~Pp’, PRO
Initial 1 mol _ _ Pa” Xa Pa”
After dissociation 1—o a 20
1 : Le ; :
Total moles = l—-a+a+4+2a=1+2a
.. Plot of —— against —— gives straight line with slope
Ya Py”
i=1+2aora

= 271_214-1 _997 or 87%.

— Pp

D D Pa”
Ai): OX 060UC—— Oo ltl A42, (c) For binary solution showing positive deviations
during mixing, entropy increases to maximum and
m(1 — 0.20) m(0.20) m(0.20) free energy decreases to minimum. AH_.. > 0.
Molal conc. in solution
A438. (a) Loss in weight of solution < p, = 2.5 g
m1 — 0.20) + 0.20 nm + 0.20 m
Loss in weight of solvent (water) «< p,° —p, = 0.06
= 1.20 m
D,° =(p,°-P,) + Py = 0.06 + 2.5 = 2.56 g
and m = 0.2
AT, = K, x mm Pa°-Py _ WpXxM,
= 1.86 x 1.20 (0.2) Pa® My XW,
= 0.446 = 0.45 0.06 — 95x18
.. Freezing point of solution = — 0.45°C. 256 7 Mp x80
A3é. (bd) For two solutions A and B M, = pee ae als
m(A) _ ¢(A) 80
x0.06
r(B) — ¢(B)
c(B) = 0.1 M, c(A) = 0.05 x 3=0.15 M
B. mcq from Competitive Examinations
Bl. (a) 98% H,SO, by mass means 98 g of H,SO, are
a) = = = 1.5
p 0.1 present in 100 g of solution
mA) = 1.5 p ; 100
Volume of solution = 1320 7 55.56 mL
A37. (c) : It is the ratio of number of particles in solution
Urea = 1, common salt = 2, sodium sulphate = 3 Molarity of solution = — x 1000 = 18.0 M
A38. (a) : Colligative properties are directly proportional to the
number of particles. Al,(SO,), will give 5 particles Now, MV, = MV.
and therefore, depression in freezing point will be 18.0 x V, = 0.1 x 1000
almost 5 times than for non-electrolyte. 0.11000
V, = ———— = 5.55 mL.
' 18.0
A89. (d) : HX —— EG &
B2. (d) AT, = 1K,m (i = 1.20)
m(1 — a) m. cl m7. OL
Total molality = m(1 — a) + ma + ma = m(1 + a) = 1.2 x 1.86 x 0.5 = 1.12 K.
AT, = Kem (1 + a) Bs. (d) : The number of moles produced by 1 mole of ionic
= 1.86 x 0.2 x (1+ 0.3) =0.48° compound
.. Freezing point of solution = - 0.48°C. AT, = 1K-m, t = AT,/
A40. (c) : tor ch AT, = 0 — (-0.00732)
(1) 2(0.15 M urea) = 1x 0.15 RT = 0.15 RT = 0.00732 °C
(2) 2 (0.05 M CaCl,) 3 x 0.05 RT = 0.15 RT K, = 1.86° C/m
(3) 2 (0.1 M MgsSO,) 2x0.1 RT = 0.2 RT m = 0.0020
(4) 2=(0.15 M glucose) == 1 x 0.15 RT = 0.15 RT a 0.00732
~. (1), (2) and (4) are isotonic. ~ 1.86
x0.0020
AA41. (b) Mole fraction of component A in vapour phase = 1.968 = 2
7. Se PaXa : Pay
Ptotal PA*A+ PBXB Paxat Pp 1-xXg)
Bo): «+ Nomis 106
x 250
Pa*Xs = 0.955 M
Xs (Pa°- Pp°)t+ Pp- Na,CO, —~> 2Nat* + CO

1 _ %,(Pa°-Pp’)+
Pp? [Nat] = 2 x 0.955 M = 1.910 M

[CO,7] = 0.955 M.
Ya Xa Pa”
 MODERN'S abc + OF CHEMISTRY-Aill

B5. (5) : According to Raoult’s law B14. (6) : 1.00 msolution means that 1 mol of solute is present
D, = p°x, (x, = mole fraction of solvent) in 1000 g of water.
On addition of water the mole fraction of water in Moles of solute =]
the solution increases, therefore vapour pressure
Moles of water = aul = 55.55
increases. 18
B6. (c) : AT, = K.m 1
Mole fraction of solute = ————— = 0.0177
1+ 66.55
Molality, m = “— x 1000 = 0.2
B15. (c) : Mole fraction of benzene (x,) = 5
AT; = Se x 02 = 0.372
‘. Freezing point of solution = 0 — 0.372 Mole fraction of toluene (x,) = >
= — 0.372°C.
| 1
B7.(c) : For dissociation, i > 1 Vapour pressure of benzene (p,) = 12.8 x 5 6.4 kPa
For association, t < 1
B8. (d) : According to Raoult’s law Vapour pressure of toluene (p,) = 3.85 xs = 1.925 kPa
P = XP, + XpPp Total vapour pressure of solution (p) = 6.4 + 1.925
For binary solution, x, +x,=1 or x,=1-x,
= 8.325 kPa
p 2 bil Hap,
Mole fraction ofbenzene in vapour phase = ae =0.77
XsPa + Pp-*, Pp
or = Ppt X(Ps — Dp) ; 1.925 |
Mole fraction of toluene in vapour phase = 8.325 =0.23
| 6.02 x 10” _—
B9. (d) : Moles of urea = 602x107 = 1x10 The vapour will contain higher percentage of benzene.
: 1x10" Dp —Ps _ Mp _WpxMy
iz) ‘

Molarity = ~ x1000 = 0.01 M B16. (

(c) p?° ny Mpxu,
oe | . Moles of HNO,
B10. (d) : Molarity = Volume
of solution * 1000 760-732 6.5x18
760 M,x100
2 = Ass SSx 1000
28 _ 6.5x18
2 x 250 760 M, x100
Mass of HNO, = axe =315¢

: 31.5 x 100 M,, = X18x

8:0 160 _ 91 46
Mass of HNO, required for 70% solution = “re 28 x 100

= 45.0 g. Now, AT, _ K,+b x Wp

wp x 1000
= 0.52| 6.5 x 1000 -1.06
w, X Mp 100 x 31.76
B11. (c) : Largest freezing point depression 1s shown by solute
having largest (same 0.1 m concentration) value Boiling point of solution = 100 + 1.06 = 101.06°C
of Van't Hoff factor (z). =101°C
AT, = 1K-m
B18. (d) : Ba(OH), —— Ba** + 20H
i (KCI Y &02,,74C,,O,) = 1;
1=3
i [Al,(SO,)s] 5; 1 (K,SO,) =3 B19. (c) : The value of molal depression constant (Ky) 1s
B12.(c) : AT,= «K, m constant for a particular solvent. Therefore, it will
be unchanged when molality of the dilute solution
or AT, « i for equimolar solution
is doubled.
't' of solution X > 'z' of solution Y
This is possible if X undergoes dissociation. B2l.(e) : t= mRT
V
B13. (6) : For Al,(SO,), === 2A}8*+ + 380," ,i =5
10 0.082xT
Now AKNO,), ———> Al®* + 8NO; ;i=4 164 - 180
100/1000
K,[Fe(CN),] ———> 4K* + [Fe(CN),]#;i =5
16.4 *100 x180
K,SO, ——» 2K* + SO.” ;i=8 or T =
10 x 1000 x 0.082
K,[Fe(CN),] ———> 8K* + [Fe(CN),]*-;i = 4 360 K
SOLUTIONS

B22. (a) : According to Raoult’s law B29. (c) : ABe== <At+E-

pos Pax, + PRX, Initial 1 0
1 2 Atequ. l-a a a
p = 500 mm Hg, x, = g?*B= 3 Total moles = l-ata+a=l+a
; l+a
iL o 2 a C=
500 = =5 Pa + —3 Pz 1
Observed colligative property
or 1500 = Pa +2Pp (i) Normal colligative property
On adding 1 mole of B, 0.81 -15
1 3
P = $80 im He7 s+,
a = =,
4 “aE - |— 0.54
l+a 1.5
525 = =Ps + “Dr or a 0.5 or 50%
B30. (d) AB = At*t+B-
or 2100 = Ps +3Pp (ii) 1=@%
Subtracting (z) from (iz)
;Wp , RE
600 = Dp t=
Mp V
1500 = p, +2 x 600
or
10 ,0.0821 x 300 = 24.6 atm
P, = 300 mm Hg. 200 100/1000
| 1 _ B31. (a) 2 M solution means that 2 moles of solute are
B23. (d) : p=, * Solubility
present in 1000 mL of solution.
Solubility = Kp Wt. of solution = 1000 x 1.2 = 1200 g
Wt. of solute = 2 x 100 = 200 g
= 0. x 14 x 10? mol/L
Wt. of solvent = 1200 — 200 = 1000 g
= 0.5.x 14x 10% 32 g/L
= 22.4 x 10° g/L, Molality = eee
1000
=2m

Amount dissolved in 100 mL B33. (c) For complete dissociation of electrolyte AB,,
224x107 AB, —> A** + 2B” i=3
7 10 Relative lowering in vapour pressure,
= 2.24 x 103g = 2,24 mg. P — Pee
B26. (b) : AT; = 4 K-m Pp Ny + My
100—p 1
For NaCl, AT; =. 22 =o x
100 1+99
c= 2S K; x m
3 x 100
For BaCl,, AT, = 7. t=3 100 —p = —— =8
100
AT; = Ss K- x m . p =100-3=97mm Hg
Since K, and m are same (equimolal solution) B34. (e) x = iCRT
AT, 3 or TK 1
a = g or AT, =e
Hence, KC] > CH,COOH > Sucrose
(Strong electrolyte) (Weak acid) (Non electrolyte)
.. Freezing point of BaCl, solution = 0 — 3 = - 38°C.
B35. (d) For isotonic solution, C, = C,
B27. (a) AT; = K, x m = 1.56 x 0.100 = 0.186
1.5
AT, (observed) = (0.197 Bee ee or M = 210 g mot".
M 60
0.197
B36. (c) 29% H,SO, by mass means that 29 g H,SO, are
0.186 — 1.06 present in 100 g of the solution. If d g mL is
If a is the degree of ionization, the density of the solution, then
HF = Ht + F 100
Initial moles 1 0 0 Volume = 7
After ionization 1l-a cL ol
29
Total number of moles after ionization Moles of H,SO, = 98
= l-a+t+a+t+aqa=l+a.
: 29/98 x 1000
1+. Molarity = ——————— = 3.60
= — = 1.06 or a = 0.6 or 6% f 100/d
B28. (c) : According to Henry’s law, 3.60 x 100 x 98
or f= a ee
a
1000 x29 = 1.22 g mL”.
-1

p(N,) = x,, x x(N,)

0.76 atm = 7.6 x 10* atm x x(N,) B37. (a) Pity = PA*A + PaXp
x(N,) = 1x10° 760 = 520 x, + 1000 (1 —~x,)
 MODERN'S abc + OF CHEMISTRY-Aill

760 520 x, + 1000 — 1000 x, K, x 1000 x w,

480 x, 240 B43.
a
(c) AT,
f
=
w, x M,
Xa 0.5 or Moles of A = 50.
18 @ 1.86 x 1000 x wy
B38. (a) : Moles of glucose 4000 x 62
180 =o
178.2 w, = 6 x 4000 x62 _ 800 g.
Moles of water = 9.9
18 1.86 x 1000
Oo
PoP 0.1 B44, (c) A,B = cA + yu
p 0.1+9.9 Moles at l-a@ xa ya
17.5-—p
Lich
0.1 equi :
Total no. of moles = 1-a@ + xa + ya
10
ed Le Oo + xO + YO
_ 0.1*17.5 - 0.175
17.6=p 1
10 (¢-—1) = alfx+y-1)
17.5 — 0.175
- —t-1
p=

= 17.325 mm Hg ** @+y-)
B39. (c) : According to Raoult’s law B45. (a) : Density of water at 25°C = 1 g/mL
P Volume of water= 0.3 x 1000 = 300 mL
= Pyxy,+ PYyxy
Mass of water = 300 x 1=300¢
Initially, p = 550 mm Hg, x, = . Moles of urea = 0.01
4 * a
ms
Co
| Ges of urea = —
500 = ol
Px-7 ale
PY-7ca
o
Az)
Madigan 1
On adding 1 mole of Y 60 x 300
p = 560 mm Hg, x, = ao am
_4 B46. (bd) I, = Wo
O1| or C, = CG,
560 == PX-e
P%-=+ PY->
pe-— ..(it) 5&6 1
342 M
Solving eq. (i) and (ii), Pk = 400 mm Hg
PY = 600 mm Hg. M = = = 68.4.

B40. (d) : For complete dissociation of Na,SO, B47. (c) Mass of urea = 120 ¢
Na,SO,—> 2Na* + SO,2- Moles of urea =
120
rT he 2

0011 2061
i= a
Mass of solution = 1000 + 120 = 1120 g
WL
Volumeolume ofof solution
solution == ———~
77.
AT, = iK- nL
2 ae
3 x 1.86 x 0.01 Molarity = 1120 * 1000 = 2.05 M
= 0.0558K.
1.15
25. B48. (a) AT, = 0-(-—2.8) = 2.8
B41. (c) : n = — =(),25
100 Mass of aelvent = lkg=1000¢
I= 35 K, x 1000 x w
= — =(0,307
114 AT, = as descent
Wy Ms
25
mee / 0.45 08 = 1.86 x 1000 x wa,
0.25+0.307
1 — 0.45 = 0.55 1000 x 62
gh
St
oi
X,P, + XP, Ww, = 2.81000 x62 _ 999 g.
0.45 x 105 + 0.55 x 45 1.86 x 1000
A7.25 + 94.75 B49. (a) : M,V,+M,V, = M,V,
72 hk Pa. 0.5 x 750+ 2 x 250
= M, x 1000

M, = 275+500 9.675 u
B42. (a) : 5.2 molal solution means that 5.2 moles of solute
(CH,OH) are present in 1000 g of water
Moles of CH,OH, “cu,onH = 5.2 B50. (6) : Osmotic pressure,
ma = icRT
Moles of water, n._... = 1000 _ 55.56 m[C,H,OH] = 1x 0.500 RT =0.5 RT
ist
m [Mg, (PO,),] 5 x 0.100 RT = 0.5 RT
XcH;,0H = __ 9%
5.2 +55.56
_ ooge.
x{K Br] = 2 x 0.250 RT = 0.5 RT
SOLUTIONS

m[Na, PO,] = 4x 0.125 RT =0.5 RT 1 o i o ®

Therefore, all have some osmotic pressure. or 9 Px + 9PY = 400 mm ..(L)

B51. (d) : |
as a ee ee When —* = 2 at the same temperature
p? Na +p es
ny 2
We * Ma
wy, * Mz 5 wh Se
=,
wae ot3
185 — 183 1.2 * 58
185 100
x M, p' = Py X Xx + Py XXy: = 550 mm

_ 12%*58x185 l «22 ”
M = 64.38 = 64 or 3 Px eg3x = 350 mm ltt)
= 2x 100
B52. (c) : At 1 atm, the vapour pressure of water, p° = 760 torr. Solving (i) and (ii) Py = 550 mm, p, = 250 mm.
= 18 g;: M, = 180 g mol*; w, = 178.2 g: p, =?

Pa-Pa_
_ WpMy B56. (d) : bane -C
Pa ~ w,My
‘60
x100 urea
glucose

760-—P, 18x18 flucose

- IM
or =
760 178.2 x 180 B57. (d) : Let w be the mass of sucrose dissolved in 100 g of
760— pa
—— = =().0101
water

ve 760 Molality, m = Saale yeL000

342 100
or Ps, = 752.3 torr
= 0.0292 w
a | ix K, x 1000 Xw, AT; = K, x ml |
B53. (d) : AT, = —_w,xM,
= 1.86 x 0.0292 w
_ tX512x*1000 x0.2 AT, = K, xm
Bese 20 x60 = 0.51 x 0.0292 w
0.45 x 20 x 60 T, = 0-—1.86 x 0.0292 w
* == —_____—_=
52x 1000 x0.2 (1.627
T, = 100 + 0.51 x 0.0292 w
T,-T; = 100+ 0.51 x 0.0292 w
2CH,COOH = (CH,COOH),
—0 + 1.86 x 0.0292 w
1-a o/2
= 100 + 0.0692 w
Total number of moles = 1-a@+0/2=1-a/2 or 105 = 100 + 0.0692 w
; 1-0/2 0.0692 w = 5
1 = = = 0.527 _ 5
_a/2 = 0.527 -1=-0.473 ~ = 0.0692
= 72.2 ~ 72g.
a= 0.473 x 2 = 0.946
. M
Percentage association = 94.6% B58. (6) - eae
Pa ek
Pa w,M,
B54. (d) : [Co(H,O),]Cl, ——— [Co(H,0),]* + 3Cl-
10 swag X18
(4 particles per mole)
100 180 x60
[Co(H,O),CIC1,.H,O —— [Co(H, 0), Cll?* + 2CI-
10 180x60 |
(3
gepyicles per mole)
[Co(H,0),Cl,]Cl.2H,O <= [Co(H,O), CL,]?* + Cl “p= i00* ig 8
bo particles
arti per mole) 1000 x Ky x We
B59. (e) : M, =
[Co(H,O),Cl,]. 3H,0 ——— [Co(H, 0), Cl,] w, x AT;
(1 particle per mole) AT, = 0 — (— 0.465) = 0.465
Now AT, « i (no. of particles)
_ 1000 x 1.86 x 1.8
So, [Co(H,O), Cl,]. 3H,O0 will have minimum depression = 180
40 x 0.465
in freezing point and hence maximum freezing point.
Empirical formula mass = 12 + 2 x 1+ 16 = 30
ny
B55. : (e) : — =
ny=ny=1or —-=1
< _ Molecular mass
1 4 1 *ae
us Empirical formula mass
a nos

“x 75y 02°°% 141 2 oY

30
p = PyXxXy+py
Xxy = 400 mm
Molecular formula (CH,O), = C,H,,O,-
 MODERN'S abc + OF CHEMISTRY-All

98.9/98.5 B65. (a) : For equimolar solution, x, =x, = 0.5

B60. (a) : Molality of NaCl = x1000 =1m
Pp, =X, x p= 0.5 x 100 = 50 mm
1000
(for water = 1000 mL = 1000 g
p, =x, xp, = 0.5 x 50 = 25 mm
’ density of water = 1) Total vapour pressure, p,,, = 50 + 25 = 75 mm
Molality of glucose Mole fraction of benzene in vapour phase,
180 /180 Dy Ts
50 |= 0.67
= ———x1000
1000 x = lm y, = oom

i for NaCl = 2, i for glucose = 1 B66. (d) : AT; = 0-—(-0.125) = 0.125°C

AT, = 1x K, xm Ky XWp X 1000
AT, for NaCl > AT, for glucose. ar ~ Mp xw,

B61. (e) AT, _ Ky 0.125 = 1.86 x 3 x 1000

111.6xw,
AT, = 0 —(— 0.186) = 0.186°C w, = 400g
B67. (a) : As P undergoes association:
0.186 _ 1.86
er = fF,
AT, 0.52
If a is the degree of association
or Ai, =: ee ee one Initial 1 0
1.86 After association 1-a o/2
Px ~PA — 20 _ |
B62. (a) Total number of moles = 1- a + o/2 = 1_—
Pe 00S 1-a/2
2
Let mass of non volatile solute be added = x g
1
a x
Now, observed molar mass,
A
#218 100 »=6114 1000
xK, xwz
4) 114 114 Wa, X AT,
x 20 40 x 20
_ 1000 x 1.86 x 1.25 155
or 40
——— =
100
—— =
* = "100
=

50
x 0.3
B63. (5) : Let vapour pressure of A be p so that vapour
Normal molar mass
pressure of B is 2p.
Observed molar mass
Total vapour pressure of solution.
1 2 op - »* _0 606
=px—+ x -— = — 155
P* 3 * ie;
In vapour phase, mole fraction of A is 0.606
is
Ya = = = 0.20 = 0.606-1
3 = -—0.394
B64, (5) AT, = 0.19, m = 0.1, K, = 1.86 Km? 0.788 or 78.8%
: BO%
, . AT,
AT; = i Kex m ori = K, xm B68. (5) K,[Fe(CN),] == 3K* + [Fe(CN),]*-
If a is the degree of dissociation, then
0.19
= ————_ =].02 1-a 3c ol
1.86 x 0.1
Total moles after dissociation = 1-a + 3a+a
If a is the degree of dissociation,
= 1+3ca
CH,COOH = — CH,COO- + Ht
1+3a
Initial moles 1 0 0 i= = d.000
After dissociation l-a a Oo
90 = 3.4005 — 1 = 2.5335
Total number of moles after dissociation
7.355
=~ l-at+ata=l+a. Co = = 0.78 or 78%

i=
1+@
—— = 1.02 or a = 0.02
B69. (d) Molarity of 0.06% (w/v) aqueous solution of

a H ca? = 0.1 x (0.02)? = 4 x 10° urea is molarity = — x aie 0.01 M

60 100
SOLUTIONS

As osmotic pressure, = = cRT, Where m= icRT

0.01 M solution of urea will be isotonic with 0.01 M For the given solutions at the same temperature, T
glucose solution. and R are constant

B71. (a) : For 0.01 M NaCl (a) For urea, ei m= 1001. RT

AT, = 2 x 0.01 K, = 0.02 K, (ary ey For NaCl, age 2, T= 2 x 0:01ET
For 0.01 m Na,SO, (6) For NaCl, rae r= 2 = 0.02 KT
AT, = 3x 0.01 K, = 0.03 K, Coe =o) For Na,SO,, i= 3, g= 3 x 0.02 ET
For 0.1 M sucrose (c) For NaCl, Pee m= 2x 0.03 RT
AT, = 0.1 K, (ae 1) For MgCl,, P=, n=3 x 0.02 RT
For 0.1 M NaCl t (NaCl) = x (MgCl,) : isotonic
AT, = 2 x 0.1 K,-= 0.2 K, (= 2) (d) For sucrose, a t= 1x 0.01
RT
Therefore, the depression in freezing point will be minimum For glucose, a m= 1 x 0.02RT
in 0.01 M NaC] solution and hence its freezing point will B80. (5) : Van't Hoff factor (1) expresses the extent of
be highest. dissociation of solute in the solution.
B72. (a) : AT, =373.413 - 373 =0.413 KR B81. (5) AT, = i K.m
K, = 0.52 _ ixKp Xwp x 1000
AT, 2
K, x 1000 x w
ee Mp UW a
M, XW,
Wp, = 61g, w, = 100g, M, = 122
jae 0.62 x 1000 x 2.44
tx6x61x 1000
a M, x 76 , =
122
x 1000
0.52 x 1000 x 2.44
- M,= oe = 40.96 g mol”! =
2x 122 «1000
0.67
- 0.413 x 75 6x61x1000 —
B73. (c) : According to Raoult's law Benzoic acid dimerises as
2 C,H,COOH == (C,H,COOH),
=px
P= P Xslute eee
p=pPp ny eee
+ Ny | Initial 1 0
after association 1—a a/2
B74. (6) : Mass of CCl, = 500 x 1.6 = 800 g
Total moles after association = 1— a + a/2 = 1-a/2
Molecular mass of naphthalene (C,,H,) = 10 x 12+8x1 ——
= 128 oe oo 8
1
51.2 1000
i = ————_ = 0.500 m 1—w/2 = 0.67
Molality = “y58x800
—w/2 = 0.67 -12=-0.33
K,xXw, x 1000 |
B75. (b) - AT, _ fp SB A 2 2%381x1000 _ ok a = 0.66 or 66%
ws XMp 500
x 62
B82. (a) : Molar mass = 59 + 14 x 24+12 x 16 + 12x1 = 291
Freezing point of solution = 273 — 2 = 271 K
30
B77. (a) : 3 M solution of methanol means that 3 moles of Moles of Co(NO,),.6H,O = ——
methanol are present in 1 L or 1000 cm? of solution. | 291
30
Molarity = ———— = 0.023 M
Mass of solution = 1000 x 0.9 = 900 g 2914.3
Molar mass of methanol CH,OH =129+4x1+16 B83. (5) AT, = 1K, m
= 32 g mol
Since concentration (m) 1s same,
Mass of methanol = 3 x 32 = 96 g
AT, xt
Mass of water = 900 — 96 = 804 ¢ i(for NaOH) = 2, :(for Na, 5O,) = 3

Molality = 2229" = e752 i(for NH,NO,) = 2, i(for KNO,) = 2

So, elevation in boiling point will be maximum for
B78. (e) :D-Fructose does not ionise and therefore, i = 1. It
Na,SO, solution and hence 1.0M Na,SO, will have
will have minimum depression in freezing point
highest boiling point.
and hence highest freezing point.
B85. (c) : Molality of NaCl solution = 1 m
B79. (c) : For isotonic solutions, mt, = t,
 MODERN'S abc + OF CHEMISTRY-All

1 = 2 for NaCl B92. (d) : As T increases, the vapour pressure increases.

AT, =iK,m=2x 052x1=1.04 Therefore, options (a) and (d) are not correct.
Boiling point of solution = 373.15 + 1.04 = 374.19K K, x wp, x 1000
a a My XW,
B86. (a) AY. Sz. Hy
2x 34.5 x 1000
CuCl, ——> Cu** + 2Cl 46x500 © os
_ 13.44 <iiien AT,= 273(K) — T,= 3K
134.4
or T,= 273 — 3 = 270K
Assuming 100% ionization, i = 3
Therefore, option (6) is correct.
AT, =3 x 0.52 x 0.1
= 0.156 or = 0.16 C. mcq with more than one correct answer
B87. (a) AT, = iK- 711
C4. (a, d) :When a solute is added to a solvent, its vapour
20 4000 pressure becomes less and during freezing, only
ii = jz = 2.326
solvent molecules solidify. Therefore, statements
50
(a) and (d) are correct.
9 = 1x 1.72 x 2.326
2 C7. (b, c, d) : For an ideal solution
= — _— = 9,50.
' = 1.722.326 (1) AG < 0 for mixing
B88. (a) : Pr, = Ky
X xy, (i) AS. +e, > 0 because disorder increases
(air) (dissolved)
(ii) AS... = 0 ; no heat is exchanged in case of
ideal solution
PNg = *Ne (iv) AH icing =0
(air)
Xy_ (air). Therefore, statements 6, c and d are correct.
fos “= ae e DBXS — 4x10°
(dissolved) Ky 10 Cs. (a, c) : Osmotic pressure of urea solution,
Moles of N, in 1 mole of water = 4 x 10° C = 62/100 cm?
= 60 g/L
Moles of N, in 10 moles of water = 4 x 10+
60
B89. (c) : Total mass of solution = 1000 + 120 = 1120¢ m™ (urea) }= —RT=
60 1RT

Volume of solution = 1120 = 973.9 (a) C (glucose) = 18g/100 cm? = 180 g/l
1.15
mt (glucose) = 180 pr = 1RT
Molarity = edt x 1000 = 2.05 M. 180
973.9
(6) n(BaCl,) =3 x 0.5 RT=1.5 RT @ = 3)
B90. (a) K,[Fe(CN),] = 3K* + [Fe(CN),]?- (c) (Sucrose) = 1RT = RT
Here i= a4 (d) x (acetic acid) = 2x 1 x RT = 2RT (fi = 2)

ixK, x 1000
x w, C10. (a, d) :
Zz
w, x M,
_ 41.86x 1000
4x1. 1000 x x 0.1 93x10”
100 x 329
Xx, = 1 x, = 0
Freezing point = 0—2.3 x 10° (Pure M) x, =
= = st x 10-7 °C,
(Pure L)
There is positive deviation from ideal solution as
B91.
ee
(a) M, =
K, ~*~ 1000
AT, Xw,
~ Wy,
indicated by graph above dotted line. Therefore,
L—M interactions are less than L-L and M—M
‘ 0.76 x 1000 x 2.5 | 95 interactions. Point-Z represents vapour pressure
7 2x100 i of pure liquid L. At x, —— 1, the solution is very
dilute of M in L and is nearly ideal. Therefore, it
Pa — Pa
a." =x, : 27 = Ig
— (asn, 9 << 7,) obeys Raoult's law (p, = x, p’,).
pe Oh 1

Pa — Pa _ Ws /M, D. mcq based on passage/comprehension

PA 7 w, / M, PassageI
D1. (d) Pya=X,xXpP,° or 32 =x, x 40
760 ~ 100/18 ~— es
32
760-—p, = 0.0474 x 760 = 36 or X,= —=0.8
or DP, = 760-36 = 724 mm.
SOLUTIONS

Ds. (5) For pure octane, x = 0 al _ 7.8 bar

p (sol) = p (octane) = 35 + 65 x 0 = 35 mm of Hg iRT 2 x 0.083 bar LK! mol x 310 K
D4, (5) For ideal solutions, AH_ .. _=0
Passage II. = 0.15 mol L"!

7.2/180 Assertion Reason Type Questions

D5. (a) Molarity of solution = iGO x 1000 = 0.4
3 (e): Correct assertion : 0.1 M glucose and 0.1 M urea
AT, = K. xm=1.86 x 0.4=0.744 solution have same freezing point.
Freezing point of solution = 0 — 0.744 =— 0.744 °C Correct reason : Both have the same molar
concentration of the solute and are non-associated
Py -Pa Wp
/Mg non-electrolytes.
DS. fF) & "26" =
Pa 4. (a): Reason is correct explanation of assertion.
0.024-P, 7.2180 5. (5): Both assertion and reason are correct but reason is
0.024 100/18 not correct explanation of assertion.
Correct reason : NaCl is an electrolyte and
0.024-—p, = 0.024 (0.0072) = 0.0001728
dissociates to give two ions. Therefore, osmotic
P, = 0.024 —0.0001728 = 0.0238 atm
pressure of 0.1 M NaCl is almost double than that of
D7. (b) : AT; = i Kp m 0.1 M urea solution.
0.744 = 2x186xm Correct assertion : Elevation in boiling point of two
or m = 0.2 isotonic solutions is the same.
Amount of NaCl to be dissolved = 0.2 x 58.5=11.7¢ Correct reason : Elevation in boiling point depends
in 1000 gor 1.179 gin 100g. upon the concentration of the solute.
10. (ec): Correct reason : Camphor has large K, value and
Ds. (d) Molality of solution = 0.2 m
therefore, causes greater depression in freezing point.
AT, (calculated) = 1.86 x 0.2 = 0.372
AT, (observed) = 0.698 Integer type or Numerical Value Type Questions
0.698 | 1.88
0.372 — I. (A): Chloroform + diethylether, acetone + aniline, water
Na —> Nat + Ch + nitric acid, chloroform + nitric acid.
It a is the degree of dissociation, 2. (8): sea Wee: ek x+2=2+6=85.
l-a OL OL
3. (5): p°(C,H.OH) = 142, p°(CH,OH) = 126 + 142 = 268
Totalmoles = l-a+a+a=l+a
Peotation = 142 x 0.5 + 268 x 0.5 = 71 + 134 = 205
; = 14° _1 28 “.y + 200 = 205 and y = 5.
1
bal a 0.88 or 88% A, (4): A,B, == 2A" + 3B?
Passage ITI. Initial 1 0 0
D9. (bd) For two solutions After 1-0.75 1.5 vet

(A) c(A) ionization = 0.25

(B) c(B) Total moles after ionization = 0.254+1.54+2.25=4

oT =Cd — Il 0.1 M, c (A) = 0.02 x 4 = 0.08 M C= = = 4.

l
0.08 mh. (5) AT,-= LK, x m1
“2 = 01/7
For 0.6 m Al,(SO,),,
mA) = 0.8p AT; - 5~x Kx 0.6 = 3.0 Kia = 5)
D10. (c) HX (ag) ———> H+ - -- For 0.2 m Na,SO,,
m(1 — 0.20) m(0.20) m(Q.20)
AT; = 3x Kx 0.2=0.6 Kia = 3)
Molal cone. of soln.=m (1 — 0.20) + 0.20 m + 0.20 m
Thus, AT, for Al,(SO,), solution is 5 times that for
1.20 m
Na,SO, solution.
AT, = K, x m
6. (8) : Mass of HCl = 29.2 g
= 0.52 x 1.20 (0.2) = 0.1248
Volume of solution
100 g
—_° =80mL
Boiling point = 100.1248°C 1.25
D11. (5) Na,PO, —— 3Na* + PO; (produces 4 ions) g mol
Molarity of solution x 1000
Volume of solution
D138. (d) : NaCl sol. used should be isotonic with blood stream.
For NaCl, i = 2, x = icRT _ 29.2/36.5 «1000 =10M
80
 MODERN'S abc + OF CHEMISTRY-Aill

Using M,V, = M.V, 2. (d): Since the solution is cool to touch, the dissolution is
10x V, = 200x04 endothermic. Therefore, high temperature will favour
dissolution. Further, powdered sugar has large surface
200 x 0.4
Le = a =§ area and is favourable for dissolution.
7. (2): MX, === M+ 2X" 3. (c): At equilibrium, rate of dissolution = rate of
If a is the degree of dissociation crystallisation.
l-a CL 2a 4, (6): In super saturated solution, substance starts
Total moles after dissociation precipitating.
=l-a+a+20=1+20 6. (b) : According to Henry’s law, solubility of oxygen in blood
and tissues of people is low because of low atmospheric
= I+2a =1+ 2a
pressure. However, temperature of human body
=1+2x05=2 remains constant.
8. (1): AT,= 1 K-m 7. (a): Solution of methanol and acetone will show positive
Given: m = 0.01 molal, AT, = 0 — (0.0558°) = 0.0558°C deviation because intermolecular H-bonds of methanol
K,= 1.86 Kkg mol"! will break when acetone is dissolved in it. As a result,
rate of evaporation increases.
_
i=
AT;
—_+ Ss —_
0.0558 =
K; x Mm 1.86 x 0.01
9. (6): 10M Na,SO, because: = 3.
11. (c) : 0.01 M glucose (2 = 1) and 0.01 M MgCl, ( = 3)
Since three ions are produced by the complex, the
molecular formula of the complex is [Co(NH,),Cl]Cl,. Since AT,= iK,m, MgCl, will show about three
Thus, the number of Cl ions in the coordination sphere times depression 1n freezing point.
is only one. 14. (a): Depression in freezing point depends upon the nature
9. (9): Mole fraction of solute 0.1 means that 1 mol of solution of the solvent.
has 0.1 mol of solute and 0.9 mol of solvent. 15. (6b) : KC1—+K* + Cl (@ =2), NaCl—+Nat+Cl (i = 2),
If M, is molar mass of solute and M, is molar mass of
: K,SO,—> 2K* + 50,7 (@ = 3).
solvent, then
Mass of solvent = 0.9 x M, 2 p,=we Kx,,
18. (6): or K,=as ek.
Xa

Molality = 0.1 x 1000 Hence, lower the value of x, (solubility), greater will
0.9 M 2
be the value of K,, at the same partial pressure and
Mass of solute + Mass of solvent at the same temperature.
Volume of solution = :
Density
19. (6): It represents reverse osmosis.
_ 0.1M,+0.9 M,
22. (a): Vapour pressure decreases when a non-volatile solute
2 is dissolved in it.
Molarity =
: 0.1
x 21000 24. (d): M,V, = M,V,; 0.02x4= M,x5 ..M, = 0.016
(0.1 M, + 0.9 M,)
26. (c) : Lower the value of K,,, higher is the solubility.
Since molality = molarity
NCERT Exemplar Problems : MCQs Type-IT
0.1 x 1000 = ae
0.1x2x1000
0.9 M, 0.1 M, +0.9M, 28. (c, d): They will form ideal solution and therefore A_.. H=0.
The statement (c) and (d) are not true.
100 _ 200
0.9M, 0.1M,+0.9M, 31. (c, d): Isotonic solutions have same molar concentration
and hence have same elevation in boiling point and
10 M, + 90 M, = 180 M, same depression in freezing point.
10 M, = 90 M, My _ 32. (b, c): These are non-ideal solutions, which form azeotropic
M, mixtures and have same composition in liquid phase
10.(19.00): Refer Advanced Level Problems; Problem. 6 (page 33) and vapour phase.
11.(0.05) :Refer Advanced Level Problems; Problem 19 (page 64) 34. (a,d): p = py°X%, + Pp Xp
This shows that solutions (a) and (d) are
NCERT Exemplar Problems : MCQs Type-I possible depending upon which component
is more volatile.
Pa°-Ps
1. (a): P, = x, (mole fraction of solute) OO
SOLUTIONS 2/131 —

y Unit Practice Test g

Examination

Time Allowed : 2 Hrs. Maximum Marks : 35

1. State the condition resulting in reverse osmosis. (1)

2. 2.5 g each of two solutes X and Y (molar mass of X > Y) are dissolved separately in 50 g each of the same solvent.
Which will show greater elevation in boiling point? (1)
3. Write the mathematical form of Raoult’s law of relative lowering of vapour pressure. (1)
4, What is the value of van’t Hoff factor for a compound which undergoes tetramerisation in an organic solvent ? (1)
5. How is the molarity of a solution different from its molality ? (1)
6. Why does solution of ethanol and cyclohexane show positive deviation from Raoult’s law. (2)
7. Why do gases always tend to be less soluble in liquids as the temperature is raised? (2)
8. How many grams of potassium chloride should be added to 1.5 kg of water to lower its freezing point to —7.5°C?
K, for water = 1.86°C kg mol}, (2)
9. Sodium chloride solution boils at higher temperature than water, while it freezes at lower temperature than
water. Explain. (2)
10. Why is the freezing point depression of 0.1 M KC] solution nearly twice that of 0.1 M sucrose solution? (2)
11. Asolution contains 0.8960 g of K,SO, in 500 mL solution. Its osmotic pressure is found to be 0.690 atm at 27°C.
Calculate the value of Van’t Hoff factor. (R = 0.082 L atm K~ mol") (3)
12. State Raoult’s law. How would you distinguish between ideal and non-ideal solutions with the help of the law. (3)
138. Why do we get sometimes abnormal molar masses of the substances by using colligative properties of the solutions?
State the factors with suitable examples which bring abnormality in results. (3)
14. Two aqueous solutions containing respectively 7.5 g of urea (molar mass = 60) and 42.57 g of substance X in
100 g of water freeze at the same temperature. Calculate the molecular mass of X. (3)
15. Benzene and toluene form ideal solution over the entire range of composition. The vapour pressure of pure benzene and
toluene at 300 K are 50.71 mm Hg and 32.06 mm Hg. respectively. Calculate the mole fraction of benzene in vapour phase if
80 g of benzene is mixed with 100 g of toluene. (3)
16. (a) What is relative lowering in vapour pressure? Show that relative lowering in vapour pressure Is a colligative
property.
(6) Calculate the normal freezing point of a sample of sea water containing 3.8 % NaCl and 0.12% MgCl, by
mass. Given K.= 1.86 K kg mol, molar mass of NaC] = 58.5 and MgCl, = 95 g molt.
(c) Calculate the volume of 80% H,SO, by weight (density = 1.8 g/mol) required to prepare 1L of 0.2 M solution.
(5)

To check your performance, see HINTS AND SOLUTIONS TO SOME QUESTIONS at the end of
Part I of the book.
OBJECTIVES (in, “Sa
Building on..... Assessing..... Preparing for Competition.....
@ Understanding Text 1 3 @ Quick Memory Test with @ Additional Useful Information 98
Conceptual Questions 21,72 Answers B7 @ Topicwise MCQs 100
@ Advanced Level Problems 21,44, ¢ HOTS & Advanced Level » G titive E ination G
51, 62 Questions with Answer BS f °
dibei 7 ‘is aa ;
SOLUTION FILE REVISION EXERCISES » BIPMT & Other State Boards
@ Hints & Solutions for Practice (with Previous Years’ CBSE Qs Medical Entrance 1038
Problems 74 & Other State Boards Qs) 90 »& JEE(Main) & Other State
CHAPTER SUMMARY & QUICK Hints & Answers for Revision Boards’ Engineering Entrance 105
aaciuhe acdalaieealuestints’ 78 Exercises 96 > JEE (Advance) for IIT Entrance 109
praca Aine: ee ¢@ NCERT Exemplar Problems
. rere caitlin 81 i peucemoue) 114
@ NCERT Exemplar Problems with ® Hints & Explanations for
Answers & Solutions (Subjective) 85 UNIT PRACTICE TEST 130 Difficult Questions 118

a E lectrical energy plays an important role in many chemical reactions. The branch
2— van “a

Pa *& an of science which deals with the production of electricity from energy
qe = 2 ae released during spontaneous chemical reactions and the use ofelectrical
| energy to bring about non-spontaneous chemical transformations
is called electrochemistry. The basis of these types of processes
\ are redox reactions, which we have learnt in the previous class.
Large number of chemical and biological reactions are redox
| reactions. These are used in burning of fuels for obtaining energy
| for domestic, transport or industrial purposes, digestion of food
in animals; photosynthesis to capture energy from the sun, many
/ industrial processes for extracting metals from their ores and
/ manufacture of important chemicals, operation of dry and wet
J batteries, fuel cells etc.

REDOX REACTIONS __
As we have learnt in previous class, oxidation is a process which involves loss of electrons and reduction is a process
which involves gain of electrons. The reactions which involve both oxidation and reduction are called redox reactions.
In these reactions, electrons are transferred from one reactant to another. The substance which can lose one or more
electrons (1.e., get oxidised) is called reducing agent or reductant while the substance which can gain one or more
electrons (1.e., get reduced) is called oxidising agent or oxidant. Thus, in a redox reaction, one substance acts as a
reducing agent and itself gets oxidised while another substance acts as an oxidising agent and itself gets reducecd.
 MODERN'S abe + OF CHEMISTRY
-AIl

A simple example of a redox reaction is the reaction between zinc and copper
(II) salt occurring in a battery. In this reaction, zinc loses electrons and gets
oxidised whereas Cu** ions gain electrons and get reduced.
loses 2e~ : oxidation

Zn(s) + Cu2*(ag) ———> Zn2*(aq) + Cu(s)

gains 2e- : reduction

In this case, zinc acts as a reducing agent or reductant while Cu** ions act
as oxidising agent or oxidant. Some other examples of redox reactions are :
Zn + 2HCl ——-+> ZnCl, +H,
5Fe** + 8H* + MnO; ——— 5Fe** + Mn** + 4H,O
These redox reactions are very important reactions and play significant
role in chemistry.
METALLIC AND ELECTROLYTIC CONDUCTANCE
All substances do not conduct electrical current. The substances which allow
the passage of electric current are called conductors. The best conductors
are metals such as copper, silver, tin, etc. On the other hand, the substances
Electronically conducting
which do not allow the passage of electric current through them are called
polymers
non- conductors or insulators. Some common examples of insulators are
Mac Diarmid, Hegger and rubber, glass, ceramics, wood, wax, etc.
Shirakawa in 1977 discovered that
Types of conductors.
when polyacetylene (a polymer of
The conductors are broadly classified into two types :
acetylene) was exposed to traces
1. Metallic conductors or Electronic conductors
of iodine or bromine vapours, the
These are metallic substances which allow the electricity to pass through
thin polymer film behaved like a
them without undergoing any chemical change. Metals and their alloys have
metal exhibiting metallic lustre
very large conductivity and are called conductors. For example, copper,
and conductivity. It was discovered
silver, etc. The flow of electric current through metallic conductors is due to
that by purposely adding selected the flow of electrons in the metal atoms. Electrical conductance through
impurities to polyacetylene, its metals is called metallic conductance or electronic conductance. The
electrical conductivity could be electronic conductance depends on
made to range widely behaving (1) the nature and structure of the metal
as an insulator like glass or to (it) the number of valence electrons per atom
a conductor like a metal. After (iii) the density of metal and
this discovery, several organic (tv) temperature (it decreases with increase of temperature, discussed
polymers have been made such later).
as polyaniline, polypyrrole and As the electrons enter at one end and go out at the other end, the composition
polythiophene. These organic of the metallic conductor remains unchanged.
polymers mainly composed of Certain non-metals like carbon black, graphite and some organic polymers
elements like carbon, hydrogen are also electronically conducting. Hence, they are collectively called as
and occasionally nitrogen, oxygen electronic conductors.
or sulphur. These are much lighter 2. Electrolytes or Electrolytic conductors
than normal metals and can be
These are substances which allow the electricity to pass through them
used for making light weight
in their molten states or in the form of their aqueous solutions and undergo
batteries. In addition, they have the
chemical decomposition. For example, acids, bases and salts are electrolytes. The
mechanical properties of polymers
flow of electric current through an electrolytic solution is called electrolytic
such as flexibility so that these
conduction. In this type of conduction, charge is carried by ions. Therefore,
can be used to make electronic
it is also called ionic conductance. Thus, the conduction will not occur unless
devices such as transistors which
the ions of the electrolyte are free to move. Therefore, these substances do
can bend like a sheet of plastic.
not conduct electricity in the solid state but conduct electricity in the molten
For the discovery of conducting
state or in their aqueous solutions due to the movement of ions.
polymers, Mac Diarmid, Hegger
and Shirakawa were awarded Non-electrolytes. The substances, which do not conduct electricity either
Nobel Prize in Chemistry for in their molten state or through their aqueous solutions are called non-
the year 2000. electrolytes. For example, sugar, glucose, ethyl alcohol, urea, etc.
ELECTROCHEMISTRY

Differences between Metallic and Electrolytic Conduction Some substances like silicon,
Metallic conduction Electrolytic conduction silicon doped silicon, gallium
. Metallic conduction 1s carried by the Electrolytic conduction is carried by the arsenide have conductivity between
movement of electrons. movement of ions. conductors and insulators. These
. Itinvolves no changein the chemical It involves the decomposition of the elec- are called semiconductors and
properties of the conductor. trolyte as aresult ofthe chemical reaction.
. It does not involve the transfer of
are important electronic materials.
It involves the transfer of matter as ions.
any matter. There are certain materials which
. Metallic conduction decreases with Electrolytic conduction increases with have zero resistivity or infinite
increase in temperature. increase in temperature. conductivity known as super
conductors. Earlier only metals
Classification of Electrolytes
All electrolytes do not ionise to the same extent in solution. On this basis, and their alloys at very low
electrolytes are broadly divided into two types : strong electrolytes and weak temperature of the range 0 to
electrolytes. 15 K were known to behave
(1) Strong electrolytes. The electrolytes which are almost completely super conductors. But nowadays
dissociated into tons in solution are called strong electrolytes. For example, a number of ceramic materials
NaCl, KCl, HCl, NaOH, NH,NO,, ete. and mixed oxides are also known
(iz) Weak electrolytes. The electrolytes which do not ionise completely to exhibit superconductivity at
in solution are called weak electrolytes. For example, CH,COOH, H,CO,, temperatures as high as 150 K.
H,BO,, HCN, HgCl,, ZnCl,, NH,OH, etc. Thus, in case of weak electrolytes,
an equilibrium is established between the unionised electrolyte and the ions
formed in solution. The extent of ionisation of a weak electrolyte is expressed
in terms of degree of ionisation or degree of dissociation. It is defined as
the fraction of total number of molecules of the electrolyte which
ionise in the solution. REMEMBER
It is generally denoted by alpha (q). eMetallic conductance
For strong electrolytes, & is almost equal to 1 and for weak electrolytes, decreases with increase in
it is always less than 1. temperature.
Factors Affecting Electrical Conductivity of Electrolytic Solutions e Electrolytic conductance
The conductivity of electrolytic (or ionic) solution depends upon the following
increases with increase in
factors :
(4) Nature of electrolyte. The conductance of an electrolyte depends temperature.
upon the number of ions present in the solution. Therefore, the greater the e For strong electrolytes, degree of
number of ions in the solution, the greater is the conductance. The strong dissociation, ois almost equal to
electrolytes dissociate almost completely into ions in solutions and therefore, 1 and
their solutions have high conductance. On the other hand, weak electrolytes, e For weak electrolytes, degree
dissociate to only small extents and give lesser number of ions. Therefore, of dissociation, &% is always less
the solutions of weak electrolytes have low conductance. than 1.
(ii) Nature of the solvent and its viscosity. Electrolytes ionize more
in polar solvents. Therefore, greater the polarity of the solvent, larger is the
ionization and hence greater is the conductance. Similarly, greater is the
viscosity of a solvent, lesser is its conductance.
(111) Size of the ions produced and their solvation. If the ions are
strongly solvated, their effective size will increase and hence their conduc-
tance will decrease.
(jv) Concentration of the electrolytic solution. Higher the concen-
tration of the solution, less is the conductance. This is because, in a weak
electrolyte, the ionization is less whereas in a strong electrolyte, the interionic
attractions are large at higher concentrations. In general, the conductance of
an electrolyte increases with decrease in concentration or increase in dilution.
With dilution, in case of weak electrolytes, ionization increases and hence
conductance increases. In case of strong electrolytes, the interionic attractions
decrease with dilution and therefore, conductance increases.
(v) Temperature. The conductivity of an electrolyte depends upon
the temperature. With increase in temperature, the conductivity of an
electrolyte increases due to decrease in interactions between ions.
ELECTROLYTIC CONDUCTION
When a voltage is applied to the electrodes dipped into an electrolytic
solution, ions of the electrolyte move and, therefore, electric current flows
through the electrolytic solution. The power of the electrolytes to conduct electric
current is termed conductance or conductivity. Like metallic conductors,
electrolytic solutions also obey Ohm's law.
 MODERN'S abe + OF CHEMISTRY
-AXIl

The SI base unit of resistance 1. Ohm’s law

can be obtained as:
This law states that the current flowing through a conductor is directly
proportional to the potential difference across it, 1.é.,
I x. ¥
@ where I is the current strength (in amperes) and V is the potential difference
applied across the conductor (in volts)
Work per unit charge or I= —v or V=IR tl)
A where R is the condtitit of proportionality and is known as resistance of the
Work 1 conductor. It is expressed in ohms and is represented as Q. The above equation
is known as Ohm's law. Ohm’s law may also be stated as the strength of current
Charge : A
flowing through a conductor is directly proportional to the potential difference
Force x Length 1 applied across the conductor and inversely proportional to the resistance of the
conductor.
AxXs A
Let us explain some basic terms commonly used.
mxaxl 1. Resistance. It measures the obstruction to the flow of current. The
A’s resistance of any conductor is directly proportional to the length (Z) and inversely
proportional to the area of cross-section (a) so that
kg xms* xm
Ro “ or R=p “
A?s
where p (Greek, rho) is the constant of proportionality and is called specific
kg m2?
resistance or resistivity. The resistance depends upon the nature of the material.
3A” Units. The unit of resistance is ohm (Q). In terms of SI, base unit is equal
to (kgm?)/(s®A2).
2. Resistivity or specific resistance. We know that resistance R is
IUPAC recommends the use
> E2
of term resistivity over specific a

resistance. In the present Now, if/ = 1 cm,a =1cm/?, then R=p

book, we shall use the term Thus, resistivity is defined as the resistance of a conductor of 1 cm
length and having area of cross-section equal to 1 em?.
resistivity.
In other words, resistivity or specific resistance is the resistance between
opposite faces of one centimetre cube of the conductor. In terms of SI units,
resistivity of a substance may be defined as its resistance when it is 1m long
It may be noted that the
and its area of cross section is 1 m? i.e., resistance of one metre cube of the
symbol G or C may be used for conductor.
conductance. However, symbol G It can be seen that
is preferred because symbol C is 1Qm = 100Qcm = or 1 Gem = 0.01 42m
used for concentration or Coulomb. Units. The units of resistivity are
9
p=R. 2 = ohm =ohm em —-
l cm
Its SI units are ohm metre (Q m). But quite often ohm centimeter (Q cm)
is also used.
1 ohm m = 100 ohm cm
3. Conductance. [ft ts a measure of the ease with which the current flows
through a conductor. It its expressed as 'G'. It is reciprocal of the resistance, 1.e.,
Solution of 1
G=F
@, an electrolyte
Units. The units of conductance are reciprocal ohm (ohm!) or mho. Ohm
is also abbreviated as Q so that ohm may be written as Q-1.
According to S.I. system, the units of electrical conductance are siemens,
Ste, 15210).
4, Conductivity. The inverse of resistivity is called conductivity (or
specific conductance). It is represented by the symbol, « (Greek kappa). It may
be defined as the conductance of a solution of 1 em length and having
1 sq. em as the area of cross-section. In other words, conductivity is the
conductance of one centimetre cube of a solution of an electrolyte
(Fig. 1). Thus,
Fig. 1. [lustration of conductivity. 1
ke
p
ELECTROCHEMISTRY

Units. The units of conductivity are

The IUPAC has recommended
c= _} = ohm em or Q+*em™! the use of term conductivity
ohm.cm over specific conductance.
In SI units, / is expressed in m, area of cross-section in m? so that the
units of conductivity are S mt.
1 San ]107 San
The conductivity of some substances are given in Table 1.
Table 1. Conductivities of some substances at 298 K

Material Conductivity Material Conductivity

(Sm) (Sm)
Conductors Aqueous Solutions
Sodium a eo Pure water ae ee
Copper 6.9 x 10° 0.1 M HCl 3.91
Silver 6.2 x 10° 0.1 M NaCl 0.20
Iron Lox 0.01 M NaCl 0.12
Gold 4.5 x 10° 0.01 M KCl 0.14
Graphite 120 0.1 M CH,COOH 0.047
0.01 M CH,COOH 0.016
Insulators Semiconductors
Glass tt. ih Si mh x 10
Teflon Lee i104 Ge 2.0
CuO Bx 10°'

It can be seen from Table 1 that the magnitude of conductivity varies a

great deal and depends upon the nature of the material.
5. Molar Conductivity or Molar Conductance
Molar conductivity is defined as the conducting power of all the tons
produced by dissolving one mole of an electrolyte in solution.
It is denoted by A,, (lambda). Molar conductance is related to specific con-
ductance (Kk) as:

where C is the molar concentration. If C is in the units of molarity i.e. moles

per litre (mol L—), then A,, may be expressed as : REMEMBER
kK x 1000 The symbols used in the present
f= es il2) unit
where C is molarity (M). e Resistance = R
Relation between Conductivity and Molar Conductivity e Resistivity or specific
The above relation can be easily obtained from the definitions of the terms. resistance = p
Suppose 1 cm? of a solution of an electrolyte is placed between two large e Conductance = G
electrodes of 1 sq. cm area of cross-section lying 1 cm apart. The measured e Cell constant = cor =|
conductance of the solution will be its conductivity (by definition because it a
gives conductance of 1 cm cube of solution). Further, suppose that this solution e Conductivity or specific
contains one gram mole of the electrolyte, then the measured conductance of conductance = «
the solution will be equal to the molar conductance (A). Thus, for this solution e Molar conductance = Am
containing 1 gm mole of electrolyte placed between two parallel electrodes of _ «x1000
1 sq. cm area of cross-section and one cm apart, mM
Conductance = Conductivity («) e Equivalent conductance = A,
= Molar conductivity (A) k x 1000
Now suppose that solution is diluted to 100 cc. There are now 100 cm C eg

cubes of the solution. The conductance of each one cm cube will be conductivity
 MODERN'S abe + OF CHEMISTRY
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so that the conductance of the solution will be 100 times of its conductivity.
But even now the solution contains 1 gram mole of the electrolyte therefore,
the measured conductance will be the molar conductivity. Thus,
Molar conductivity, A, = 100 x Conductivity
In other words,
A, = K Xx V
where V is the volume of the solution in cm® containing one gram mole of
the electrolyte.
If C is the concentration of the solution in mole per litre i.e., molarity, then
M mole of electrolyte is present in 1000 cm.
1 mole of electrolyte is present in
1000
_, ee
=> ™ enn of solution
:

Thus, A, = « x Volume in cm® containing 1 mole of electrolyte.

oe A_/= K x 1000
M

Units of Molar Conductance

The units of molar conductance can be derived from the formula,
k x 1000
ar
The units of « are S em! and units of A are

7 ; em? L?
It may be noted that in non SI units, A. =P ~s%” -...7
when « is in S em! and molarity is mn mol L*
in mol L-!, then
or = S em” mol"!
i Kk x 1000
= C According to SI system, if « is express in Sm“ and the concentration, C
in mol m™ then units of A,, are in S m* mol”. This is because :
and A, has the units 5 cm? mol.
But in SI units, when K is in S m! pags mol
1 mol me = 1000(—5 |x molarity (L
ti +

and molarity is in mol m™, then

K «x (S m7)
Now, a
c¢ ~ (1000 Lm) x Molarity (mol L')
and A, has the units $8m? mol”. = Sm? mol
Thus, the units of molar conductivity are S m? mol (SI) and S cm? mol".
REMEMBER Both types of units are used in literature and are related to each other as:
>» There is no multiplication with 1S m? mol! = 1017S em? mol!
1000 in SI units. 1S em? mol! = 1077S m? mot!

Electrolytic conductance is also expressed frequently as equivalent

conductance. However, the recent trend is to express electrolytic conductance
in terms of molar conductance.
6. Equivalent Conductivity
It is defined as the conducting power of all the ions produced by dissolving
one gram equivalent of an electrolyte in solution.
It is expressed as A, and is related to specific conductance as
k x 1000
A, = ——
eq
where C is the concentration in gram equivalent per litre (or normality).
This term has earlier been quite frequently used. Now it is replaced by
molar conductivity. The units of equivalent conductivity are ohm@!em?
(g equiv!) as obtained from the formula :
ELECTROCHEMISTRY

A k x 1000
= Ee.
eq
4 37-1
= Sem xem 1b = Sem? (g equiv)
g equiv L-

In terms of SI units, the units of equivalent conductivity are S m? equiv?

and A is expressed as :

where Kk is in S m™ and C,, is in g equiv m™~. It may be noted that like

molar conductivity there is no multiplication with 1000 in SI units.
Experimental Measurement of Conductance and Conductivity of Ionic
Sol ns
a. ieasurement of conductance
(Unknown)
The conductance of a solution is reciprocal of the resistance, therefore,
the experimental determination of the conductance of a solution involves the
measurement of its resistance. The resistance can be measured by the principle
of wheatstone bridge method as shown in Fig. 2.
It consists of four arms containing the resistance R,, R,, R, and R,. R, is
the variable resistance and R, is the unknown resistance. When the current
flows through the circuit, the variable resistance is so adjusted to get no
current position. This is indicated by no deflection in the galvanometer and
is called null point. At null point,
R, _ Rk,
Ro R, Key cease
Knowing the values of R,, R, and R,, unknown resistance R, can be ee ||!
calculated as: Fig. 2. Principle of wheatstone
R = R re. R P
bridge.
27 R,

However, for measuring the resistance of an ionic solution, we face two

main difficulties.
(4) For electrolytic solution, direct current (dc) cannot be used
because it causes electrolysis of the solution. As a result the concen-
tration of the electrolyte near the electrodes changes and this results in the
change in the resistance of the solution. These effects are called polarisa-
tion effects. To overcome this problem, alternating current (ac) in the audio
frequency range 550 to 5000 cycles per second is provided by using a suitable
electronic circuit commercially available. However, when alternating current
is used, ordinary galvanometer fails to detect null point. Since the frequency
of alternating current is within the range of human
ear, the galvanometer may be replaced by a set of head Connecting
phones. Now, several other visual sensing devices are wires
Connecting wires
being used in the place of head phones.
(iz) A solution of unknown resistance cannot be
connected to the bridge like a metallic wire or other solid
conductor. This problem is solved by using a specially
designed vessel called conductivity cell for taking
the ionic solution. A variety of designs of conductivity
cells are available. Two simple conductivity cells are
shown in Fig. 3. The electrodes of the cell are made
up of platinum, coated with a thin layer of finely
Platinized Platinized
divided platinum called platinum black. This is done Pt electrode Pt electrode
by the electrolysis of a solution of chloroplatinic acid.
The coating of electrodes with platinum black reduces Fig. 3. Two common conductivity cells.
polarization effects.
 MODERN'S abe + OF CHEMISTRY
-AIl

The complete assembly for the measurement of resistance of the electrolytic

solution is shown in Fig. 4. The bridge is connected to a suitable source of
alternating current. An alternating current at a frequency 550 — 5000 cycles
per second is passed. The solution whose resistance is to be measured (say X) is
placed in the conductivity cell and is attached to the wheatstone bridge between
points B and C. The cell is placed in a thermostat to keep the temperature
constant. A variable standard resistance box is attached between points A and
B. A suitable value of resistance R is taken out from the standard resistance
box. The null point is detected by moving the sliding contact (1.e., Jockey J)
on the wire AC so that minimum sound is obtained in the earphone. This
corresponds to null point and let this point be D. At this balance point
Resistance R Resistance of wire AD
REMEMBER Resistance ~ Resistance of wire CD

¢ For electrolytic solutions, direct Now, resistance of a conductor is proportional to its length, so that,
current (DC) cannot be used
because it causes electrolysis of Resistance R _ Length AD
the solution. Resistance X Length CD
e Alternating current in the audio ; , Length CD
Barres cease wet FP oles Resistance X = Resistance R (plugged out) x Tancih
eth AD
AD
per second is used.
Standard
resistance box
Conductivity

Water
thermostat

Ear phone

A.C. source

Fig. 4. Apparatus for measuring conductance of a solution.

Thus, by measuring the lengths AD and CD and knowing the resistance R

at the balance point D, the resistance X of electrolytic solution can be calculated.
The reciprocal of the resistance gives the value of conductance of the
solution. These days, inexpensive conductivity meters are available which can
directly read resistance or conductance of the solution in the conductivity cell.
2. Calculation of conductivity
We have seen that conductivity («) is reciprocal of resistivity (p), i.e.
Conductivity water. For

t) = sold
c= and p =R ta
accurate results of conductivity ]
measurements, the solutions
are prepared in a very purified kK =
water whose conductance is mM)
mle
very very small. Such water where G is the conductance of the cell, / is the distance of separation of two
is called conductivity water.
Alternatively, to calculate ; ; i}.
electrodes having cross-section area a cm’. The quantity (“)is called cell
conductance of the electrolyte, a
the conductance of water used constant (G*) and is expressed in em. Knowing the value of cell constant
for preparing the solution and conductance of the solution, the specific conductance can be calculated as:
may be determined and
Kk = G x Cell constant.
then subtracted from the
conductance of the solution.
ELECTROCHEMISTRY

3. Determination of cell constant

The cell constant is generally not calculated from the values of / and a
because these are difficult to measure for a given cell. However, it is usually
determined accurately by measuring the conductance of a standard solution
whose conductivity is known. For this purpose, a standard solution of KCl is
used whose conductivityisknown at different concentrations and temperatures.
The conductivities of different KCl solutions at 298 K are given in Table 2.
Table 2. Conductivity and molar conductivity of KCI solutions at 298.15 K
Molarity Concentration Conductivity Molar conductivity
(mol L~*) (mol m-~*) S cm! Sm! S cm? mol? S m?* mol!
0.11138 11.18 111.8 111.3 x 10+
0.0129 1.29 129.0 129.0 x 10+
0.00141 0.141 141.0 141.0 x 10+

For example, for 0.1 M KCl solution at 298 K, conductivity is 0.0129Scnr?.

Suppose the conductance of this solution in the given cell is measured, to be
‘X'. Then,
Conductivity _ 9.0129
Cell tant = =
ana Conductance Xx
Once the cell constant is known, the conductivity of any solution can
be easily calculated from the measured resistance or conductance of the
electrolytic solution.
K = G*/R or = G* x G.
From this, molar conductivity or equivalent conductivity may be calculated.
Units of common terms used in conductance are summed up below :

SI units
Resistance
Conductance
Cell constant
Conductivity % Sm?
Molar conductivity 5 m? mol?
Equivalent conductivity 5S m+ (equiv L)+

FORMULAE AND UNITS

a
R is resistance in ohms
Area of cross section in em*
Length between two electrodes in cm
Resistivity in ohm cm
1. (5 x 5
|
© = Conductivity in ohm! em! (SI units : 5 m4)
= Conductance in ohm! (SI unit = $)

2 is called cell constant in em— (SI units : m~)

* 1000x«
M
. = Molar conductivity in ohm“ cm? mol™ [SI units :S m™(mol Ly)“
1000 x«
C
equiv. = Equivalent conductivity in ohm™ cm? equiv 1
ano MODERN'S abe + OF CHEMISTRY
-AXIl

SOLVED EXAMPLES
L) Example 1. Solution: Conductivity = 26 x 10°? ohm? cm?
The resistance of a conductivity cell containing 0.001 M Concentration = 1MH,SO, = 98 g/litre
KCl solution at 298 Kis 1500 Q. Whats the cell constant
Equivalent weight of H,SO, = 49
if the conductivity of 0.001 M KCI solution at 298 K ts
0.146 x 107% Sem-1?
cays : 98
(A.IS.B. 2008; D.S.B. 2007, 2008, 2012) Gram equivalents per litre = — =2
Solution :
49
Conductivity, « = 0.146 x 10° S em?! , A = _—
«x1000 =
26x10" x1000
Equivalent conductivity
Resistance, R = 1500 ohm
Conductivity, («) = 130 ohm cm? equiv".
Cell constant =
Conductance (G)
L) Example 5
= Conductivity («) x Resistance (R) Resistance of a conductivity cell filled with 0.1 M
Cell constant = 0.146 x 10-3 ohm™! cm™ x 1500 ohm KCl solution ts 100 Q. Ifthe resistance of the same cell
— 0.219 cm), when filled with 0.02 M KCl solution its 520 Q, calcu-
) Example 2 late the conductivity and molar conductivity of 0.02 M
The conductivity of 0.20 M KCl solution at 298 Kis KCl solution. (The conductivity of 0.1 M KCl solution
0.025 Sem. Calculate its molar conductivity. is 1.29 S m1) (A.I.S.B. 2006, D.S.B. 2014)
(D.S.B. 2008, 2013, H.P.S.B. 2015, Hr.S.B. 2018) Solution:
Solution: Molar conductivity Step I. Let ws first calculate the cell constant.
k x 1000 Cell constant, G* = Conductivity («) x Resistance (R)
An = C Resistance of 0.1 M KCl solution = 100 Q
K = 0.026Sem!,C=0.20M Conductivity of 0.1 M KCl solution = 1.295 m+
A, = Cellconstant = 1.29(S8m )x 1000
= 129m
= 125.0 S cm? mol, or = 129cm+
Example3
Step IT. Calculation of conductivity of 0.02 M KCI solttion.
0.05 M NaO8 solution offered a resistance of 31.6 ohm
Resistance of solution = 5200
in a conductivity cell at 298 K. If the area of the plates
Cell constant(G*) = 1.29cm}
of the conductivity cell is 3.8 cm? and distance between
Conductivity,x = Cell constant
them ts 1.4 em, calculate the molar conductivity of the
sodium hydroxide solution. Resistance

Solution : Cell constant, G* = ul 1.29 em!

cl
520 Q
1-1.4cm anda —3.8 cm?
= 0.248x107Sem".
l 1.4cm 7
# —= = 7.368 cm Step IIL. Calculation of molar conductivity.
= a 3.8cm?
1000 x «
Resistance of solution = 31.6 0hm a = — EC.

Concentration, C = 0.05 M
C=0.02 M, «=0.248 x 102 Sem
.. Conductivity,
Kk = G*/R A 1000 x 0.248 x 10°
m 0.02
= : ohm? x (0.368 em—?) —- 124S cm? mol.
(31.6
L) Example 6.
= 0.0116 Sem"! A conductivity cell when filled with 0.01 M KCl has a
resistance of 745 Q at 25°C. When the same cell was
Molar conductivity, <A = «x 1000 _ 0.0116 x 1000 filled with an aqueous solution of 0.005 M CaCl, solu-
. C 0.05
tion the resistance was 874 Q. Calculate
= 232 S cm” mol". (i) Conductivity of solution
) Example 4. (it) Molar conductivity of solution.
Calculate the equivalent conductivity of 1 M H,SO a [Conductivity of 0.01 M KCI =0.141S m]
solution whose conductivity is 26 x 10°? ohm— em—.
ELECTROCHEMISTRY

Solution : Calculation of cell constant. Length of column (distance between electrodes), / = 12 cm

Resistance of KCl] solution (R) = 745 5} (ii) Conductivity, « = Gx 4
Conductivity of KCl solution («) = 0.141 S m+ a

Conductivity («) = i x Cell constant a lags te

R ~ 100 * 12.57
or Cell constant = Rxk = 9.55 x 10°S em,
(745 S*) x 0.1415 mt (zit) Molar conductivity,
= 106m tor 1.05 cm? k x 1000
Calculation of conductivity and molar conductivity for A lan
CaCl, solution
(t) Conductivity 9.55 x 10° x 1000
Cell constant
0.1
Conductivity, K =
KR 95.5 S cm* mol,
1.05em™ LJ Example 8
~ =87487 The electrical resistance of a column of 0.05 M
NaO8 solution of diameter 1 cm and length 50 cm ts
= 1.201 x 10° S env}.
5.55 x 10° ohm. Calculate its
(it) Molar conductivity
Conc. of solution, C = 0.005 M (i) resistivity
= 0.005 mol L71 (it) conductivity, and
A . KX 1000 (tt) molar conductivity.
a C (A.I.S.B. 2012, Pb. S.B.2013)
-d
A = 1.201 x10" «1000 ~940,.2 Sem? mol
Solution : Cell constant, G* = f
i 0.005
LU Example 7 i = 60 cm, diameter = 1 cm “. radius = 0.5 em
A potential difference of 20 V applied to the ends of Area of cross-section, a = tr?
a column of 0.1 M AgNO, solution, 4 cm in diameter = 3.14 x (0.5)? = 0.7865 em?
and 12 em in length gave a current of 0.20 amperes. eo wee
G* = 9785 = 93.694 cm
-
Calculate
(1) conductivity and R
(i) Resistivity, P = Ge
(it) molar conductance of the solution.
Solution : According to Ohm's law, R = 6.65x 10°Q
a
Resistance of solution,
p = ada Q cm.
ai = 87.135
Vv 63.694 cm™
aan} (ii) Conductivity, « = +
= aaa = 1002
p
0.20 =
= 1
37195 =
> 1.148 x 10° S em,-1
4
Radius of column = 9g cm = 2 em (iit) Molar conductivity, A, = <—_
Area of cross-section of the column, C = 0.05M
a = mr =
Le
x (2) cm a.aa _1148x107
0.05
x1000
— 12.57 cm? = 229.6 S cm* mol,

1. The resistance of 0.06 M NaOH solution is 31.6 © and its cell constant is
0.357 em“. Calculate its conductivity and molar conductivity. (Ar.S.B. 2018)
2. The resistance of 0.01 M Ag NO, solution dipped in a conductivity cell at 26°C was
1412 ohms. If the molar conductivity of this solution is 132.6 ohm! cm? mol",
what is the cell constant of the conductivity cell?
an MODERN'S abe + OF CHEMISTRY
-AXIl

3. Calculate the resistance of 0.01 N solution of an electrolyte whose equivalent

conductivity is 420 ohm“ cm? equiv! (The cell constant of the cell is 0.88 em“).
4, The resistance of 0.5 N solution of an electrolyte in a conductivity cell was found to
be 256 ohm. Calculate the equivalent conductivity of the solution if the electrodes in
the cell are 1.6 cm apart and have an area of 3.2 cm*. (Pb. S.B. 2009, 2013, 2016)
5. When a certain conductance cell was filled with 0.20 mol dm“ aqueous KCl
solution, its conductivity was 2.78 x 10° 5 em“! and had a resistance 82.5 ohm at
300 K. Calculate the cell constant of the cell.
6. The conductivity of a solution containing 1.0 g of anhydrous BaCl, in 200 cm? of
the solution has been found to 0.0068 5 em™?. Calculate the molar conductivity
and equivalent conductivity of the solution.
7. The resistance of a 0.6 M solution of an electrolyte was found to be 30 © enclosed
between two platinum electrodes. Calculate the molar conductivity of the solution
if the electrodes in the cell are 1.5 cm apart and having an area of cross section
2.0 em?. (Pb.S.B. 2009, 2013, 2016)
8. A conductivity cell when filled with 0.02 M KCl (conductivity = 0.002768 1
em) has a resistance of 457.3 Q. What will be the equivalent conductivity of
Answers to Practice Problems 0.06 N CaCL, solutionifthe same cell filled with this solution has a resistance of 202 Q?
1. 226 ohm cm? mol! 9. When a certain conductance cell was filled with 0.1 mol L KCl, it has a resis-
2. 1.87 em. tance of 85 Q at 25°C. When the same cell was filled with an aqueous solution of
0.062 mol L~! of an electrolyte solution, the resistance was 96 Q. Calculate the
3. 209.6 ohm.
molar conductivity of the electrolyte at this concentration. (Conductivity of 0.1
4, 40 ohm? em? equiv? mol L~ KCI solution is 1.29 x 1075 cm“) (D.B.S. 2004 C)
5, 0.2209 cm. 10. The resistance of a conductivity cell with 0.1 M KCl solution is found to be 200 Q
6. A, = 241.675 cm* mol", at 298 K. When the same cell was filled with 0.02 M NaCl solution, the resistance
at the same temperature is found to be 1100 Q. Calculate :
A = 120.83 5 cm? equiv.
(1) the cell constant of the cell in m™.
7. 60 ohm? molt.
(iz) the molar conductivity of 0.02 M NaCl solution in 8 m? molt.
8. 125.4 ohm! em? equiv. Given : Conductivity of 0.1 M KCl solution at 298 K=1.29S m™?.
9, 219.65 S cm? mol. 11. The molar conductance of 0.06 M solution of MgCl, is 194.6 Q+ cm? mol at 25°C.
10. (2) 258 nm}, A cell with electrodes having 1.50 cm? surface area and 0.50 cm apart is filled
with 0.05 M solution of MgCl,. How much current will flow when the potential
Gre lelie. 10-3 me male
difference between the electrodes is 5.0V?
11. 0.146A 12. Specific conductivity of N/36 KCl at 298 K is 0.002768 ohm cm?! and it has resis-
12. 119.5 S em? equiv. tance of 520 ohm. A N/265 solution of a salt kept in the same cell was found to have
Hints & Solutions on page 74 a resistance of 300 ohm at 298 K. Calculate equivalent conductance of the solution.

VARIATION OF CONDUCTIVITY AND MOLAR CONDUCTIVITY

WITH CONCENTRATION
We have learnt that electrolytic conductance decreases with increase in
concentration or increases with increase in dilution. This is because conductance
of ions is due to the presence of ions in the solution. The greater the number
of ions, the greater is the conductance. As with dilution, more ions are
produced in solution so conductance also increases on dilution. Both specific
conductance or conductivity and molar conductivity change with concentration
of the electrolyte. However, conductivity of an electrolyte decreases with the
decrease in concentration both for weak and strong electrolytes, whereas
molar conductivity increases with decrease in concentration. Alternatively
upon dilution, specific conductance or conductivity decreases while
molar conductivity increases. This can be easily explained, as :
Conductivity is the conductance of one centimeter cube of the solution.
Upon diluting the solution, the concentration of ions per centimeter cube
decreases and therefore, the conductivity decreases.
On the other hand, the increase in molar conductivity on dilution is due
to the fact that it is the product of conductivity (k) and the volume (V) of the
solution containing one mole of the electrolyte.
A =KxV
ELECTROCHEMISTRY

On dilution, conductivity decreases but volume containing one mole of

an electrolyte increases. It has been found that the increase in volume on
dilution is much more than the decrease in conductivity. As a result molar
conductivity increases with dilution.
The molar conductivity of a few electrolytes in water at different
concentrations are given in Table 3.
Table 3. Molar conductivity (S em? mol!) of a few electrolytes
in water at 298 K
C HCl KCl KNO, CH,COOH NH,OH REMEMBER
0.1 391.3 129.0 120.4 6.2 3.6 With dilution or decrease in
0.05 399.1 133.4 126.3 = = concentration
0.01 412.0 141.3 132.8 16.3 11.3 econductivity (or specific
0.005 416.8 143.5 131.5 7 = conductance) decreases
0.001 421.4 146.9 141.8 49.2 34.0 e molar conductivity increases.
0.0005 492.7 147.8 142.8 67.7 46.9
0 (infinite
dilution) 426.2 149.9 146.0 390.7 271.0
Inspection of Table 3 reveals that the molar conductance of strong (HCl,
KCl, KNO,) as well as weak electrolytes (CH,COOH, NH,OH) increase with
decrease in concentration or increase in dilution. The variation is however
different for strong and weak electrolytes.
Like molar conductivity, equivalent conductivity also increases with dilution
because of increase in volume containing one gram equivalent of the electrolyte.
Variation of Molar Conductivity with Concentration for Strong and
Weak Electrolytes
(4) Variation of Molar Conductivity with Concentration for Strong
Electrolytes
In case of strong electrolytes, molar conductivity increases slowly with
dilution and there is a tendency for molar conductivity to approach a certain
limiting value when the concentration approaches zero i.e., when the dilution is
infinite. The molar conductivity when the concentration approaches zero (infinite
dilution) is called molar conductivity at infinite dilution. It is denoted by
AY or A. Thus,
A =A,,° When C ——~ 0 (at infinite dilution)
It has been observed that the variation of molar conductivity with
concentration may be given by the expression
A _f= RGWo ¥6

where A is a constant and A° is called molar conductivity at infinite dilution.

This equation is called Debye Huckel Onsager equation and is found to hold
good at low concentrations.
The variation of molar conductivity with concentration can be studied by
plotting the values of A, against square root of concentration (C*). The plots
of variation of molar conductivity with C* for KCl and HCl are given in
NaCl is known as 1:1 electrolyte,
Fig. 5.(a). It has been noticed that the variation of A,, with concentration, C*
CaCl, as 1:2 electrolyte,
is small (between 4 to 10% only) so that the plots can be extrapolated to zero
MgsO, as 2:2 electrolyte and
concentration. The intercept gives the limiting value of molar conductivity when AICl, as 1:3 electrolyte, etc.
the concentration approaches zero, called molar conductivity at infinite depending upon the charges on
dilution, A_°. The slope of the line is equal to — 'A'. The value of constant the cation and anion.
A for a given solvent and temperature depends on the type of electrolyte
i.e., the charges on the cation and anion produced on the dissociation of the
electrolyte in the solution. Thus, NaCl is known as 1-1 electrolyte, CaCl, as
 MODERN'S abe + OF CHEMISTRY
-AXIl

2-1 and MgSO, as 2—2 electrolytes. All electrolytes of a particular type have
the same value for A.
(it) Variation of Molar Conductivity with Concentration for Weak
Electrolytes
The weak electrolytes dissociate to a much lesser extent as compared to
strong electrolytes. Therefore, the molar conductivity is low as compared to that
of strong electrolytes.
However, the variation of A,, with C% is very large and so much so that we
cannot obtain molar conductance at infinite dilution (A,,°) by extrapolation of
the A, versus C* plots. The behaviour of weak electrolytes such as CH,COOH
is shown in Fig. 5 (0).
It may be noted that the A,,° value for weak electrolytes can be obtained by
an indirect method based upon Kohlrausch law (discussed later).
Explanation for the Variation of Molar Conductivity with
Concentration
The variation of molar conductance with concentration can be explained on
the basis of conducting ability of ions for weak and strong electrolytes.
Weak electrolyte (¢) Conductance behaviour of weak electrolytes. The variation of
A,, With dilution can be explained on the basis of number of ions in solution.
The number of ions furnished by an electrolyte in solution depends upon the
degree of dissociation with dilution. With the increase in dilution, the degree of
CH3;COOH dissociation increases and as aresult molar conductance increases. The limiting
value of molar conductance (A_,°) corresponds to degree of dissociation equal
to 1, i.e. the whole of the electrolyte dissociates.
Thus, the degree of dissociation can be calculated at any concentration as:

w= —™ sl)
Fig. 5. Variation of molar conductance Am
(A,,) with square root of concentration where ois the degree of dissociation, A°_is the molar conductance at concentration
C and A°_ is the molar conductance at infinite dilution.
C™” for (a) strong electrolytes and
(b) weak electrolytes. (44) Conduetance behaviour of strong electrolytes. For strong
: electrolytes, there is no increase in the number of ions with dilution because
strong electrolytes are completely ionised in solution at all concentrations (by
definition). However, in concentrated solutions of strong electrolytes there
are strong forces of attraction between the ions of opposite charges
called interionic forces. Due to these interionic forces, the conducting ability
of the ions is less in concentrated solutions. With dilution, the ions become
far apart from one another and interionic forces decrease. As a result, molar
conductivity increases with dilution. When the concentration of the solution
becomes very very low, the interionic attractions become negligible and the
molar conductance approaches the limiting value called molar conductance at
infinite dilution.This value is characteristic of each electrolyte.

rs SOLVED EXAMPLES
- Sa a ty of sodium chloride at208 Khas 6 Calculate A for all concentrations and draw a plot
conductivity of sodium chloride at 2 as been 1 Tp °
determined at different concentrations and the results ECE TURE Enea EEE AY ne
are given below :
Coneenudinn 0
(P0.S.B. 2010)
102 x x (S m4) ve. Solution:
A, at different concentrations maybe calculated

0.001 1.237 k x 1000

0.010 11.85 m= Ng
0.020 23.15 At 0.001 M, x =1.237x102S m7 = 1.237x10¢Scm!
0.050 55,53 —4
0.100 106.74 : A. = a = 123.7 S em? mol
ELECTROCHEMISTRY 3/15 —

At0.010M, x=11.85x10?Sm? = 11.85 x10*Sem!

130
_ 11.85 x 107% x 1000
— 118.5 S em? mol!
= 0.010
At0.020M, x=23.16 x 102S m7? = 23.15 x 104Sem_2 ies (0.032, 123.7)
—
23.15 x 107 x 1000
ooo.
Z
= 115.75 S em? mol! 120 (0.10, 118.5)
ce (0.14, 115.8)
At 0.060 M, «=656.53 x 10° S m7? = 6565.63 x 10¢Sem! Ete
— ™

A_= 55.53
x 10°" x 1000 _ 441.06 S cm? mol 5
0.050 ar (0.22, 111.1)
<_ 1
AtO.100M, «=106.74x10"?Sm7?!=106.74x10?Sem!

A. _
|
106.74
19-4
x 10 x 1000 — 106.748 em? mol! 40
(0.32, 106.7)
0.1 0.0 0.05 0.40 015 0.20 025 0.30 0.35
The values of A, and C” at different concentrations are: cM”) +
ACS em? mol) 123.7 118.6 116.76 111.06 106.74 The extrapolation of the straight line to zero concentration
C4(M"*) 0.0316 0.10 0.141 0.294 0316 (intercept) gives the value of A, = 124.6 5 cm? mol.
Plot of A, and C” is given below :

13. The molar conductance of KCI solutions at different concentrations at 298 Kare — Answers to Practice Problems —
given below : _ | 5 a
C(mol L>) 0.000198 0.000309 0.000521 0.000989 a a Bor org cess
ACS em? mol-) 148.61 148.29 147.81 147.09 P
: = 87.46 S em? mol }/(mol L“1)”.

andAfor KCL emma oS 2015

Show that a plot of A, and C” is a straight line. Determine the values of A

KOHLRAUSCH’S LAW
Kohlrausch obtained very interesting pattern between the values of A°
for different strong electrolytes. It was observed that the difference of A° of
different pairs of electrolytes having a common cation or a common anion was
almost same. For example, the difference between the molar conductance of
K* and Nat is 23.4 ohm! cm? mol! irrespective of the anion.
A°KCl) = 149.9 A°(KNO,) = 145.0
A°(NaCl) = 126.5 A°(NaNO,) = 121.6
Difference = 23.4 BoA.

A*KBr) = 151.9
A°(NaBr) = 128.5 gf oh? (K*) —A°(Na?*) = 23.4 S em? mol
25.4
Similarly, the difference between the molar conductivities of chloride and
nitrate ions is 4.9 ohm cm? mol" irrespective of the cation :
A° (KCl) = 149.9 A° (NaCl) = 126.5
A° (KNO,) = 1465.0 A° (NaNO,) = 121.6
Difference = 4.9 4.9
A°(laCD = 115.0
A° (LiNO,) = 110.1 (Clr) -ANO,) = 4.95 cm? molt.
4.9
Thus, it may be concluded that each ion makes definite contribution to
the molar conductivity at infinite dilution irrespective of the other ions. The
"ane. MODERN'S abe + OF CHEMISTRY

individual contribution of an ion towards the total molar conductivity of the

-AXIl

electrolyte is called molar ionic conductivity. This led him to postulate a

law known as Kohlrausch’s law of independent migration of ions. This
law states that,
the limiting molar conductivity of an electrolyte can be expressed
as the sum of the limiting tonic molar conductivities of the cation
and the anion.
For example, if A°(K*) and A°(CIL-) are limiting ionic molar conductivities of
potassium and chloride ions respectively, then the limiting molar conductivity
for potassium chloride is given by the equation:
v, and v_ are the number of cations
and anions into which an electrolyte A®° (KCI) = 2° (K*) + 2° (CL)
dissociates e.g., In general, if an electrolyte on dissociation gives v, cations and v_ anions,
then its limiting molar conductivity is given as:
Mau, de,+ ied
where A°, and i°_ are the limiting 1onic molar conductivities of the cation
and the anion respectively. For example,
For NaCl A°(NaCl) = 2° (Nat) + 4° (CL)
For KNO, AS(KNO,) = 4° (K*) + 4° (NO,>)
For MgCl, A°(MgCl,) = 2° (Mg?) + 24° (CL)
For Al,(SO,), A°IAL,(SO,)q] = 2A°(Al5+) +322 (SO,2>)
The values of molar conductivities of some cations and anions are given
in Table 4.
Table 4. Limiting molar conductivity for some ions in water at 298 K.
Ion A? Ion A
(S cm? mol-') (S cm? mol!)
Ht 049.6 Cr eed
Nat 60.1 Br- 78.1
Kt 73.5 i 76.8
Meg?* 106.0 OH- 199.1
he 119.0 NO,” 71.5
Ba@t yr 5O Fal 160.0
Sr2+ 118.9 CH,COO- A0D.9

Applications of Kohlrausch’s Law

Some of the important applications of Kohlrausch’s law are :
1. Calculation of Molar Conductance at Infinite Dilution for Weak
Electrolytes
We have learnt that it is not possible to determine the value of limiting molar
conductivity at infinite dilution for weak electrolytes by extrapolation of A versus
Jc graph. However, this can be calculated easily by using Kohlrausch’s law.
Let us calculate the limiting molar conductivity for CH,COOH. According
to Kohlrausch’s law,
A° (CH,COOH) = A° (CH,COO_) + A° (H*) sak}
This equation can be obtained by the knowledge of molar conductivity at
infinite dilution for some strong electrolytes. For example, consider the strong
electrolytes HCl, NaCl and CH,COONa. From Kohlrausch's law,
A°(CH,COONa) = A° (CH,COO) + A®° (Na*) elt)
A° (HC) = A° (H*) + A° (CL) (Ltt)
A° (NaCl) = A? (Nat) + A° (CL) (iv)
It is clear that
A(CH,COO) + ACH") = [A°(CH,COO) + A°(Na*)] + [A°CH*) + ACCT)]
— [A.°(Nat) + A°(CL)]
ELECTROCHEMISTRY

or A\(CH,COOH) = A°(CH,COONa) + A°CHCI — A°(NaCl) WATCH OUT !

Similarly, we have Ionic mobility or absolute
A®(NH,OH) = A°(NH,Cl) + A°CNaQH) — A*(NaCl) velocity
The actual velocity of an ion
2. Caleulation of Degree of Dissociation of Weak Electrolytes
depends upon the potential
Molar conductance of a weak electrolyte depends upon its degree of
oradient. Ifthe potential gradient
dissociation. Higher the degree of dissociation, larger is the molar conductance.
is 1V cm, the velocity ofthe ion
With increase in dilution, the conductance increases and at infinite dilution,
is called its absolute velocity
the electrolyte is completely dissociated so that degree of dissociation becomes
or ionic mobility. It is defined
one 1.€., A = A° (at C —-3 0). Thus, if
as the speed of the ton in cm/sec
A® = molar conductance of solution at any concentration
under a potential gradient of 1
A° = molar conductance at infinite dilution.
volt perem. (Potential gradientis
Then, degree of dissociation at any concentration is:
AS
applied EMF/distance between
g=
the electrodes).
o

It can be shown that

Thus, measuring the molar conductance at any concentration (A°) helps to
Tonic mobility (U1 ,)
calculate degree of dissociation () if A° is known.
— lonic conductance
3. Caleulation of Dissociation Constant of Weak Electrolytes
96500
In previous class, we have learnt that the dissociation constant (K) of e.g., lonic conductance of Lit
weak electrolytes can be given as
is 38.6 Q-! cm? eq t. Its ionic
K = Ca? mobility is :
| l-a
where C is the concentration and © is the degree of dissociation. Substituting 38.6 Q! cm” eq?
Met) = “96500 C eq
| Lat —

value of @ (calculated from molar conductance) in the above relation the

dissociation constant (K) for weak electrolytes can be calculated.
- 40x10? Q!cm?C!
2
o(A or = 40x10?cm*s!?V1
(G = As; CO = As O but AQ=V
(1-A/A°) AY (as A A) Tel geo We al
4, Caleulation of solubility of sparingly soluble salts
The sparingly soluble salts such as AgCl, PbSO,, BaSO, etc. dissolve to a
very little extent in water. Since these dissolve only to a small extent, their Transport Number
solutions are considered as infinite dilute. Moreover, as their solutions are The fraction of the total current
saturated, their concentration may be taken equal to their solubility. Therefore, carried by anion 1s called its transport
by measuring the specific conductivity (<) and knowing molar conductivity number.
(A°) of such a solution, the solubility can be calculated as : Transport number of a cation,
pee Current carried by cation
Ac = Kx1000 «x1000
Total Current
+

m ~~ Molarity Solubility
Transport number of anion
eae x 1000 _ Current carried by anion
Solubility = — ft =
Total Current
A® can be calculated by applying Kohlrausch law. For example, for AgCl If, there is only one cation and one
anion, then
A®(AgCl) = A° (Ag*) + A°(CT)

i SOLVED EXAMPLES &

J Example 10 Solution : Molar conductivity at infinite dilution for acetic
The molar conductivities at infinite dilution for sodium acid can be calculated as :
acetate, hydrochloric acid and sodium chloride are aie P ‘
91.0, 425.9 and 126.4 S cm? mol-! respectively at 298 COO = aye CH3COOg
K. Calculate the molar conductivity of acetic acid at = M cetgcoo-t A Nat thet Mg Mo a A? cr
infinite dilution.
A*(CH,COOH) = A°(CH,COONAa) + A® (HCI) — A® (NaCl)
(D.S.B. 2010, Uttarakhand S.B. 2014, H.P.S.B.
A°*(CH,COONAa) —- 91.08 ecm? mol?!
2015, Meghalaya S.B. 2016, Assam S.B. 2015, 2017,
Mizoram S.B. 2017, Nagaland S.B. 2017, Kerala S.B. 2017) A®C(HCI) —= 425.95 em? mol
ane Solution:
MODERN'S abe + OF CHEMISTRY-AXIl

According to Kohlrausch’s law,

A°(NaCl) = 126.45 cm? mol!
A*(CH,COOH) = 91.0 + 426.9 — 126.4 A° [A1,(SO,),] = 2 4° (Al**) + 34° (SO, 7)
= 390.5 S cm? mol". A® [A1,(SO,),] = 858 5 cm? mol’,
LJ Example 11. (SOS = 16058 en? nick”
The molar conductivities at infinite dilution for Nal, = 858 = 2 4° (Al®*)
+ 3 x 160
CH,COONa and (CH,COO), Mg are 12.69, 9.10 and or 2° (Al®*) = 858 — 480
18.78 mSm? mol! respectively at 25°C. What is the = 378
molar conductivity of Mg, at infinite dilution?
Solution : Molar conductivity at infinite dilution for Mgl,, = ° (ALS*) = = = 189 S cm? mol.
may be calculated as: LJ Example 15
A® (Mgl,) = A®[(CH,COO),Mg] + 2A°(Nal) The molar conductivity at infinite dilution for HCl,
— 2 A° (CH,COONa) KCl and CH,CICOOK are 4.26 x 10“, 1.50 x 107 and
A® ((CH,COO), Mg] = 18.78m5 m? mol! 1.13 x 107 S m? mol respectively. Calculate the molar
A®° (Nal) = 12.69mS m? mol? conductivity at infinite dilution for monochloro acetic
acid (CH,Cl(COOH).
A® (CH,COONa) = 9.10m5 m? mol!
Solution : Molar conductivity at infinite dilution for
A® (Mgt) = 18.78 + 2(12.69) — 2 (9.10)
monochloro acetic acid (CH,CICOOH) may be calculated as:
25.96 m S m? mol.
A° (CH,CICOOH) , = A° (CH,Cl COOK) + A° (HCI)
LJ Example 12.
— A® (KCI)
The molar conductances of ammonium hydroxide at
A° (CH,CICOOK) = 1.13 x 10S m* mol
concentrations 0.1 Mand 0.001 M are 3.6 and 34.0 Sem?
A° (HCl) = 4.26 x 1075S m? mol!
mol respectively. Calculate the degree of dissociation of
A° (KCl) = 1.60 x 10° S m? mol
NH_,OH at these concentrations. Molar conductance at
A* (CH,CICOOH) = 1.18x10°+4.26 x 107 -1.50x 107
infinite dilution for NH_,OH is 271.1 ohm cm? mol.
AS = 3.89 x 10-°S m* mol,
Solution : Degree of dissociation is given as = Ae where LJ Example 16.

Af is the molar conductance at concentration C and A° is the

The conductivity of a 0.01 M solution of acetic acid at
molar conductance at infinite dilution. 298 Kis 1.65 x107 Scem-*. Calculate
(z) At C = 0.1M, Ac = 3.6, (i) molar conductivity of the solution
A? = 271.1 (it) degree of dissociation of CH,COOH
3.6 | (tit) dissociation constant for acetic acid.
a = O711 = 0.013 Given that
1.2. 1.8% dissociated. .° (H+) = 349.1 and
(it) AtC = 0.001 M, AS = 34.0, A° = 271.1 a° (CH,COO) = 40.9 S cm* mol.
34.0 Solution : (1) Calculation of molar conductivity of solution.
aaa 4 =AdeiZo
Oo = 9711 kK x 1000
i.e., 12.5% dissociated. 7 C
x = 166x10*Sem1t,C=0.01M
LJ Example 138. 4

Calculate the molar conductivity of a solution ofMgCl, i — SOsa 15 8 oat nl.

0.01
at infinite dilution given that the molar tonic conduc-
(it) Calculation of degree of dissociation of acetic acid.
tivities of 4° (Mg"*) = 106.1 S cm? mol and 2°(CID = AS
76.3 S em? molt.
A
Ch = Le]

Solution: A°(MgCl,). = 4° (Mg**) + 22° (CL)

A®° (CH,COOH) = (4° (H*) + 4° (CH,COO-)
i? (Mg?*) = 106.1 5 cm? mol",
— 349.1 + 40.9 = 390 5 cm? mol?
A° (CL) = 76.3 5 em? molt.
A® (MgCl) = 106.1 + 2 (76.3) = 16.5
390
— 0.04238.

= 258.7 S em? mol".

(iit) Calculation of dissociation constant, K
LJ Example 14
Acetic acid dissociates as :
The molar conductivity at infinite dilution of Al,(SO)
CH,COOH CH,COO”- + Ht
is858Scm? mol. Calculate the molar ionicconductivity
Initial conc. c 0 0
of Al?* ion given that 0° (SO_7-) = 160 Scm? mol”.
Equilibrium cone. c(1 — a) CO. COL
(Mizoram S.B. 2014, 2018)
ELECTROCHEMISTRY

kK = 1.386 x 10° S em!

Dissociation constant, K = [CH,COO™ |[H*| Kae « x 1000 = k X 1000
CH,COOH
= M Solubility
CX COL
~ e(1-a@) Solubility = —
Itt
= K = cal
_ 1.386
10% x 1000
1-o
- 138.3
Substituting the values,
1.0 x 10° mol L-
K 0.01x (0.0423) or 1.0 x 10 x 143.5 el,
7 1-0.0423 1.485 x 102 g 1-1
= 1.87x 10°. Example 19.
Example 17. The molar conductance of acetic acid at infinite dilution
Conductivity of 0.00241 M acetic acid is 7.896 x 10° is 390.7 Scm? mol. Calculate the molar conductance of
Sem. Calculate its molar conductivity and if A° for 0.01 M acetic acid solution, given that the dissociation
acetic acid is 390.5 S em? molt. What is its dissociation constant of acetic acidis 1.8 x 10~.
constant ? (A.ILS.B. 2004; D.S.B. 2004 ; 2008) Solution: Acetic acid dissociates as :
Solution: Molar conductivity, CH,COOH =~ CH,COO- + Ht
A — kx1000 Initial conc. c 0 0
M Equilibrium cone. c(1—«) cL cul
K = 7.896 x 10° S em“, M = 0.00241 M
[CH,COO ][H*]
A — 7.896x 10° x 1000 Dissociation constant, =
0.00241
Se = “TCH,COOHI
= 82.76S cm? mol? (co) (co) _ co?
c(l-a@ 1l-a
Ac 82.76
Now, ao = rc = 3905 = 0.0859
Assuming 1 — 0 = 1, we get K, = co?

Ca? 0.00241 x (0.0839)

or a = (Ka)?
(l-a)” (- 0.0839) c
= 1.85 x 10-4,
An i
Example 18. mune “= he > 390.7
The specific conductance ofa saturated solution ofAgCl at Substituting the values, we get
298 Kis found to be 1.386 x 10° Sem, Calculate its solu- 1
-5 \o
bility (h°4,+=62.0Scem “mol and i° 4, = 76.3 Sem? mol). i =: eee wea
Solution: A,*(AgCl = 2° (Agty eae (Cl) 390.7 0.01

= 62.0 + 76.3 A. it = 4.2438 x 10 x 390.7

= 138.3 5 em? mol! = 16.58 S cm? mol!

=Diatik
Dm Aalto
14. Calculate the degree of dissociation (0) of acetic acid 1f its molar conductivity (A,)
is 39.05 S em? mol!.
Given A°(H*) = 349.6 S em? mol! and A°(CH,COO) = 40.98 em? mol}.
— Answers to Practice Problems =
(D.S.B. 2017)
15. Calculate the molar conductivity at infinite dilution of AgCl from the following 14, 10%.
data : 15. 13.84 m §S m? mol1.
A°(AgNO,) = 13.34 m5 m? mol’, A° (KCl) = 14.99 m S m? mol"! and 16. 38.6 S em? mol!.
A® (KNO,) = 14.49m5 m? mol?
16. The A° values of KNO, and LiNO, are 146.0 and 110.1 Scm? mol respectively.
Hints & Solutions on page 74
The 2° value for Kt ion is 73.5 S em? mol!. Calculate 4° (Li*). (Pb.S.B. 2011)
17. The conductivity of 0.001 mol L™ solution of CH,COOH is 3.905 x 10° 5 em™.
Calculate its molar conductivity and degree of dissociation (a).
a0 MODERN'S abe + OF CHEMISTRY
-AXIl

Given 1°(H*) = 349.65 S em? mol and 4° (CH,COO_) = 40.9 S em? mol?
(A.LS.B. 2016)
18. The molar conductivity at infinite dilution for NH,Cl, NaOH and NaCl are 129.8,
217.4 and 108 S cm? mol? respectively. If the molar conductivity of 0.01 M solution
of NH,OH is 9.33 5 cm? mol. Calculate
(1) what is the percentage dissociation of NH,OH at this dilution ?
(iz) dissociation constant of NH,OH. (A.LS.B. 2005 C)
19. The conductivity of 0.1 M solution of AgNO, is 9.47 x 10° Sem at 291 K. The ionic
conductivities of Agt and NO, at the same temperature are 55.7 and 60.8 5 cm?
equiv’ respectively. Calculate the degree of dissociation of AgNO, in 0.1 M solution.
- Answers to Practice Problems 20. The molar conductivity of 0.025 M HCOOH (ag) solution was measured as
4.61m5 m? mol". Calculate pK, value for formic acid (A°(H*) = 34.96, A°CHCOO)
17. A,, = 39.05 S cm? mol
—-6.46m5 m? mol.
Oo Gal
21. Calculate A®° for CaCl, and MgSO, from the following data :
18. (1) 3.90%, A° values are Ca** = 119.0, Cl = 76.8, Mg** = 106.0, SO,?" = 160.0 all in S em? mol".
(ii) 1.58 x 107°.
19. 59%.
22. The conductivity of 0.001028 mol L™ acetic acid is 4.95 x 10° S em'!. Calculate
20. 3.4816. its dissociation constant if A° (CH,COOH) is 390.6 S cm? molt. N.CE.R.T
21. 271.6, 266 S em? molt. 23. The molar conductances of NaQH, NaCl and BaCl, at infinite dilution are
22. Linx 1. 2.481 x 10°, 1.266 x 10? and 2.800 x 10 5 m? mol respectively. Calculate A°_
23. bese ie en me for Ba(OH),.
24, 2960 x 106 Li 24, The conductivity of a saturated solution of BaSO, at 296 K, is found to be
3.768 x 10° ohm" em“! and that of water used is 1.36 x 10-°ohm™ cm“. Molar
ionic conductances at infinite dilution of Ba** and SO,” ions are 110 and 136.6
Hints & Solutions on page 74 ohm cm? mol respectively. Calculate the solubility of BaSO, at 2965 K (Atomic
masses: Ba = 137, 5 = 32, O = 16).

earning Plus
Ionic product of water can also be calculated by knowing the specific
conductivity of water as illustrated below.
> At 298 K, specific conductivity of water, kK is 5.54 x 10° S em and
limiting molar ionic conductances of Ht and OH are 349.6 and 199.1
S cm? mol respectively. Calculate ionic product of water at 298K.
@® Competition Plus Q A°(H*) = 349.6 S em? mol
Conductometric titrations can also W(OH-) = 199.1 S em? mol
be used for titrations of acids and bases
A°%H,O) = A(H*) + 4° (OH)
and precipitation reactions. For detail,
refer Competition File (Page 98). = 549.6 + 199.1
548.7 S em? mol
« xX 1000
Ae — Molarity
. KX L000
Molarity AC

5.54 x10 x 1000

= 548.7
Oe ie! omelolie
Now, Molarity = [H*] or [OH-] = 1.01 x 10-7
.. Ionic product of water, K, = [H*] [OH]
= Peis ae ee oie
= 1.02 x 107!4
ELECTROCHEMISTRY

Accelerate Your Potential

td 540) 3) a (for JEE Advance)
For dissociation of a weak monobasic acid,
i) The conductivity of a saturated solution of [H*] = cxa
AgBr at 25°C is 8.5 x 10°78 cnt. If the limiting molar ionic where = degree of dissociation
conductances of Agt and Br ions are 62 and 78S cm? mol", 10* = 0.0015xa
ve

[Solution Jax(AgBe)— 12,(Ag") «42,07

then calculate the solubility product of AgBr.
or @ = 10 = as
0.0015 15
= 62+78=140.0Scm? mol! AS

Now for saturated solution, Alsom = .

K x 1000
Ty 40
iM

A? (AgBr) = <a
where s is the solubility 15 AS
| ee ae
ne 8.510 «1000 x tA 40x 16
s 6 x 107 Scm? mol!
or $s =
8.5x10-'
140.0
x 1000 =
=6.07x10° molL
a The limiting molar conductances of sodium
chloride, potassium chloride and potassium bromide are
Now AgBr = Agt + Br 126.45, 149.86 and 151.92 ohm?! cm? mol" respectively.
Calculate limiting molar ionic conductance of Na‘* given
K., = [Ag*] [Br] that limiting molar ionic conductance of Brion is 76.34
= (6.07 x 10°) x (6.07 x 10-*) ohn! em? mol.
- 86.8x 10°" mol L~
This can be calculated with the help of
Kohlrausch’s
A The conductance of a 0.0015 M aqueous
law because limiting molar ionic conductances are additive:
solution of a weak monobasic acid was determined by
using aconductivity cell consisting of platinized platinum A° (KBr) = 4°(K*)
+42 (Br)
electrodes. The distance between the electrodes is 120 cm A® (KBr) — 161.92 ohm? cm? mol,
with an area of cross section of 1 cm*. The conductance of ac (Br) — 76.34 ohm! em? mol-!
the solution was found to be5 x 10-78. The pH of thesolution Ac (K*) = At (KBr)—A? (Br)
is 4. Calculate the limiting molar conductivity (A,°)ofthis 161.92 — 76.34
(JEE Advance 2017)

cateonstant{t) = 222.200 of
22 EEL 75.68 ohm! em? mol"
Now ASORC)) = kek) A (Ch)
a lem A® (KCl) — 149.86 ohm? cm? mol’,
kK = Cx Cell constant DORE) 2 716s ohm! em? mol"!
= (6x107S) x(120 cm) Eley = Aes(KCI) — 4°,(Kt)
= 6x10°Scm! = 1]49.86—75.568
« x 1000 = 74.28 ohm! cm? mol
= M Now A® (NaCl) = 2° (Nat) +A° (CL)
6x10"
x1000 A®(NaCl) = 126.46 ohm? cm? mol,
0.0015 (CL) = 74.28 0hm cm? mol
= 40Sem? mol? Ae(Nat) = A® (NaCl —A° (Cr)
Now, pH, =. —log [H*])=4 = 126.46 —74.28

id 08 |
HL »yi0= = §2.17 ohm! cm? mol!

C OTLCED Cul
Q. 1. What is the relationship between equivalent conductance and molar conductance ? Illustrate by taking
the example of Al,(SO,),.
Ans. Molar conductivity A, and equivalent conductivity A, are :
1000« 1000«
An = =~ C¢
x. C
A. M
Now, Normality = 4x Molarity
where 41s the number of unit positive charge or negative charge per molecule of the electrolyte.
An
A
= 7
eé
ane For Al,(SO,),, which ionises as :
MODERN’S abc + OF CHEMISTRY
-XII

Al(SO,), === 2Al5+ + 380,2-

Z=6 . A =6 Ay
» Which will have greater molar conductivity?
(4) Solution containing 1 mol of KCl in 200 cc or 1 mol of KCl in 500 ce.
(74) Solution containing 1 mol of LiCl in 500 cc or 1 mol of KCl in 500 ce.
Ans. (z) 1 mol of KClin 500 ce (zz) 1 mol of KCl in 500 ce.
Q. 3. Why is it not possible to determine AL for weak electrolytes by extrapolation ?
Ans. Because A for weak electrolytes does not increase linearly with dilution as for strong electrolytes.
Q. 4. What are the units of cell constant ?
Ans. em? or m™?.
Q.5. Why is alternating current used in place of direct current in measuring the electrolytic conduction ?
Ans. Direct current results in the electrolysis of the electrolytic solution. As a result, concentration of the electrolyte near
the electrodes changes and these results change 1n the resistance of the solution.
Q.6. Which of 0.1 M HCI and 0.1 M NaCl do you expect to have greater A°,, and why ?
Ans. 0.1 M HCl will have greater A |, value because H* ions are smaller than Na* ions and hence have greater ionic mobility.
Q.7. Which of the following pairs, will have greater conduction ?
(7) 0.1 M acetic acid solution or 1 M acetic acid solution.
(iz) 0.1 M NaCl solution at 25°C and 0.1 M NaCl solution at 50°C.
(711) Copper wire at 25°C and copper wire at 50°C.
Ans. (z) 0.1 M acetic acid because with dilution dissociation increases and therefore, conductivity increases.
(zz) 0.1 M NaCl solution at 50°C because with increase in temperature, ionic mobilities of strong electrolytes
increase.
(111) Copper wire at 26°C because with increase in temperature metallic conduction decreases due to vibration of
kernels.
Q.8. A solution is placed in two different cells having cell constant 0.1 and 0.5 cm™ 1 respectively. Which of
the two will have greater value of specific conductance ?
Ans. Both will have same value of specific conductance.
Q.9. Define conductivity and give its units. (H.P.S.B. 2005)
Ans. Conductivity is the conductance of a solution of 1 cm length and having 1 sq. cm as the area of cross-section.
Units :Q? emt.
Q.10. Write an expression for molar conductivity of Al,(5O,), at infinite dilution in terms of their ionic molar
conductivities.

Ans. A= 2d 3 + 3h co

Q.11. What is the effect of temperature on the electrical conductance of

(7) metallic conductor (11) electrolytic conductor ?
Ans. With increase in temperature, the electrical conductance of metallic conductor decreases whereas that of electrolytic
conductor increases.
Q. 12. Express the relation between conductivity and molar conductivity of a solution.
(A.LS.B. 2008, D.S.B. 2008, 2011)
Ans. Molar conductivity (A,) 1s related to conductivity (Kk) as :
= a where M is the molarity of the solution.

Q. 13. Calculate the limiting molar conductivity of CaSO, if limiting molar conductivities of calcium and
sulphate ions are 119.0 and 106.0 S cm? mol" respectively. (CBSE Sample Paper 2012)
Ans. AS, (CaSO,) = A, (Cat) +4 (SO,2
119.0 + 106.0
= 226.0S em? mol”.
Q.14. A 0.01 M solution of MgCl, is diluted by adding water. What will happen to its conductivity and molar
conductivity?
Ans. With dilution, conductivity will decrease while molar conductivity will increase.
Q.15. Arrange the following solutions in the decreasing order of specific conductance.
(7) 0.01M NaCl (77) 0.05M NaCl (ii7)0.1M NaCl (iv) 0.5M NaCl (Kolkata S.B 2016)
Ans. (tv) 0.6M NaCl > (zzz) 0.1M NaCl > (21) 0.05M NaCl > (z) 0.01M NaCl
ELECTROCHEMISTRY 3/23 —_—

ELECTROCHEMICAL CHANGES : ELECTROCHEMICAL CELLS AND

ELECTROLYTIC CELLS
The chemical changes which involve the flow of electric current are called
electrochemical changes. These are broadly of two types :
1. Electrochemical cells or Galvanic cells
These constitute the electrochemical reactions in which chemical energy
is converted to electrical energy. In these cells, spontaneous redox reaction is
used to generate an electric current.
The devices in which chemical energy of a spontaneous redox reaction
is converted into electrical energy are called electrochemical cells or
galvanic cells.
These cells are very important because of their many practical applications.
relates
An early example of a galvanic cell is a Daniell cell which was invented by
the British chemist John Daniell in 1836. Daniell cell was constructed on
the basis of the following spontaneous redox reaction :
Zn(s) + Cu?*(aq) — Zn**(aq) + Cu(s) ery
Energy Energy

2. Electrolytic cells or Electrolysis A onverted Canverted

These constitute the electrochemical reactions in which electrical energy to electrical to chemical
is converted into chemical energy. energy energy
The phenomenon of chemical changes taking place by the passage of
electrical energy from an external source is called electrolysis. The devices Galvanic cells Electrolytic
or cells used to carry out electrolysis are called electrolytic cells. For (voltaic cells) cells
example, when electric current is passed through molten sodium chloride, ————
sodium is produced at cathode and chlorine is liberated at anode.

2Nac] Electric,
current
ona 4+ C1 2
Cathode Anode

The electrolysis is used to extract many metals such as Na, K, Ca, Sr, Mg,
Al, etc. and manufacture of chemicals such as NaOH, Cl,, F., etc. H. Davy
isolated the element potassium by passing electric current through molten KOH.
ELECTROCHEMICAL CELL OR GALVANIC CELL
The devices in which electrical energy ts produced from chemical reactions
are called electrochemical cells or galvanic cells or voltaic cells. In these
cells, oxidation and reduction reactions occur in separate containers called
half cells and the redox reaction is spontaneous. Electrical energy is produced
during such reactions. Let us explain the working of an electrochemical cell,
known as Daniell cell with the help of a redox reaction:
Zn(s) + Cu**(aq) ¢ ——> Zn**(aq) + Cu(s)
The arrangement consists of two beakers, one of which contains 1.0 M solution
of zinc sulphate and the other 1.0 M solution of copper sulphate. A zinc rod is
dipped into ZnSO, solution while a copper rod is dipped into CuSO,
solution. These metallic rods are known as electrodes. The metallic ,
rods in the beaker are connected to the ammeter by means of Electrons flow
an insulated wire through a key. Ammeter is used to know the
passage of current which moves in opposite direction to the flow
of electrons. The solutions in the two beakers are connected by an
inverted U-tube containing saturated solution of some electrolyte
such as KCl], KNO, or NH,NO, which does not undergo a chemical
change during the process. The saturated solution is generally taken
in agar-agar jelly or gelatin.
The two openings of the U-tube are plugged with some porous
material such as glass wool or cotton. The U-tube which connects 1M ZnSO, (aq) 1M CuSO, (aq)
the two glass beakers is called a salt-bridge. Its function will be
Fig. 6. A simple galvanic cell.
discussed later. The arrangement is shown in Fig. 6. |
ane When the
MODERN'S abe + OF CHEMISTRY
-AXII

circuit is completed by inserting the key in the circuit, it is

observed that electric current flows through external circuit as indicated by
the ammeter. The following observations are made:
(i) Zine rod gradually loses its weight.
(ii) The concentration of Zn**(aq) in the ZnSO,(aq) solution increases.
(111) Copper gets deposited on the electrode.
(iv) The concentration of Cu**(aq) in the CuSO,(aq) solution decreases.
(v) There is a flow of electrons in the external circuit from zinc rod to
e Electrodes are the surfaces on copper rod. Therefore, the current flows from copper to zinc. Jt may
which oxidation or reduction be noted that as a convention, the flow of electric current is taken
half reactions occur. These may opposite to the flow of electrons.
or may not take part in the These observations can be explained as follows :
reactions. Those electrodes which During the reaction, zinc is oxidised to Zn** ions which go into the
donot take part in the reactions solution. Therefore,
are called inert electrodes. Zn(s) ———> Zn** (ag) +2e (Oxidation)
the zinc rod gradually loses its weight. The electrons released at the zinc
electrode move towards the other electrode through outer circuit. Here, these
are accepted by Cu** ions of CuSO, solution which are reduced to copper. The
metal gets deposited on the copper electrode.
Cu** (aq) + 2e~- ——> _ Cu(s) (Reduction)
The zinc electrode where electrons are released or oxidation occurs is called
anode while the copper electrode where electrons are accepted or reduction
occurs is called cathode. As the electrons move from zinc rod to the copper
rod, the zinc rod is regarded as negative terminal while copper rod is regarded
as positive terminal. There is flow of electrons from negative terminal (anode)
to positive terminal (cathode).
The two containers involving oxidation and reduction half reactions are
called half cells. The zinc rod dipping into a ZnSO, solution is oxidation half
cell and the copper electrode dipping into a CuSO, solution is reduction
half cell.
Salt Bridge and its functions. A salt bridge has a vital role to play in an
electrochemical cell. It is usually an inverted U-tube filled with concentrated
solution of inert electrolyte. The essential requirements of electrolyte are :
(4) The mobility of the anion and cation of the electrolyte should be
almost same.
(ii) The ions of the electrolyte are not involved in electrochemical change.
(111) The ions do not react chemically with the species of the cell. Generally,
salts like KC], KNO,, NH,NO,, etc. are used. The saturated solutions of these
electrolytes are prepared in agar agar jelly or gelatin. The jelly keeps the
electrolyte in semi-solid phase and thus prevents mixing.
The important functions of the salt bridge are :
REMEMBER (i) Salt bridge completes the electrical circuit. The salt bridge
In an electrochemical cell connects the two solutions of the half cells and their electrodes are connected
e Oxidation occurs at anode by means of a wire. Therefore, the salt bridge completes the circuit.
(-ve terminal) (ii) Salt bridge maintains electrical neutrality of two half cell
e Reduction occurs at cathode solutions. To understand the function of the salt bridge, let us consider
(+ve terminal) the cell without a salt bridge. The electrons released by the oxidation of Zn
e Electrons flow from anode to to Zn** ions will be accepted by the Cu** ions of CuSO, in the other half
cathode. cell and the latter will be reduced to copper. The positively charged Zn?*
ions pass into the solution. After sometimes, this results into accumula-
tion of extra positive charge in the solution around the anode. Similarly,
In salt bridge, the electrolytes
due to reduction of some Cu** ions to Cu, the solution around cathode will
such as KCl, KNO, or NH,NO, are
acquire extra negative charge due to excess of s0,7- ions. The accumula-
generally preferred because their tion of positive charge around zinc rod will prevent the further flow of
ions have almost equal mobility. electrons from the zinc rod. Similarly, the accumulation of negative charge
around copper electrode will prevent the flow of electrons to the copper
ELECTROCHEMISTRY

Klectrons flow
Ammeter

Anode f Cathode

|
1M (aq)
CuSO,
LM An SO, ‘or |
(aq) :

Oxidation Reduetion
7n —> Zn** + 2e7 Cut” + 8e°—> Cu

Fig. 7. Working of an electrochemical cell.

ions. Thus, the flow of electrons will occur only momentarily and the cell
will stop working.
However, the accumulation of charges in the two half cells is prevented
by using salt bridge, which provides a passage for the flow of the charge
in the internal circuit. When the concentration of Zn** ions around anode
increases, sufficient number of Cl ions migrate from the salt bridge to
the anode half cell. Similarly, to neutralise the excess negative charge due
to the additional SO, ions in cathode half cell, sufficient number of K*
ions migrate from the salt bridge to this half cell. Thus, the salt bridge
provides cations and anions to replace the tons lost or produced in the two
half cells.
The working of the electrochemical cell and the functions of salt bridge
are represented in Fig. 7.
Functioning of the cell when external opposing potential is applied
Consider a Daniell cell in which the zinc electrode is dipped in ZnSO, (aq)
and copper electrode is dipped in CuSO,(aq). The cell reaction occurring is
Zn(s) + Cu**(aq) ———=> Zn**(ag) + Culs)
The electrical potential (called emf) of the cell is 1.10 V when concentration
of Zn** and Cu** ions is 1 M (1 mol dm-*)*.
Let us consider an arrangement in which an external opposite potential is
applied as shown in Fig. 8(a). When the external opposite potential is increased
slowly, we observe that the reaction continues to take place till the opposing
voltage reaches the value of 1.1 V.
As long as the external opposite is less than 1.10V, the electron continue
to flow from Zn rod to Cu rod and hence current flows from Cu to Zn. Zinc
dissolves in anode and copper deposits at cathode.
When the opposing voltage reaches the value 1.10 V, the cell reaction
stops altogether and no current flows through the cell as shown in
[Fig. 8(6)] ahead. There is no chemical reaction.
Further increase in the external potential now again starts the reaction
but in the opposite direction shown in [Fig. 8(c)] ahead. The cell now starts
ZnSO, Cuso,
functioning as an electrolytic cell. In this case electrical energy is used to carry E. < 1-10 V
Electrochemical cell continues working.
out non-spontaneous chemical reaction. The electrons flow from Cu to Zn rod
and current flows from Zn to Cu. As a result of electrolysis, zinc is deposited Fig. 8(a)
at the zinc electrode and copper dissolves at copper electrode.
* Strictly speaking, 'activity' should be used instead of concentration. It is directly proportional to concentration. However, in dilute solutions, it is
equal to concentration. You will learn about it in higher classes.
ane MODERN'S abe + OF CHEMISTRY-AIl

Thus, it may be concluded

that for a Daniell cell having
emf 1.10 V,
(a) When E,_, < 1.1 V (Fig. 8 a)
(z) Electrons flow from Zn rod to
Cu rod
(11) Current flows from Cu to Zn
(221) Zn dissolves at anode and Cu
deposits at cathode
(6) When KE. = 1.1 V (Fig. 8 5)
(z) No flow of electrons.
CuSO,
(it) No flow of current.
E..,> 1-10 V
(111) No chemical reaction.
No flow of current and no reaction Cell acts like an electrolytic cell
(c) When E,., > 1.10 V (Fig. 8 ce)
(z) Electrons flow from Cu to Zn. Fig. 8(b) } Fig. 8(c)
(iz) Current flows from Zn to Cu
(111) Zn is deposited at Zn electrode REPRESENTATION OF AN ELECTROCHEMICAL CELL
and Cu dissolves at Cu
An electrochemical cell or galvanic cell consists of two electrodes : anode
electrode.
and cathode. The electrolyte solution containing these electrodes are called haif
cells. When these two half cells are combined, a cell is formed. The following
conventions are used in representing an electrochemical cell :
1. A galvanic cell is represented by writing the anode (where oxidation
occurs) on the left hand side and cathode (where reduction occurs) on the
right hand side.
2. The anode of the cell is represented by writing metal or solid phase
first and then the electrolyte (or cation of the electrolyte) while the cathode
is represented by writing the electrolyte first (or cation) and then metal
and solid phase.
The metal and the cation are separated either by a semicolon (;) or by a
vertical line. For further information, the concentration of the electrolyte is
also mentioned within bracket after the cation, i.e.,
Zn ; Zn** or Zn | Zn** or Zn | Zn** (1M) (Anode)
Cu** ; Cu or Cu** | Cu or Cu** (1M) | Cu (Cathode)
3. The salt bridge which separates the two half cells is indicated by two
vertical lines. For example,
Zn | Zn?* (1M) || Cu?* (1M) | Cu
The complete formulation of a cell which is also known as cell notation
is represented as follows :
Electrons flow

© Pole Conventional current flow (F) Pole

Zn” (1M) Cu” (1M) Cu

Anode Anodic Cathodic Cathode
Electrolyte Electrolyte

OXIDATION OCCURS
SALT REDUCTION OCCURS
BRIDGE
Sometimes negative and positive signs are also put on the electrodes to
show the release and loss of electrons taking place on them. Anode is a negative
pole while cathode acts as positive pole. The electrons flow from the negative
pole (anode) to the positive pole (cathode) in the external circuit. On the other
hand, conventionally, the current is said to flow in the opposite direction.
Memory Aid
Sometimes we get confused in the nomenclature of electrodes. As a memory
aid keep in mind the alphabetical order of the first letter e.¢., A(anode) comes
before C(cathode). The cell may be written by arranging each of the pair left-right,
ELECTROCHEMISTRY 3/27 =

anode-cathode, oxidation-reduction, negative and positive in the alphabetical order as :

e where reduction occurs

e where electrons are consumed
Left Brid Right :
Anode marae CORES e towards cations migrate
Oxidation Reduction e has +ve sign
Negative Positive
CATHODE
Representation of Some Common Cells by Cell Notation
Some common cells may be represented as given below :
(1) Cu-AgNO, cell. The reactions occurring in the cell are :
Oxidation half reaction :
Cu —— Cu#* + Qe-
WTOOLOLTOLOTODOLOZOLALA
Reduction half reaction :
2Ag* + 2e° —— > 2Ag
Overall cell reaction :
Cu + 2Ag* ——> Cu** + 2Ag
The cell may be represented as :
Cu(s) |Cu** (aq) ||Ag*(agq) |Ag(s)
(ii) Ni-AgNO, cell HOQU
QUDQQU00000
DOQOUO0000

Oxidation half reaction :

Ni(s) ———> Ni** (aq) + 2e7
Reduction half reaction: e where oxidation occurs
2Acg*(ag) + 2e- —- 2Ag(s) e where electrons are produced
Overall cell reaction : « towards anions move
Ni(s) + 2Ag*(ag) ——> Ni**(aq) + 2Ag(s) e has —ve sign
The cell may be represented as:
Ni |Ni**(aq) ||Ag*(aq) |Ag(s)
(iii) Zn-HCl reaction
Oxidation half reaction :
Zn(s) —— Zn**(aqg) Ae;
Reduction half reaction :
2H*(ag) + 2e- — H,{g)
Overall cell reaction :
Zn(s) + 2H*(aq) ———> Zn**(aq) + Hg)
Cell may be represented as:
Zn(s) |Zn2*(aq) ||H*(aq) |H., Pt
ELECTRODE POTENTIAL AND. E.M.F. OF A GALVANIC CELL
Electrode Potential
The flow of electric current in an electrochemical cell indicates that a
potential difference exists between two electrodes. To understand the potential
difference between two electrodes or electrode potentials let us consider the
redox reactions occurring at these electrodes.
When an electrode say copper, is immersed in a solution of its ions, then
either of the following three possibilities can take place :
(a) The metal ions (Cu**) may collide with the electrode and do not undergo
any change.
(6b) Cu* ions may collide with the electrode, gain electrons and get
converted into metal atoms (i.e., the ions are reduced).
Cu** + 2e-§ ——> Cu (Reduction)
(c) Cu atoms on the electrode may lose electrons to the electrode and
become Cu** ions and go into the solution (i.e., oxidation occurs).
Cu —— Cu2* + 2e- (Oxidation)
These possibilities are shown in Fig. 9.
Now, if the metal has relatively high tendency to get oxidised, its atoms
will lose electrons readily and form Cu* ions, which go into the solution. The
ane MODERN'S abe + OF CHEMISTRY

electrons lost on the electrode would be accummulated on the metal electrode

-AXII

and the electrode acquires a slight negative charge with respect to the solution.
Some of the Cu** ions from the solution will take up electrons and become Cu
atoms. After some time, an equilibrium will be established as :
Cu(s) === Cu" + 2Qe-
Electrode Solution (on electrode)
When such an equilibrium is attained, it results in separation of charges
(negative on the electrode with respect to the solution).
Similarly, if the metal ions have relatively greater tendency to get reduced,
they will take electrons from the electrode. As a result, a net positive charge will
Metal ions collide but do not be developed on the electrode with respect to the solution. This will also result
undergo any change. into separation of charges (positive on the electrode with respect to the solution).
Due to separation of charges between the electrode and the solution, an
electrical potential is set up between metal electrode and its solution.
The electrical potential difference set up between the metal and its
ions in the solution is known as electrode potential.
Thus, the electrode potential is a measure of the tendency of an electrode
Cu**+ 2e
“| 2 —
Cu
to gain or lose electrons when it is in contact with solution of its own ions. The
electrode potential may be of two types:
(4) Oxidation potential. The tendency of an electrode to lose electrons
or to get oxidised is called its oxidation potential. Thus, oxidation potentials
Metal ions gain electrons and get
converted to metal z.e., reduction give the tendency of an electrode to lose electrons, i.e,
occurs, (electrons are lost by metal f__>
Ms) <= M"™*(aq) + ne-
rod and it acquires +ve charge).
é.g., af —— Zn**(aq) + 2e7
a.

H, == 2H*(aqg) + 2e
(11) Reduction potential. The tendency of an electrode to gain electrons
or to get reduced is called its reduction potential. Therefore, it measures
the tendency of an electrode to gain electrons, i.e,
M**(ag) + ne = MG)
e.2., Cu2+(ag) + 2e° — Culs)
2H (aq) + 2e° =—— 4,
It is evident that the oxidation potential is the reverse of reduction potential.
Metal atoms on electrode lose
For example, if reduction potential of Zn is — 0.76 volts, its oxidation potential
electrons to form metal ions i.e.,
oxidation occurs. Electrons lost is +0.76 volts.
by metal accumulates on metal rod. According to the latest convention, the half cell reactions are always
(Metal rod acquires -ve charge).
written as reduction half reactions and their potentials are represented
as reduction potentials. These are called electrode potentials.
Fig. 9. Electrode equilibrium.
The electrode potential depends upon :
(1) the nature of the metal and its tons,
(it) concentration of the tons in the solution, and
It may be remembered that for (111) temperature.
calculating e.m.f. of the cell.
E.M.F. or Cell Potential of a Cell
e The electrode potentials are
Electrochemical cell consists of two half cells. The electrodes in these half
always taken as reduction
cells have different reduction potentials. Therefore, they have different tendency
potentials (as a convention)
for both the electrodes. to lose or gain electrons. The electrode having higher reduction potential will
e The cell is always written have higher tendency to gain electrons whereas the electrode having lower
as anode on the left (where reduction potential will have lesser tendency to gain electrons, rather it loses
oxidation occurs) and cathode electrons. As a result of this potential difference, there is a flow of electrons from
on the right (where reduction the electrode with a lower reduction potential (higher tendency to lose electrons)
occurs). to the electrode with higher reduction potential. The difference between the
e Reduction potential = electrode potentials of the two electrodes constituting an electochemical
— Oxidation potential cell is known as electromotive force or cell potential of a cell. This acts as
a driving force for the cell reaction. The potential difference is expressed in volts.
ELECTROCHEMISTRY

Therefore, the cell potential or e.m.f. arises from the difference in the
ca
tendencies of the two ions to get reduced. It is equal to the reduction potential @ Competition Plus
for the substance that actually undergoes reduction minus the reduction There are different types of electrodes
potential of the substance that undergoes oxidation. such as metal-metal ion electrodes,
As already studied, the reduction occurs at cathode and oxidation occurs metal-metal insoluble salt electrodes,
gas electrodes, amalgam electrodes,
at anode. Therefore, oxidation-reduction electrodes. For
e.m.f. = Reduction potential of cathode — Reduction potential of anode detail, refer Competition File
(Page 98).
or E..,, = HE(cathode) — E(anode)
In the representation of an electrochemical cell as a convention, cathode is
written on right hand side and anode on the left hand side. Therefore, e.m-f. REMEMBER
of a cell may also be written as :
E.., = E (Right) — E (Left) Beit = Ee Anode = Hed
= [Reduction potential of
Thus, e.m.f. of a cell may be defined as reduction half reaction]
the potential difference between two electrodes of the cell when — [Reduction potential of
either no or negligible current is allowed to flow in the circuit. oxidation half reaction]
The e.m.f. of the cell is measured with the help of a potentiometer. It se eget eee
ge petee
depends upon the nature of the electrodes, temperature and the concentrations
of the solutions in the two half cells. For example, the e.m.f. of a Daniell cell
in which the concentrations of aqueous solutions of CuSO, and ZnSO, in the
two half cells is 1 M at 298 K is 1.10 volts.

Difference between E.M.F. and Potential Difference

The differences between e.m.f. and potential difference may be given as
follows :

1. Itis the potential difference between It is the difference of the electrode

the two electrodes when no current is potentials of the two electrodes when the
flowing in the circuit i.e., in an open cellissending current through the circuit.
circuit.
. Itismaximum voltage obtainable from It is less than the maximum voltage
the cell. obtainable from the cell (z.e., e.m.f. of
the cell).
. The work calculated from e.m.f. is the The work calculated from potential
maximum work obtainable from the difference is less than the maximum
cell. work obtainable from cell.
. Itis responsible for the flow of steady Itis not responsible for the flow of steady
current in the cell. current in the cell.

STANDARD ELECTRODE POTENTIAL

Since a half cell in an electrochemical cell can work only in combination
with the other half cell and does not work independently, it is not possible to
determine the absolute electrode potential of an electrode. We can, therefore, Bubbles of |~
find only the relative electrode potential. escaping H,
This difficulty can be solved by selecting one of the electrodes as a reference
electrode and arbitrarily fixing the potential of this electrode as zero. For this
purpose, reversible hydrogen electrode has been universally accepted as a
reference electrode. It is called standard hydrogen electrode (S.H.E.) or normal Platinum
hydrogen electrode (N.H.E.). foil
coated
Standard hydrogen electrode. It consists of platinum wire sealed in a
with finely
glass tube and has a platinum foil attached to it (Fig. 10). The foil is coated with 1M HC! solution — divided Pt
finely divided platinum and acts as platinum electrode. It is dipped into an acid
solution containing H* ions in 1 M concentration (1 M HCl). Pure hydrogen gas Fig. 10. Standard hydrogen electrode.
aco MODERN'S abe + OF CHEMISTRY

at 1 bar (atmosphere) pressure is constantly bubbled into solution at constant

-AXIl

temperature of 298 K. The surface of the foil acts as a site for the reaction.
Reference Electrodes
The following reactions occur in this half cell depending upon whether it
It may be noted that it is not always
acts as anode or as cathode.
convenient to use standard hydrogen
electrode as reference electrode If S.H.E. acts as anode
because of experimental difficulties H,(g) ——> 2H* +2e
in its preparation and use. Some of If S.H.E. acts as cathode
these are:
(1) It is difficult to maintain unit
9H++2e- —> Hg)
concentration of H* ions. This standard hydrogen electrode is also regarded as reversible electrode
(11) The hydrogen electrode gets Hoy) — 2Ht + 2e7
poisoned even in the presence
The electrode potential of an electrode can be determined by connecting
of traces of impurities.
(iz) It is difficult to maintain 1 atm this half cell with a standard hydrogen electrode. The electrode potential of
pressure of H, gas uniformly for the standard hydrogen electrode is taken as zero. The electrode potential of a
a long time. metal electrode as determined with respect to a standard or normal hydrogen
Therefore, some other secondary electrode is called standard electrode potential (E® or E®°). Standard
reference electrodes are used. electrode potentials are always associated with the reduction reactions occurring
The most commonly used reference at the electrodes.
electrode is calomel electrode. Its
Measurement of the Standard Electrode Potential (E®)
reduction potential depends upon the
concentration of KC] solution used as
To measure the standard electrode potential of a metal electrode, 1.0 M
given below: solution of the electrolyte is taken in a beaker and a metal electrode is dipped
(a) Saturated calomel : in it. This constitutes the metal-metal ion electrode, M/M”* (aq). This half cell
Hg | Hg,Cl, | (s) KCl (saturated) is connected to S.H.E. through a salt bridge. The electrodes are connected to a
E® = 0.2415 V at 26°C voltmeter. From the measured e.m.f. of the cell, the standard electrode potential
(6) IN calomel: of the half cell is calculated. This method is illustrated as follows :
Hg | Hg, Cl,(s) | KC1(N)
1. Measurement of Electrode Potential of Zn**|Zn Electrode
E®? = 0.2800 V
(c) 0.IN calomel : An electrode consisting of zinc rod immersed in 1 M solution of ZnSO, is
Hg | Hg,Cl,(s) | KCl (0.1N) combined with S.H.E. as shown in Fig. 11.
E® — 0.3338 V To obtain the cell reaction, we have to Know what is oxidised
and what is reduced to know the cathode and anode in the cell.
We can determine this by measuring the charges of the electrodes
because we Know that in a galvanic cell, cathode is the +ve electrode
and anode is the —ve electrode. When we connect the two electrodes
0.76V
with a voltmeter, the proper measurements (e.m_-f. of the cell) are
obtained only if the +ve terminal of the voltmeter is connected to
salt bridge the +ve electrode and —ve terminal of the voltmeter is connected
to the —ve electrode. If the connections are not correct, no reading
will be obtained in the voltmeter. Thus, if the voltmeter gives the
proper reading, it indicates that the electrode connected to +ve
terminal of the voltmeter is +ve (acts as cathode) and the electrode
connected to —ve terminal of the voltmeter is —ve (acts as anode).
The electrons flow from anode to cathode.

In this case, the electrons flow from zinc electrode to

hydrogen electrode and therefore, the zinc electrode acts
Fig. 11. Measurement of a standard electrode potential as anode and 8.H.E. acts as a cathode. The cell may be
(reduction potential) of zinc by combining with 8.H.E. represented as:
Zn |Zn** (1 M) ||H* (1M) |H, (1 atm), Pt
The cell potential has been measured to be 0.76 V.
Now, e.m.f. of cell,

Eo oy — E°, = E°,
— E*(H*| H,) — E® (Zn?+| Zn)
0.76 = 0—E® (Zn** |Zn)
E? (Zn* |Zn) = — 0.76 V
ELECTROCHEMISTRY 3/31 =

Thus, by combining with S.H.E. reduction potential value of Zn has been

found to be — 0.76 V.
2. Measurement of Electrode Potential of Cu**+ | Cu Electrode
To measure electrode potential of copper-copper ions, a cell
consisting of copper electrode immersedn 1M CuSO, solution Voltmeter
and S.H.E. is set up as shown in Fig. 12.
In this case, the hydrogen has greater tendency to lose
electrons in comparison to copper. Therefore, oxidation occurs
at hydrogen electrode and reduction occurs at copper electrode. Ho gas
Consequently, the hydrogen electrode acts as anode and copper ince
electrode acts as cathode. Thus, the cell may be represented as
Pt , H, (1 atm) | H* (1M) || Cu** (1M) | Cu
The cell potential has been measured to be 0.34 V.
o _ Fe o
E cll ~~ E R i L
= E® (Cu”*| Cu) -E® (Ht | H,)
= = a+ _
0.34 = E® (Cu™ | Cu)—0 Fig. 12. Measurement of standard electrode
orE® (Cu** | Cu) = 0.84 V potential of copper.
Thus, the standard electrode potential of copper is + 0.34 V.
Similarly, the standard reduction potentials of other
metals can be calculated.
Thus, the electrode at which reduction occurs with respect to S.H.E. has
+ve reduction potential while the electrode at which oxidation occurs with
respect to S.H.E. has -ve reduction potential.

SOLVED EXAMPLES

LJ Example 20
Calculate the standard reduction electrode potential of the Ni**|
Ni elec-
trode when the cell potential for the cell Ni | Ni** (1M) || Cu?* (1M) | Cu is
0.59 V (E* Cu**| Cu = 0.84 V).
Solution: The cell is
Ni | Ni?* (1M) ||Cu?* (1M) | Cu
The e.m.f. of the cell
Go
EE? £= i >

= E° (Cu? | Cu)
- E® (Ni? | Ni)
Here, E° = 0.59 V, EY (Cu*| Cu) = 0.34V
0.59 = 0.34-—E® (Ni?* | Ni)
or E©( Ni2* | Ni)= 0.34 — 0.69 = — 0.25 V.

ELECTROCHEMICAL SERIES
The standard reduction potentials or standard electrode potentials of a [Ugts/S\/e}an
large number of electrodes have been measured using standard hydrogen e@ A negative E® means that the
electrode as the reference electrode. These various electrodes can be arranged redox couple is a stronger reducing
in increasing or decreasing order of their reduction potentials. agent than pale couple.
The arrangement of elements in order of increasing electrode A positive value means that the
: ; : i redox couple is a weaker reducing
potential values is called electrochemical series. -
a agent than H*|H, couple.
The electrochemical series, also called activity series, of some typical
electrodes is being given in Table 5.
ane Table 5. Standard reduction electrode potentials at 298 K.
MODERN'S abe + OF CHEMISTRY
-AIl

Electrode Electrode reaction E* (Vv)

(Oxidized form + ne~- —~> Reduced form)

ee ee Strongest oxidizing | F, (g) + 2e- —. 2F™ (aq) Weakest reducing | 2-87

(Co*+ | (92+
agent Co? +2 (o**
agent 1.81

H,O, | H,0 H,O, + 2H* + 2e- 2H,O 1.78

MnO,, Ht | Mn?+ MnO, (s) + 4H* + 2e7 Mn** + 2H,O 1.61
Au®* | Au Au®+ + 3e7 Au (s) 1.650
MnO, | Mn** MnO _ * SH* + Be- Mn** + 4H,0 1.49
Cl, | Cr Cl, (g) + 2e7 2Cl- 1.56
Cr. A | ae Cr,0,* + 4H* + 6e7 2Cr** + 7H,O 1.53
O,,.H* |.H,0 O, + 4H* + 4e7 2H,O 1.23
Br, | Bro Br, (1) + 2e7 2Br- 1.09
NO,,, H* | NO NO, + 4H* + 3e7 NO (g) + 2H,O 0.97
Hg?* | Hg,** 2He** + Qe Hg,**
0.92
C1lO- | Cr ClO” + H,O + 2e- Clr + 20H- 0.89
Hg** | Hg Hg** + 2e7 Hg 0.86
Agt | Ag Agt + e7 Ag 0.80
Hig,** | Hg Hg,2* + e7 2H¢g 0.79
Fe=t | Fe2t Fe** + e Fe*t
0.78
MnO, | MnO, MnO, + & Mn0O,?- 0.56
Ls I, + 2e7 2I- 0.54
Cu* | Cu Cu* + e Cu 0.52
Cu?* | Cu Cu?* + Qe- 0.54
AgCl |Ag AgCl + e~ 0.22
Cu?* | Cu AGENT
OXIDIZING
OF
STRENGTH Cu2t + e AGENT
REDUCING
OF
STRENGTH 0.15
AgBr | Ag AgBr + e 0.10

Fe** | Fe
yest ||8136
Sn** | Sn
Ni** | Ni
Co" | Cc
Cd** | Cd INCREASING
Fe** | Fe
OFarictal [PsOF
Zn** | Zn
Mn | Mn
Als | Al
Mg** | Mg
Ce** | Ce
Nat | Na
Ca** | Ca
Ba** | Ba
Cst | Cs
K+ | K Weakest oxidizing
agent
Lit | Li
ELECTROCHEMISTRY

Applications of the Electrochemical Series

The main applications of the electrochemical series are given below :
1. Relative strengths of oxidising and reducing agents. With the
help of electrochemical series, we can predict the relative oxidising or reducing
strengths of substances. In the electrochemical series, the substances are
arranged in the decreasing order of electrode potential i.e. decreasing tendency
for reduction to occur or power as oxidising agent. Therefore,
® the elements at the top of the table have maximum tendency to get
reduced and consequently, they will act as good oxidising agents. On the
other hand,
® the substances at the bottom of the table have lower electrode potential
values, therefore they have least tendency to get reduced. Consequently,
they may be oxidised and act as good reducing agents.
® Table 4 shows that standard electrode potential of fluorine is the highest
in the table indicating that the fluorine gas (F,) has maximum tendency to
get reduced to fluoride ions (F-) and therefore, fluorine gas is the strongest
oxiding agent and fluoride ion is the weakest reducing agent. On the other
REMEMBER
hand, lithium has the lowest electrode potential in the table indicating that
e The substances which have
lithium has the maximum tendency to get oxidised and hence lithium metal
lower electrode potentials
is the most powerful reducing agent or lithium ion is the weakest oxidising
are stronger reducing agents
agent in aqueous solution.
while those which have higher
2. Calculation of the E.M.F. of the cell. The E.M.F. of the cell which
electrode potentials are stronger
is the difference between the reduction potential of the cathode and anode is
oxidising agents.
determined by the following steps :
Step I.
Write the two half cell reactions in such a way that the reaction taking place
at the left hand electrode is written as an oxidation reaction and that taking
place at the right hand electrode is written as reduction.
Step II.
Multiply one of the equations if necessary by suitable number to equate
the number of electrons in the two equations. However, if may be noted that
electrode potential values, E® are not multiplied.
Step ITI.
The e.im.f. of the cell is) is equal to the difference between the standard
electrode potential of the cathode and the standard electrode potential of the
anode. Thus,
E® = E™ (cathode) — E® (anode)
The electrode potentials of both the electrodes are taken to be reduction
potentials.
Step IV.
If the e.m.f. of the cell is +ve, the reaction is feasible in the given direction.
But if e.m.f. of the cell is —ve, the cell reaction is not feasible in the given
direction. The reaction must be occurring in the reverse direction. Thus, to
get positive value for the e.m.f. of the cell, the electrodes are reversed.

i SOLVED EXAMPLES
LJ Example 21
Write the half cell reaction and the overall cell reaction for the electrochemical
cell :
Zn | Zn?* (1.0 M) || Pb?* (1.0 M) | Pb
Calculate the standard e.m.f. for the cell if standard electrode
potentials (reduction) for Pb**| Pb and Zn**| Zn electrodes are — 0.126 V
and —0.763 V respectively.
aca MODERN'S abe + OF CHEMISTRY

Solution: Zn electrode acts as anode while Pb electrode acts as cathode and,

-AXIl

therefore, oxidation occurs at zinc electrode and reduction occurs at lead electrode. The
half cell reactions are:
Oxidation half reaction : Zus) —— > Zn** (ag) + Qe
Reduction half reaction: Pb**(ag) + 2e— = ——> Phbis)
Overall cell reaction : fnu(s) + Pb*ag)—— Zm*"ag) + Pb(s)
1 -&
K cell — EP. i L
~ 0.126 — (— 0.763)
= 0.637 V.

WATCH OUT ! 3. Predicting feasibility of the reaction. The electrochemical series

eFor cell reaction to be helps in finding out whether a given redox reaction is feasible or not in the
spontaneous, EMF must be given direction from the E° values of the two electrodes. In general, a redox
reaction is feasible only if the species which has higher reduction potential
positive.
is reduced t.e., accepts the electrons and the species which has lower electrode
e Reduction will occur at the
potential ts oxidised 1.e., loses the electrons. Otherwise, a redox reaction is not
electrode having higher reduction
feasible. In other words, the species to release electrons must have lower electrode
potential.
potential as compared to the species which is to accept electrons.
e Oxidation will occur at the
The electrochemical series (Table 4) gives the increasing order of electrode
electrode having lower reduction
potential (reduction) of different electrodes on moving down the table. This
potential (or higher oxidation
means that the species to accept the electrons (getting reduced) must be
potential) lower in the electrochemical series as compared to the other which is to lose
e EMF of cell electrons (getting oxidised).
E* (cathode)—E
°(anode) Let us illustrate this by predicting the feasibility of the reaction :
= E°(R.H.S.) — E*%(L.H.S.) Cu**+(aq) + 2Ag(s) ———> Cu(s) + 2Ag*(aq)
From the electrochemical series (Table 5), E° value of Cu = +0.34 V and
the E° value of Ag = + 0.80 V. Since the electrode potential of Ag is more
than that of Cu, this means that silver has greater tendency to get reduced
in comparison to copper. Thus, the reaction
Agt(ag) +e ——> Ag(s)
occurs more readily than the reaction
Cu**(aqg) + 2e79 = ——> Cu(s)
REMEMBER Similarly, since reduction potential of Cu is less than that of Ag, this means
® In general, metals having negative that Cu will be readily oxidised in comparison to Ag. Thus, the reaction
E~ values can evolve hydrogen Cu(s) ——> Cu“*(aq) + 2e7
from an acid on reacting with dilute occurs more readily than the reaction
acids while those with positive E® Ag(s) ——> Ag*(aq)+e7
values cannot do so. Therefore, silver will be reduced and copper will be oxidised and the above
Metals like Na, K, Zn, Mg, Ni, Al reaction is not feasible. Rather the reverse reaction,
ete. which can liberate H, from Cu(s) + 2Ag+(ag) ———> Cu**(ag) + 2Ag(s) can occur.
an acid are called active metals. Similarly, we can predict that iron will reduce Cu** to Cu, zinc will reduce
Metals like Cu, Hg, Ag etc. which
Pb?* to Pb, zine will also reduce Cu** to Cu, etc. and the following redox
donot liberate H, from an acid are
reactions can occur :
called inactive metals.
Fe + Cu** —> Fe* + Cu
“7n + Pb?t — > “Zn? + Pb
Zn + Cut ——> Zn + Cu
4. To predict whether a metal can liberate hydrogen from acid or
not. The electrochemical series can also be used to predict whether a metal
can liberate hydrogen from the acid or not. Metals like zinc, magnesium and
nickel can liberate hydrogen from the acids like HCl, H,SO,, etc. while metals
like copper and silver cannot do so. In general, only those metals can liberate
hydrogen from the acid which have negative values of reduction potentials 1.e.,
—E° values. Obviously, hydrogen will have greater tendency to get reduced
(accept electrons) and the metal can lose electrons (get oxidised) and hydrogen
gas is liberated. These metals are also called active metals.
M ——> Mi(aq) + e&
(Monovalent)
ELECTROCHEMISTRY

H* (aq) +e ——> H or =H,

Metals like copper and silver have +E“ values i.e., electron accepting
tendencies. Their atoms are not in a position to lose electrons to H* ions of
the acid. Therefore, hydrogen gas is not liberated.
This can also be stated as ifthe standard electrode potential of an electrode
is greater than zero (i.e., +ve), then its reduced form is more stable as compared
to hydrogen gas. On the other hand, if the standard electrode potential is
negative, then hydrogen gas is more stable than the reduced form of the species.

SOLVED EXAMPLES ———

LJ Example 22 (11) half reaction will proceed to the right. We therefore, reverse
lodine (I,) and bromine (Br,) are added to a solution the first reaction and after multiplying by appropriate coefficients
containing todide (I-) and bromide (Br) tons. What add it to reaction (iz)
reaction would occur ifthe concentration of each species (z) Fe) +> Fet++e¢]x65
is 1M ? The electrode potentials for the reactions are: (ii) MnO, + 8H* #5e- ——> Mn +4H,O
(1) I,+2e ——> 27, h°=+0.54V
(11) Br,+2e ——> 2Br-, F®°=+1.08 V 6Fe** + MnO, + 8H* ——-> 6Fe*+ + Mn* + 4H,O
Solution : Since the reduction potential of Br, is more than The above reaction will be spontaneous.
that of I,, it means that bromine can readily be reduced and it Had e E® (cathode) —E® (anode)
will oxidise I" to I. Therefore, the following reaction will occur: = 149-0.77=+ 0.72 V.

Br, + 2I- —— > 2Br+lI, L}) Example 24

Since for the feasibility of the reaction, the E.M.F. should be In asimple electrochemical cell, whichisin the standard
+ve, therefore, to get +ve valuefor the overall cellreaction, subtract state, the half cell reactions with their appropriate
the equation representing lower value of E~ from the equation reduction potentials are :
representing the higher value of E_ . Thus, subtract Pb**(aq) + 2e- ——> Pb(s); (F°=-0.13 V)
Eq. (2) from Eq. (zz). Ag*(aq) +e ——~ Ag(s); (E°=+0.80V)
Br, + 2I- ——> 2Br-+lI, (a) What ts the cell reaction for the cell ?
E* =1.08 — 0.54 = 0.54 V. (b) Calculate the e.m.f. of the cell.
LJ Example 238 Solution : The reaction potentials of the two half cell
What will be the spontaneous reaction when the following reactions are :
half reactions are combined ? Pb?*(aq) + 2e09 ——> Pb(s); (E°% =-0.13V)
(1) ie ee” ———> fet. Agt(aq)+e ——> Ag(s); (E% =+0.80V)
Ee =40.77V The reduction potential of Agt | Ag electrode is more
(it) MnO, + 8H* + 5e——+ Mn** + 4H,0, than that of Pb**| Pb. Therefore, reduction will occur at silver
electrode and oxidation will occur at lead electrode and the cell
(BE? =+1.49 V)
reaction will be
What is the value of E° _,,, ?
2Ag*(aqg) + Pb(s) ———> 2Ag(s) + Pb**(ag)
Solution: The reduction potential of (iz) half reaction The cell may be represented as :
is more than that of (z) half reaction. It means that reduction
will occur in (71) half cell and oxidation will occur in (z) half
Pb | Pb?+|| Agt | Agand
EP on — E® (cathode) — E* (anode)
cell. Therefore, (i) half cell reaction will proceed to the left, and
= 0.80 —(— 0.13) = 0.98 V.

=prat Lower

25. An iron wire is immersed in a solution containing ZnSO, and NiSO,. When the
concentration of each salt is 1M, predict giving reasons which of the following
reactions is likely to proceed ?
(c) Iron reduces Zn** ions (ii) Iron reduces Ni*+ ions
Given E*® (Zn?*/Zn) =— 0.76 V, E® (Fe?*/Fe) = — 0.44V and E® (Ni?*/Ni) = — 0.25 V.
26. Cana solution of 1 M CuSO, be stored in a vessel made of nickel metal ? Given
E® (Ni? |Ni) = — 0.25 V and E® (Cu2* |Cu) = 0.34 V.
ane 27. What is the standard e.m.f.
MODERN'S abe + OF CHEMISTRY

of the cell containing Sn**|Sn

-AXIl

and Br,|Br-
electrodes ?
(E* (Sn?* |Sn) = — 0.14 V, E*(Br, |Br-) = 1.08 V)
28. Calculate the standard reduction potential of Ag* |Ag electrode when the cell
potential for the cell,
Cu(s) |Cu?* (1M) ||Agt (1M) Ag is 0.46 V. Given that Cu?* |Cu = 0.34 V
29. Calculate the standard reduction potentials of galvanic cells in which reactions
are as follows :
(1) 2Cr(s) + 3Cd2+ —__5 2C r+ + 3Cd (s)
(it) Fe**(aq) + Ag*(ag) ———> Fe** (aq) + Ag(s)
Given that E® (Cr**/Cr) = — 0.74 V, E® (Cd?*/Cd) = — 0.40V,
Answers to Practice Problems = E® (Fe?+/Fe**) = 0.77 V, E® (Agt/Ag) = 0.80 V.
30. Can chlorine gas be stored in a copper cylinder ? Given E® (Cu?*/Cu) = 0.34 V
Zo. Iron reduces Ni** ions. and E* (CL/CI) = 1.36 V.
26. No. 31. Why does blue colour of copper sulphate get discharged when zinc rod is dipped
Qi. 1.22 V. in it ?
28. 0.80 V. Given E*(Cu?*/Cu) = 0.34 V, E@ (Zn?* |Zn) = — 0.76 V.
29, (z) O.34V, (iz) 0.08V. 32. A copper wire is dipped in silver nitrate solution in beaker A and a silver wire is
oO. No. dipped in a solution of copper sulphate kept in beaker B. Ifthe standard electrode
potential for
cate In beaker A, Ag* will be reduced.
Cu** + 2e- ———> Cuis + 0.34 and for Ag* + e ——> Agis 0.80 V
Hints & Solutions on page 74 Predict in which beaker the ions present will get reduced ?

DEPENDENCE OF ELECTRODE AND CELL POTENTIALS ON

CONCENTRATION : NERNST EQUATION
The standard electrode potentials given in Table 4 are measured in their
standard states when the concentration of the electrolyte solutions are fixed
as 1M and temperature is 298 K. However, in actual practice electrochemical
cells do not have always fixed concentration of the electrolyte solutions. The
electrode potentials depend on the concentration of the electrolyte solutions.
Nernst gave a relationship between electrode potentials and the concentration
of electrolyte solutions known as Nernst equation. For a general electrode
reaction,
M"*(aqg) +ne~ —— M(s)
the Nernst equation is

E (M"*| M) = E°(M"*| M)— i mal

nF [M"'(aq)]

or E(M™*|M) = E° (| M) — 2:308RT) LM(s)1

Cin x = 2.303 log x)
where E (M"* |M) = Electrode potential.
E~ (M** |M) = Standard electrode potential [for a 1 M solution of metal
ions, M"* (aq)I.
R = Gas constant, T = Temperature, F = Faraday of electricity
n = Number of electrons gained during the electrode reaction.
[M"*(aq)] = Molar concentration of ions, [M] = Molar concentration of metal
Substituting the values of R (8.314 JK" mol) , T (298 K) and F (96500
coulombs), the Nernst equation at 25°C becomes

E(M**|M) = E® (M|M) — 2:308%8.314x298 ),_ IAMS)

n x 96500 [M"*(ag)]

0.059 1
or E(M™*|M)=
i+ =
E~ - (M™*|M)
f+
- —)_
—— = Ae
8inpecag]
ELECTROCHEMISTRY 3/37 —

It may be noted that concentration of the solid phase, [M(s)] is taken

to be unity.
The above equation may also be written as:

E(M**|M) = E® a7) — 2:059 log i

[M"*(aq)]
iL

For simplicity, we may write this equation as :

0.059 |
Se 1
at 25°C.
~ [M""(aq)]

SOLVED EXAMPLES ss
Example 25 p(CL,) =2.6 atm, [CI] = 0.01 M (same as the concentration of
Zine rod ts dipped in 0.1M solution of ZnSO, . The salt HCl)
1s 95% dissociated at this dilution at 298 K. Calculate the E~ (Cl, |2Clh) 21.36 V
electrode potential given that E* (Zn?* |Zn) = — 0.76 V. (0.059) P (0.01)
E(CL, |2CI) = 1.36 —
(A.P.S.B. 2009) 2 (2.5)
Solution : The electrode reaction is : = 1.56 + 0.0296 x 4.398

Zn2++2e0° = SZ ns) = 1.36+0.135 = 1.49 V.

LJ. Example 28
According to Nernst equation, at 298 K
(a.) Calculate the electrode potential of a silver electrode
0.059
E(Zn?* | Zn) = E°(Zn® | Zn)- —— [Zn | dipped in a 0.1M solution of silver nitrate at 298 K
log [Zn2*(aq)]
assuming AgNO, to be completely dissociated. The
E*(Zn?* | Zn) = — 0.76 V, [Zn] = 1, standard electrode potential of Ag* |Ag is 0.80 V at
[Zn2*(ag)] = 0.1 x 95/100 = 0.095 M 298 K.
(6) At what concentration of silver tons will this elec-
E (Zn? | Zn) =~ 0.76 -—2™
n
log 0.095
—— trode have a potential of 0 volt ?
Solution : (a) The reduction electrode reaction is :
= —0.76 — 0.03 =- 0.79V.
Example 26 Agt(aq)+e [— Ag(s)
If E° for copper electrode is + 0.84 V, how will you 2 i (0.059) [Ag]
E(Ag*
| Ag) = E (Ag* | Ag)- — 8 Ag]
calculate e.m.f. value when the solution in contact with
it is O.1 M in copper tons? How does e.m.f. for copper [Ag*] = 0.1M, [Ag] = 1, E~ (Ag* |Ag) = 0.80 V
electrode change when concentration of Cu** ion in the (0.059) 1
solution is decreased ? (A.LS.B. 2000) EK (Agt
| Ag) = 0.80— - 8 OD
Solution : EMF of the cell can be calculated by using Nernst = 0.80 — 0.059 = 0.741 V.
equation as
(6) For the reduction electrode reaction of silver,
Cu** +2e° — _4 Cu

H=_ EK peo
0.059
Aosy
9 log FF
1
(Gu2*] E (Agt |Ag) = E° (Ag* |Ag) — >? log
When [Cu2*] = 0.1 M E (Ag* | Ag) = 0, E~ (Agt | Ag) = 0.80,
E-f.34~ CePA og 1
2 (0.1) [Ag]
i 0 = 0.80 — 0.059 log [Ag*]
= 0.94 — 0-059 x 1=0.54—- 0.0296
or 0.059 log [Ag*] = — 0.80
= 031V. —0.80
Example 27 or log [Ag*] = 0.059= — 18-559
Calculate the reduction potential of the following elec-
[Agt] = 2.76 x 10-4 M.
trode at 298 K:
Pt,Cl,(2.5atm)|HCI (0.01M); E® Cl, |2 Cl- = 1.36 V. LJ Example 29.
Solution : The electrode reaction is: Calculate the potential for half-cell containing 0.10 M
CL(g) + 2e— —— 2CI (aq) K,Cr,O,(aq), 0.20 M Cr**(aq) and 1.0 x 10+ M H* (aq)
The half-cell reaction ts :
E (Cl, |2Ch) = E~ (Cl, | 2ch) - (0.059)
2
lo
[Cl-F
8D) Cr, Oz” (aq) + 14 H* (aq) + Ge: —> 2Cr**
(aq) + 7H,0 )
a 3/38 MODERN’S abe + OF CHEMISTRY-XII
and the standard electrode potential ts given as | — 0.0591 (0.20)?
h°=71.38V. (A.LS.B. 2011) - cell = 1:0 108 (0.10104)

Solution:
olution E_,ell = Et,-
cell
0.0591 [Cr+ ?
og £ ——_,—___
[Cr,02- Tithate = 1.33— 0.0591
VV!G log 0.4 x 10 56

0.0591 |
0 = 1.83 V, [Cr] =0.20M ie ae
[Cr,02-] = 0.1M, [Ht] =1.0x 104M,n=6 = 1.33 — 0.65 = 0.78 V.

Applications of Nernst Equation

1. Calculation of cell potential using Nernst equation. Let us illustrate
this by considering a Daniell cell in which the concentration of the solution
may not be 1M. The cell is:
Zn (s) |Zn2* (ag) || Cu2+(aq) |Cu
The e.m.f. of the cell is:
Ey = & (cathode) — E (anode)
= EF (Cu |Cu) — E (Zn?* |Zn) weak)
The electrode reactions are:
7u(s) —-+ > “En*(gq) + 2e-
Cu** (ag) + 2e—- =——> Cu(s)
The electrochemical cell reaction is
Zn(s) + Cu2*(ag) ——~+ Zn**(aq) + Cu(s)
The electrode potential for the two electrodes can be calculated by using
Nernst equation as :
Electrode potential for copper electrode,
E> aia /, 2.303 RT jee [Cu]
Cut | Cie | Cutt |Cu) +
It must be remembered that ms ps nl [Cu**(aq)]
while writing the Nernst equation Similarly, electrode potential for zinc electrode,
for fe overall cell reaction, the log A Le. _ 2.303RT [Zn]
term is the same as the expression (Zn2+ |Zn) — *4(Zn2+ |Zn) | a og [zZn2" (aq)
for the equilibrium constant for the 7 mE
reaction. However, some books use Substituting these values in Kq. (2)
the expression in the reverse form
as the expression for the equilibrium Kit = eae Ca) ean 08 ei
constant but, sign afterE°1s changed. | Cu" (aq)
The two relations are same. Ee 2.303 RT [Zn |
7 Big. 9m +98 teas...
(Zn*" |Zn) 2F [Zn**(aq)|
gE? — 2-303RT [CrP
= LOE _po 2.303RT. _[Cul[Zn*(aq)]
nk [AP [BP or Fee = EE Cu2+| cay ~ EF =a gn? |zn) — * u A aie!
nF’ [Cu*(ag) [Zn]
E- EV 4.
2.303RT, lor Zoe
[AFBI Now EY oy2+ | Cu) ~ EY n+ | Zn) = Ee oy and the concentration of solids is
+r SiGr Dr taken as unity so that [Zn] = 1, [Cu] = 1.
Similarly, for the electrode reaction:
Me + neo
ON
M L By = B®, - 2808R7
2F
,,(Zn** (ag)
[Cu™ (aq)]
2+

The Nernst equation is

0.059 [Zn**(aq)]
ie E® a =e
i log i
1 ;
or E_.,=cell E°_,, cell -————log
9
—,——— at 298K
ecu (aq)!
nk = [ m+

303 RT logiM"* J
(. 2:303RT _ 9.059 at 298 K)
Lan a
nF In the Daniell cell, the valencies of zinc and copper are the same i.e.,
But in the present text, we shall n = 2. Let us consider an example, in which the valencies of the two metals
use the first form, which is same as used in the two half cells are not same. Consider the cell.
equilibrium expression. Cu |Cu** (aq) ||Ag* (ag) |Ag
ELECTROCHEMISTRY

The cell reaction is:

Cu(s) + 2Ag*(aq) ———> Cu** (aq) + 2Ag (s) TR U Curious... ®
|
The EMF of the cell,
O Will E° value change when
E11 = & (cathode) — E (anode) wwe)
the coefficients in chemical
During the reaction, two electrons are released by one copper atom but one equation change ?
electron is accepted by Ag* according to the reaction, » E° values donot depend on the
Cu (s) ———> Cu** (aq) + 2e~ (oxidation half cell) coefficients in the chemical
Ag* (aq)+e° —— Ag(s) (reduction half cell) equation i.e. when you double or
To balance the loss and gain of electrons, the reduction half cell is multiplied triple the coefficients, E° values
by 2 so that the net reactions are : donot change.
Cu(s) ——>_-Cu** (aq) + 22" For example :
2Ag* (aq) + 2e~§ ——> 2Ag(s) ins ae —_> 7m: E° =-— 0.76V
The electrode potentials of two electrodes may be written according to 97 F + 4e-—__> 27n: E° =—0.76V
Nernst equation as
San” +6e —+3Zn: E°=—0.76V
Electrode potential for copper electrode,
In a half reaction, if the coef-
a _ 2.303RT, [Cul ficients change, the number of
(Cu2+ |Cu) ~ (Cu? |Cu) — nF : [Cu* (ag)]
electrons, n will change to cancel
Electrode potential for silver electrod e, the effect of the change in the

_ Te 2.303 RTEg ees

ee [Agl’ coefficient.
Fiagt
ag = EF agtiag~ op 8 [Ag (aq)
lt must be remembered that E° (Ag* |Ag) remains unchanged.
Substituting the values in Eq. (7)

E = Hi
2.303 RT [Ag]?
cell + Semmens rama
(Ag™ | Ag) PA ° [Ag™ (aq)I

7 2?303 RT [Cu]
SBroxticw or 8 ae"
_ 7 2.303RT, [AgP[Cu**(aq)]
Or Bean = TE (ag
age cuecw!— Top 8 FAs (aq) FiCul
Oy) Liquid Junction Potential. In
Now E®(a.+)ag)~ EB (cu2+|
Cu)= E~ coy and [Cu] =), [Ag] = 1 a concentration cell when the two
electrolytic solutions are directly
2.303RT ips [Cu (aq)] in contact, ions move across the
Koei = EB oi QF [Ag* (aq) junction with different speeds. As a
result, a potential difference is set up
At 298 K, the relation becomes at the liquid junction and it is called
_ 0.059, [CuX (ag) liquid junction potential (LJP). The
e.m.f. of the cell will depend upon
Koei = E on
2 *TAg*(aq)P the speeds of the ions. Such cells
In general, for an electrochemical cell reaction : are also called concentration cells
with transference. The e.m.f. of
aA+bB —“—> cC+dD the cell will be equal to E__,, + Ki,
The Nernst equation may be written as: where E__,, is the potential of the
cell that would be observed in the
absence of junction potential and
Ki is the junction potential. It can
be calculated as :
E - EY
2.303RT,
—_ ——— log ———
[Cripr K, = H-E.y
This type of junction generally
At 298 K, the equation becomes applied in galvanic cells is the salt
bridge which contains salts like
0.059 og CI [Dr KCl, in which the mobility of the
Foci = EF” oot 7 ——
[AF [BP ions is almost equal. Hence K, is
taken as zero.
The value of a, b, c, d andn are obtained from the balanced cell reactions.
a MODERN'S abe + OF CHEMISTRY
-AXIl

Concentration cells
WD) Competition Plus A cell in which both the electrodes are of the same type but the solutions
The solubility product of sparingly of electrolyte in which they dip have different concentrations is called
soluble salts can be determined concentration cell. For example, consider a copper ion concentration cell
from e.m.f. data. For detail, refer in which copper electrodes are dipped in two different concentrations C,
Competition File (Page 98).
and C,,.
Cu|CuSO,(aq) (C,) || CuSO,(aq) (C,) |Cu
In this case, the standard potential of the two electrodes will cancel
and the cell potential is given as:
RT , Gp
Bon = op oe

or Ken 0.059
7 16 oo
C, at tbC
Obviously for EMF to be positive
Co >G
so that the reaction proceeds in the direction indicated. In such a cell,
oxidation occurs at the electrode with lower concentration. Hence,
it acts as anode (—ve pole). The reduction occurs at the electrode with
higher concentration and therefore, it acts as eathode (+ve pole)
This type of cell is shown in Fig. 18.

Current
——__—

Porous
barrier

Fig. 13. A copper ion concentration cell.

For example, consider the following concentration cell:

Zn |ZnSO, (0.01 M) || ZnSO, (0.1 M) | Zn

The e.m.f. of the cell will be
0.059. CG
E = log —2
n . C,

0.059. 0.10
E — ——" log —— — 0.0205V
2 = 001

Some Examples of Nernst Equation for Cells

1. Al] Al**(aq) ||Nit |Ni

The cell reaction is:

2 Al (s) + 3Ni2* (ag) —“—> 3 Ni(s) + 2Al3+ (aq)

ELECTROCHEMISTRY

Here n = 6. The Nernst equation is :

0.059 Al** : FORMULAE AND UNITS

Koen = EB” colt — fo INizt cogll
(aq)e at 298 K
6 (a @F For the cell reaction :
2. Mg |Mg** (aq) ||Ag* (aq) |Ag ae
a aA+6B ——> cC+dD
The cell reaction 1s :
Nernst equation is
Mg(s) + 2 Ag* (ag) ———> Meg** (aq) + 2 Ag (s)
Here n = 2. The Nernst equation is : Ti er lel [DI
.. ata “TAF BP
E_, = EO —20m jog Me I ot 208 K
2 [Ag* (aq)P = Ke, 9.059), [CIDP
8. Zn |Zn** (aq) || H* (aq) |Ho. Ft oa n [AF [BP

The cell reaction is : at 298 K.

Zn (s) + 2H*(aq) > Zn2+ (ag) + H.(g) For pure solids, pure liquids
and gases at 1 atm pressure, molar
Here n = 2. The Nernst equation is : concentration is taken as 1.
0.059 [Zn* (aq) > While applying Nernst equation,
Koen = EY on ~ 9 og acca at 298 K. electrode potential is always
taken as reduction potential.

SOLVED EXAMPLES
lL} Example 30
Solution : The electrode reactions and cell reaction are:
Calculate the standard electrode potential of Ni** |Ni
Cu (s) —— >» Cu* (aq) + 2e7
electrode if the cell potential of the cell :
2Ag* (aq) + 2e- ——+> 2Agis)
Ni |Ni** (0.01M) || Cu?* (0.1 M) |Cu is 0.59 V Cu(s) + 2Ag* (aq) ——+ Cu** (aq) + 2Ag (s)
Given: E™ 02+ Cu = 0.34 V. Nernst equation is :
(Mizoram S.B. 2013, Nagaland S.B. 2015)
Cu**
Solution : Ni |Ni** (0.01M) ||Cu?* (0.1 M)|] Cu
Bon = Eo on- — log | |
The cell reaction for the cell is:
& &
|Ag* |
Ni(s) + Cu**(ag) ———> Cu(s) + Ni?*(aq) EK = E%(Ag*|Ag) E (Cu2+ | Cu)
EE Eo 0.059 lo D+ (aq)|
nA
= 0.80 — 0.34 = 0.46 V
[Cu™ (aq)]
0.69= Ee cell — 9.009
9
1,>_ (Here
n = 2) E = 0.46 — —
0.059 (0.130)
log ———__
= 2” (.0x104)
0.569= EY, - 0.059
ee =~
cll 10 = 0.46 -— 0.069 log 1.30 x 10° = 0.46 — 0.21 = 0.25 V.
2
0.69= E+ 0.0296
E* _.,= 0.69 — 0.0295 = 0.5605 WATCH OUT !
2 2 r=.
Now, EY n= E (Cu2+ |Cu) ~ 1D (Ni2+ |Ni) While balancing oxidation and reduction reaction, we
0.5605 = 0.34 —E*(Ni?* |Ni) multiply by certain number to cancel the electrons in the
overall reaction. Butit must be remembered that electrode
E (Ni? |Ni) = 0.34 = 0.5605 = — 0.2205 V. potential is not to be multiplied.
lL] Example 31
LJ Example 382.
Write the Nernst equation and calculate the e.m.f. of
the following cell at 298 K: Write Nernst equation and calculate e.m.f. of the
following cells at 298 K:
Cu(s) |Cu** (0.130 M) ||Ag* (1.0 x 10 M)) | Ag (s)
Given : E* (cu2+ |cu) = + 0.34V and (i) Mg (s)|Mg** (0.001 M) ||Cu** (0.0001 M)| Cu (s)
Eevagt | Ag) —+0.80V Given: Ege Mg=~2-37V, E* 6,24) Cy = 0.84V
(A.LS.B. 2004, Pb. S.B. 2010, 2018, 2015, (Pb.S.B. 2010, 2014, Uttarakhand S.B. 2014,
Mizoram S.B. 2015, Hr. S.B. 2017) Ar. S.B. 2018, 2017, Karnataka S.B. 2018)
lau MODERN'S abe + OF CHEMISTRY
-AXIl

(ii) Fe (s)|Fe** (0.001 M)||H* (1M)H, (1 atm), Pt E* 4 = E°(H* | H,)- E® (Sn** | Sn)
Given 2 E* (92+ \ ne) =—-0.44V E°(H* | H,)= 0.0 V, E*(Sn* | Sn) =- 0.14V
(DSB. 2073, ArS.B. 2073, Pb.S.B. 2013, 2015) E® 4, = 0.00 —(— 0.14) = 0.14 V
(iii) Sn (s)|Sn** (0.050
M) || H* (0.020 M)|H, (1 atm) |Pt [H*] = 0.020 M, [Sn?*] = 0.060 M
Given 2 eee =—0,.14V 0.059 , _ (0.050)
(Ar S.B. 2018, Pb.S.B. 2015, ALS.B. 2018) B= 0.14— "9 °° (0.020
Solution : (1) The electrode reactions and cell reactions are: = 0.14 - 0.06 = 0.08 V.
Mg (s) —> Mg?*(aq) + 2e- (At anode) LJ Example 33
Cu** (ag) + 2e° ——> Cuts) (At cathode) Represent the cellin which the following reaction takes
Mg(s) + Cu** (ag) — Meg"* (aq) + Cu(s) (Overall cell reaction) place:
Since the reaction involves 2 moles of electrons and therefore, Mg (s) + 2Ag*(0.0001M) ——> Mg**(0.130M) + 2Ag(s)
n = 2 and the Nernst equation for the cell at 298 Kis:
Calculate its E if E~ is 3.17 V
— 0.059 | [Me**(aq)]
2 = icu*agl 7”
as
or Beet = Econ W.C.E.R.T)\(P0.S.B. 2011, H.P.S.B. 2015, Assam S.B. 2018)
Solution: The cell may be represented as
E® = E® (Cu |Cu) — E® (Mg?* |Mg)
Mg |Mg** (0.130M) ||Ag* (0.0001 M) |Ag
E°(Cu2* |Cu) = 0.34 V, E® (Mg?* |Mg) = — 2.37 V The cell reaction for the cell is
E*? = 4 = 0.34 —(-2.37) = 2.71
Me(s) + 2Ag*(ag) —> Me**(aqg) + 2Ag(s)
Substituting the values in Eq. (z)
The Nernst equation for the cell is
0.059. J 0.001 ‘Mo 2+ |
E.2,= Zii— ———_ m _ po_ 0.059 ioe .L
cell 2 © 0.0001
2 [Ag™ ]
E cei = 2.71 — 0.0295 = 2.6805 V.

1,
0.059 (0.180)
(ii) Fe(s) |Fe?*(0.001 M) ||Ht (1M) |H, (1 atm) |Pt = 3.17—- —
The electrode reactions and overall cell reactions are:
2” (9.0001)
3.17-—0.21 —2.96 V.
Fe(s) ———> Fe?*(aq) + 2e7 (At anode)
LJ Example 34
2H*(aq) + 2e°- ———> H,(g) (At cathode)
Calculate the e.m.f. of the following cell:
Cd |Cd** (0.01M) ||H*(0.02M) |Pt, H,(0.8 atm)
Since the reaction involves 2 moles of electrons, therefore, Given : K°(Cd?* |Cd) =— 0.40 V
n = 2 and the Nernst equation at 298 K is:
Solution : The cell reaction is :
0.059 [Fe?*]
Keel = EY en — log Cd(s) + 2H*(aq) ——> Cd**(aq) + H,)
2 (Ht?

According to Nernst equation,

E*4 = E°(H* | H,)- E?(Fe** | Fe) ait.0.059 Jog Ca"
2+
x pHs) '
E*(H* | H,) = 0.0 V, E*(Fe?* | Fe)=- 0.44 V [H*P
E* 4 = 0.0 -(— 0.44) = 0.44 V
E E"(H*| —H,)-E%(Cd®*| Ca)
0.0 ).001
Ect — 0.44 — ON? log die
= 0-—(— 0.40) =0.40 V
2 (1)
0.44 + 0.0885 = 0.5285 V. 0.059, (0.01)x0.8
3 | (Ape oe ua =
(iit) The cellis: 2 (0.02)
Sn(s) | Sn?*(0.050M) ||H*(0.020M) | H,(1 atm) | Pt
0.059
The electrode reactions and cell reactions are : = 0.40- * 1.3010
Sn(s) ———> Sn**(ag) + 2e— (At anode)
2H"(aq) + 2e~ ———> H,(g) (At cathode) = 0.40 —0.04
0.36 V
Sn (s) + 2H*(aq) ———> Sn**(aq) + H,(g) (Overall reaction)
The reaction involves 2 moles of electrons, therefore,
LJ Example 35.
n = 2 and the Nernst equation is : Calculate E°_,,, for the following reaction at 298K:
2Cr(s) + 8Fe* (0.01M) —+ 2Cr** (0.01M) + 8Fe(s)
0.059 [Sn?*]
i= 1 & = > Say
ee (Given : E,,,, = 0.261V) (A.I.S.B. 2016)
ELECTROCHEMISTRY

Solution : 2Cr (s) + 3Fe?*(ag) — 2Cr**(aq) + 3Fe(s) Example 37

uo]
, 0.059, [Cr**(aq)I? A copper-silver cell is set up. The copper ton concentra-
K ce| E ceu¢.
6 TBa2t(aa\e
[Fe*"(aq)| tion ts O.10 M. The concentration of silver ion is not
known. The cell potential when measured was 0.422 V.
E41 = 0.261V
2
Determine the concentration of silver tons in the cell.
0.261 = E°_,- 0.059 ie a (Given E™ ,.+,,, /Ag = + 0.80 V, E* .,2+;¢, = + 0.84V)
6 (0.01)
\2 (D.S.B. 2010)
Es, _ 029614 eee pg Solution: The cell may be represented as :
6 (0.01) Cu(s) | Cu?* (0.10 M) || Ag* (aq) | Ag (s)
= 0.261+ i log 10 The cell reaction is
Cu(s) + 2Ag*(ag) —> Cu**(ag) + 2Ag(s)
0.059
= 0.261 + —
6
x (2) E*(Cu?*| Cu) = + 0.34 V, E*(Ag* |Ag) = + 0.80 V
E* of = E*(Ag* |Ag) — E@(Cu?*| Cu)
= ().261 + 0.0197
— 0.80 — 0.34 = 0.46 V
= 0.2807V. [Cu2*] = 0.10 M, [Ag*] =?
2. Caleulation of Concentration of a Solution of BE, —0.059 j,5 [Cul2+
Half Cell 2 [Ag*F
When in a galvanic cell, all the concentrations except
0.422 = 4G— > tog a
one are known, then the unknown concentration can be 2 [Ag™ |
calculated by measuring the cell potential and using 0.059 |, 30-10
9 [Agt}? = 0.46
— 0.422
Nernst equation. This can be illustrated by the following
example: 0.059 og 0.10
9 [Ag* = 0.038
Lj Example 36.
The EMFof the cell, Zn |Zn** (0.1M) || Cd?* (M,) | Cd 0.10 2 x 0.038
log [Ag* ? = 9059. = 1.2881
has been found to be 0.8805 V at 298 K.
Calculate the value of M, LE (zn2+ | Zn) = — 0-76V, = #16
E og2+ | Ca) =— 0.40V). [Ag* |
Solution : The cell 1s: Ae = =p x0
19.42
Zn | Zn?* (0.1M) ||Cd?* (M,) | Cd [Ag*] = 0.0717M
The cell reaction is : Lj Example 38
Zn(s) + Cd**(aq) = Zn**(aq) + Cd(s) A cell contains two hydrogen electrodes. The
negative electrode is in contact with a solution of
0.059 | [Zn**] 10° M hydrogen ions. The e.m.f. of the cell is 0.118 V
E.. = E* - at 298 K
2 °° [ca] at 25°C. Calculate the concentration of hydrogen ions
at the positive electrode.
EY oot = EF oat | Cd} > Ey 2+ | Zn)
Solution: The cell may be written as:
= — 0.40 —-(— 0.76) = 0.36V
H, | H*(10-° M) ||H*(M,) |H,
E = 0.3306V, [Zn**(aqg)] = 0.1 M Applying Nernst equation,
O1 Hy

0.3506 = 0.56— ie log W E = Fe 0.059 log Jemode

1
1 Ht
cathode
— 0.0295 = 0.0296 log 10 M, -_#

or 0.0296 log 10 M, = — 0.0295 pte .0. 02089 (10°)

; = 0- —— lg ,,
0.0295 + 0.0295 log M, = — 0.0296 i ” M,
0.0295 log M, = — 0.0295 — 0.0295
og 10 _ _ O18
=, ——-0.059 ~
— 0.059
6
log M, =
0.059 10” = 102
0.0295 — M,

M, = 0.01 M. or M. = 10¢?*M
a MODERN'S abe + OF CHEMISTRY
-AIl

= Pra ea
oo. Calculate** emf of the following cell at 298 K:
Mg(s) |Mg** (0.1M) || Cu?* (0.01M) |Cu(s). Given E°__,, = +2.71 V, F = 96500 C mol.
(D.S.B. 2014)
34, One half cell in a voltaic cell is constructed from a silver wire dipped in silver
nitrate solution of unknown concentration. Its other half cell consists of a zine
electrode dipping in 1.0 M solution of Zn(NO,),. A voltage of 1.48 V is measured
for this cell. Use this information to calculate the concentration of silver nitrate
solution used.
[E° ,.2+ 17,= — 0.76 V, Ea +14, 54 O180VI (D.S.B. 2009)
3D. Calculate the potential of the following cell rection at 298 K :
9§n**(1.50 M) + Zn (s) ——> Sn** (0.6 M) + Zn7*(2.0 M)
The standard potential of the cell is 0.89 V. Will the potential of the cell will
increase or decrease if the concentration of Sn** is increased in the cell ?
36. Consider a cell composed of the following half cells:
(i) Mg (s) |Mg?* (aq) and (iz) Ag(s) | Ag* (aq)
The e.m.f. of the cell is 2.96 V at [Mg?*] = 0.130 M and [Ag*] = 1.0 x 10* M.
Calculate the standard e.m-f. of the cell (R = 8.3 JK“! mol, F = 96500 C).
of”. Calculate the e.m.f. of the cell at 25°C
Zn | Zn?*(0.01 M) ||Fe?* (0.005 M) | Fe
E* (Zn?* |Zn) =-0.763V and E® (Fe?* | Fe) =-0.44V
(Pb.S.B. 2005, 2010, 2011)
38. Calculate the e.m.f. of the following cell at 298 K,
Fe | Fe** (0.1M) ||Ag* (0.1 M) | Ag
— Answers to Practice Problems = Given : Ef wc ire) = —0.44V
ooe 2.6806 V. and i At paf = 0.80V
a4, 0.044 M. (R = 8.31 JK mol, F = 96500 C mol!)
ooe 0.896 V. (Pb. S.B. 2005, 2011, Mizoram S.B. 2014)
36. oer ¥ 359. Caleulate e.m.f. of the following cell at 298K
ov. 0.314 V.
2Cr(s) + 3Fe** (0.1M) ——-> 2Cr**(0.01M) + 3F e(s)
Given: E(Cr** | Cr) =— 0.74 V, E°(Fe** | Fe) =- 0.44V (D.S.B. 2016)
38. 1.2106 V.
(z) Caleulate the electrode potential at a copper electrode dippedina0.1M solution
og. 0.31 V. of copper sulphate at 298 K, assuming CuSO, to be completely ionised. The
40. (i) 0.3106 V_ (ii) 2.98 x 10-*. standard electrode potential of Cu**|Cu is 0.34 V at 298 K.
(11) At what concentration of copper ions will this electrode have a potential of
Hints & Solutions on page 74
zero volt ?

Advanced p
api»
Accelerate Your Potential
PROBLEM S (for JEE Advance)
= ery Ms 4 1 For the cell reaction,
[Problem
em 9
{> e standard reduction potential for Cu2* + 267 . C
Cu*' | Cu is + 0.34V. Calculate the reduction potential at
ar 0.059 : it
pH = 14 for the above couple. ae of Cu(OH), is 1.0 x 10°",

ForpH=14,alii08°)—10
E = E°-—— log er Te

pha K 10°4
=
<4
[ Ht] 107
— 0.34-
2
. log
1.0x 10-9
4 Wu ao

oh <== 20 = 0.34- — x19 =—0.22V

Ke = in| bal? Problem 64) Two students use same stock solution of
1.0x 10-19 = [Cu2*] (1)? ZnSO, and a solution of CuSO,. The e.m.f. of one cell is
[Cu2*] = 1.0x 10-19 0.03V higher than the other. The concentration of CuSO,
ELECTROCHEMISTRY
us)
in the cell with higher e.m.f. value is 0.5 M. Find out the or —Alog|H*] = 6.78+5=11.78
concentration of CuSO, in the other cell. (2.303 RT/F =
0.06) or —log [H*] = = =2.95

The two cells may be represented as: or pH = 2.95 (— log [H*] = pH)
Zn |Zn?* (cone = C) ||Cu2* (C =?)|Cu EMF =E, (say)
(8 The K,, for AgCl at 298 K is 1.0 x 107%
Zn |Zn** (cone = C) ||Cu?* (C = 0.65 M)| Cu EMF = E, (say) Calculate the electrode potential for Agt |Ag electrode
fk a immersed in 1.0 M KCI solution. Given: E* = 0.80 V.
Ag’ |Ag
The cell reaction is
AgCl(s) = Ag* (ag) + CT (aq)
Zn(s) + Cu?*(aq) —— Zn?*(aq) + Cu(s)
K,, = [Ag*lICh, [Cr]=1.0M
ao 2.303RT_ [Zn**]
Ect =i cell oF Og [Cu2*]
Koel O10” =1x10M
or [Ag*] =
_pe 0.06 ine [Zn** 2+
| [cr] 1.0
cell 9 (Cu?*]
Now Agt(ag) + e— ——> Agis)
0.06 C
the = EF a oe log [Cu2*] According to Nernst equation,

B= Ee_ 9:959 10, L

“: 0.06 C

wn fal) (3)
E, — E | oe a De ate
1 [Ag™ ]
0.059 1
0.06 oF C_ = 0.80- log |5-10

0.5 0.80 —0.059 x 10 =0.80—0.59=0.21 V

0.03 = 0.038 log iCu2*]
u Problem} For the electrochemical cell

or lo ay Mg(s) | Mg** (aq, 1 M) || Cu** (ag, 1M) | Cu(s)

© Cu] the standard emf of the cell is 2.70 V at 300 K. When the
0.5 concentration of Mg™ is changed tox M, the cell potential
ou 2+]
[Cu* | changes to 2.67 V at 300 K. What is the value of x?

[Cu2+] = 2° =0.05M. (Given, — = 11500 KV-1, where F is the Faraday

10
constant and R is the gas constant, /m(10) = 2.30)
4) Consider the following cell: (JHE Advance 2018)
The cell reaction.
2Fe(s) + O,(g) + 4H* (ag) ——> 2F e** (aq) + 2H, O01)
Meg(s) + Cu**(ag) = Mg (aq) + Cu(s)
E? 4, = 1.67 V. When [Fe**] = 1x10-°M, p(O,) = 0.1 atm,
e.m.f. ofthe cellis 1.57 V. Calculate the pH ofthe solution. Ee

pH can be calculated from the concentration of 0.059, [Mg?*

Ht ions in the solution. EK = E°+ BALE g
2 [Cu™ J
For the cell reaction,

E — Ref? meen t
2+ 8
2.67 = 2.70 2:303RT
1005
nF
4 x
p(O.) [H*?
2.67—-2.70 = — SoA Lu logx
10g 00
\—-3 2
1.57 - QF 2 F
4 (0.1)x[H*?
siege aap 2.303 x 300 ie
0.059, 10°
qa) = aa BATH
2x 11500
4

0.03 x 2* 11500
= log logx = ———_____—__- ]
0.059 ita 2.303
x 300

6.78 = —6 log 10—4 log [H*] Ore 1)

a 3/46 MODERN’S abe + OF CHEMISTRY-XII

EQUILIBRIUM CONSTANT FROM NERNST EQUATION

The e.m.f. of the cell may be used to calculate the equilibrium constant for
the cell reaction. At equilibrium, the electrode potentials of the two electrodes
become equal so that e.m.f. of the cell is zero. Consider the
following redox reaction :
Zn(s) + Cu**(aq)==== Zn**(aq) + Cu(s)
(4) The reaction taking place in the oxidation half cell is
©
a Zn(s) ——~> Zn?*(aq) + 2e-
ec
om
—
oO
Equilibrium point As the reaction progresses the concentration of Zn** ions in
poe
ce rf the solution increases and consequently its reduction potential
=
—
=
increases.
=
=|
oO (iz) The reaction taking place in the reduction half cell is
oe
Cu**(ag) + 2e- ==>. Cu(s)
As the reaction progresses, there is a decrease in the
concentration of Cu** ions and consequently the reduction
potential of copper electrode decreases with passage of time.
Progress of reaction ——> Thus, the reduction potential of anode (oxidation half cell)
Fig. 14, Change in reduction potential of the electrodes increases whereas reduction potential of the cathode (reduction
with the progress of the reaction. half cell) decreases with the progress of the reaction. The change
in reduction potentials of the two electrodes with progress of the
reaction are graphically shown in Fig. 14. Ultimately a stage is reached when
the reduction potentials of the two electrodes become equal and have the same
value. The e.m.f. of the cell becomes zero and the reaction stops. Under these
conditions, the electrochemical cell is said to have attained equilibrium value.
Let us assume that the concentrations of Zn?*(ag) and Cu?*(aqg) are
It may be noted that the expression | equilibrium concentrations and the equilibrium constant, K, is:
for equilibrium involves E”“cal,_,, and x - en ag)
not E,_.,, because E__,, at equilibrium {.* [Zn(s)] = 1 and [Cu(s)] = 1}
© [Cu** (aq)
is zero.
The Nernst equation for the above reaction is:

_ 2.303RT [Zn**(aq)]
Beet = Ee ceit oF "8 TCu**(aq)

At equilibrium, E = 0 so that the above equation becomes

we EY ou = —— 08 ae
or Ey = — log K,

where K, = Ps At 298 K,

0.059
log K, at 298 K
n
Ais es |
or 0.059 at 298 K

In general,
20a RL
log K
nk =

Significance of K.. The value of K, gives the extent of the cell reaction.
If the value of K, is large, the reaction proceeds to larger extent.
ELECTROCHEMISTRY

SOLVED EXAMPLES
LJ Example 39. LJ Example 40
Calculate the equilibrium constant for the reaction at Calculate the value of equilibrium constant for the
298 K following cell reaction :
Cu (s) + 2Agt(aq) ———> Cu?*(aq) + 2Ag(s) 4Br-+0,+4H" ——» 2Br, + 2H,O
Given that
E* y,+ | 4g)= 0.80V and E™ 2+ |g = 0.34V. Given that E~ on = 0.16 V. Comment on the reaction.
N.C.E.R.T, (Kolkata g B. 2016)
Solution:
olution : E~_,,, isis related to
related to eq equilibririum constant,
Solution: is is related to equilibrium constant K_ at K. as:
298 K as: e@ — 0.059 _ AE
e — 0.059 _ nE*., a= — Ha log K, or log K = saris
Ba. = logK. or log K,= aa
In this reaction, four electrons are transferred so that n = 4
o o o
Bn = EH (agt | Ag) ~ (Cu2+ | Cu) 4=xQ0.16V
= 10.847
= 0.80 — 0.34 = 0.46 V log K. = “9.059V
2x 0.46 = 15.59 K, = 7.03 x 10*°.
or log =
* 0.059 The value of equilibrium constant shows that the equilibrium
position lies far to the right and therefore, large amount of
products are formed.

41. Calculate the equilibrium constant for the reaction,

2Fe**+ 2-0 == 2Fe** +1,
rig cad cel! = 0-236 V.
42. Calculate K. for the reaction :
NiO, + 2Cl + 4H* = — Cl, +Ni** + 2H,0
at 208 K if E©,, is 0.320 V.
43. Calculate at 25°C, the equilibrium constant for the reaction:
9Fe"++Sn** == 2Fe*+Sn* — Answers to Practice Problems =
: =3
Given that E 5+) 9,24, Pt = 0.771 V, E™ i441 5,24 Pt = 0.160 V. 41. 9.26 x 10%.
44, Fora cell reaction:
42. 7.04 x 107°.
A(s) + 2B* (ag) —M—— A** (aq) + 2B (s)
the equilibrium constant is 1 x 10+. Calculate sl AS. 1.0% 1074.
45. Calculate the equilibrium constant for the reaction : 44, 0.118 V.
Cd**(aq) + Zn (s) M——> Zn** (ag) + Cd (s) 45. 1.596 x 10".
If E*(042+)ca)= — 0-403 V and
Hints & Solutions on page 74
E* (Zn2* |Zn) =— 0.763 V (CBSE Sample Paper 2007) ld d_iv0TTy_ym_iY_!|_!yMVVNVVMV_r_rYY2Y}yN”rlTw_lYloYMN YN yttVNVNVNVY"N"”Yrws"l"tyTyVv Tl_loNy i occ ____ __.;

ELECTROCHEMICAL CELL AND GIBBS ENERGY OF THE REACTION

In electrochemical cells, the chemical energy is converted into electrical
energy. The cell potential is related to Gibbs energy change. In an electrochemical
cell, the system does work by transferring electrical energy through an electric
circuit. Electrical work done in one second is equal to the electrical potential
multiplied by the total charge passed. We know that A.G for a reaction is a
measure of the maximum useful work that can be obtained from a chemical
reaction. We may write
A.G = maximum work
For a reaction, occurring in an electrochemical cell whose electrodes differ
in a potential by E_,,, the work done when amount of charge nF is pushed
along by the potential of the cell is given by nF E__,, so that
Maximum work = nF E,,,,
aus where F is the Faraday constant (the charge on one mole of electrons) and
MODERN'S abe + OF CHEMISTRY
-AXIl

Relationship between Cell

n is the number of moles of electrons transferred in them. When voltaic cell
Potential, Gibbs Energy and
operates, work is done on the surroundings, as electrical energy flows through
Equilibrium Constant
the external circuit. Such work by convention is taken as negative.
The relation between cell potential
Thus,
(E~ _.,), Gibbs energy change (AG~) a = —s
and equilibrium constant can be easily A.G a Ww max =—n¥ ki cell

understood as: In order to compare cell voltage, we use standard cell potential, iy.
=
= —nFE Ly Therefore,
o 2.303 Aor
A G~ =—nF iia
But EK cel! = ar Pole log 1

2.303 where A.G® is the standard Gibbs energy for the reaction.
AG =-nFx RT log K,
nF If the activity of all the reacting species is unity, then E = E© and we have
= — 2.303 RT log K, AG? =—nF EY
or =— KY in ik Thus, from the measurement of E~ we can calculate an important
(2.308 log X = In X) thermodynamic property. From the temperature dependence of E® we can also
So, if we know the standard free calculate AH* and A'S*.
energy change or e.m.f. of the
From the standard Gibbs energy, we can also calculate equilibrium constant
cell, equilibrium constant can be
calculated. by the equation :
AGS RD ink.
Significance. The above equation helps us to predict the feasibility of the
It may be noted that E® is an cell reaction. For a cell reaction to be spontaneous, AG must be negative. This
intensive property but nah is an means that EK must be positive for a spontaneous cell reaction.
extensive property and the value
depends upon n. For example, for Summary of relationship among E° ,,, AG° and K and spontaneity ofa
the reaction : redox reaction
TAH eee tse) a FAM Lt Sila en AG® K Redox reaction
> a
AG’ =-2FE_,
Positive —ve ll favours formation of products
But when we write the reaction as:
27n(s) + 2Cu** (aq) > 0 0 = reactants and products are equally
27n**(aq) + 2Cu(s) favoured

we ee Se
for. & cell Negative +ve <1 favours formation of reactants

SOLVED EXAMPLES
LJ Example 41. Solution : The maximum work that can be obtained from
Calculate A G° for the reaction: a cell is equal to free energy change for the cell reaction.
Mg(s) + Cu**(ag) —> Mg**(aq) + Cu(s) Zn(s) + Cu**(ag) ——> Cu(s) + Zn**(aq)
Given E®,, = 2.71 V, 1F = 96500 C mol (A..S.B. 2014)
E®.,
cell —
=E® (cathode) — E® (anode)
Solution. A .G°=— nF E*,, & &
=i (Cu2* | Cu) EK Zn=+ | Zn)
Eu = 2.71 V,1 F = 96600 C mol, n =2
— 0.34 —(-0.76) = 1.10 V
A G° = —2x 96500 C mol x 2.71 V
= —623030 J mol tv a1) Now, AG? =-nF E®,
or — -—§23.030 kJ mol-! E®,, = 1.10 V, n = 2, F = 96500 C
Ll Example 42.
AG® =~—(2 mol) x (96500 C mol) x (1.10V)
Calculate the maximum work that can be obtained from
the Daniell cell : = — 212,300 CV (1J=1C xV)

Zn |Zn**(aq) || Cu**(aq) |Cu ~— 2123003 or ~ 212.3 kJ.

Given that E™ p24 Zn) = — 0.76 V and
Thus, 212.3 kJ is the maximum work that can be obtained
(Mizoram S.B. 2013, 2018) by the operation of this type of cell.
ELECTROCHEMISTRY

L) Kxample43 — 212300 J = —(8.314 JK“! mol) x (298 K) In K.

The zinc / silver oxide cell is used in hearing aids and or In K, —
212300
8.314 x 298 = 86.69
electric watches.
Zn ——> Zn**+2e E* =-0.76V or K, = 1.64 10%,
Ag,O + H,O + 2e——> 2Ag+ 20H E® =0.344V Example 46
(a) Which is oxidised and which ts reduced ? For the cell, Mg |Mg**(aq) ||Agt(aq) |Ag, calculate the
(b) Find E® of the cell and AG™ in joules. equilibrium constant at 25°C and also the maximum
(CBSE Sample Paper 2011) work that can be obtained by operating the cell.
‘=. =
E (Mg2+
|Mz) = —2.387 Vand E > (Agt
|Ag) —= + 0.80 V.
Solution : (a) Zn is oxidised and Ag,O is reduced.
> a = Solution: The cell is:
(b) BF ell = E eae © (anode)

Eu = EE (45,0 |Ag) EY ent | Zn)

Mg | Mg?*(aq) ||Agt(aq) | Ag
= 0.344—(—0.76)=1.104V The cell reaction is :
Now, n = 2mol,F=96600C mol, E® ,=1.104V Me(s) + 2Ag*(ag) ——> #£Meg**(aqg) + 2Ag(s)
AG? = —-nFE®, Calculation of Be,
= —(2 mol) x (96500 C mol) x (1.104 V) E*,, = E® (cathode) -E* (anode)
= —213072 CV (1CV = 1) = E*(Ag* |Ag) - E* (Mg** |Mg)
= —213072 J or = —2.138 x 10° kJ.
= 0.80 —(-2.37) =3.17 V.
LJ EKxample44 Calculation of equilibrium constant
Calculate the cell emf and AG for the cell reaction at
25°C for the cell : logK. = NE
oll at 298K
: 0.059
Zn(s) |Zn** (0.0004 M) || Cd?* (0.2 M)|Cd(s)
E® values at 25°C : Zn?* | Zn = — 0.768V; n= 2,E%,=3.17V
Cd?*|Cd = -0.403V
ig, = 2 aa?
F = 96500 C, R= 8.314 J K? molt. c 0.059
(D.S.B. 2000, Hr. S.B. 2005, Pb.S.B. 2013) f. K, = 2.66 x 10°”
Solution : Cell is Calculation of maximum work that can be obtained from
Zn(s) |Zn2* (0.0004 M) ||Cd?* (0.2M) |Cd(s) the cell. The maximum work obtained is equal to AG® so that
Zn(s) + Cd**(ag) ————> Zn*"(agq) + Gdi®) AG” = iF E=y
n = 2,F=96500C, ESy =3.17V
Een - EF oat | cd) ~ Ee an? | ah
AG? = —2 x (96600 C) x (3.17 V)
— — 0.403 —(— 0.763) = 0.36 V
— — 611800 CV =- 611810 J
According to Nernst equation,
(1CV=15)
E = EY Maximum work obtained = 611.8 kJ.
0.059 log Ne
2 [Cd™ ] LJ Kxample 47
[Zn2*] = 0.0004 M, [Cd**] = 0.2 M Estimate the minimum potential difference needed to
0.059 0.0004 reduce Al,O, at 500°C. The free energy change for the
E = 0.386- lo decomposition reaction :
2 0.2 2
=Al,0,; ——> 4Al + O, is| AG = +960kI
0.0
= 0.56-— 7 - log 2x 10°
(F = 96500 C mol) (D.S.B. 2002)
— 036—- — 2 x (— 2.6990)
= 0.36+ 0.08 =0.44 V
Solution : Al,O, (2AI* +302) —>2Al4 :O 2

Cellemf = 0.44V This reaction involves 6 electrons, n = 6

Now AG = —nFE 4
n = 2mol,F-96500C,E-0.44V : =ALO; ——> gAl+0,;n= 6x2 _ Ap-

AG = —2-»x 965600 x 0.44 CV

= — 84920 CV = - 84.920 kJ.
AG =—nFE
LJ) Kxample 45 AG = 960x 10° J, =4, F = 96500 C mol
The AG® for the Daniell cell has been found to be . 960 x 10° =— 4 x 96500 x E
—212.8 kJ at 25°C. Calculate the equilibrium constant
960
x 10°
for the cell reaction. or B= — 796500 -—2A87 V
Solution: AG? = —RTin K,
Here AG? = — 212.3 kJ =-212300 J, T = 298 K, “. Minimum potential difference needed to reduce
R = 8.314JK7? mol
aso
lL] Example 48
MODERN'S abe + OF CHEMISTRY
-AXIl

0.226 — 0.0295 x (-4)

For the reaction : = 0.226 + 0.1180 = 0.344V

2AgCl (s) + H, (g) (latm) ———-> 2Ag(s) + 2H* (0.1M)
+2CL(0.1M) U Example 49.
AG° = —48600 J at 25°C Determine the values of equilibrium constant (K,) and
Calculate the e.m.f. of the cell. (A.I.S.B 2018) AG* for the following reaction :
Solution : AG’ = —nFE* a
Ni(s) + 2Ag*(aq) —> , Ni**(aq) + 2Ag(s), E = 1.05V
43600 = -2 x 96500 x E°_, (IF = 2eG0e (nro? . (8.8. POT)
43600 Solution: AG? = —n FE ce
oy = eee S
2x 96500 n 4.2 By = 1.05 V, F = 96500 C mol
2AgCl (s) + H, (g) (1 atm) ——-> 2Ag(s) + 2H * (0.1M) “ AG? = —(2mol) x (96600 C mol?) x (1.05 V)
+ 2CT (0.1M) |
: ~ — 202650 CV
+ - —
, 0.059 |H | |Cl | = — 202.650 kJ (Ova)
[H2(e)| AG® = —RTInK,
2
0.1)" x (0.1
2
AG oO x 103
— 202.650
log (0.1) x(0.1)
= 0.226—0.0295 or InK, = - a aise 81.79

— 0.226 — 0.0296 x log 10 off K = 2.82 x 1035

46. Calculate AG® and the equilibrium constant for the cell reaction,
(et 27> 2Clr +I,

Given that BE? gy, 7)= 1.36 V,E* Gg, 5 = 0.536 V.

The cell in which the following reaction occurs :
2 Fe** (aq) + 2 I (aq) ——> 2 Fe** (aq) + I, (s)
has £2), = 0.236 V at 298 K. Calculate the standard Gibbs energy of the
cell reaction. (Given : 1 F = 96500 C/mol) (A.1.S.B. 2017)
Calculate AG® and E...7; tor the cell

Al | Al?* (0.01M) || Fe** (0.02 M) |Fe

Given that E® 5+) 4) = -1.66 Vand E®, e“* | Fe) — — 0.44\V.

49. Calculate the standard cell potential of the galvanic cell in which the following
reaction takes place :
= Answers to Practice Problems y=
2Cr (s) + 8Cd**(ag) ———> 2Cr** (aq) + 3Cd (s)
46 . — 159.0 kJ, 7.36 * 1077) Also calculate the A.G* value of the reaction.
AT . — 46.648 kJ mol}.
[Given E* 3+) 9) =— 0.74 V, i= (cd"* |cd) = — 0.40 V and F = 96500 C mol]
48 - 1.209 V, — 706.38 kJ.
(A.IS.B. 2007)
49. 0.34V, — 196.86 kJ molt.
50. — 48.250 kJ. 50. Write the Nernst equation and calculate the value of AG® for the galvanic cell :
Hints & Solutions on page 74 Cu(s) | Cu?* (0.130 M) | | Agt (1.00 x 10+M)| Ag(s)
Given E® ..2+),, = 0.34 V, E® Ag’ |Ag = 0.80 V (Hr. S.B. 2005)
ELECTROCHEMISTRY

Accelerate Your Potential

PROBLEMS (for JEE Advance)

US For the cell reaction: ai) Ca eee a t=?

Sn(s) + Pb**(ag) —> Sn**(aq) + Ph(s) AG, = —-2xFx
EQ 2h,F
E%,,2+) gq =~ 0.140, E%,2+) p, = — 0.126V
Now AG. = AG. FAG,
Calculate the ratio of concentration of Pb** to Sn**
ion at which the cell reaction be reversed. —2E.F = —(#). Tea 0.50 F ——0.66 F

For the cell,

EK —— — 0.325 V
B® _ Exo Pb ~ 2 Gn2+) gn = —0-126— (0.140)
= 0.014V 18 Consider an electrochemical cell:
Applying Nernst equation A(s) |A™* (aq, 2MD ||B*** (aq, 1M) |B(s). The value of AH”

E = Ee- 0.059, [Sn”*]

for the cell reactionis twice that of AG’ at 300 K. Calculate
2. Pp] AS° (in JK-! mol") of the c ell per mole of B formed at
300 K if the e.m.f. of the cell 1s Zero.
0.059, [Pb?*]
0.014+ log (Given: [n(2)= 0.7, R (universal gas constant)= 8.3 JK-!
2 [Sn?*]
mol". H,S and Gare enthalpy, entropy and Gibbs energy,
At equilibrium, E = 0
respectively). (JEE Advance 2018)
0.014 + 0.059 1,5[Pb] 2+
oe eae a
ed

or log
[Pb?* ] 0.014x2
[Sn] 0.059 ~ “4
0.059 B2"++42ne- —>B

QA + Bent SSS er
[Pb?*]

to rotate
antilog (—0.474) = 0.336
[Sn?*]
2+ RT , ol
| en-eecia TL a

till is more than 0.356 V. nF (sed

b2*
less than
When ae.becomes V, E.__,willbecomenegative
0.336
n? | eel cage uid In (2)?
and the reaction will be reversed. nF

or 0= E°- RT In 4
The reduction potential for the two half Ink
cell reactions are:
Cu** +e —> ACT E°=0.15 V aan
Cut +e —_§—_/ ao E° = 0.50 V cael _2nF RT
Calculate reduction potential for the following
Nae A= opie = eee
Ink
reaction: = -RTin4
Cu* + 2ef7._ Cu 1] hee AS
This can be solved in terms of their free energy Aiea ee
ae
(i) Cu2* +e —>»Cut KS = 0.15 V or TAS? = AG®

0 i
AG, = -IlxFx0.165 =—0.15F AS? — AG
May eye er
Jl T
(it) Cut+e7 — > Cu KE -Ualv AS°= —8.3x2x0.7

el ee ee — -11.62 JK-! mol!

asa ELECTROLYTIC CELLS AND ELECTROLYSIS
MODERN'S abe + OF CHEMISTRY
-AXIl

Electrolysis is a process of decomposition of an electrolyte by the

passage of electricity through its aqueous solution or molten (fused)
state of electric current.
The cells used to carry out electrolysis are electrolytic cells.
Process of electrolysis
The process of electrolysis is carried out by taking the
solution of an electrolyte in a suitable vessel. The vessel is
called electrolytic tank (Fig. 15.) It is made up of either
glass or of a material which is a bad conductor of electricity.
Two metallic rods or plates are suspended in the electrolytic
solution. These are connected to the terminal of a battery
with the help of metallic wires. These metallic rods or plates
allow the passage of current and are called electrodes. The
electrode connected to the positive terminal of the battery is
called anode while the electrode connected to the negative
Electrolytic terminal of the battery is called cathode.
Oo. tank When an electrolyte is dissolved in water, it splits up
solution of electrolyte into negative and positive ions. The positively charged ions
are called cations and negatively charged ions are called
Fig. 15. Process of electrolysis. anions. On passing electric current through the solution,
the ions are attracted by the oppositely charged electrodes.
As a result, cations move towards cathode while anions move
towards anode. This movement of ions in solution is known
as electrolytic or ionic conduction and constitutes flow of current through
the solution.
The anions on reaching the anode give up their electrons (which flow
out of the solution). On the other hand, cations take up the electrons from
the cathode. Therefore, cations and anions get discharged at the respective
electrodes and are converted to neutral particles. This is known as primary
change. The primary products may be collected as such or they undergo
further changes to form molecules or compounds. These are called secondary
products and the change is known as secondary change.
The process of electrolysis was explained by the theory of ionisation.
According to ionic theory, the electrolytes are present as ions in solution and the
function of electricity is only to direct these ions to their respective electrodes.
The electrolytes can be electrolysed only in the dissolved or molten state.
One of the simplest electrolytic cell consists of two copper rods dipping in
an aqueous solution of copper sulphate. When electric current (DC voltage)
is applied to the two electrodes, then Cu** ions discharge at the cathode
(negatively charged electrode) and the following reaction takes place :
Cu**(ag) + 2e- ——> Cu(s)
(at cathode)
Copper metal is deposited at the cathode.
At the anode, copper is converted to Cu** ions by the reaction :
Cu(s) ———> Cu?*(aq) + 2e-
Thus, copper is dissolved at the anode. In terms of oxidation and reduction,
we can say that copper is oxidised at anode while it is reduced at cathode.
This is the basis of an important industrial process in which impure copper
is converted into copper of high purity. Many other metals such as Na, Mg,
Al, ete are also produced on a large scale by electrochemical reduction of their
respective cations where no suitable chemical reducing agents are available
for the reduction. This is one of the important method in metallurgy.
For example, sodium and magnesium metals are produced by the electrolysis
of their fused chlorides and aluminium is produced by the electrolysis of
aluminium oxide in the presence of cryolite (Na,AIF,).
ELECTROCHEMISTRY

Quantitative Aspects of Electrolysis

The chemical equivalent
Michael Faraday performed a large number of experiments during weight is atomic mass divided by
1833—34 on electrolysis and summarized the results of his experiments in the the number of electrons required
form of two laws known as Faraday's laws of electrolysis.
to reduce the cation.
Faraday's laws of electrolysis
1. Faraday's first law of electrolysis. It states that
the amount of any substance deposited or liberated at any electrode
is directly proportional to the quantity of electricity passed through
the electrolyte (solution or melt).
The amount of any substance obtained gives the amount of chemical
reaction which occurs at any electrode during electrolysis.
Thus, if w gram of the substance is deposited on passing @ coulombs of
electricity, then
wee @ or w = LQ
where Zin a constant of proportionality and is called electrochemical equivalent.
If a current of I amperes is passed for ¢ seconds, then
Q=Ixi
so that raf%o aA TK
Now, if @ = 1 coulomb
or I = 1 ampere and f = 1 second, then
w=Lx1x1 or wih
Hence electrochemical equivalent of a substance may be defined
as the mass of the substance deposited when a current of one ampere
is passed for one second, 1.e., a quantity of electricity equal to one
coulomb’ is passed.
Faraday's second law of electrolysis. It states that
when same quantity of electricity is passed through different
electrolytic solutions connected in series, the weights of the
substances produced at the electrodes are directly proportional to
their chemical equivalent weights.
For example, when same current is passed through two electrolytic solutions,
During Faraday’s times, there
containing copper sulphate (CuSO,) and silver mitrate (AgNO) connected in
were no devices available tosupply
series, the weights of copper and silver deposited are :
constant current. Therefore, the
Weight of Cudeposited _ Eq. wt. of Cu quantity of electricity passed was
Weight of Ag deposited Kq. wt. of Ag measured by using an apparatus
called coulometer. Generally,
However, in modern terms, the term equivalent weight is not used.
copper and silver coulometers
The Faraday's laws of electrolysis may be stated in terms of moles of electrons
were used and the quantity of
exchanged during an electrochemical change.
electricity passed was calculated
According to Faraday's law, the amount of chemical change occurred t1.e.,
from the amount of copper or
the moles of substances deposited or liberated is proportional to the number of
silver deposited or consumed in
moles of electrons exchanged during the oxidation-reduction reactions that occur.
the coulometer. From the weight,
Therefore, by knowing the amount of electricity passed, we can easily
the quantity of electricity passed
calculate the number of moles of products formed from the appropriate electrode
through the coulometer could
reaction. From the moles of the products formed, we can calculate the masses
be calculated using Faraday’s
of the products or their volumes if they are gases.
laws of electrolysis. Nowadays
Therefore, the amount of electricity needed or amount of products formed
coulometers are not used and
can be calculated from the equation for the appropriate electrode reaction.
we have devices which supply
For example, during the passage of electric current through molten NaCl,
constant current and quantity
sodium gets deposited at cathode and chlorine is liberated at anode.
of electricity can be calculated
NaCl ——>» Na + = Cl, from the formula:
i =o
(At cathode) (At anode)
where | is the current in ampere
During electrolysis, sodium ions move towards cathode, accept electrons
and tis the time in second during
and get deposited as:
which current was passed. The
Nat(ag) + e@ ———> Na(s)
quantity of electricity, Q will be
It is clear that the passage of one electron produces one sodium atom. The
in coulombs.
passage of 1 mol of electrons produce 1 mol of sodium (or 23 g).
as MODERN'S abe + OF CHEMISTRY

Similarly, at anode, chloride ions give up electrons and produce Cl atoms as:
-AXIl

1
It may be noted that earlier, the
term equivalent weight was used. or 2Cl — 2e7 —— CL{g)
This can be easily correlated to mole It is clear that 2 mol of electrons produce 1 mol of Cl, or 1 mol of electrons
ratio. For example, for the above produce 1/2 mol of Cl, (35.5 g).
experiment, we can say We know that charge on an electron = 1.602 x 10-" C
Weight of silver Now 1 mole of electrons = 6.022 x 107° electrons
Weight of copper Charge on 1 mole of electrons = 6.022 x 107° x 1.602 x 10°C
= 96485 C mol
_ Equivalent weight of silver The charge on one mole of electrons is called 1 Faraday, F, in honour of
Equivalent weight of copper Michael Faraday. Thus,
1F = 964865 C or approximately 96500 C.
Weight of silver Thus, charge on n mol of electrons will be equal to
and
Weight of gold Q =nF
_ Equivalent weight of silver Now, the production of 1 mol of sodium or 23.0 g by reduction of sodium
~ Equivalent weight of copper ions require 1 mol of electrons. Therefore, amount of charge required,
Q@ =nF = 1x 96500 C = 96500 C
Now, equivalent weight ofmetal Similarly, 1 mol of Cl, is obtained by 2 mol of electrons or 2 x 96500 C of
Molecular Mass charge during electrolysis of NaCl. Similarly, in the reaction :
~ Charge on its ions Agt +e ——— Ag(s)
One mole of electrons is required for the reduction of 1 mol of silver ions.
Thus, when 96500 C of electricity
(corresponding to 1 mol ofelectrons) Therefore, the quantity of electricity required for reduction of 1 mol of Agt
ig passed then amounts of silver, ions is 96500 C or 1 Faraday.
copper and gold deposited will be Now, 1 mole of copper will be produced by 2 mol of electrons or 2 x 96500
equal to their equivalent weights C of charge :
a ae Cu*+ +2e° ——>Cu
For 1 mol of electrons or 96500 C of Thus, from the knowledge of moles of electrons required during the electrode
electricity passed. reaction, the amount of substance deposited or evolved can be calculated. For
Silver deposited
example, aluminium gets deposited as :
=lgmequivalentofAg = 107.87¢
Al?* + 38e —— Al
1 mol 3 mol 1 mol
or =1 mol
Thus, 1 mol of Al will be deposited by 3 mol of electrons or 3 Faraday (or
Copper deposited
8 x 96500 C) of electricity.
= 1 gm equivalent of Cu = 31.77 ¢
Similarly, when the same quantity of electricity is passed through different
_ imol electrolyte solutions, connected in series, the weights of different substances
2 produced at the electrodes can be calculated from the mole ratios of their
Gold deposited = 1 gm equivalent of electrode reactions.
For example, consider an experiment in which same amount of current is
Aaepeoge Hay passed simultaneously through three aqueous electrolytic solutions connected
in series containing aqueous solutions of silver nitrate, copper sulphate and
gold chloride as shown in Fig. 16.

AgNO.(aq) CuSO, (aq) AuCl,(aq)

Fig. 16. An electrolysis experiment
ELECTROCHEMISTRY

When enough current is passed through the cells to deposit 1 mol of silver
(107.87 g), it is observed that amount of copper and gold deposited are also in
the ratio of their molecular masses. Using the mole ratio of reduction half cell
reaction shows that liberation of 1 mol of Ag has required the passage of 1 mol
of electrons (or 96500 C of electricity). Simultaneously with the deposition of 1
mol of silver, it is found that 1/2 mol of copper and 1/3 mol of gold have been
produced in their respective cells. The formation of these products is explained
on the basis of the stoichiometry of the half cell reactions and the passage of
1 mol of electrons through the solutions.
Cu** + 2e-§ ——> Cu(s)
1 mol of Cu is deposited by 2 mol electrons

‘. 1 mol of electrons deposit = 1 mol Cu

Similarly, -
Au®+ + 3e—- ——> Au(s)
‘. 1 mol of Au is deposited by 3 mol electrons
; 1
‘. 1 mol of electrons deposit = s mol of Au.
Thus, we conclude from these observations :
1 1
1 mol of electrons will deposit 1 mol of Ag, a mol of Cu and 7 mol

of Au.
In general, amount of element deposited (in mol)
_ No. of moles of electrons
~ No. of charges on ion of the element

For example, during electrolysis of CrCl, (aq), 1 mol of electrons (96500 C of

electricity) will deposit:
Cr** +3e —-> Cris)
| 1
Amount of chromium deposited = = mol

Similarly, 2 mol of electrons (2 x 96500 C of electricity) will deposit:

Amount of Cr deposited = : mol.

PRODUCTS OF ELECTROLYSIS
We have seen that during electrolysis, the reactions occurring at the electrodes
are oxidation and reduction reactions. Therefore, the products of electrolysis can be
predicted on the basis of electrode potentials of different reactions. The products
of electrolysis depend on the nature of material being electrolysed and the types of
electrodes being used. If the electrode is inert such as gold or platinum, it does not
take part in the chemical reaction and acts only as a source or sink for electrons. On
the other hand, if the electrode is reactive, it takes part in the electrode reaction.
Thus, the products of electrolysis may be different for inert and reactive electrodes.
The products of electrolysis mainly depend on the different oxidising and reducing
species present in the electrolytic cell and their standard electrode potentials. It
may be noted that some electrochemical processes, though feasible, are so slow
kinetically that at lower voltages, these donot seem to occur. The slowness of
electrode reaction creates electrical resistance at the electrode surface. Therefore,
for the occurrence of such reactions (e.g., processes involving liberation of gases)
some extra potential or voltage is required than the theoretical value of their
standard electrode potential. This extra voltage required is called over voltage.
Let us discuss some examples :
1. Electrolysis of molten sodium chloride. The molten sodium chloride
has Na* and CI ions,
NaCl = Nat + Cl
a 3/56 MODERN'S abe + OF CHEMISTRY-AXIl

During electrolysis, it has been observed that sodium metal is deposited at

the cathode while chlorine gas is liberated at the anode. When electric current is
passed through molten sodium chloride, the chloride ions are attracted towards
anode. These ions give up one electron each to the anode and become chlorine
atoms. The chlorine atoms are unstable and combine in pairs to form chlorine
molecules.
On the other hand, Na* ions move towards the cathode, take up one electron
each and become neutral atoms. As a result, sodium metal is obtained at the
cathode.
The reactions may be expressed as :
At cathode : Nat+e ——> Na _ (reduction)
At anode : Cl—e ——> Cl (oxidation)
Cl+Cl ——> Cl 2
Thus, the overall reaction is:
2NaCl —Stese, 2Na/ + CL,(g)
(molten) (at cathode) (at anode)
2. Electrolysis of aqueous sodium chloride. In water, sodium chloride
i0nises as :
NaCl mm Na‘ (aq) + Cl (ag)
Water also dissociates into ions, though to very slight degree as :
HQ) Qe H*(aq) + OH“(aq)
Thus, the aqueous solution of sodium chloride contains Nat, Ht, OH” and
Cl ions. When electric current is passed through the solution, Cl, gas is evolved
at the anode and hydrogen is evolved at the cathode. The resulting solution
contains Na* and OH ions.
At cathode, there is a competition for reduction between the following reactions:
Na*(ag) +e ——> Na(s) EB? =—2.71 ¥

H*(aq) +e-° ——> =HA@) E* = 0.00 V

The reaction with higher value of E® is preferred and therefore, the reaction
at the cathode during electrolysis is :
1
H*(ag) +e-§ ~——> 5 H,@) i)
But H*(aq) ions are produced by the dissociation of water as:
H,OW7) ———-+ H*(aqg) + OH (aq) alto
Therefore, the net reaction at the cathode may be written as the sum of
reactions (i) and (ii)

H,O@) +e- ——> =Hg) + OH-(aq) (Lit)

On the other hand, at the anode, the following reactions are possible :

Cl(ag) > =OL(g) + e« EY =4+1.386V

2H,O() ——> O,(g) + 4H*(aq) + 4e° EY = + 1.23 V
The standard reduction potential of water is slightly less and therefore, it has
slightly more chances of getting oxidised. However, in concentrated solution of
NaCl, oxidation of chloride ions is preferred than water at anode and therefore,
Cl, gas is liberated. The unexpected result is due to the fact that sometimes
higher voltage is required for electrolysis due to over voltage.*

*It has been found experimentally that the actual voltage required for the electrolysis is larger than that calculated from standard
electrode potentials. This extra voltage is required because the rate of transfer of electrons at the interface of electrode and solution
for both the half reactions is slow. The slowness of the electrode reactions create an electrical resistance at the electrode surface.
Therefore, some extra voltage is required to overcome the resistance. This extra voltage required is called over voltage. The over
voltage for the formation of oxygen is much larger than that required for the formation of Cl,. Therefore, the half reaction at anode
is oxidation of CI to Cl, gas.
ELECTROCHEMISTRY 3/57 —

The reaction occurring at anode is :

1
Cl(ag) —- 3 CL@) + e&

Thus, the net reactions during the electrolysis of aqueous sodium chloride
solution my be summerized as :

NaCl(ag) —2°., Nat (ag) + Cag)

al
At cathode : H,O(W) + eX ——~+ 5 Hi) + OH (aq)

At anode: Cl(ag) ———> = CL@) + e7

; 2
Net reaction:

NaCl(ag) + H,O(@) ——> Na‘ (ag) + OH-(aq) + ~H,@) + =Ol(@)

Thus, during the electrolysis of aqueous sodium chloride, H, gas
is liberated at the cathode and Cl, gas is liberated at the anode and
the solution contains sodium hydroxide.
3. Electrolysis of molten lead bromide using platinum
electrodes
In the molten state, PbBr, exists as
PbBr, Pb2+ + 2Br-
The electrolysis may be carried out by taking solid lead bromide in
a silica crucible. Two electrodes of graphite are used (Fig. 17). When
a D.C. voltage source is applied, no current is observed. However, |
when the crucible is heated so that lead bromide metals the current Y. bisitch
is found to pass. During electrolysis, metallic lead is produced at the | lead biciile
cathode while bromine gas is liberated at the anode. When electric i ,
current is passed through the molten lead bromide Pb** ions move
towards the cathode while Br’ ions move towards the anode. The
folowing reactions occur at the electrodes :
At anode:
2Br- +——> 2Br + 2e- (oxidation)
2Br ——— Br,g)
At cathode:
Pbh*t + 2e- ,-+—> Pb (reduction)
Thus, the overall reaction is

(molten) (at cathode) (at anode)

4. Electrolysis of water. Pure water is a poor conductor of electricity. Apaaied

However, water containing a few drops of acid or alkali becomes good conductor.
The electrolysis of water may be carried out by taking some water in an
electrolytic cell as shown in Fig. 18. Introduce two graphite electrodes into
it. Connect these electrodes through an ammeter to a battery. It is observed
that ammeter does not show any deflection. This shows that water is a bad
conductor of electricity. However, when a few drops of dil. H,SO, are added
to water, the ammeter shows deflection and electrolysis starts.
Water is only weakly ionized but in the presence of an acid, its degree
of ionization increases. Upon passing the electric current, it dissociates as :
H,0@ H*(aq) + OH“(aq)
Fig. 18. Electrolysis of water.
(Cathode) (Anode)
ase At cathode
MODERN'S abc + OF CHEMISTRY-XIl

2H*(aq) + Qe~- Seduction , oF or H,

At anode:
Oxidation OH
OH (aq) ————— + €
40H ——>» 2H,0 + O,
It may be noted that in case we add a few drops of dilute H,SO, to water
before carrying electrolysis, the SO,? ions will also be formed at the anode
along with OH™ ions.
H,SO, (aq) 2H*(ag) + SO,7 (aq)
In this case, both OH and SOye- ions move towards anode. However,
SO, ions will not be released since their discharge potential is more as
compared to OH ions.
The gases oxygen and hydrogen are collected at the anode and cathode
respectively. On measuring the volumes, the volume of hydrogen collected is
found to be twice the volume of oxygen. This shows that the two elements H
and O are present in water in the ratio of 2: 1 and thus, the formula of the
compound is H,O.
5. Electrolysis of aqueous copper sulphate solution. Copper sulphate
and water ionise as
CuSO,(ag) MM Cu** (ag) + SO,7 (aq)
H,O07) == Ht (ag) + OH (aq)
During electrolysis, copper is deposited at the cathode while oxygen is
liberated at the anode. The following reactions occur at the elelctrodes :
At anode:
2H,O ——> 4H* + O, + 4e7 (oxidation)
At cathode:
Cu**(ag) + 2e- ———> Cu(s)] x 2 (reduction)
The overall reaction is :
2Cu**(aq) + 2H,O ——-> Cu(s) + 4H* + O, g)
or 2Cu**(aqg) + 2807 + 2H,0 ——> 2Cu(s) + 4H* + 28507 (aq) + O, (g)
It may be noted here that in the above examples, the electrodes used are
those which are not attacked by the ions (for example, platinum). However,
if the electrodes are attacked by the ions, then the reactions taking place
during electrolysis are different. For example, let us consider the electrolysis
of aqueous solution of CuSO, using copper electrodes.
6. Electrolysis of CuSO, using copper electrodes. In the electrolysis,
copper sulphate and water ionise as :
CuSO, =~ Cu** +580,7
H,O =~ H* + OH
At cathode : Cu** ions are deposited at the cathode.
Cu2+ + 2e°9 ——> Cu
(deposited)
At anode : Unlike electrolysis of CuSO, using Pt electrodes, no ions are
liberated. On the other hand, anode itself undergoes loss of electrons to form
Cu** ions which go into the solution.
Cu—2e ——> Cu*
So, the net result of electrolysis is that copper is deposited at the cathode
from the solution and an equivalent amount of copper from the anode dissolves
into solution as Cu** ions.
ELECTROCHEMISTRY 3/59 —

7. Electrolysis of sulphuric acid. During the electrolysis of sulphuric

acid, hydrogen is liberated at cathode :

At cathode : H* + e —~> =H,

The following two reactions occur at anode :

2H,O0(7) ——-+ O,(g) + 4e7 E@ 241.938 «fi
2807 (aq) ———> 5,0,” (aq) + 2e° ES = 1.96 V_ ...(ii)
For dilute solution, reaction (/) is preferred and O, liberates at anode.
But at higher concentration of sulphuric acid, reaction (iz) is preferred and
solution of peroxodisulphuric acid (H,S,O,) is obtained.

Thus, when more than one substances are present in an electrolytic cell
during electrolysis, we can make the following generalisations :
1. The ion which has higher reduction potential will be reduced
first at the cathode. For example,
(i) The ions such as Nat (E° = — 2.71 V), Ca®* (E* = = 2.87@,
K* (E° = — 2.93 V), Mg** (e° = — 2.37 V), Al** (E° = — 1.66 V) ete. cangiot
reduced in aqueous solution as their reduction potentials are less than water
(E° = — 0.83 V). Water will be reduced preferably and H, will be liberated as:
2H,O0 + 2e° ——-> H, @) + 20H (aq)
(ii) The ions such as Cu? (E° = 0.34 V), Ag* (E° = 0.80 V) have larger
reduction potential than water and, therefore, are easily reduced and get
deposited at the cathode as Cu and Ag respectively.
2. The ion which has lower reduction potential will be oxidised
first at the anode. For example,
(1) Br’ (E° = 1.08 V) and I" (K° = 0.77 V) are preferably oxidised to Br,
and I, respectively in aqueous solution because they have lower reduction
potentials than water
1
oS ING Wile fl 2 gee a K7= 1.23 V).
(it) F- ion (E° = + 2.87 V) is not oxidised to F, in aqueous solution
because it has higher reduction potential. In this case, water will be oxidised.

= Xo) Be >PN
LJ Example 50 (ii) produce 10.0 g of Al from molten Al,O, ?
A solution of CuSO, is electrolysed for 10 minutes (6) How many moles of electrons are given by
with a current of 1.5 amperes. What is the mass of (i) 8960C (tt) a current of 1.5 A for 30 s?
copper deposited at the cathode ? (c) How many minutes it would take to reduce
(Pb. S.B. 2012, Meghalaya S.B. 2017) 0.20 mol of Cu?* to Cu using a current of 10 A.
Solution : Current strength (I) = 1.6 A Solution : (a) Moles of electrons required :
Time (4) = 10 min=10x 60 = 600s (i) MnO, + 5e& ——> Mn2+
Quantity of electricity passed = I xt 1 mol of MnO, will be reduced by 5 mol of electrons
= (1.5 A) x (600 s) i meal
-900C (As=C) (1) ee =
Copper is deposited as : 3 mol of electrons are required to produce 1 mol or 27 g of Al
Cu?* + 2e—-> Cu(s) . 10 g of Al will be produced by = _?_ x 10
2 mol of electrons or 2 x 96500 C of current deposit copper 27
= 63.56g = 1.11 mol electrons.
900 C of current will deposit copper (D) (2) 96500 C of electricity = 1 mol of electrons
— 638.56 ,9090
96500
2x 8960 C of electricity — —+— x 8960
96500

isiarciaiss 0.0928 mol elect

(a) How many moles of electrons are required to (zz) Quantity of electricity,
(i) reduce 1 mol of MnO, to Mn?* 2 ate 1a
co Now, 96500 C of electricity = 1 mol of electrons
MODERN'S abe + OF CHEMISTRY

(iv) reduction of 1 mol of Cu** to Cu

-AXIl

45 C of electricity = : x 45
(v) reduction of 1 mol of Al** to Al
96500 Solution : (1) Oxidation of H,O to O,
— 4,66x10-* mol electrons. 2H,0 =—— 4Ht+0, + 4e7
(c) Cu*t + 2e ——> Cu Oxidation of 2 mol of H,O require = 4 x 96500 C
2 mol of electrons are required to reduce 1 mol of Cu?* Oxidation of 1 mol of H,O requires = 2 x 96500 C
= 1.93 x 10° C.
~. 0.20 mol of Cu** will be reduced by 7 x 0.20
(11) Oxidation of 1 mol of FeO to Fe,Q,
0.40 mol of electrons Fe* fas > Fe + 27
Now, 1 mol of electrons = 96500 C Oxidation of 1 mol of Fe** require = 1 x 96500 C
0.4 mol of electrons = 96500 x 0.04 = 38600 C = 96500 C.
(iii) Reduction of 1 mol of MnO, to Mn**
@ = Ix
38600 = 10Ax f(s)
MnO, + 8H* + be] ——-> Mn** + 4H,0
Reduction of 1 mol of MnO, requires = 6 x 96600 C
or t = 38600 _ 360 = 4,825 x 10°C.
10
(iv) Reduction of Cu** to Cu
or = 64.3 min.
Cu*ir2e —— > Cu
Example 52. Reduction of 1 mol of Cu** requires = 2 x 96600 C
Calculate how long itt will take to deposit 1.0 g of = 1.93 x 10° C.
chromium when a current of 1.25 A flows through a (v) Reduction of 1 mol of Al** to Al
solution of chromium (ILD sulphate. (Molar mass of Al**+ + 3e—° ——> Al
Crao2) Reduction of 1 mol of Al** requires = 3 x 96500 C
Solution : Cr+ + 3e- ——> Cris) = 2.895 x 10° C.
3 mol or 3 x 96500 C of electricity are needed to deposit
LJ Kxample 55
1 mol or 62 g of Cr.
A solution of Ni(NO,), was electrolysed between
62 g of Cr require current = 3 x 96500C
platinum electrodes using a current of 5 amp for 80
1 g of Cr will require current = a C min. What ts the mass of Ni deposited at the cathode ?
(Pb. S.B. 2012, Meghalaya S.B. 2013)
= 6667.3 C Solution: The electrolysis of Ni(NO,), may be represented
Now, number of coulombs = Current (Ampere)
x t (seconds) Ni(NO,), ———> Ni?t + 2NO,-
or Ni** + 2e°§ ——> Ni
No. of coulombs
Ti ’ 7 d _— ——— Quantity of electricity passed
mbes) adore Current (Ampere) = Current in amperes (I) x Time 1n seconds (¢)
= 6.0 x 30 x 60 = 9000 C(t = 30 x 60 sec)
5567.3 C
2 mol of electrons or 2 x 96500 C of current produce 1 mol
= 1.25 A
or 68.5 g of Ni so that 2 x 96500 C of electricity deposit
4453.8 s Ni = 58.5 g
or = 1.24 hr.
LU) Example 53
9000 C of electricity deposit Ni = 28-2 * 9000 _ 9.73 g,
2 x 96500
How many coulombs are required to deposit 40.5 g of LJ Example 56
aluminium when the electrode reaction ts :
How many hours does it take to reduce 3 mol of Fe?*
Ai** + 3e°- ——> Al (Nagaland S.B. 2015) to Fe** with 2.0 A current? (F = 96500 C)
Solution : Als+ ff ¥ se ——> Al
Solution : Reduction of Fe** to Fe**
1 mol of Al requires 3 mol of electrons or 3 x 96500 C
Fe*t +e ——> Fe?*
1 mol ofAl = 27 ¢
Reduction of 1 mol of Fe** requires = 96500 C
27 gof Alrequire = 3 x 96500 C
Reduction of 3 mol of Fe** require = 3 x 96600 C
3x 96500 Cx 40.5 = 2.895 x 10°C
40.6 gof Alrequire =
27 Now, Quantity of electricity = Current x Time
434,250 C. 2.895 x 10° = 2x Time
Example 54
5
How many coulombs of electricity are required for Time = ee 1.4475 x 10° s
(1) oxidation of 1mol of H,O to O,
(it) oxidation of 1 mol of FeO to Fe,O, 1.4475x10° en
(iit) reduction of 1 mol of MnO,; to Mn?*
ELECTROCHEMISTRY

LU) Example 57 LJ Example 59

Three electrolytic cellsA, B and C containing electrolytes Predict the products of electrolysis of an aqueous
of zinc sulphate, silver nitrate and copper sulphate solution of CuBrs.
respectively were connected in series. A steady current Solution: The probable reactions at cathode are :
of 1.50 amp was passed through them until 1.45 g of
(i) Cu?* (ag) + 2e°-———> Cu(s), E® =0.34V
silver were deposited at the cathode of cell B.
(t) How long did the current flow ? (zt) 2H,O (D + 2e°- ——-> H,(g) + 20H (aq), EE? =-—0.83V
(it) What weight of copper and zinc get deposited ? Since the reduction potential of Cu** ions is higher than that
(D.S.B. 2008, Assam S.B. 2013, 2017 of water, copper will be reduced preferably at cathode.
The probable reactions at anode are :
Meghalaya S.B. 2014, 2016)
2Br- (aq) ——— Br, (g) + 2e7 E? =1.08V
Solution: Cell B contains AgNO, and reaction may be
represented as : H,O (1) => ; O, (g) + 2H* + 2e- E® = 1.23V
AgNO, = Ag*t+NO,
Since the reduction potential of Bris less than water, it will
Agt+e === Ag (At cathode)
be readily oxidised to Br, at anode. Therefore, the reactions are:
According to the equation,
At cathode : Cu?* (aq) + 2e° ——> Cu(s)
1 mol or 108 g of silver is deposited by 96500 C
At anode : 2 Br (aq) ——> Br, (g)+2e
1.45 g silver is deposited by = 96500 x 1.45
LJ Example 60
108
Two electrolyticcells containing silver nitrate solution
= 1295.6 C.
Q =Ixt and dilute sulphuric acid solution were connected in
Now,
series. A steady current of 2.5 amp was passed through
1205.6 = 15xt
them till 1.078 g of silver was deposited.
1295.6
“ t = = 863 s. [Ag = 107.8g mol-1, 1F = 96500 C]
1.5 (t) How much electricity was consumed ?
The weights of copper and zinc can be calculated by
using Faraday’s second law of electrolysis.
(it) What was the weight of oxygen gas liberated ?
In cell A, the electrode reaction is (C.B.S.E. Sample Paper 2011)
Zn** +2e ——> Zn Solution : (z) In first cell, silver is deposited at cathode as
2 mol of electrons or 2 x 96500 C of current produce 1 mol Ag*(ag) + e ——> Agi(s)
or 66.3 g of Zn so that
107.8 g of Ag require electricity = 96500 C
2 x 96500 C of electricity deposit Zn = 65.3 g
1.078 g of Ag require electricity = 965 C
65.3
1295.6 C of electricity deposit Zn = x 1295.6 (zt) O, gas liberated at anode of first cell and second cell
2 x 96500
according to the equation:
= 0.438 g.
In cell C, the electrode reaction is
2H, OW) ——> 4H*(aq) + 4e- + O,(g)
2 mol of electrons or 2 x 965600 C of current produce 4 x 96600 C electricity = 1 mol of O, at each cell
1 mol or 63.5 g of Cu so that = 32 g of O, at each cell
2 x 965600 C of current deposit Cu = 63.5 ¢
a2
63.5 x 1295.6 965 C ofelectricity = x 966 =0.08 gO, ateach cell
1295.6 C of current deposit Cu 4 x 96500
2 x 96500 Total amount of O, at anode of both cells = 2 x 0.08=0.16g.
= 0.426 g. L) Example 61
LJ Example 58
How many moles of mercury will be produced by
In the electrolysis of acidulated water, it is desired to
electrolysing 1.0 M Hg (NO,), solution with a current
obtain hydrogen at the rate of Icc per second at STP of 2.00 A for 3 hours ?
conditions. What should be the current passed ?
Solution :
[Hg(NO,). = 200.6 g mol-4] (A.LS.B. 2011)
2H* + 2e~.——-> H, Solution : Hg?* + 2e° —> Hg
1 mol of H, or 22400 cc of H, at STP requires = 2 x 965600 C Quantity of electricity passed = I x ¢ (sec.)
2x 96500 = 2.0 Ax 3.0 x 60 x 60
.. lec of H, at N.T.P. requires = =. Sees
22400 = 21600C
2 x 965600 C of electricity produce mercury = 1 mol
Now, Q=Ixt
21600 C of electricity will produce mercury
l= Q__ 8.616 1
t ls = 9x96500 * 71600
8.616 ampere. = 0.112 mol.
ca MODERN'S abe + OF CHEMISTRY
-AIl

=prak em
51. Calculate the mass of Ag deposited at cathode when a current of 2 amperes was
passed through a solution of AgNO, for 15 minutes.
(Given : Molar mass of Ag = 108 g mol, 1F = 96500 C mol) (D.S.B. 2017)
52. When a current of 0.76 A is passed through a CuSO, solution for 26 min, 0.369 g
of copper is deposited. Calculate the atomic mass of copper.
53. How many grams of chlorine can be produced by the electrolysis of molten NaCl
with a current of 1.00 A for 15 minutes?
54. How many coulombs of electricity are required for the following processes :
(t) oxidation of 1 mol of FeO to Fe,O,
(iz) oxidation of 1 mol of H,O, to O,
(zit) reduction of 1 mol of F, to 2F°?
— Answers to Practice Problems —= -
The same quantity of electrical charge that deposited 0.583 g of silver was passed
51. 2.014¢. through a solution of gold salt and 0.356 g of gold was formed. What is the oxidation
Be. Go. LL.
state of gold in this salt ?
53. 0.331 g. = How many hours does it require to reduce 3 mol of Fe** to Fe** by passing 2.00 A
54. (2) 96600 C arent?
(iz) 195000 C 57
What current in amperes is required to produce 50.0 ml of O, gas measured at
(iii) 193000 C. °
STP by electrolysis of water for a period of 3 hrs ?
Tae ne
How much electricity in terms of Faradays is required to produce ?
56. 40.21 hr. .
(z) 10.0 g of Ca from molten CaCl,
57. 0.0798 A.
(11) 81 g of Al from molten Al,O,
58. (2)0.6 F (22) 9.0 F
Silver is electrodeposited on a metallic vessel of surface area 800 cm? by passing
59. 2.89 x 10-4 em. 59.
a current of 0.2 ampere for 3 hours. Calculate the thickness of silver deposited,
60. 4.44 PF.
given its density is 10.47 g/cc. (At. wt. of Ag = 107.92).
Hints & Solutions on page 74 60. How much electricity in terms of Faraday is required to produce 40 g of Al from
molten Al,O,? (Atomic mass of Al = 27) (Hr. S.B. 2071)

2 PROBLEMS Accelerate Your Potential

Problem }? Silver is electrodeposited on a metallic

3600 C of electricity deposited Ag = x 3600
vessel of total surface area 900 cm* by passing acurrent of 96500
0.5 ampere fortwo hours. Calculate the thickness of silver = 4.029 g
deposited (given density of silver = 10.5 g cm-, atomic Let the thickness of silver deposited = x cm

mass of silver = 108 amu, F = 96500 C mol). (A.LS.B. Weight = Volume x Density
2006) = Area x Thickness x Density
4.029 = 900 x x x 10.59
Silver is deposited as
4.029
Agt+e— ——> Ag ie eee ee :
Quantity of electricity passed, Q = I xt
5 ~ = 900
x10.59 ae oe,
brats— oe iEx Chromium metal can be plated out froman
D-05x
2x 00% 60 — sod acidic solution containing CrO, according tothe following
96500 C of electricity deposited = 108 g Ag reaction:
ELECTROCHEMISTRY

CrO, (aq) + 6 H* (aq) + 6e- —> Cr (s) +3H,O 10800 C of current reduce palladium ions

Calculate (7) how many grams of chromium will be — 106.48 , 10800

plated out by 24,000 coulombs and (77) how long will it 96500 n
take to plate out 1.5 go0f chromium using 12.5 amp current But amount of palladium ions reduced = 2.977 ¢
? (Atomic mass of Cr = 52),
106.4
—— *& 0800 = Zari
CrO, (aq) + 6Ht (ag) + 6e-> Cr(s) + 3H,O 96500 n

Since 6 mole of electrons are required to deposit 1 mol of Cr, 106.4 x 10800
or ee
(4) 6x 96500 C of electricity deposit Cr = 52 g 96500 x 2.977
24,000 C of electricity will deposit Cr
Palladium ions are Pd** or charge on palladium is +4.
_—°*D2 __ 94 000 = 2.1554
96500 x6 8
14 Acurrent of 1.5Ais passed through 500 mL of
(11) Amount of electricity needed to plate out 1 mol Cr
0.25 M solution of zine sulphate for 1 hr with a current
(62 g)=96500 x 6C
efficiency of 90%. Calculate the final molarity of Zn**
Amount of electricity required to deposit 1.5 g of
assuming volume to be constant.
Cr

Sen eno Quantity of electricity passed, Q =I xt

52
Time for which electricity is to be passed,
Is 1 Bx t= 1 60x 60 = J600s
2 Nhe 100

16071.9 = 12.5xt Q = 15x" x 3600

100
t baad et 1356.15 = 4860C
~ to7

s 22,27 min.
Faraday of electricity passed = cata = 0.060F
iE An aqueous solution of an unknown salt 96500
of palladium is electrolysed by a current of 3.0 A passing Now Zn** + 2e-—>Zn
for 1 hr. During electrolysis, 2.977 g of palladium ions 2F of electricity convert 1 mol of Zn** to Zn.
are reduced at the cathode. What is the charge on the 1
0.06 F of electricity will convert Zn** to Zn = 2 x 0.05
palladium ions in solutions ?
= 0.025 mol

Quantity of electricity passed, 0.25

Initial moles of Zn2+ in 600 mL solution = 1000 x 500
Q = lw
= 0.125 mol
= 3.0 x 1.0 x 60 x 60 = 10800 C
Moles of Zn** ions left in the solution = 0.125—-
Now, palladium ions are reduced at cathode as
0.025
| sas + ne> ——> Pd
= 0.10 mol
1 mol n-mol 1 mol (106.4 g)
Q.1
n mol of electrons or n x 96600 C produce 106.4 g of pal-
Final molarity of Zn?* solution = 500 x 1000
ladium.
= 0.2M
96600 nC of current reduce palladium ions = 106.4 g
ac DIFFERENCES BETWEEN GALVANIC CELL AND
MODERN'S abe + OF CHEMISTRY
-AIl

Electrochemical cell
Cathode is +ve (Reduction)
ELECTROLYTIC CELL
Anode is —ve (Oxidation) The main points of differences are summed up below :
Electrolytic cell Electrochemical cell Electrolytic cell
Cathode is —ve (Reduction)
I It is a device which converts chemical It is a device which converts electrical
Anode is +ve (Oxidation)
energy into electrical energy. energy into chemical energy.
2. In this case, the redox reaction is The redox reaction 1s non-spontaneous
spontaneous and is responsible for the and electrical energy is supplied to
production of electrical energy. make the reaction to occur (1.e., chemical
change to take place).
. The two half cells are set up in different Both the electrodes are placed in the
containers and are connected through salt solution or molten electrolyte in the
bridge or porous partition. same container.
. In electrochemical cell, anode 1s negative In electrolytic cell, anode is positive and
and cathode is positive electrode. cathode is negative electrode.
. Oxidation occurs atnegative electrode and Oxidation occurs at positive electrode and
reduction occurs at positive electrode. reduction occurs at negative electrode.
. The electrons move from anodeto cathode The electrons are supplied by the
REMEMBER in external circuit. external battery and enter through
Electro Electrolytic cathode and come out through anode.
chemical
cell SOME COMMERCIAL CELLS : BATTERIES
Cathode One of the main uses of galvanic cells is the generation of portable electrical
Sign +ve —ve energy. These cells are also popularly known as batteries. The term battery
is generally used for two or more galvanic cells connected in series. Thus, a
Function electron cation
battery is an arrangement of electrochemical cells that can be used as a source
accepting attracting
(reduction) or cation of direct electric current at a constant voltage. The basis of an electrochemical
reduced cell is an oxidation-reduction reaction. However, for practical purposes there
are some limitations to the use of redox reactions.
Anode
A useful battery should also fulfil the following requirements :
Sign —ve +ve (4) It should be light and compact so that it can be easily transported.
Function electron anion (it) It should have reasonably long life both when it is being used and
supplying attracting when it is not used.
(oxidation) or anion (iit) The voltage of the battery should not vary appreciably during its use.
oxidised
Types of commercial cells. There are mainly two types of commercial
cells :
(1) Primary batteries or cells
(11) Secondary batteries or cells.
(4) Primary batteries or cells. In these cells, the electrode reactions
cannot be reversed by an external electric energy source. In these cells,
reactions occur only once and after use they become dead. Therefore, they
are not chargeable. Some common examples are dry cell, mercury cell.
(i1) Secondary batteries or cells. In the secondary cells, the reactions
can be reversed by an external electric energy source. Therefore, these cells
can be recharged by passing electric current and used again and again.
Metal cap §
These are also called storage cells. Examples of secondary cells are : lead
Seal storage battery and nickel-cadmium storage cell.
Graphite Let us discuss some examples :
(cathode)
A. Primary Cells
MnO, + C 1. Dry cells. The most familiar commercial cells are dry cells. These are
used in torches, toys, flash lights, calculators, tape recorders and many other
devices. These are based on Leclanche cell invented by G. Leclanche in 1868.
Paste of
| NH,Cl + ZnCl, A dry cell is shown in Fig. 19. It consists of a zinc cylinder. This is filled with
a moist paste of NH,Cl and little of ZnCl,. The zinc cylinder acts as a anode.
™~ Zinc anode The cathode is a graphite (carbon) rod. The carbon rod is surrounded by a black
paste of manganese dioxide (MnO,) and carbon powder. The zinc case has an
outer insulation of cardboard case. During use, the zinc case gets consumed
Fig. 19. A dry cell. and in the end, it will develop holes which are responsible for leakages. The
leak proof cells or dry cells have an iron or steel sheet covering the zinc.
ELECTROCHEMISTRY

When the cell is working, zinc loses electrons and Zn** ions dissolve in
the electrolyte. The electrons pass around the external circuit and are taken
up at cathode. This causes discharge of NH,* ions from the electrolyte. The
reactions taking place at the electrodes are :
Anode: Zn ——> Zn** + Qe
Cathode : 2NH,*(aq) + 2MnO,(s) + 2e°§ ——-> 2MnO(OH) + 2NH,

Overall: Zn + 2NH,*(aq) + 2MnO,(s) ———> Zn**+ + 2MnO(OH) + 2NH,

In the cathode reaction, manganese is reduced from +4 oxidation state to REMEMBER
+3 oxidation state. Ammonia formed is not liberated as a gas but it combines @® Primary cells in which electrode
with some of the Zn** ions and Cl ions produced from the anode to form reactions cannot be reversed by
complex ion having the formula [Zn(NH,).Cl,]. This also prevents the seal of external electric energy source.
the cell to crack because of developed pressure. = not chargeable.
It gives voltage of approximately 1.2 to 1.5 V. There are many varieties @® Secondary cells in which
of dry cells such as silver cell or lithium cell. electrode reactions can be reversed
by external electric energy source.
This dry cell does not have an indefinite life because of acidic conditions
— chargeable
due to the presence of NH,Cl. Due to the action of Ht ions from NH,’ the
are called batteries.
zinc container (anode) corrodes even when not in use.
Zn(s) + 2H* (ag) —> Zn** (aq) + H,(g)
To avoid this difficulty, a modified form of dry cell called alkaline dry
cell has been prepared. In alkaline dry cell the electrolyte NaOH or KOH
is used in place of NH,Cl.
2. Mercury cell. A new type of cell which has found use in small electrical
circuits such as hearing aids, watches and cameras is the mercury cell. It
consists of a zinc-mercury amalgam as anode and a paste of mercury (II)
oxide and carbon as the cathode. The electrolyte is a paste of KOH and ZnO.
A lining of porous paper keeps the electrolyte separated from the zinc anode.
A commercially used mercury cell is shown in Fig. 20. The reactions occurring
in the cell are as follows :
Anode: Zn(Hg) + 20H” ——-> ZnO(s)+ H,O + 2e- CELL CAN
(Amalgam) SEPARATOR CATHODE

Cathode: HgO(s)+H,O + 2e° ——_> Hg) + 20H™ Fig. 20. A commercially used
mercury cell.
Overall : Zn(Hg) + HgO(s) ——> ZnO(s) + HegiZ)
(Amalgam)
In this case, the overall cell reaction does not involve any ion in solution
whose concentration can change. Therefore, it has the advantage that its
potential remains almost constant throughout its life. This is its special
feature. By contrast, the potential of the ordinary dry cell decreases slowly but
continuously as it is used. The voltage of mercury cell is approximately 1.35 V.
B. Secondary Cells
Ordinary cells are not rechargeable. However, there are some cells which
can be recharged. These are called accumulators or storage cells. These can
be recharged and used again and again as a source of electric current. The
most popular example is lead storage cell which is used in automobiles such
as cars, buses, trucks, ete.
1. Lead Storage Cell
This is the most commonly used battery in automobiles. Each battery
consists of a number of voltaic cells connected in series. Three to six such cells O When a car is running its
are generally combined to get 6 to 12 volt battery. In each cell, the anode is a battery gets charged itself.
grid of lead packed with finely divided spongy lead and the cathode is a grid > When an engine of an automobile
of lead packed with PbO.. The electrolyte is aqueous solution of sulphuric acid (car)is running, electrical energy
(38% by mass) having a density 1.30 g mL sulphuric acid (Fig. 21). When the is produced in the alternator
lead plates are kept for sometimes, a deposit of lead sulphate is formed on them. which keeps on charging the
At the anode, lead is oxidised to Pb** ions and insoluble PbSO, is formed. battery.
At the cathode, PbO, is reduced to Pb** ions and PbSO, is formed.
ce MODERN'S abe + OF CHEMISTRY
-AXIl

© Anode

ii
| G@) Cathode

Lead plates PbO, plates

Aqueous H,SO,

(a)

Fig. 21. (a) Lead storage battery; (6) Lead storage battery (commercial design).

The following reactions take place in the lead storage cell :

At anode. Lead loses two electrons and is oxidised to Pb** ions
Ph(s) —A— Pb**(ag) + 2e-
Pb**(aq) + SO,? (aq) ———> PbSO,(s)
The overall anode reaction may be written as :
Pb(s) + SO,*7 (aq) ———> PbSO,(s) + 2e7
At cathode. The PbO, is reduced as :
PbO,(s) + 4H* + 2e°- ———> Pb**(aq) + 2H,O
Pb**(aq) + SO,? (aq) ———> PbSO,(s)
The overall cathode reaction is :
PbO,(s) + 4H*(aq) + SO j/ (aq) + 2e- —>PbSO, (s) + 2H,O(/)
Thus, the complete electrode reactions and overall cell reaction are :
Lithium Batteries
Anode :
@® These days a large number of
Pb(s) + SO, (ag) ———> PbSO,(s) + 2e7
batteries are known in which
lithium metal is used as an anode
Cathode :
and are known as lithium batteries PbO,(s) + 4H* + SO,? + 2e~- ———> PbSO,(s) + 2H,O
and have different cathode and Overall :
electrolyte. Lithium is a light metal Ph(s) + PbO,(s) + 2H,SO,(aq) ———> 2PbS0,(s) + 2H,O (2)
and has low electrode potential
The cell may be represented as:
and good conductivity. Therefore,
lithium is a good material for Pb | PbSO, ||H,SO,(aq) | PbO, | Pb
batteries which provide high The potential of the cell depends on the concentration (density) of H,SO,.
potential. These may be primary It is clear from the above reactions that during the working of the cell, PbSO,
or secondary. is formed at each electrode and sulphuric acid is used up. As a result, the
Lithium ion batteries are concentration of H,SO, decreases and the density of the solution also decreases.
rechargeable and are now becoming
When the density of H,SO, falls below 1.2 g mL-1, the battery needs recharging.
very popular for use in lap tops,
computers, cell phones, MP-3 Recharging the Battery
players, etc. These provide high The cell can be recharged by passing electric current of a suitable voltage in
voltage in the range 3.6—3.7 V.
the opposite direction. The cell works like an electrolytic cell and the electrode
These cannot be discharged by
reactions get reversed. All the cell reactions that occur during discharge are
themselves easily and therefore, can
be used for longer periods. These reversed where H,SO, is generated and its concentration is increased. During
consist of cathode made of lithium charging process, the functions of anode and cathode are reversed. Now PbO,
cobalt oxide (LiCoO,) and anode electrode is anode (+ve) and Pb is cathode (—ve).
made of graphite. The electrolyte At anode. It is the reverse reaction at cathode during discharge.
used is lithium salt (commonly
LiPF,) dissolved in some organic
PbSO,(s) + 2H,O() ———> PbO,(s) + 4H*(aq) + SO,7 (aq) + 2e7
solvent (ethylene carbonate or At eathode. It is reverse of oxidation at anode during discharge.
dimethyl carbonate). PbSO,(s) + 2e° ——— Ph(s) + SO,* (aq)
ELECTROCHEMISTRY

The net cell reaction is

Anode: PbSO,(s) + 2H,O(W@) ——— PbO,(s) + 4H*(aq) + SO,7 (aq) + 2e°
Cathode : PbSO,(s) + 2e° ———> Pb(s) + SO,7 (aq)
Overall 2PbSO,(s)+2H,0()——> Pb(s) + PbO,,(s) + 4H*(aq) + 280,,2(aq)
or 2PbS0O,(s) + 2H,OW@) ———+ Ph(s) + PbO,(s) + 2H,50,(aq)
Such an operation is possible because the PbSO, formed during discharge
is a solid and sticks to the electrodes. Therefore, it can either take or give up
electrons during electrolysis. Thus, the overall reaction is exactly opposite
the normal cell reaction. The reaction shows that H,SO, is regenerated and
its density increases. Hence, cell potential increases and the cell is recharged.
It may be noted that storage battery acts as voltaic cell as well as electrolytic
cell. For example, when it is used to start the engine of the automobile, it
acts as a voltaic cell and produces electric energy. During recharging, it acts
as an electrolytic cell.
2. Nickel Cadmium Storage Cell
This is also a rechargeable cell. It has longer life than the lead storage
cell but more expensive than lead storage battery. However, it has some
advantages because it is smaller and lighter. It can be used in portable and
cordless appliances. It consists of a cadmium anode and a metal grid containing
NiO, acting as a cathode as shown in Fig. 22. The electrolyte in this cell is
KOH. The reactions taking place during discharge and charge are :
Anode:
. __Discharge |
Cd(s) + 20H a CdO(s) + HOW + 2e
Cathode:
Disch
2Ni(OH), (s) + 2e7 ===
Charge
2Ni(OH), - (s) + 2OH(aq)
Overall :
Cd(s) + 2Ni(OH), (s) Pischarge_. CdO(s) + 2Ni(OH),(s) + H,OW
harge
In these reactions, there is no formation of gaseous products. The reaction Positive plate
products generally remain sticking to the electrodes and can be reconverted Separator plate
by recharging the cell. The charging process is similar to lead storage battery.
It produces a potential of about 1.4 V. It has longer life than lead storage cell. Fig. 22. Nickel-cadmium cell
Some main characteristics of common cells are :

Graphite/Zine MnO, + © “én —> A ee oe a

(touching cathode)| Cathode : MnO,(s) + NHj (ag) + e= ~—> MnO(OH) + NH,]x2

NH,Cl + ZnCl, 4n + 2Mn0O,(s) + 2 NH; (ag) —3 Zn*++ 2MnO(OH)+ 2NH,

(touching anode)

Mercury | }Hg(II) oxide/Zinc| Paste of KOH and| Amode : fn(Hg) + 20H” —> én hs} + HO + 2e™
cell Cathode: HgOis) + HO + ze —> Hg?) + 20H

4n(Hg) + HgO(s) —> ZnO(s) + Hgi2)

Lead Lead packed with 2807 H,SO, Anode : Pb(s) + SOF (ag) —> PbSO,(s) + 2e7
storage
PbO, / Lead solution
Cathode : PbO,(s) + SO* (ag) + 4H* (ag) + 2e° —> PbSO,(s) + 2H,O
cell
Pb(s) + PbO,(s) + 2H,SO,(aq) —> 2PbSO,,(s) + 2H,O
Nickel- NiO, /Cd KOH solution Anode : Cd(s) + Z0H —> CdO(s) + H,O() + 2e7
Cadmium Cathode: 2Ni(OH),(s) + 2e~ —-> 2Ni(OH),(s) + 2OH- (ag)
storage
cell Cd(s) + 2Ni(OH), (s) —> CdO (s) + 2Ni(OH), (s) + H,O(@)
FUEL CELLS
Fuel cells are galvanic cells in which the energy of combustion of
fuels like hydrogen, methane, methanol, etc is directly converted
into electrical energy.
ace MODERN'S abe + OF CHEMISTRY
-AXIl

H,0 we In these cells, the reactants are continuously supplied to the electrodes
Anode © © Cathode eae and the products are continuously removed from the electrolyte compartment.
Therefore, these fuel cells differ from the ordinary galvanic cells in that the
reactants are not placed in the cell but are continuously supplied to the
electrodes from the reservoir. The common example is hydrogen-oxygen fuel
cell as described below:
=—0O,
Hydrogen-Oxygen Fuel Cell
In H, — O, fuel cell, hydrogen gas is used as fuel and oxygen gas acts as the
Electrolyte
oxidising agent. The energy of combustion of H, is converted into electrical energy.
Porous carbon
The cell consists of porous carbon electrodes immersed in concentrated
electrodes aqueous sodium hydroxide or potassium hydroxide solution. Catalysts like finely
Fig. 23. A simple H,—O, fuel cell. divided platinum or palladium metal are incorporated into the electrodes for
increasing the rate of electrode reactions. Hydrogen and oxygen are bubbled
through porous electrodes into the NaOH or KOH solution (Fig. 23). Hydrogen
(the fuel) is fed into the anode compartment where it is oxidised. The oxygen
is fed into cathode compartment where it is reduced. The diffusion rates of
developments. Fuel cells based on the
combustion of hydrocarbons such as the gases into the cell are carefully regulated to get maximum efficiency. The
CH,, C,H,, CsHg, ete. in the presence net reaction is the same as burning of hydrogen and oxygen to form water.
of catalysts have been designed. Many
varieties of fuel cells are possible andin Anode: 2[H,(g) + 20H (aq) ——> 2H,O(/) + 2e7]
some the electrolyte 1s a solid polymer
membrane or a ceramic. Depending Cathode: O,(g) + 2H,O(W) + 4e— ——> 40H (aq)
upon the different types of electrolytes
used, the fuel cells are classified as
Overall : 2H,(g) + O.(¢) ———> 2H,O()
(1) alkali fuel cellsl[electrolyte is The theoretical voltage of an ideal H, — O, fuel cell at standard conditions
KOH(aq)] of 1 atm pressure and 298 K temperature is 1.23 V. However, the typical
(it) phosphoric acid fuel cells
[electrolyte 1s H,PO,(aq). operating voltage is about 0.6 — 0.7 V for high performance fuel cells. This cell
(111) Molten carbonate fuel cells runs continuously as long as the reactants are fed. These fuel cells are more
[electrolyte is K,CO,(J)/ efficient than conventionally used methods of generating electricity on a large
Li,COQ,(2)].
In this, methane is used as a fuel.
scale by burning hydrogen, carbon, fuels because these fuel cells convert the
Recently, a zinc-air fuel cell (ZAFC) energy of the fuel directly into electricity.
is developed in USA as a source of This cell has been used for providing electric power in the Apollo space
power in automobiles in which zine
metal is used 1n place of hydrogen gas.
programme. Fuel cells offer great promises for energy conversion in future.
The important advantages of fuel cells over ordinary batteries are:
Efficiency of a Fuel Cell (1) High efficiency. The fuel cells convert the energy of a fuel directly
The theoretical efficiency of a fuel into electricity and therefore, they are more efficient than the conven-
cell can be calculated from enthalpy of tional methods of generating electricity on a large scale by burning
combustion (AH) and useful work done hydrogen, carbon fuels. Though we expect 100% efficiency in fuel
(AG)z.e., electricity produced. The thermo-
cells, so far 60 — 70% efficiency has been attained. The conventional
dynamic efficiency (1) of a fuel cell is
methods of production of electrical energy involve combustion of a
Efficiency (n) = = X100 fuel to liberate heat which is then used to produce electricity. The
efficiency of these methods is only about 40%.
For example, AH for H,—O, fuel (11) Continuous source of energy. There is no electrode material to
cell has been found to be —285.6 kJ mol be replaced as in ordinary battery. The fuel can be fed continuously
and theoretical voltage of the cell has
to produce power. For this reason, H, — O, fuel cells have been used
been found to be 1.23 V.
in space crafts.
AG (uel cell) — —2kE
(iit) Pollution free working. There are no objectionable by-products
= (—2) x (96500 C mol)
and, therefore, they do not cause pollution problems.
x (1.23 V)
Another common fuel cell is propane-oxygen cell. The half cell reactions are:
= —237390 J mol!
= —237.39 kJ mol
Anode: C,H,(g) + 6GH,07@) ———> 3CO,@) + 20H* + 20 e-
~237.39 kJ mol
~ 985.5 kJ mol
x 100 = 83%
Cathode: 50,(g) + 20H*(aq) + 20 e- ——> 10H,O(2)
The actual efficiency of the cell is Overall : C,H,(g) + 50,(g) ——> 3C0,(g) + 4H,O@)
60-70%
ELECTROCHEMISTRY

Since fuel cells are efficient and free from pollution, attempts are being
made to get better commercially practical fuel cells.

CORROSION
When metals are exposed to atmospheric conditions, they react with air
or water in the environment to form undesirable compounds (usually oxides).
This process is called corrosion. Almost all metals except the least active
metals such as gold, platinum and palladium are attacked by environment
i.e., undergo corrosion. For example, silver tarnishes, copper develops a green
coating, lead or stainless steel lose their lustre due to corrosion. Corrosion
causes enormous damage to buildings, bridges, ships and many other articles
made of iron. Thus,
corrosion is a process of deterioration of a metal as a result of its
reaction with air or water (environment) surrounding tt.
In case of iron, corrosion is called rusting. Chemically, rust is hydrated
form of ferric oxide, Fe,O, . xH,O. Rusting of iron is generally caused by
moisture, carbon dioxide and oxygen present in air. It has been observed that
rusting takes place only when iron is in contact with moist air. Iron does not
rust in dry air and in vacuum.
Factors which affect corrosion. The main factors which affect corrosion
are :
(1) Position of metals in e.m.f. series. The reactivity of metal depends
upon its position in the electrochemical series. More the reactivity of
metal, the more will be the possibility of the metal getting corroded.
(i1) Presence of impurities in metals. The impurities help in setting
up voltaic cells, which increase the speed of corrosion.
(iit) Presence of electrolytes. Presence of electrolytes in water also
increases the rate of corrosion. For example, corrosion of iron in sea
water takes place to larger extent than in distilled water.
(iv) Presence of CO, in water. Presence of CO, in natural water
increases rusting of iron. Water containing CO, acts as an electrolyte
and increases the flow of electrons from one place to another.
(v) Presence of protective coatings. When the iron surface is coated
with layers of metals more active than iron, then the rate of corrosion
is retarded. For example, coating of zinc on iron prevents rusting.
Mechanism of Rusting of Iron
Electrochemical theory of rusting. The phenomenon of corrosion can
be explained with the help of electrochemical theory which involves oxidation
and reduction reactions. According to electrochemical theory of corrosion, it is
believed that non-uniform surface of metal or impurities present in iron behave
like small electric cells (called corrosion couples) in the presence of water
containing dissolved oxygen or carbon dioxide. A film of moisture with dissolved
CO, constitutes electrolytic solution covering the metal surface at various places.
The schematic representation of mechanism of rusting of iron AIR
is shown in Fig. 24. Drop of moisture
In the small electrolytic cells, pure iron acts as anode
while cathodes are impure portions. The overall rusting
involves the following steps :
At a particular spot of an object made up of iron, oxidation
takes place and the spot behaves as an anode.
At anode Fe(s) ———> Fe** (ag) +2e _...(4)
Thus, the metal atoms in the lattice pass into the solution Fig. 24. Schematic representation of mechanism of
as ferrous (Fe**) ions, leaving electrons on the metal itself. rusting of iron.
 MODERN'S abe + OF CHEMISTRY-AIl

These electrons go to another spot on the metal and reduce atmospheric

oxygen to water in the presence of H* ions.
The H+ ions are obtained either from water or from acidic substances
(e.g., CO,) in water:
HO -——>..H&-+ OB! si)
or CO, + H,O ——-> H,CO, vk)
HCO, a3 G0." ea
This spot behaves as cathode and the reaction is
4H* +O, + 4e— ———> 2H,O ...(8)
The overall redox reaction may be written by multiplying reaction at
anode Eq. (4) by 2 and adding reaction at cathode Eq. (8) to equalise number of
electrons lost and gained i.e.,
Oxidation half reaction
Fe(s) ———> Fe?*(aq) + 2e] x 2 (E? =_0.44 V)
Reduction half reaction
4H* +O, + 4e- ——> 2H,0O (E* = 1.23 V)
Overall cell reaction
2Fe(s) + 4H* +O, ——> 2Fe**(ag)+2H,O (E* ,,, = 1.67 V)
The ferrous ions are oxidised further by dissolved oxygen or atmospheric
oxygen from air to form ferric oxide with further production of H* ions. The
ferric oxide then undergoes hydration and the hydrated form of iron(II) oxide
is known as rust:
4Fe**(aq) + O,(g) +4H,O ———> 2Fe,0, + 8H*
and Mega? +4a7,0 ——> Fe,0,.xH,O
Rust
It may be noted that salt water accelerates corrosion. This is mainly due to
the fact that salt water increases the electrical conduction of electrolyte solution
formed on the metal surface. Therefore, rusting becomes more serious problem
where salt water 1s present.
Prevention of Corrosion
The prevention of corrosion is very important and essential. It not only
saves money but also helps in preventing serious accidents such as a bridge
collapse or a failue of a key component due to corrosion. This can be prevented
or retarded by the methods given below :
1. Barrier protection. This is one of the simplest methods to prevent
rusting ofiron. In this method, a barrier is placed between iron and atmospheric
air. The barrier protection can be achieved by any of the following methods :
(4) the surface is coated with paint or some chemicals (e.g., bisphenol).
(11) the surface is protected by applying a thin film of oil or grease.
(iii) the metal is electroplated with metals like tin, nickel, zinc, chromium,
aluminium, ete.
For example, many vehicles such as cycles, motors, cars made from iron
sheets are protected from rusting by paints. Many iron articles are electroplated
with coating of other metals. The electroplating is carried not only for achieving
brightness but also to protect from corrosion.
2. Sacrificial protection. In this method, iron is protected from rusting
by covering it with a layer of a metal more active than iron. This prevents loss
of electrons from iron. The active metal loses electrons in preference to iron and
goes into ionic state. Therefore, the covering metal is consumed with time, but
as long as it is present on the surface of iron, the latter is not rusted. This type
of process in which rusting of iron is protected is called sacrificial protection.
ELECTROCHEMISTRY

Zine is commonly used for covering iron surfaces. The process of covering
iron with zine is called galvanization. The galvanized iron materials maintain
their lustre due to the coating of invisible layer of basic zinc carbonate, ZnCO,.
Zn(OH), on the zinc film. If some scratches occur on the protective zinc film
on coated iron, even then iron will not be rusted. This is due to the fact that
because of scratches, both zinc and iron get exposed to oxidation but zinc
undergoes oxidation in preference to iron. This is so because the reduction
potential of zinc is less than the reduction potential of iron.
Zn2*(aq) + 2e- ———_ Zn(s); EX =- 0.76 V
Fe2* + 2e- ===> Fe(s); EX =—0.44V

Drop of moisture

Flow of
electrons

Iron (cathode)

Fig. 25. Protection of rusting of iron with a film of zinc. Rusting will not occur even
when iron surface 1s exposed.

Therefore, zinc undergoes oxidation in preference to iron.

However, it may be noted that in the case of tin plating, i.e., tin coating on
iron, the film will be effective as long as it is intact. When scratches occur at Mg-> Mg** + 2e7
the coating surface both the metals are exposed to oxygen and iron is preferably anode
Ground level
oxidised and is rusted. This is due to the fact the reduction potential of tin
is more than that of iron.
Sn2+(aqg) + 220° =m Sn(s); BE? =-0.14V
Fe** + 200 = Fe(s); E°=-0.44V Magnesium lron pipe
(anode) (cathode)
Thus, iron will be oxidised in preference to tin.
O, + 4H* + 4e- > 2H,0
3. Electrical protection. This method is used for protecting iron articles
or O, + 2H,O + 4e- > 40H”
which are in contact with water such as underground water pipes. The article
of iron is connected with more active metals like magnesium or zinc (Fig. 26). Fig. 26. Protection of rusting of
The active metal has lower reduction potential than iron and will lose electrons underground iron pipes by
electrical protection method.
in preference to iron. For example, magnesium has lower reduction potential
than iron :
Mg** (aq) + 2e° ——> Meg(s); E* =-2.37V
Fe2* (aq) + 2e —— Fe(s); E° =—0.44V
Therefore, magnesium will be oxidised in preference to iron and therefore,
it will protect iron from being rusted.
4. Using anti-rust solutions. To retard the corrosion of iron, certain
anti-rust solutions are used. For example, solutions of alkaline phosphates
and alkaline chromates are generally used as anti-rust solutions. Due to the
alkaline nature of these solutions, the Ht ions are removed from the solutions
and rusting is prevented. For example, iron articles are dipped in boiling
alkaline sodium phosphate solutions, when a protective insoluble sticking film
of iron phosphate is formed.
 MODERN'S abe + OF CHEMISTRY-AXIl

» How many electrons flow through a metallic wire if a current of 0.5 A is passed for 2 hours?
(Given : 1F = 96,500 C mol!) (A.I.S.B. 2017)
Q=Ixt
—- 0.6 x 2 x 60 x 60
= 3600 C
Now, 96600 C = 6.022 x 10”° electrons
aanate 6.022 x10*° x 3600
_ 96500
= 2.25 x 10” electrons
Q. 2. Write the name of the cell which is generally used in hearing aids. Write the reactions taking place
at the anode and the cathode of this cell. (A.LS.B. 2017)
Ans. Mercury cell
At Anode: Zn (Hg) + 20H-——-> ZnO + H,O + 2e-
(Amalgam) z
At Cathode: HgO + H,O + 2e ———> Hg (J) + 20H
Q. 3. Write the name of the cell which is generally used in transistors. Write the reactions taking place at
the anode and the cathode of this cell. (A.LS.B. 2017)
Ans. Dry cell
Anode: Zn (s) ——> Zn** + 2e7
Cathode: MnO, + NH,* +e ——> MnO(OH) + NH,
. Write the name of the cell which is generally used in inverters. Write the reactions taking place at
the anode and the cathode of this cell. (A.LS.B. 2017)
. Lead storage battery
Anode: Pb(s)+ so? (aq) ———> PbSO, (s) + 2e7
Cathode: PbO, + Soy (aq) + 4H* + 2e° ———> PbSO,(s) + 2H,O(Z)
. From the given cells:
Lead storage cell, Mercury cell, Fuel cell and Dry cell
Answer the following:
(4) Which cell is used in hearing aids?
(74) Which cell was used in Apollo Space Programme?
(tit) Which cell is used in automobiles and inverters?
(tv) Which cell does not have long life? (D.S.B. 2016)
(2) Mercury cell
(it) Fuel cell
(111) Lead storage cell
(iv) Dry cell
- What happens if external potential applied becomes greater than E’,_,, of electrochemical cell?
(A.LS.B. 2016)
. IfE®_., (external) is greater than E”__,, the cell starts acting as an electrolytic cell. In this case, electrical energy
is used to carry out non-spontaneous chemical reaction.
. Using the E° values of A and B, predict which one is better for coating the surface of iron [E°(Fe**/Fe
= -0.44V] to prevent corrosion and why?
Given : E° ((A** |A) = -2.37 V and E? (B**|B) =-0.14 V (A.LS.B. 2016)
. ‘A’ will prevent iron from rusting. So, we can coat the iron surface with metal A because it has more negative value.
. Given that the standard electrode potentials (E°) of metals are:
Kt |K =- 2.98V, Ag* |Ag = 0.80V, Cu**|Cu = 0.34V, Mg** |Mg = - 2.37V, Cr**/Cr = - 0.74V and
Fe** |Fe = - 0.44V. (A.LS.B. 2010)
Arrange the metals in the increasing order of their reducing power.
Ans. Ag*|Ag
< Cu**|Cu < Fe?*| Fe < Cr?*|Cr < Mg**/Mg
< Kt| K.
Q. 9. What is change in free energy for (a) galvanic cell and (6) electrolytic cell ?
Ans. (a) For a galvanic cell, free energy decreases i.e., AG < 0
(6) For electrolytic cell, free energy increases 1.e., AG > 0.
Q. 10. Is it safe to stir 1 M AgNO, solution with a copper spoon ? Given E* Agt| Ag = 0.80 V, Ec */ Cu
= 0.34 V. Explain. (Pb.S_B. 2004)
Ans. No, copper spoon will dissolve as Cu** ions because copper has more tendency to get oxidised than silver.
Q. 11. Can Fe** oxidise Br to Br, 2 under standard conditions ?
E* 23+) pe2t = 0.771 V, E*,) p= 1.09 V.
ELECTROCHEMISTRY 3/73 —

Ans. No, because for the reaction,

Fe* + Br-—> Fe? + + Br,
E® = 0.771 — 1.09 =— 0.319 V is negative.
Q. 12. Two metals A and B have reduction potential values — 0.76 V and + 0.34 V respectively. Which of these
will liberate H, from dil H,SO, ?
Ans. Metal having higher oxidation potential (or lower reduction potential) will liberate H, from H,SO,. Thus, A will
liberate H, from H,SO,.
Q. 13. Can tin coating on iron act as sacrificial anode in protecting iron against corrosion ?
Ans. No, because tin is less readily oxidised in comparison to iron (EY 2+ |e =-—044V, E? sn2*| sn =~ 0.14 V). Tin
protects iron only as a cover.

:
Q. 14. What is role of ZnCl, in a dry cell ?
ZnCl, combines with NH, produced to form the complex [Zn(NH,),Cl,], otherwise the pressure developed due to
NH, would crack the seal of the cell.
Q. 15. When the silver electrode having reduction potential 0.80 V is attached to NHE, will it act as anode or
cathode ?
Ans. It will act as cathode.
Q. 16. Name the cell which were used in Apollo space programme.
Ans. Hydrogen-oxygen fuel cell.
Q. 17. How does concentration of sulphuric acid change in lead storage battery when current is drawn from it?
Concentration of sulphuric acid decreases.
8. What is the effect of carbon dioxide in water on corrosion ?
The presence of carbon dioxide in water increases rusting of iron. Water containing CO, acts as an electrolyte and
increases the flow of electrons from one place to another.
9. Why is it not possible to measure the voltage of an isolated half reaction ?
Ans. It is not possible to measure the voltage of an isolated half reaction because neither the oxidation nor the reduction can
occur by itself. Therefore, we can only calculate the relative electrode potential by connecting it to some standard electrode.
Q. 20. Why does a dry cell become dead after a long time, even if it has not been used ?
Ans . Adry cell becomes dead after a long time because the acidie NH,Cl corrodes the zinc container.
Q.. 2 21. Why does the cell potential of mercury cell remains constant throughout its life? (A.LS.B. 2015)
Ans . Thisis because the overall cell reaction does not involve any ion in the solution whose concentration changes during
its life time.
Q. 22. Why is the equilibrium constant K related to only E° cell and not E__,,? li
(D.S.B. 2003)
Ans . This is because at equilibrium, E___,, = 0.
Q. 2 3. How can you increase the reduction potential of an electrode ?
Ans . By increasing the concentration of the ions.
Q. 24. The E° values of MnO,,, Ce* and Cl, are 1.507, 1.61 and 1.358 V respectively. Arrange these in order of
increasing strength as oxidising agent.
Ans. Cl, < MnO, < Ce*.
Q. 25. E° values for Fe** |Fe** and Ag* |Ag are respectively 0.771 V and 0.800 V. Is the reaction :
Fe** + Ag ——> Fe* + Agt spontaneous or not ?
Ans. E° for the reaction is 0.771 — 0.800 =— 0.029 V.
Therefore, the reaction is not spontaneous.
Q. 26. The electrode potentials are :
O,+4e +4Ht — > 2H,0 E° = 1.228 V
Ce* +e — > #£x.Ce* E° = 1.60 V
Will Ce* oxidize H,O to O, in acidic solution ?
Ans. Ce** can oxidize wateras: 4Ce*+2H,O — + O,+4Ce** + 4Ht ali)
Let us calculate its E°.
aa => ier E° = 1.60 V Ait)
O,+4e° +4Ht —-> 2H,O E° = 1.228 V ...(111)
Reversing eqn. (zi1) 2H,Q0O —-> O, + 4e- + 4H* E° = —1.228 V ...(1U)
Multiply eqn. (it) by 4 4Ce*+4e — > £4Ce* E° = 1.60 V (0)
Adding eqn. (iv) and (v) 2H,O0 +4Ce*#* — > O,+4Ce%* + 4Ht E° = 0.372 V
Since E® is positive, reaction is spontaneous and so Ce** will oxidize H,O to O,.
Q. 27. What is the chemical formula of rust ? (H.P.S.B. 2005)
Ans. The chemical formula of rust is Fe,O,. x H,O.
Q. 28. Can we store copper sulphate in an iron vessel or not? Explain. (H.P.S.B. 2005)
Ans. The reduction potentials of Cu** | Cu and Fe** | Fe are + 0.34 V and — 0.44 V respectively. This means Cu** will be
reduced to Cu and iron will be oxidised to Fe**. In other words, the vessel will dissolve. Therefore, it is not possible
to store CuSO, 1n an iron vessel.
Q. 29. Is e.m.f. extensive or intensive property ?
Ans. Intensive property.
Q. 30. What is the use of platinum foil in the hydrogen electrode ?
Ans. It is used for inflow and outflow of electrons.
 MODERN'S abe + OF CHEMISTRY
-AIl

Cell cons tan t l

O11. Conductivity(K) = CTs kK = Gx —-
Resis tan ce a
= Fg AM os0.025 S em!
0.357 cm 30 2.0
31.6 ohm i = kK X 1000
0.0113 ohm! cm M
K xX LOOO = ae = 50 ohn! cm? mol!
Molar conductivity
M Sk Pai wandiaki= conductivity _ 0.002768
0.0113 x 1000 conductance 1/ 457.3
= 1.266 em!
0.05
For CaCl, solution,
226 ohm! cm? mol! « = 1x 1.266 = 0.00627 ohm- cm
202
A — «1000 _ 0.00627 x 1000
M CVs 0.05
132.6 = «xx 1000 = 125.4 ohm cm? equiv!
0.01
Oo. K=Gx GtorGt= —
ee SPR UM 1 Set char a where G is conductance and G* is cell constant
1000

Cell constant GF =
_ 129x107 Sem™ = 1.0965 a1
Now « = —————_
R 1/85 =
or cell constant = « x K « for 0.052 mol L7 solution,
=(1.326 x 10° ohm! em“) x (1412 ohm) k= Gx G*

= 1.87 cm! = 55 1.0965 = 1.142 x 10°°S em!

« x 1000
« x 1000 AxC
U3. A= Ee or K = 1000 M
1.142 x 107 x 1000
— 4200.01 _ - 4 0.052
K = —T000 =-492x10°S cm
-—3
= 219.6 S em? mol!
0110. Cell constant = 1.29 x 200 = 258 m™ or = 2.58 em?
Cell constant 0.88
1
— 4.77 x 107 ohm K = 2.58 x—— = 2.345 x 107 S em).
1100
: ]
Resistance = 477 %102.— 209.5 ohm =|
A = 2.345 x 10™ x 1000 = 117.25 S em mol}

0.02
il 1.4 _¥
Li4. Cell constant = — =— =0.5 em or — 1.175 x 10° Sm? mol.
a soe

« = 1 05+20.~ 102 S em O11. oo ‘4

25 M
x _9
A = 2.0 x107 x 1000 _
0.5
AQ) S cm” equiv-
194.5 =

O15. Cell constant (G*)

K
= — = —————_
2.78x10° 194.5 0.05
Cc 1/ 82.5 ur x= —T000
= 0.229 cm! — 9.725 x 10° S em? mol.
416. Molarity of solution = on = 0.0240 M Now, R= i x L
K a
= 0.0058 x 1000 = 241.67 ohm em? mol
sala 1/104 x 1000
_~_ 1, 9 _ 3497 ohm
Normality of solution = — = 0.0480 N 9.725x10” 1.50

A= Leon 120.83 ohm! cm? equiv! V=TRorI- » ~~ 2° =0.146A

0.0480 R 34.27
ELECTROCHEMISTRY

(11 12. Cell constant = « x KR «x1000 3.905 x10” x 1000

= 0.002768 x 520 = 1.43936 cm? = M | 0.001
specific conductivity for salt solution, = 39.05 S cm? mol
k = Cell constant x conductance
CH,COOH GHCO! di
1
1.438936 x — A. SLA cH,coo- + A” sy
300
— 40.9 + 349.6 = 390.5 S cm* mol!
— 0.00478 ohm cm
Degree of dissociation,
_ 0.00478 x 1000
Am _ 39.05
1/25
Cyn,” 96 — Oo!
= 119.5 S cm? equiv!.
L) 18. (i) A°CNH,OH) = A°CNH,Cl) + A*™CNaOH) — A”(NaCl)
1113. Taking the square root of concentrations, we get,
— 239.2 ohm! cm* mol-!
C (mol L7*) C2(mol L-4)? A,, (S em? mol)
0.000198 0.01407 148.61 o — 9-33 _ 0.039 or 3.90%
(it)
0.000309 0.01768 148.29 239.2
0.000621 0.02283 147.81 Co? — 0.01 x (0.039)? _ :
0.000989 0.031465 147.09 ee «i-th
Plot of A, and C?”? is given below :
Li 19.
_ «x1000 _ 9.47x 10" x 1000
C 0.1
= 94.75 cm? equiv!
A’ = Am (Agt) + A(NO,-) = 106.5 S em® equiv”

94-7 _ 0.80 or 89%

> Gone:
L) 20. A° HCOOH) = A°(H*) + ACH COO)
= 40.42 S em? mol
4.61
= 94
|
0.114
2 2

0 0.005 0.010 0.015 0.020 0.025 0.030 0.035 1-oa (1-—0.114)

pK, = — logK, = — log (3.30 x 10“)
C’2(mol L-)14 = 3.4815
The extrapolation of the staight line to zero concentration Ly 21. ACaCl,) = A°(Ca?*) + 20°(CL)
(intercept) gives the value of A® = 160.0 5 cm? mol.
— 271.6 S cm? mol!
A = — slope = 87.46 5 cm? mol / (mol L“+)*?
A°(MgSO,) = A°(Mg**) + A°(SO,°)
O14. A°(CH,COOH) = 4° (CH,COO-) + A° (H*)
— 266 S cm? mol!
= 40.9 + 349.6
= 390.6 S cm? mol? 4.95 x 10° x 1000
Ly 22. A= ote ee = 48.15 § em? mol
A = 39.05 5 cm? mol 1.028 x 10°
_ AS 39.05 oO = 48.15_ 9 1933
A° 390.5 390.5
= 0.10 or 10% mc
3

O15. <A™~(AgCl) = A*(AgNO,) + A*( KCl) — A*(KNO,) 1-a

13.84 m 8S m? mol _ 1.028 x 10° —3 x (0.1233? 2

_ 1 ag 195.
O16. A “~NO,-)= A*(KNO,) — A°(K*) 1— 0.123
= 145.0 — 73.6 = 71.5 S em? mol L) 28. A°[Ba(OH),] = A°[BaCl,] + 2A°[NaOH] — 2A°[NaCl]
(Lit) = A*(LiNO,) — A*(NO,7) — 2.800 x 10°? + 2(2.481 x 10-7) — 2(1.265 x 107%)
= 110.1 — 71.5 = 38.6 S cm? mol" — 5,232 x 107 S m? mol.
 MODERN'S abe + OF CHEMISTRY
-AXIl

Lj 24, «(BaSO,) = « (solution) — « (water)

—0.08 = rca |
= 38.768 x 10-°— 1.36 x 10-6 an 2 [Ag*P
= 2.398 x 10-°° ohm! em"!
A,° = 110+ 186.6 = 246.6 ohm cm? mol
og 10 2x 0.08
0.059
= 2.712
[Ag*P
Molar mass = 187+32+4x
« x 1000
16=233
1.0 = 616.2
Solubility = [Ag*P
A it [Ag* Se oe ee 1.941x107
2.398 x 10° x 1000 515.2
[Ag*] = 0.044 M
7 246.6
L) 35. For the cell reaction
9.724 x 10° mol L
on* + Zine > Sntt A Zn**
or = 9.724x10°x233 = 2.266x10"¢ L-!
The Nernst equation is
L} 205. Reduction potential of Ni**|Ni is more than that of
Fe*t| Fe. Therefore, nickel will be reduced by iron. w 0.059, 1,5_ian"
We — 9:059 [Sn?*][Zn2*]
on |
L} 26. No, nickel will gradually pass into solution and copper a a en
will be precipitated.
= 0BOS 0.059, ig_(0.5) x (2.0)
(| 27. Sn |Sn** ||Br,
| Br-
8 (150)
E® = 1.08 — (-0.14) = 1.22 V
L} 28. 0.89 -
0.059 log 0.667
E*ca = Ee agt Ag) = EE cu? [Cu
0.46 = EW iy +14.) — 0.84
9
0.89 — (-0.005) = 0.895V.
BY sian = 0.80 V
L) 36. Mg(s) | Mg**(0.130M) || Ag*t (1.0 x 10-*M) |Ag(s)
Lj 29 . (4) Cr |Cr** || Cd?*| Cd The cell reaction is :
E? = E* (cathode) a EF (Anode) Me(s) + 2Ag* (ag) ——> Mg** (ag) + 2Ag(s)
According to Nernst equation,
(it) Fe?* |Fe* ||Ag* |Ag
E* a EE cea}
e 0.059 [Me"*]
7 EE cane)
= 0.80 — 0.77 = 0.038 V aa Wis
O30. No, because reduction potential of Cu** |Cu is less than e 0.059) __(0.130)
that of Cl,.
ome = (1.0x10+)
(131. Copper ions get reduced to copper.
0.059
(132. Inbeaker A, Ag* will be reduced to Ag because reduction 2.96 - BY? log(0.130x 10°)
potential of Agt|Ag is more than that of copper.
2006 . Re _ 0.059
Agt +e — > Ag(s) x 7.114
2
038. Cell reaction: Mg(s) + Cu?*(ag)——> Mg**(aq) + Cu(s)
2.96 = E* — 0.2099
E = Fe 4 0.059 1.
ZAE p ny
Lt (aq)|
E?
= 2.96 + 0.2099 = 3.1699 V = 3.17 V.
2 {Cu**(aq)} 0.059, [Zn**]
L) 37. E = EY 1- —— log
_ 97, _ 0.059 log 0.1 2. ? ire]
2 0.01 Ee. = —0.44 — (— 0.763) = 0.323V
= 2.71 — 0.0295 x 1 = 2.6805 V 0.059. 4, 9:01
_ 0,323 — 2:059 0.01
N34. Zn(s) + 2Ag*(ag) —=> Zn**(aqg) + 2Ag(s) ica 2 © 0.005
G us G _ 0.314 V
cn Ee agt ag Ean? |zm)
= 0.80 —(—0.76) =1.656V LI of. E — EO a
0.059 ia [Fe**]
y) [Ag*}?

a. Er 0:291o5 0.80 — (— 0.44) = 1.24V

Tas
Eh oa —

_ 124- 0.059 be OD
2 (0.1)
148 = 1.66— 9:959 og 1.0
= 1.2105 V
2 [Ag*P
1.48-1.56 = — 2:99 jog _1.0
39. 2Cr(s) + 3Fe?**(aqg) ——> 2Cr**(ag) + 3Fe(s)

. [Ag*P _ 0.059 | [Cr

EK = Eo
6» [Fe*P
ELECTROCHEMISTRY

E* 4 = —0.44 — (0.74) = 0.30V ~159 x 10°

0.059. (0.01) = 9.303 x 8.314 x 298 ~ 7/8081
Oe Ip
Feet 6 (0.1 K, = 7.85 x 10?7
_ 0.31 V L) 47. AG = «FE
r cell
OD) 40. (¢) Cu**(aq) + 2e- —+ Cu(s) AG = (2 mol) x (96500C mol™)x(0.236 V)
0.059 1 = — 45,548 kJ mol
E = E°-—, [Cu*]

L} 48. Ge _ 0.059, loc [Al*]

0.059,
Fb 1 Fon FB ct g * [Fe*]
= OT 8 OF E*on «= — 0.44—=(- 1.66) = 1.22 V
~ 0.8105 V
(ii) For E=0 a 122
—0.059 jg ,(1x10)242
0.059 1 6 (2x 107)
1 ee eat | = 1.209 V
2 Gu]
AG? = =(6 mol) x (96600 C mol“) x (1.22V)
a1 0.34 ~ 11.5254
= ~ 706.38 kJ
iia[(Cu*] 0.0295
L) 49.
~ EB ca? 104) ~ Er eaiey
[Cu2*] = 2.98 x 10°!°, —- — 0.40 —(_ 0.74) = + 0.34 V
O41. Em = 0.059
—-— logk, AG — _nFE?
— — 6 x (96600C mol) x (0.34V)
= -196.86 kJ mol-'.
or dog B. = 0059 L) 50. EE? cell
. = 0.80-—0.34=046V
2x 0.235
0.059, [Cu**]
~ 0.059
K._ = 9.25 x 10°
B= EY > 8 ag?
0.059 (0.130)
Lj 42. log K. =
2x 0.320
= 10.847 = 046-98 Toxi0F
. 0.059 = 0.25 V
K. = 7.04 x 101° AG = —2 x 96500 x 0.25
LU 43. EY on = Ee re re ~ E sott|sa2)
— 48.250 kJ
= 0.771 — 0.160 = 0.621 V L) 51. I = 2A, t = 15 min = 15 x 60 = 900s

2x 0,621 Q=Ixt=2x 900 =1800C

1 — “2 "= 21.05
og B= 0 059 96600 C of electricity deposit Ag = 108 ¢
K, = 1.0 x 107! 1800 C of electricity will deposit Ag =
108 x 1800
96500
Lj 44, | an = 0.059
Fane K. = 2.014¢
L) 52. Cu**(aq) + 2e- —> Cu (s)
= — x log 1 x 10* = 0.118 V.
Quantity of electricity passed = I x t
U1 45. EY = E* (ca?*Hea) ~ EB” Gn? |Z0) 0.75 x 25 x 60
= 0.403 —(— 0.763) = 0.360 = 1125C
| RES 1125 C of electricity produces copper = 0.369 g
log B= 0.059 2 x 965600 C of electricity produce copper
2x 0.36 |
= Dopg = 12.203 0.369
x 2x 96600 = 63.3 u
K. = 1.596 x 10! ~ 1125
Atomic mass of Cu = 63.3 u.
O46. C= Eo, chy — EY eis
L) 53. Quantity of electricity = 1.0 x 15 x 60 = 900 C
— 0.824 V 2 x 96500 C of electricity produced Cl, = 71 g
AG? = _nFE®_,, = — 2 x (96500C mol) 900 C of electricity will produce
x (0.824V) V1
- -159x 10? J Cl,
2
= ————_*x
2 x 96500
900
AG?
0.331 g
log K. = 9303RT
 MODERN'S abe + OF CHEMISTRY
-AXIl

Lj 54. (i) Fe+ —-> Fe'++e £.. 96500 C = 861.6 C

(ii) 2H,O, —>4H* +0, + 4e .. 2 x 96500 C Now, Q=Ixt
(for 1 mole of H,O,) 861.6 =I x3 x 60 x 60
(iii) F,+2e—> 2F -. 2 x 96500 C I = 0.0798 A
O58. (2) 40 g of Ca is produced by 2F
L} 50. 0.583 g of Ag is deposited by charge = a x 0.583 -. 10 g of Ca will be produced by - x10_ 9.5 F

~ §20.9C (ii) 27 g of Al is produced by 3F

Now, 197 g of Au is deposited by electric current 81 g of Al will be produced by ~ “81 3 Fr

(x 1s the oxidation state of gold) Quantity of electricity passed = I x t

0.356 g of Au will be deposited by current 2 Q = 0.20 x 3 x 60 x 60C = 2160C
_ — x 0.355 96500 C of electricity deposit = 107.92 g Ag

n X 96500 | 107.92
F097 * 0-355. = 520.9 2160 C of electricity deposit = Sg599 * 216° = 2.42 g
n= 2.99 or =+3 Let the thickness of silver deposited = x cm
L} 56. 3 = » Fe?
Fe’ +e Fe" Weight = volume x density
3.0 mol of Fe*+ will require = 3 x 96500 C een se ieee denny

Naw, te = —_ (.. Volume = area x thickness)

2.42 = 800 x x x 10.47
= 144750s_ or 40.21 hr. x = 0.000289 or 2.89 x 10 cm.
L157. 2H,O —Bemlyes_. OH, + O, (22.4 L) O60. Al + 3c —> Al
22.4 L of O, is produced by electricity = 4 x 96500 C 1 mol of Al requires 3 mol of electrons or 3F
50.0 x 10° L of O, is produced by electricity 27 g of Al require = 3F

4% 96500 50.0 x 10 83
22.4 AOg of Al require = a7 * AO = 4.44F.

Metallic conductors are the substances which allow the passage of electric current through them without undergoing
any chemical change.
Electrolytes are the substances which allow the passage of electric current through them in their molten states or in the
form of their aqueous solutions and undergo chemical decomposition.
Specific resistance or resistivity. The resistance of a conductor 1 cm in length and having 1 cm? area of cross-section.
Specific conductance or conductivity. It is the conductance of a solution of 1 cm length and having 1 square centimetre
as the area of cross-section. Or it is the conductance between the opposite faces of 1 centimetre cube of a conductor.
Molar conductance. It is the conducting power of all the ions produced by dissolving one mole of an electrolyte in solution.
Electrochemical cell. It is the device in which electrical energy is produced from chemical reactions.
Electrode potential. It is a measure of tendency of an electrode in a half cell to lose or gain electrons.
Electromotive force or cell potential. It is the difference between the electrode potentials of two electrodes constituting
an electrochemical cell.
Electrochemical series. The arrangement of elements in the order of increasing reduction potential values is called
electrochemical series.
ELECTROCHEMISTRY 3/79 =

® Electrolysis. It is the process of decomposition of an electrolyte by the passage of electricity through its aqueous solution
or molten state.
® Electrolytic cell. The device which converts electrical energy into chemical energy.
® Corrosion. [tis a redox reaction which occurs at the surfaces of metals when exposed to atmospheric conditions and form
undesirable products (usually oxides).
® Kohlrausch law. It states that at infinite dilution when the dissociation 1s complete, each ion makes a definite contribution
towards molar conductance of the electrolyte irrespective of the nature of other ions with which tt is associated.
® Faraday’s first law of electrolysis. It states that the amount of any substance deposited or liberated at any electrode
is directly proportional to the quantity of electricity passed through the electrolytic solution.
® Faraday’s second law of electrolysis. It states the when same quantity of electricity is passed through different
electrolytic solutions connected 1n series, the weights of the substances produced at the electrodes are directly proportional
to their chemical equivalent weights.

QUICK CHAPTER ROUND UP)

CONDUCTORS

Metallic conductance Electrolytic conductance

» movement of electrons » movement of ions

Ohm's law
V 7A

Resistance Conductance Molar conductance

Obstruction to flow of current Reciprocal of resistance x x 1000
l | 1 a M
R = p— : i
a R 7. Es penton (veerses)
p = specific resistance > G: ohm! or mho >» A, | chm™ em" mol

Equivalent conductance
K X L000
Specific resistance or resistivity Specific conductance or ee eens
mee eq C
conductivi
ty Rhee ohm cm? equiv?

With dilution or decrease in concenration > Kohlrausch law ofindependent migration ofions:
e Conductivity decreases A*AB) = dat + Mp
e Molar condutance increases A® (A,B) = xPn+4+YAS
Molar conductance varies as

A, = AZ — A C* (Debye-Huckel-Onsager equation
> Degree of dissociation of weak electrolytes :
AS
a= 7 at concentration C
| 3180 MODERN'S abe + OF CHEMISTRY-XII
Electrochemical Cells

= convert chemical energy into electrical energy

Cathode is +ve (reduction), Anode is —ve (oxidation)

e For an electrode reaction, Nernst equation is: 2.303 RT

~~ I g Kor = pine log K at 25°C
M** + ne~ ————> M(s) 7
n
a RT all ee Re; |
ae
nF pM" ] AG = -RTinK RT log K
or=—2.303
e For
a cell reaction
aA+bB — cC+dD
Nernst equation is

ee ee cy[pD]’
eee)
n [Al [By

Faraday's laws of Electrolysis

e First law ie! (or wt

® Secondlaw : amount ofsubastance deposited « moles of electrons exchanged during oxidation-reduction reaction

Cells or Batteries

Primary cells Secondary cells (batteries)

e electrode reactions cannot be reversed e electrode reactions can be reversed
e not chargeable e chargeable

Dry cell : Anode Cathode Electrolyte Lead storage cell

Zinc Graphite MoO, + © Anode : Lead
BEE 20 Cathode : PbO,
Mercury cell : Zinc Graphite HgO + KOH Electrolyte : Aqueous H,SO,

Fuel cell : H,—O, Fuel cell - Energy of combustion — Electrical energy

Porous carbon electrodes immersed in NaOH or KOH solution (Electrolyte).
Electrode reactions
Anode : Ae Gh se eels (tr <=» MARLO = ie |
Cathode : O,(g) + 2H,O(/) + 4e7 ——-> 4OH~ (aq)
Overall : 2E (oy -- Ol (g) ——> 2H OlF
ELECTROCHEMISTRY

CORROSION :
Process of deterioration of a metal as a result of its reaction with air or water (environment) surrounding it
= corrosion of iron — Rusting (Fe,O,. xH.,O)
Redox reactions during rusting
Oxidation half reaction:
Fe(s) Fe** (aq) + 2e7] x 2 (E) = —0.44 V)
Reduction half reaction
4H*+ + O, + 4e7 2H,O (a = £29 yy]
Overall cell reaction
2Fe(s) + 4H* + O, 2Fe2+ (aq) + 2H,O (E-_,=
cell 1.67. V)
4Fe*t (aq) + O,(g) + 4H,O 2Fe,O, + 8Ht
and Fe,O, + xH,O Fe,O, . xHL,O
Rust
protect it from rusting is galvanization.

WAN Solved
In-text Questions

Q.1. How would you determine the standard electrode Q.4. Calculate the potential of hydrogen electrode in
potential of the system Mg** |Mg ? contact with a solution whose pH is 10.
Ans. The standard electrode potential of Mg** |Mg system can Ans. pH = 10
be measured by connecting the Mg electrode immersed in [H+] = 10-19

1M Meg** solution with 5.H.E. This may be represented

gz - po. 2.059), 1
1 [H™ |
Mz |Mg2* (1M) ||H* (1MD |H,, 1 atm, Pt 0.059 1
From the measured potential E~ (Mg2+ |Mg)
can be calculated i i9
7
E = 0-—0.069
x 10
Een = E~ (H*|Ho) 7 i aug?*|Mg)
Ene?) = 0 - Ese = = 0.59 V~.

This is similar to the method discussed for Zn?*|Zn Q.5. Calculate the e.m.f of the cell in which the following
system. (Refer Page 30, Fig 11). reaction takes place :
Q.2. Can you store copper sulphate solution in a zinc Ni(s) + 2Ag* (0.002 M) ———> Ni** (0.160 M) + 2Ag
pot ? Given that E~ __,,= 1.05 V
Ans. No, because zinc is more reactive than copper and it will
2 0.059, [Ni]
displace copper from copper sulphate solution as : Ans. E.=E ce 9 108 [Ag P
Zn(s) + CuSO, (ag)——> ZnSO,(aq) + Cu(s)
As a result, zinc will gradually pass into the solution _ 1.05 — 8:92 log me
and copper will be precipitated. 2 (0.002)
Q.3. Consult the table of standard electrode potentials
= 1.05 - — x 4,602
and suggest three substances which can oxidize
ferrous ions under suitable conditions.
= 1.05 — 0.14 = 0.91 V.
Ans. The electrode potential of Fe*+|Fe** is 0.78 V. The
Q.6. The cell in which the following reaction occurs :
substances having electrode potential more than 0.78 V
will be reduced and hence act as oxidising agent. For
2Fe**(aq) + 21-(aq) ——— 2Fe**(aq) + I,(s)
example, has E”,_,, = 0.236 V at 298 K. Calculate the standard
(z) acidified KMnO, (zz) acidified Cr,O,*" (tii) acidified Gibbs energy and the equilibrium constant of the
cell reaction.
H,O>.
 MODERN'S abe + OF CHEMISTRY
-AXIl

E°_,, = 0.236 V Ans. Sodium, potassium, calcium, magnesium, aluminium, etc.

AG? = —nFE* Q.12. Consider the reaction :
n = 2, F = 96500C Cr,O,? + 14H* + 6e- ——-> 2Cr** + 7H,O
AG = 2 x (96600 C) x (0.236 V) What is the quantity of electricity in coulombs
— 45648 J or = — 46.55 kJ needed to reduce 1 mol of Cr,O,*7 ?
AG =-— 2.303 RT log K. Ans. 6 mol of electrons are required to reduce 1 mol of Cr,O,77
Now 1 mol of electrons = 96500 C
AG=
= log Kk. = — 3303 RT 6 mol of electrons = 96500 x 6 = 5.79 x 10°C

— 45.55 Q.13. Write the chemistry of recharging of the lead

storage battery, highlighting all the materials that
~ 2303 x 8.314 x 10° x 298
are involved during discharging.
= 7.983
Ans. A lead storage battery consists of anode of lead, cathode
K. = antilog (7.983) = 9.62 x 107
of a grid of lead packed with lead dioxide (PbO,) and 38%
Q.7. Why does the conductivity of a solution decrease
H,SO, solution as electrolyte. The following reactions
with dilution ?
occur when the battery is in use :
Ans. Conductivity of an electrolyte solution decreases with
Anode: Pb(s) + 50,7 (aq) ——> PbSO,(s) + 2e-
dilution because the number of ions per unit volume
Cathode :
furnished by an electrolyte decreases with dilution.
PbO,(s) + SO," (aq) + 4H*(aq) + 2e° —-> PbSO,(s) + 2H,O(7Z)
Q.8. Suggest a way to determine A’, value of water.
Ans. Overall reaction:
Am (H,0) =m cat) + MoH)
We determine A*op, A’ maraoHy 820 A®, aracy: Then Pb(s) + PbO,(s) + 2H,SO,(aq) —> 2PbSO,(s) + 2H,O(2)
On charging the battery, the reverse reaction takes place
A" m(H,0) = Macy + A mataoH ~ A'm avach
= A. at) + aan (cl) + Ae on (Nat)
i.e., PbSO, deposited on the electrodes is converted back
into lead and PbO, and H,SO, in regenerated.
+ OM OH Mm ataty ~ mer)
= fe oe qat) + VM (OH)
Q@.14. Suggest two materials other than hydrogen that
can be used as fuels in fuel cells.
Q.9. The molar conductivity of 0.025 mol L“! methanoic
acid is 46.1 S cm? mol". Calculate its degree of Ans. (2) Methane (21) Ethane
dissociation and dissociation constant. Given Recently zinc metal has been used in place of hydrogen
i” (H*) = 349.6 S cm? mol! and 1° (HCOO-) = 54.6 S cm* gas in USA to develop a source of power for automobiles.
motl!, Q.15. Explain how rusting of iron is envisaged as setting
Ans. A" GacooH) — Mast) - M007) up of an electrochemical cell.
= 5349.6 + 54.6 Ans. Water layer present on the surface of iron (particularly
= 404.2 S em? mol during rainy season) dissolves acidic oxides present in
air such as CO,, SO,, ete to form acids which dissociate
fi ee
AT 404,23 to give H* ions :
H,O + CO, ——> H,CO, =——— 2H* + CO,”
2
eo In the presence of Ht ions, iron starts losing electrons
= 1l-«a
at a particular spot of iron object to form ferrous ions.
_ 0.025 x (0.114)? Therefore, oxidation takes place and that spot behaves
7 1-0.114 as anode.
— 3.67 x 10+
Fe(s) ———> Fe** (ag) + 2e7
The electrons released at anodic spot move through
Q.10.If a current of 0.5 ampere flows through a metallic
the metal to reach another spot where H* ions and the
wire for 2 hour, then how many electrons would
dissolved oxygen take up these electrons and reduction
flow through the wire ?
takes place. Hence this spot behaves as cathode
Ans. Coulombs of electrons = Current x time
—- 0.6 Ax 2x 60 x 60s = 8600C O,(g) + 4H* (aq) + 4e- ——-+ 2H, O()
Now, the current of 1F (96500 C) is equivalent to 1 mole The overall reaction is :
i.e., 6.022 x 107° electrons. 2Fe(s) + O,(g) + 4H*(ag) —> 2Fe**(aq) + 2H,O(/)
3600 C of current is equivalent to flow of electrons Thus, an electrochemical cell sets up on the surface.
_ 6.022
x10°° x 3600 = 2.246 x 10** electrons.
Ferrous ions are further oxidised by atmospheric oxygen to
96500 ferric ions which combine with water molecules to form hydrated
Q.11. Suggest a list of metals that are extracted ferric oxide, Fe,O,. xH,O, which is rust.
electrolytically.
ELECTROCHEMISTRY
|
Textbook Exercises //
Q.1. Arrange the following metals in the order in which 0.80 — 0.77 = + 0.03V
they displace each other from the solution of their AG? —=7FE"
salts — 1x 965600 x 0.038
— 2896500 CV mol!
Al, Cu, Fe, Mg and Zn.
— 289600 J mol!
Ans. Mg, Al, Zn, Fe, Cu.
= — 289.5 kJ mol
Q.2. Given the standard electrode potentials,
K*/K = -2.93 V, Ag*| Ag = 0.80 V nE®ce!)
log K.= Harq
Hg** |Hg = 0.79 V 0.059

Mg** |Mg = -2.37 V, Cr**|Cr = - 0.74V 1x 0.03

= = 0.508
0.059 ian
Arrange these metals in their increasing order of
K = 3.22
reducing power.
Q.5. Write the Nernst equation and calculate emf of the
Ans. Ag*t| Ag, Hg**| Hg, Cr?+| Cr, Mg**| Mg, Kt|K
following cells at 298K :
Q.3. Depict the galvanic cell in which the reaction (4) Mg(s) |Mg?*(0.001M) | |Cu?*(0.0001M) |Cu(s)
Zn(s) + 2Ag*(ag) —> Zn**(aq) + 2 Ag(s) (ii) Fe(s) |Fe?*(0.001M) ||H*(1MD |H,(g)(1bar) |Pt(s)
takes place. Further show : (iii) Sn(s) | Sn?*(0.050M) H*(0.020M)H,(g¢)(1bar) |Pt(s)
(i) Which of the electrode is negatively charged ? (iv) Pt(s) |Br,(1) |Br (0.010M) ||H*(0.030M) |H,(2)
(74) The carriers of the current in the cell. (1Ibar) Pt(s)
Ans. Parts (z), (22) and (111) Refer Solved Example 32 (page 41)
(111) Individual reaction at each electrode.
(D.S.B. 2008; A.L.S.B. 2008) (iv) Pt(s)| Br,(Z) |Br-(0.010M) | |H*(0.030M) |H,(g)
(1bar) |Pt(s)
Ans. The cell may be depicted similar to Fig. 6 (Page 23). The
2Br+ 2H* —-> Br, +H,
cell may be represented as :
Zn(s) |Zn°*(aq) ||Ag*(aq) |Ag(s) EK = E®-
0.059 ™ 1
(:) Zine electrode (anode) 2 (Br PIH*P
(21) Current will flow from silver to zinc in the external E? = 0—1.08 =— 1.08
circuit.
0.059 1
(iit) At anode : Zn(s) —> Zn** + Qe- = ie pe
E = 2 = (.01* (0.030!
At cathode : Ag*(ag) + e~ ——> Agis)
Q.4. Calculate the standard cell potentials of galvanic = -—1.08- — log (1.11 x 10")
cells in which of the following reactions take
0.059
place: = —1,08—- * 7.0457
(i) 2Cr(s) + 3Cd**(ag) ——> 2Cr**(agqg) + 3Cd
= — 1.08 — 0.208
(ii) Fe** (aq) + Ag*(aq) —> Fe**(agq) + Ag(s) —- - 1.288 V
Calculate the AG” and equilibrium constant of The given reaction is not feasible. Thus, oxidation will
the reactions. occur at the hydrogen electrode and reduction on the Br,
electrode and EY oy = 1.288 V.
Ans. (7) E* ot = i» > FE anode)
= — (0.40 —(- 0.74) = + 0.34 V Q.6. In the button cells widely used in watches and
other devices the following reaction takes place :
AG = — nFE°
Zn(s) + Ag,O(s) + H,O(1) — Zn** (aq) + 2Ag(s)
— 6 x 96500 x 0.34
+ 20H (aq)
= — 196860 CV mol? Determine AG? and E® for the reaction.
= — 196860 J mol? (Meghalaya S.B. 2015)
= — 196.86 kJ mol Ans. Refer Solved Example 43.(page 48)
nE®, Q.7. Define conductivity and molar conductivity for the
log K, = solution of an electrolyte. Discuss their variation
0.059
with concentration.
= 6 x0.34 = 34.576 Ans. Refer Text page 4, 5 and 12.
0.059
Q.8. The conductivity of 0.20 M solution of KCI at 298K
K_ c = 3.76 x 10** is 0.0248 S cm. Calculate its molar conductivity.
= & G =
(it) EK cell — K (cathode) — E (anode)
Ans. Refer Solved Example 2. (page 10)
a Q.9. The resistance of a conductivity cell containing Q.14
MODERN'S abe + OF CHEMISTRY

How much electricity is required in coulomb for

-AXIl

0.001M KCI solution at 298 K is 1500 ©. What is the oxidation of

the cell constant if conductivity of 0.001 M KCl (z) 1 mol of H,O to O,
solution at 298 K is 0.146 x 10° S cm. ?
(zt) 1 mol of FeO to Fe,O, ?
Ans. Cell constant, G* = Conductivity Ans. Refer Solved Example 54. (page 60)
Conductance
Q.15. A solution of Ni(NO,), is electrolysed between
1 platinum electrodes using a current of 5 amperes
Conductance = 1500 5
for 20 minutes. What mass of Ni is deposited at the
0.146x10° Scm"™ cathode ?
Cell constant = F500. . Refer Solved Example 54. (page 60)
= 0.219 em"! Q16. Three electrolytic cells A, B, C containing solution of
Q.10. The conductivity of sodium chloride at 298 K has #nSO,, AgNO, and CuSO,, respectively are connected
been determined at different concentrations and in series. Asteady current of 1.5 amperes was passed
the results are given below : through them until 1.45 ¢g of silver deposited at the
cathode of cell B. How long did the current flow?
Concentration/M 0.001 0.010 0.020 0.050 0.100
What mass of copper and of zinc were deposited ?
107 x W/S m! 1.2387 11.85 23.15 55.55 106.74
Ans. Refer Solved Example 57. (page 61)
Calculate A, for all concentrations and draw a
plot between A, and C™. Find the value of A°_. Q.17. Predict if the reaction between the following is
feasible :
Ans. Refer Solved Example 9. (page 14)
Q.11. Conductivity of 0.00241M acetic acid is 7.896 x (i) Fe* (aq) and IT (aq)
10°S cm. Calculate its molar conductivity and if (i) Ag* (aq) and Cu (s)
A_,° for acetic acid is 390.5 S cm? mol", what is its (ii) Fe** (aq) and Br (aq)
dissociation constant ? (iv) Ag(s) and Fe**(aq)
c Kk * 1000 (v) Br, (aq) and Fe** (aq)
Ans. A =
ie M Given standard electrode potentials :
7.896 x 10°S em x 1000 cm® L" E®,,. L/I = 0.54 V, E® ,,. Cu”*/Cu = 0.34 V,
0.00241 mol L' E* ,. Br/Br = 1.09V, E* ,,. Ag* / Ag = 0.80V and
= 32.76 S em? mol E*,. Fe** /Fe?* = 0.77V

ae
AS
Ans. (1) A reaction is feasible if EMF of the cell is positive.
A» Fe** (aq) + (aq) —> Fe** (aq) + 1/21,
Cell is : Pt|1,| aq) || Fe**(aq) | Fe**(aq) |Pt
_ 9216 _ 3309 x 102 E* 4 = EO (Fe* | Fe?+) — Ee (1/21, |)
390.5
= 0.77 — 0.64 = 0.238 V
K — Coe _ 0.00241
x(8.39 x10°)”
Reaction is feasible.
a l= (1-—8.39
x 107)
(11) 2Ag*(aq) + Cu(s) —> 2Ap(s) + Cu?*(aq)
— 1.86 x 10°
Cu|Cu**(aq)| |Ag*(aq) |Ag
Q.12. How much charge is required for the following
| ala E*(Agt| Ag) — E*(Cu?*|Cu)
reduction of
= 0.80 — 0.34
(4) 1 mol of Al** to Al.
(i¢) 1 mol of Cu** to Cu = 0.46 V
(iii)1 mol of MnO, to Mn** ? Reaction is fesaible.
Ans. Refer Solved Example 54. (page 60) (iii) Fe**(aqg) + Br (ag) —> Fe**(aq) + 1/2Br,
Q.13. How much electricity in terms of Faraday is required | eae = E®*(Fe*
| Fe®*) — E* (Br, | Br-)
to produce
0.77 — 1.09
(7) 20.0 g of Ca from molten CaCl,
(it) 40.0 g of Al from molten AI,O, ? = —0.52V
Ans. (1) Ca?* + 2e° ——> Ca Reaction is not feasible.
1 mol of Ca z.e., 40 g require electricity = 2F (iv) Ag(s) + Fe**(aqg) ——> Ag* (aq) + Fe** (aq)
EY = E®(Fe**
| Fe®+) — E®(Ag*
| Ag)
_ 2x 20
20 g of Ca will require electricity = 40 = 0.77 — 0.80
= 1F = — 0.03V
(iz) Al?* + 3e° ———> Al Reaction is not feasible.
1 mol of Al = 27 g (v) 1/2Br,(aq) + Fe? (aq) ——> Br + Fe**(aq)
27 g of Al require electricity = 3F E®_, =E®(Br,|Br-) — E®(Fe* |Fe?*)
AO g of Al will require electricity
3
= 07 * AQF
1.09 - 0.77
= 0.32 V
= 4,4F Reaction is feasible.
ELECTROCHEMISTRY

Q.18. Predict the products of electrolysis in each of the OH” and NO, ions, OH” ions have lower discharge
following : potential and hence OH ions will be discharged in
(7) An aqueous solution of AgNO, with silver preference to NO,-. The OH” will decompose to give
electrode. (),,.
(it) An aqueous solution of AgNO, with platinum OH(ag) — > OH+e
electrodes. 40H — > 2H,O(7) + O, &)
(ii) A dilute solution of H,SO, with platinum (it) Electrolysis of H,SO, with Pt electrodes
electrodes. H,SO,(aq) ——~ 2H* (aq) + 80,* (aq)
(jv) An aqueous solution of CuCl, with platinum H,O F@_ Ht + OB”
electrodes. At cathode: Ht+e—— H
Ans. (7) Electrolysis of aqueous solution of AgNO, using H+ “a> HAg)
silver electrodes : At anode: OH — > OH +e
AgNO,(s) + nH,O —-> Ag* (aq) + NO, (aq) 40H — > 2H,0 + O,@)
H,O == H* + OH (tv) Electrolysis of aqueous solution of CuCl, with
platinum electrodes
At cathode: Ag* ions have lower discharge potential
CuCl(s) + (aq) —-> Cu**(aq) + 2CI(aqg)
than H* ions. Hence Ag* ions will be deposited as
silver (in preference to H* ions). H,O — > H* + OH
At cathode : Cu** will be reduced in preference to
At anode : Since silver electrode is attacked by
H* ions
NO, ions, Ag anode will dissolve to form Ag* ions
in the solution. Cut + 2e- — Cu

Ag ——> Agt+e At anode : CI ions will be oxidized in preference

to OH” ions
(it ) Electrolysis of aqueous solution of AgNO, using
Cr — > Clee
platinum electrodes
Cl+Cl —+ Cl,
At cathode : Same as above.
Thus, copper will be deposited on the cathode and
At anode : Since silver is not attacked, out of
Cl, will be liberated at anode.

Exemplar Problems //
Subjective Questions
cells. Will the mass of copper and silver deposited
on the cathode be same or different? Explain your
answer.
. Can absolute electrode potential of an electrode
be measured? . Mass of copper and silver deposited on cathode will be
different. It depends upon equivalent mass.
. No, absolute electrode potential of an electrode cannot
be measured. Depict the galvanic cell in which the cell reaction
is Cu + 2Agt —-> 2Ag + Cu**
Can E2) or A.G® for a cell reaction ever be
Cu|Cu** (ag,1M) || Ag* (aq,1M) |Ag.
equal to zero? Value of standard electrode potential for the
Ans. No, AG® = nFE’, if E° is zero, cell reaction will not oxidation of Cl ions is more positive than that
occur. of water, even then in the electrolysis of aqueous
Under what condition is E,,.,, = 0 or A.G = 0? sodium chloride, why is Cl’ oxidised at anode
instead of water?
Ans. When the cell reaction reaches equilibrium, E__,, = 0,
so that AG is also zero. Ans. Under the conditions of electrolysis of aqueous sodium
chloride, oxidation of water at anode requires over
What does the negative sign in the expression
potential and therefore, Cl is oxidised instead of water.
Bes ‘mn = — 0.76 V mean?
What is electrode potential?
Ans. It means that zinc is more reactive than hydrogen. The electrical potential difference set up between the
When zinc electrode is connected to SHE, zine will get metal and its solution is called electrode potential.
oxidised and H will get reduced. Consider the following diagram in which an
Aqueous copper sulphate solution and aqueous electrochemical cell is coupled to an electrolytic
silver nitrate solution are electrolysed by 1 Ampere cell. What will be the polarity of electrodes ‘A’
current for 10 minutes in separate electrolytic and ‘B’ in the electrolytic cell?
a Salt bridge 17. Which reference
MODERN'S abe + OF CHEMISTRY

electrode is used
-AXIl

to measure
the electrode potential of other electrodes?
Ans. The standard hydrogen electrode is used as a reference
electrode whose electrode potential is taken to be zero.
The electrode potential of other electrodes is measured
Solution solution
with respect to it.
ZnSO, 18. Consider a cell given below
(A) (B) Electrode Cu|Cu?* || Ci-|C1,,Pt
Electrode Flectrolytic Write the reactions that occur at anode and
cathode.
cell
Ans. Anode : Cu—4S Cu?" oe
Ans. ‘A’ will have —ve polarity and ‘B’ will have +ve polarity.
Cathode : Cl, + 2e~, ——> 2CI-
10. Why is alternating current used for measuring
Cu 1s anode because it is getting oxidised.
resistance of an electrolytic solution?
CL, 1s cathode because it is getting reduced.
Ans. The alternating current is used to prevent electrolysis
so that the concentration of ion in the solution remains 19. Write the Nernst equation for the cell reaction
constant. in the Daniel cell. How will the E,.,, be affected
when concentration of Zn** ions is increased?
11. A galvanic cell has electrical potential of 1.1V. If
an opposing potential of 1.1V is applied to this Ans. The cell reaction for Daniel cell is :
cell, what will happen to the cell reaction and Zn + Cu2+ ——3 Zn**+ + Cu
current flowing through the cell?
0.059 [Zn2*J
Ans. When the opposing potential becomes equal to electrical Beet = E? Cell — 9 log
potential, the cell reaction stops and no current flows [Cu**]
through the cell. Thus, there 1s no chemical reaction. Kio. decreases when concentration of Zn** ions [Zn**]
12. How will the pH of brine (aq. NaCl solution) be increases.
affected when it is electrolysed? 20. What advantage do the fuel cells have over
Ans. since NaOH is formed during electrolysis, pH of the primary and secondary batteries?
brine solution will increase Ans. Primary batteries contain a limited amount of reactants
13. Unlike dry cell, the mercury cell has a constant and are discharged when the reactants have been con-
cell potential throughout its life. Why? sumed. Secondary batteries can be recharged but take
a long time to recharge. Fuel cell runs continuously as
Ans. Beacuse ions are not involved in the overall cell reaction
long as the reactants are supplied to it and products
of mercury cells.
are removed continuously.
14, Solutions of two electrolytes ‘A’ and ‘B’ are
21. Write the cell reaction of a lead storage battery
diluted. The A, of ‘B’ increases 1.5 times while
when it is discharged. How does the density
that of A increases 25 times. Which of the two is
of the electrolyte change when the battery is
a strong electrolyte? Justify your answer.
discharged?
(C.B.S.E. Sample Paper 2017-18)
Ans. Electrolyte B is strong because on dilution A, increases Ans. Pb + PbO, + 2H,SO, —“=“"8° > oPpso, + 2H,O
only small. Density of electrolyte decreases because water is formed
15. When acidulated water (dil.H,SO, solution) and sulphuric acid is consumed as the product during
is electrolysed, will the pH of the solution be discharge of the battery.
affected? Justify your answer. 22. Why on dilution the A,, of CH,COOH increases
Ans. pH of the solution remains same because [H ]remains drastically, while that of CH,COONa increases
constant. gradually?
At anode : 2H,O——-> O, + AH" + 4de- Ans. In the case of CH,COOH, which is a weak electrolyte,
At cathode : 4H” + 4e7 ——_> 2H, the number of ions increase on dilution due to an
increase in degree of dissociation.
16. In an aqueous solution how does specific
conductivity of electrolytes change with addition CH,COOH + H,O CH,COO- + H,O*
of water? In the case of strong electrolyte such as CH,COONa,
Ans. On the addition of water, number of ions per unit the number of ions remains the same but the interionic
volume decreases and therefore conductivity decreases. attraction decreases.
ELECTROCHEMISTRY
307)
Memory TEST
W
Ve The electrolyte used in H, — O, fuel cell is ..........
ve Say True or False
8. In Leclanche dry cell, the cathode is ..........
1. An electrochemical cell works only if emf is negative. 9. In electrolytic cell, reduction occurs at ..........
2. In an electrolytic cell reduction occurs at cathode.
10. In lead storage cell, the cathode consists of ..........
3. Electrolytic conductance generally decreases with rise
11. The chemical formula of rust is ..........
in temperature.
12. The units of molar conductance are ..........
4, Greater reduction potential represents greater reducing
13. The equilibrium constant (K_) and e.m.f. of the cell (E°)
power of the substance.
are related as ..........
5. In Zn-Cu cell, copper acts as a cathode while in Cu-Ag
cell, copper acts as anode. ‘088 Choose the correct alternative
6. Metallic conductance decreases with increase in
1. In an electrochemical cell, reduction will occur at the
temperature.
electrode having lower/higher oxidation potential.
7. Both Ex. and AG® for the cell reaction are intensive ce, 18 intensive/extensive property.
o

properties.
. Electrolytic conductance increases/decreases with
8. Reduction potential and oxidation potential for a half decrease in temperature.
cell reaction are numerically equal but of opposite sign.
- Ina Daniell cell, when E_, > 1.10 V, then current flows
9. Out of HCl and NaCl, A, of HCl is higher. from Zn to Cu/Cu to Zn.
10. CuSO, solution can be stirred with a silver spoon but
AgNO, solution cannot be stirred with a copper spoon. + Evy 18 directly/inversely proportional to AG’.
. By passing 96500 C of electricity through aqueous Al,O,,
i:a Complete the missing links the amount of Al produced is 27¢/ 9g.
- In the electrolysis of molten PbBr,, Br,/Pb is produced
1. In an electrochemical cell, oxidation occurs at ......... and
reduction occurs at .......... at anode.
8. In Leclanche cell, zinc cylinder acts as a anode /cathode.
. AG? is related to e.m.f. (E°) of the cell as ..........
. The units of cell constant are .......... 9. Secondary cells are chargeable/not chargeable.

» In a Leclanche cell, MnO, acts as .......... 10. In mercury cell, zinc acts as anode/cathode.

. Protection of iron by coating with zinc is called .......... 11. Presence of CO, in natural water increases/ decreases
rusting of iron.
m.
OF
ao
hl
Go For the spontaneous electrochemical cell reaction, E°
should be .......... 12. Presence of electrolytes in water increases/decreases
corrosion of iron.

eWes «=Memory Test \\\

. depolarizer 5. galvanization
Say True or False
+ve 7. conc. KOH solution
1. False. For spontaneous electrochemical cell reaction emf . carbon (graphite) rod
should be positive.
Oo
Sf
0 . Cathode 10. lead packed with PbO,
2. True
11. Fe,O,xH,O 12. ohm™ cm* mol”
3. False. Electrolytic conductance increases with rise in
temperature. BE?

nek
Fi
13. at 298 K.
4, False. Greater reduction potential represents greater °8 ™e = 0.059
oxidising power of the substance.
5. True 6. True Choose the correct alternative
7. False. Keel is intensive but AG® is extensive. 1. lower 2. intensive 3. decreases
8. True 9. True 10. True 4, Zn to Cu 5. directly
6. 9g 7. Br,
|Be.) Complete the missing links 8. anode 9. chargeable 10. anode
1. anode, cathode 2, AG® = — nFE* 8. em? or m? 11. increases 12. increases
 MODERN'S abe + OF CHEMISTRY
-AXIl

Higher Order Thinking Skills

a Advanced Level }
QUESTIONS WITH ANSWERS

Q.1. What are the signs of AG, K and E’..,, for a (iit) For X, A&° can be obtained by extrapolation to zero
spontaneous cell reaction ? concentration.
Ans. AG =—ve, K= +ve, E°_, =+ve For Y, A© can be calculated by using Kohlrausch law.
Q.2. Why is a salt bridge or a porous plate not needed Q.5. Consider the following half cell reactions:
in a lead storage battery ? Br,+2e—> 2Br E°=1.09V
Ans. The half cells in a cell must be separated only if the
I, + 2e° —> 21 EK’ = 0.54 V
oxidizing and reducing agent can migrate to the other half cell.
If 1, and Br, are added to solution containing 1 M
In lead storage cell, the oxidizing agent, PbO, and the reducing
concentration of [ and Br respectively.
agent, Pb as well as their oxidation and reduction product PbSO,
are solids. Therefore, there is no need to separate half cells. (4) Write an equation for the overall cell reaction and
E* of the cell.
Q.3. Blocks of magnesium are often strapped to the
steel hulls of ocean going ships. Why ? (44) Write the cell in which the reaction takes place,
using Pt as the inert electrolyte for each electrode.
Ans. Magnesium prevents the oxidation of steel by
transferring the excess of electrons to the steel. Thus, rusting of (411) How will the increase in the concentration of
steel is protected and it is called cathodic protection. Br affect E,_,?
ce

Q.4. The following curve is obtained when molar Ans. (i) Br, + 21) —+2Br +1,
conductivity, A,, is plotted against the square root of
concentration, C!" along y and x-axis respectively for the Ee _Ee [5Br |Br] —K° (Ft ||
two electrolytes X and Y.
= 1.09—0.54=0.55 V.
= 600 (iz) Pt|1,, -(aq)|| Br (aq), Br, |Pt
L
o (iit) The value of E® will be reduced.
=
Q.6. Tarnished silver contains Ag,S. Can this tarnish
E 400
be removed by placing tarnished silver article in an
a aluminium pan containing an inert electrolyte solution
y; xX
200 y such as NaCl ? The standard electrode potentials for the
half cell reactions are:
Ag,S(s) + 2e°- —-> 2Ag(s)+S* (aq) E*=-0.71V
Al** + 3e- —> Al(s) E°=- 1.66 V
0 0.2 0.4 0.6
ce (mol Ta) ee Ans. Tarnish due to silver sulphide can be removed if the
following cell reaction occurs :
(¢) What can you say about the nature of these two Ag,S + Al——> Al** + 2Ag +8?
electrolytes ? E.M.F. of the cell will be
(it) How do you account for the increase in A, for the EK? =~E® (Ag,S |2Ag, S2)_E° (Al®* |Al)
electrolytes X and Y with dilution ? =—0.71—(-1.66) = +0.95V
(iit) How can you determine A. for these electrolytes ? Since E°__,, 1s positive, the reaction will occur and tarnish
Ans. (1) Electrolyte X is a strong electrolyte and Y is a weak will be removed.
electrolyte. Q.7. If charge on the electron is 1.60 x 107°C and
(it) Molar conductivity, A, of
X(strong electrolyte) increases 96500 C deposit 107.9 g of silver from its solution, calculate
slowly with dilution. Thisis because interionic forces of attraction the value of Avogadro’s number. (At. mass of Ag = 107.9 mu)
decrease on dilution, although the number of ions remain the Ans. 1 mol = 107.9 ¢g
same. As a result ions move more freely and hence A, increases 1 mol of Ag is deposited by 96500 C
with dilution. If charge of electron is 1.60 x 10°" C
On the other hand, for Y (weak electrolyte) A,, increases 96500C
sharply with dilution. This is because, degree of dissociation No. of electrons in 1 mol of silver =
1.60 x10°'°C
increases on dilution resulting in greater number of ions on
dilution. Hence A, increases.
= 6.03 x 107%e-
Avogadro number = 6.03 x 107°.
ELECTROCHEMISTRY

Q.8. On the basis of the following data : (tt) In neutral solution, [H*] = 10-' M
Co** + e — > Co”; E° = +1.82 V
E= 0.78- U.009 log —_
2H,O0 —+0,+4H*+4e;
explain why Co** salts are unstable in water ?
E°=+1.23 V
(107)
= 0.78-—0.069 x 14=0.78—- 0.826
Ans. The potential (Co**|Co) is large and sufficient to
—- —0.046V
oxidize water. Therefore, Co(II]) in aqueous solution has a
tendency to change to Co(II). Hence Co(III) is unstable in Q. 12. How many grams of silver could be plated out
aqueous solution. on a serving tray by electrolysis of a solution containing
silver in + 1 oxidation state for a period of 8.0 hours at a
Q.9. Show that for two half reactions having potentials
current of 8.46 amperes? What is the area of the tray if
E, and E, which are combined to give a third half reaction
the thickness of the silver plating is 0.0025 cm ? Density of
having potential E, is
silver is 10.5 g/cm’.
n Eo +n,EK,
Ans. Quantity of electricity passed
2
its = §46x8x60x60C
Ans. Let AG,,AG, and AG, are the free energy changes for the é 107.8 ,
half cell reactions having potentials E,, E, and E, respectively, Amount of silver deposited = x 8.46 x8x 60x60
96500
then
AG, = AG, +AG, = 272.18 g
Since AG =—nFE Volume ofsilver = une = 25.92 cc
or —n,FE, = —n,FE,—n,FE, 10.5
Dividing both sides by —n.,F
Areaoftray = ee 1,02
x 10* em*
n,E, +n,Ks, 0.00254
E se
tg Q. 13. What pressure of H, would be required to make
the e.m.f. of the hydrogen electrode zero in pure water at
Q.10. Calculate the reduction potential of a half cell
25°C ?
consisting of a platinum electrode immersed in 2.0 M Fe**
and 0.02 M Fe* solution (E° Fe** | Fe** = 0.771 V). Ans. The cell reaction is:
Ans. The electrode reaction is 2H* (ag) +2e°- <= H, (g)

Pe
Fe** +¢——> Fe* According to Nernst equation,
0.059, p(H,)2
E — Ee_ 0.059 4, E = E°-——lo
a Mis [Fe] ° HP
Since E = 0, [H*] = 10-7 M (pure water)
E® = 0.771 V,
[Fe**+] = 0.02 M,
0 = 0—-——]
0.059, p(H,)
[Fe*t] = 2.0M 2 10"2
(2.0)
E = 0.771~ “*** log (0.02) 0 =- — log p(H,)+ — log 10°“

0.771 —0.059 log 100 log p (H,) = log 10-*

0.771—0.118 = 0.653 V p(H,) = 10-* atm.
Q.11. Thestandard reduction potential for the half cell:
Q. 14. Conductivity of a saturated solution of
NO, (aq) + 2H* (aq) + e ——> NO, + H,O 1s 0.78 V. Co, [Fe(CN),] is 2.06 x 10-* ohm-! cm” and that of water
(t) Calculate the reduction potential at 8 M H+. used is 4.0 x 10-7 ohm cm. Calculate the solubility and
(74) What willbe the reduction potential of the half cell solubility product of Co, [Fe(CN),] in water at 25°C. [Ionic
in a neutral solution ? Assume all other species to molar conductivities: Co** = 86.0, [Fe(CN),]* = 444.0 ohm
be at unit concentration. cm? mol]
Ans. (1) The half cell reaction : Ans. Since conductivity is additive property,
NO, (aq) + 2H* (aq) + ew ———> NO, + H,O k(complex salt) = K(solution)— (water)
According to Nernst equation, 2.06 x 10-°— 4.0 x 1077

_ pe _ 0.059, [NO2][H20] = 16.6 x 10 ohm! cm

' [vos ][#"]

A (complex salt) = 2x A,(Co**) +4, ([Fe(CN),]*)
= 2x 86+ 444.0 =616 ohm? cm? molt
1 A - KX 1000
E= 0.78 — 0.059 log
(8) 7 M
where Mis the solubility of saturated solution
= 0.78— 0.1062 = 0.8862 V
 MODERN'S abe + OF CHEMISTRY-AIl

616 = 16.6x10~’ x 1000

Co, [Fe(CN),] — 2 Ca? 4+ [Fe(CN),|*"
M If's is the solubility
—7T
[Co**] = 2s, [Fe(CN),]* =s
oe M = a _2.69x 10-6 mol L22
Ko. — (2s)*(s) — 4s?
~ 4x (2.69 x 10°)? = 7.79 x 10°!" mol? L-?

Revision Exercises
Cathode : H,
ee heseernetel (co77ving 1mark RCA Anode : Cl, and not O,. Explain.
1. Write Nernst equation for the following cell reaction : (C_B.S.E. Sample Paper 2017-18)
2Al(s) + 3Fe** (aq) —> 2Al** (aq) + 3F e(s) 25. Can we keep CuSO, solution in a zine container? (Given
2. State Kohlrausch law of electrical conductance of an that E° (Cu2+| Cu) = +0.34V, E° (Zn2+|Zn) — —0.76V
electrolyte at infinite dilution. (Meghalaya S.B. 2014)
. Write the overall cell reaction for lead storage battery. 26. Name one substance other than hydrogen that can be used
for constructing fuel cell. (Assam S.B. 2016)
OO. Howis cell potential related to the free energy change? State
He
meaning of each term used.
. Can we store CuSO, solution in an iron vessel ? »> CBSE QUESTIONS <4
. What is salt bridge? (Nagaland S.B. 2018) 27. Write Nernst equation for a single electrode potential.
- Howis A.Grelated to e.m.f. of the cell ? (A.L.S.B. 2003)
o . How does the concentration of sulphuric acid change in lead
=]
wo
oO 28. How does electrical resistivity of metallic conductors vary
storage battery when current is drawn from it ? with temperature? (A.L.S.B. 2006)
9. How many coulombs are required for the reduction of 29. Whatis molar conductivity? (A.LS.B. 2010)
1 mol of Al**
to Al?
10. Define molar conductivity. (Nagaland S.B. 2016) MC@Qs. from State Boards’ Examinations
11. Why a dry cell becomes dead after a long time even if it has
30. For redox reaction to proceed in a cell, the e.m.f. must be
not been used? (Hr. SB. 2002)
(a) positive (6) negative
12. Whatis the basis of obtaining electrical energy in fuel cells ?
(c) fixed (d) zero (ALP.S.B. 2013)
(D.S.B. 1998) 31. The units of conductivity are
13. Give an example of a fuel cell. (D.S.B. 2002) (a) ohm? em? (6) ohm cm?
14, What are the units of molar conductivity? (4.P.S_B. 2009) (c) ohm (dq) ohm cm? equiv
15. Write the product obtained at anode on electrolysis of (A.P.S.B. 2013)
concentrated sulphuric acid using platinum electrodes. 32. The metal used for galvanization of iron is
16. Express the relation between conductivity and molar (a) zine (6) magnesium
conductivity of a solution held in a cell. (D.S.B. 2017) (c) copper (d) aluminium
17. Express the relation among the conductivity of a solution in (AP. S.B. 2013, 2014)
the cell, the cell constant and the resistance of the solution aa. Which of the following statements is false?
in the cell. (D.S.B. 20117) (a) Oxidation and reduction half-reactions occur at
18. Which cell was used in Apollo Space programme ? What was electrodes in electrochemical cells.
the product used for ? (Pb.S.B. 2012)
(6) All voltaic (galvanic) cells involve the use of electricity
19. Whatis the amount ofelectricity required to deposit one mole to initiate non-spontaneous chemical reactions.
of aluminium from a solution of AIC], ? (Pb.S.B. 2012) (c) Reduction occurs at the cathode.
20. How can you increase the reduction potential of an electrode? (d@) Oxidation occurs at the anode.(4.P. 8.B., 20135, 2014)
(Pb.S.B. 2012) 34, The tendency of the electrodes made up of Cu, Zn and Ag
21. Whatisthe amount ofelectricity required to deposit one mole to release electrons when dipped in their respective salt
of zinc from the solution of ZnSO, ? (Pb.S.B. 2012) solutions decreases 1n the order:
22. Whatis the reference electrode in determining the standard (a) Zn>Ag>Cu (6) Cu> Zn > Ag
electrode potential ? (Pb.S.B. 2012) (c) Zn > Cu>Ag (d) Ag > Cu > Zn
23. What is the effect of decreasing concentration on the molar (ALP. SB. 2015)
conductivity of weak electrolyte ? (Pb.S.B. 2012) 30. The units of cell constant are:
24. The products of electrolysis of aqueous NaCl at the (a) ohm? em? (6) em
respective electrodes are: (c) ohm? cm (d) em
(AP. S.B. 2015, 2016, Hr. S.B. 2015, 2018)
ELECTROCHEMISTRY

36. In a galvanic cell, which one of the following statement is 11. (a) Discuss second law of Faraday of electrolysis.
not correct? (Ar.S.B. 2018)
(a) Anode is negatively charged (6) What is corrosion ? Give two methods to prevent it.
(6) Cathode 1s positively charged (Ar.S.B. 2018)
(c) Reduction takes place at the anode
(c) Expain Kohlrausch law with a suitable example.
(d) Reduction takes place at the cathode(H.P. S.5. 2017)
(Ar.S.B. 2018)
of. Conductance of an electrolytic solution depends on
12. (a) Whatis a Galvanic cell? Give the function of salt bridge.
(a) nature of electrolyte
(6) Can a zine spoon be used to stir a solution of copper
(6) power of AC source
sulphate ? Support your answer with reason.
(c) distance between two electrodes
(d) none of the above. (Hr. S.B. 2017) EY n2+| Zn) =— 0-76V, E~ (ou2+)ou) = + 0-84V
38. For the given cell : Or
Mg|Mg?* ||Cu2*|Cu What are weak electrolytes ? Give the product formed in the
(a) Mgactsascathode (0b) Cu acts as cathode electrolysis of molten PbBr,. (Ar. S.B. 2010)
(c) Mg is oxidising agent (d) None of these 13. (a) Why does an alkaline medium inhibit the rusting ofiron?
(Hr. S.B. 2017)
(6) Why does a dry cell become dead after a long time even
359. The units of molar conductivity are :
ifit has not been used ?
(a) ohm! m? mol? (6) ohm m? mol
(c) Why is zine better than tin in protecting iron from
(c) ohm! m? mol (@) ohm? m? mol
corrosion ? (CBSE Sample Paper 2011)
(Ar. S.B. 2018)
14, What are fuel cells ? Discuss H,—O, fuel cell. List two
40). The electrode potential of SHE 1s fixed as
advantages of fuel cells. (H.P. S.B. 2012, 2015)
(a) 0.84 V (b) -0.44V 15. (a) State the law which helps to determine the limiting molar
(c) OV (d) -0.76 V (4.P. S.B. 2018) conductivity of weak electrolyte.
Al. Number of Faradays (F) required to reduce 1 mole of MnO,- (6) Calculate limiting molar conductivity of CaSO, limiting
into Mn** are molar conductivities of calcium and sulphate ions are
(a) 6F (6) 2F 119.0 and 106.0 S em? mol respectively.
(c) 1F (d) 7F (Hr. S.B. 2018) (C_B.S.E. Sample Paper 2012)

»> Te melt tee a carrying 2 or 3 marks <<

16. (a) (1) Give two points of differences between emf and
potential difference.
» Define conductivity and molar conductivity for the solution of (it) Calculate the standard electrode potential of Ni** |Ni
an electrolyte. Discuss their variation with temperature. electrode if the cell potential of the cell:
. How will you distinguish between : Ni(s)| Ni?*(0.01 M)|| Cu2*(0.1M)| Cu(s) is 0.69V.
(1) Metallic conduction and electrolytic conductance ? Given that E* (Cu2*| cu) = + 0.34 V
(11) Strong and weak electrolytes ? ie
. How is molar conductivity related to concentration of
(6) (i) Write two points of differences between galvanic cell
an electrolyte ? How will you explain weak and a strong and electrolytic cell.
electrolyte based on their conductivity values ?
(it) Calculate the maximum work that can be obtained
. What are the factors which affect the conductivity of an from Daniel cell.
electrolyte solution ? Illustrate with examples.
Zn| Zn?*(aq)|| Cu2*(aq)|| Cu
. (a) Explain normal or standard hydrogen electrode.
(b) How much amount of substance 1s deposited by passing Given :-E° (Zn2* |Zn) — —0.76
V and E®* 4.24) guy = 0-34V
one Faraday of electricity? (Pb.S.B. 2018) (Mizoram S.B. 2013)
- (a) Explain lead-storage cell.
17. (a) State Faraday’s laws of electrolysis.
(5) Define primary cell.
(6) How much copper will be deposited at cathode of an elect-
Or
rolyticcell containing Cu** ions by the passage of 2 ampere
(a) Explain electrochemical theory of rusting of iron. current for 60 minutes? (Jharkhand S.B. 20135,2016)
(b) Define fuel cell. (A. P.S.B. 2018)
18. Define molar conductivity of an electrolytic solution. How
. Why do we get different products at cathode during the
does molar conductivity vary with concentration for a
electrolysis of molten NaCl and aqueous sodium chloride ?
weak electrolyte ? (Assam S.B. 2015)
. (a) Explain Ni— Cd storage cell.
19. (a) (2) What are the functions of salt bridge in a galvanic
(6) Define secondary cells.
cell?
Or
(a) Define Faraday's first law. (iz) The molar conductivity at infinite dilution of
(6) Differentiate between primary and secondary cells. Al,(SO,), is 8658 S em? mol. Calculate the molar
(H.P.S_B. 2018) ionic conductivity of Al** ion given that A°(SO2>) =
. Can we use aluminium or copper for cathode protection of 160 S em? mol.
iron ? Explain giving reasons. Or
10. Define Kohlrausch's law. How does it help in (2) calculation (1) Write two differences between primary cells and
of A° for a weak electrolyte and (17) degree of dissociation of a secondary cells.
weak electrolyte ? (Jammu S.Z. 2018)
ase (11) Calculate the emf of the following cell at 298 K:
MODERN'S abe + OF CHEMISTRY

Or
-AXIl

Fe |Fe?*(0.1M) |Agt(0.1M) Ag Explain the recharging of a discharge lead storage battery

Given: E*°(Fe**| Fe) =—0.44 V and with electrode reactions. (Nagaland S.B. 2016)
E°(Ag* |Ag) = 0.80 V 28. Which of the following is a secondary cell?
(z) Dry cell (it) Leclanche cell
(R = 8.31 JK mol, F = 96500 C mol")
(111) Mercury cell (1v) None of these
(Mizoram S.B. 2014) (a) What is the relationship between resistance and
20. (a) Find the equilibrium constant of the following reaction conductance?
at 208 K: (6) One of the fuel cell uses the reaction of hydrogen and
Cu(s) + 2Ag* (aq) + Cu?*(aq) + 2Ag(s) ; E°__,, = 0.46 V oxygen to form water. Write down the cell reaction
Identify the cathode and anode in the cell. taking place in the anode and cathode of that fuel cell.
(6) Three electrolytic cells containing ZnSO,, AgNO, and (Kerela S.B. 2016)
CuSO, were connected in series. A steady current of 29. Give the Nernst equation for the cell:
1.56 A was allowed to pass through them till 1.45 g of Ni(s) |Ni?* (ag 0.1M) || Ag* (ag 0.1M) |Ag(s)
Ag is deposited. How long did the current flow? What and also find the cell potential.
weight of Cu and Zn were deposited? (Atomic mass of Given : E° (Ag*| Ag) = 0.80V, E° (Ni** |Ni) = —0.26V
Ag = 108, Cu = 63.5 and Zn = 65.3). (Meghalaya S.B. 2016)
(c) Can we keep AgNO, solution in a copper container ? 30. (a) Define molar conductivity of an electrolytic solution.
LE ou?*} cu) =+0.34 V, ag | Ag) = + 0.80 V] Show the variation of molar conductivity of a strong
(Meghalaya S.B. 2014) electrolyte with square root of concentration.
21. What are primary cells ? Give the construction and working (6) State Kohlrausch law.
of a dry cell. (H.P. SB. 2015) The limiting molar conductances of NaCl, HCl and
22. What are secondary cells ?Explain the working oflead storage CH,COONa are 126.46, 426.16 and 91.0 S cm?
battery. (H.P. S.B. 2015) mol respectively at 298K. Calculate limiting molar
23. What is a secondary battery ? Write the mechanism of conductance of acetic acid at 298K. (Assam S.B. 2017)
recharging of lead storage battery with the help of chemical ol. (a) Describe the construction and working of Normal
reaction. Hydrogen Electrode.
Or (6) Calculatethestandard EMF ofacellinvolvingcell reaction:
(a) Define standard electrode potential. Zn + 2Ag*—> Zn** + 2Ag
(6) Thestandard electrode potential for Daniell cellis 1.1V. Given : Eo ite2t = 0.76 V; E AglAgt =~ 0.80 V
Calculate the standard Gibbs energy for the reaction: (c) Give two differences between metallic and electrolytic
Zn(s) + Cu?*(ag) ——> Zn**(aq) + Cu(s) conductors. (Ar. S.B. 2017)
(Uttarakhand S.B. 2015) ode What is electrochemical theory of rusting of iron and
24, (a) Draw a neat labeled diagram of H, —O, fuel cell. Write give two methods of prevention of rusting of iron?
the reaction which occurs at cathode of the cell Cr
(Karnataka S.B. 2018) Write the Nernst equation and calculate the emf of
following cell at 298 K.
(6) Calculate e.m.f. of the cell for the reaction.
Ni| Ni?*(0.01 M) ||Cu?* |Cu (0.01 M)
Me(s) + Cu?* (0.0001M)—> Mg** (0.001M) + Cu(s)
Given that: E* Ms [Mg = —~2-37V Given : E°(Cu?* |Cu) = + 0.34V, E° (Ni?* |Ni) =—0.22V
(Pb. S.B. 2017)
| ee | cuz +0.354V ove Explain the variation of molar conductivity of strong
(c) (1) State Kohlrausch law. and weak electrolytes with dilution.
(11) What is meant by limiting molar conductance? Or
(Karnataka S.B. 2018) Write the Nernst equation and calculate the emf of
25. (a) Explain electrochemical series. following cell at 298 K.
(6) Can we store 1 M CuSO, in Zn vessel or not why? Mg(s) |Mg?*(0.001 M) ||Cu**(0.0001 M)| Cu(s)
or Given : Ee Mg2* \Mg= —2.37V, E°,2+ \Cu = 0.34V
(a) Explain the working of a fuel cell. (Pb. S.B. 2017)
(6) Define Faraday's Second Law. oA, What is corrosion ? What are the factors affecting
(H.P.S.B. 2018) corrosion?
Or
26. (a) What are primary cells?
Write the Nernst equation and calculate the emf of
(6) Write short note on lead storage battery.
following cell at 298 K.
(c) For the reaction:
Cu(s) |Cu**(0.130 M) ||Agt(1.0 x 10-# M) |Ag(s)
Ni(s) + 2Ag* (1M) —-> Ni?#* (1M) + 2Ag(s)
Given : E°(Cu?* |Cu) = +0.34V, E°(Ag* |Ag) = +0.80V
which species get reduced? (AP SB. 2076)
27. Write the Nernst equation for the following cell:
(Pb. S.B. 2017)
oo. (a) Zine protects iron from corrosion better than tin. Give
Zn |Zn** (aq) ||Cu** (ag)| Cu
Write the reaction occurring at each of the electrode and
reason.
(6) What are primary cells and secondary cells?
the net cell reaction. Also determine its cell potential when
(Manipur S.B. 2017)
[Zn** (aq) = 1M, [Cu** (aq)] = 1M, E°,7* | Zn =~ 0.76V
and E° cu |cu —+ 0.34 V.
ELECTROCHEMISTRY

36. (a) How many Faradays of electricity 1s required to liberate 44, Define the following terms:
1 mole of copper from copper sulphate solution? (t) Molar conductivity (A,,)
(6) Arrange Kt, Zn**, H* and Cu** ions in order of their (11) Secondary batteries (A.L.S.B. 2014)
tendency to be liberated at the cathode.
45. (a) Following reactions occur at cathode during the
[Given : FE cu2t | Cu) =+0.34 V; Hort |Ho) = 0.0V;
electrolysis of aqueous sodium chloride solution:
E Gn?*|zn) = —0-76 V; Ee gct 5 = -2.93V] Na*(ag) + e ——> Na(s) E° =—2.71 V
(West Bengal S.B. 2018) H*(aq) + e@ —> =Hale) E* = 0.00 V
37. (a) Why can limiting molar conductivity of CH,COOH not
be determined experimentally ? On the basis of their standard reduction electrode
(6) How many coulombs of charge are required to produce potential (E°) values, which reaction is feasible at the
20.0 g of calc1um from calcium chloride ? cathode and why?
(c) Whatis a salt bridge ? Give two functions of salt bridge. (6) Why does the cell potential of mercury cell remain
(Meghalaya S.B. 2018) constant throughout its life? (A.L.S.B. 2015)

D> ‘ovofrsuer vesions —EIEUTETIM<<

38. (2) What is electrochemical series? Write one of its
application. Calculate the e.m.f. of the cell
Cr |Cr+ (0.1M) ||Fe** (0.01M) | Fe.[(E° (Gr3+
|ox)= —0.76 V
and E° 24 | Fe) = —0.45V, log 10 = 1]. 1. (a) Explain Kohlrausch’s law of independent migration of
(6) Write the Nernst equation for the cell: ions. Mention one application of the law.
Zn |Zn** (1M) ||Cu?* (1M)| Cu (6) With the help of a graph, explain why it 1s not easy to
where Ban 2+ \Zn) = —0.76V; FE cu2t] Cu) = + 0.34V. Write the determine A, for a weak electrolyte by extrapolating
reaction occurring at each of the electrode and its net cell the concentration vs molar conductivity curve as for
reaction. Also determine its cell potential. strong electrolytes ?
(Nagaland S.B. 2018) 2. (a) Whattype ofa battery is the lead storage battery ? Write

»>2 CBSE QUESTIONS <4

the anode and the cathode reactions and the overall
reaction occurringin alead storage battery when current
39. Express the relation among the cell constant, the resistance is drawn from it.
of the solution1n the cell and the conductivity ofthe solution. (65) Inthe button cell, widely used in watches, the following
How is the conductivity of a solution related to its molar reaction takes place :
conductivity ? (A.7.S_B. 2070, 2022)
Zn.) +Ag,0,,) - H,0y—> Zia) + 2Ag(.) + 20H (aq)
40. Given that the standard electrode potentials (K°) of metals
are : Determine E® and AG° for the reaction.
Kt |K=— 2.93 V, Agt |Ag = 0.80 V, Cu**| Cu=0.34V,
Mg** |Mg =— 2.37 V, Cr** |Cr =— 0.74 V, Fe?* |Fe=—0.44V. (Given: EGAgtiAg)
. = +0-80V, EC -0.76V
Arrange these metals in an increasing order of their
(Zn?*|Zn) —
reducing power. Or
Oss (a) Define molar conductivity of a solution and explain how
Two half-reactions of an electrochemical cell are given below: molar conductivity changes with change in concentration
MnO, (aq) + 8H*(aq) + 5e° > Mn**(aq) + 4H, O(2), of solution for a weak and a strong electrolyte.
(6) The resistance of a conductivity cell containing 0.001 M
E* =+1.61V KC] solution at 298 Kis 1500 Q. Whatis the cell constant
on?**(ag) > Sn**(aq) + 2e-, EF =+0.15V if the conductivity of 0.001 M KCI solution at 298 K is
Construct the redox reaction equation from the two Half- 0.146 x 107° Sem? (D.S.B. 2012)
reactions and calculate the cell potential from the standard 3. You are provided with the following substances: copper rod,
potentials and predict if the reaction is reactant or product zinc rod, salt bridge, two glass beakers, a piece of wire, 1 M
favoured. (A.LS.B. 2010) CusO, solution, 1 M ZnSO, solution.
41, State Kohlrausch law ofindependent migration ofions. Why (a) Represent the cell made using the above materials.
does the conductivity of a solution decrease with dilution? (6) (1) Write the Nernst equation for the above cell.
(A. 1S_B. 2014) (iz) Calculate the standard e.m_f. of the cell, if
42. (a) Calculate A.G° for the reaction E°(Zn** |Zn) =—0.76V, E°(Cu** |Cu) = +0.34V
Mg(s) + Cu** (ag) > Mg?*(aq) + Cu(s) (Kerala S.B. 2015)
Given : E°_,, = +2.71 V, 1 F = 96500 C mol 4, (a) Write two points of differences between metallic
(6) Name the type of cell which was used in Apollo space conductance and electrolytic conductance.
programme for providing electrical power.
(6) State Kohlrausch’s law. Molar conductivity at infinite
(A..S.B. 2014) dilution for NH,Cl, NaOH and NaCl solution at 298K
43. Define the following terms:
are 110,100 and 105S cm? mol"! respectively. Calculate
(i) Fuel cell the molar conductivity of NH,OH solution.
(tt) Limiting molar conductivity (Af) (A.L.S.B. 2014)
= Or
MODERN'S abe + OF CHEMISTRY

10. (a) Calculate the equilibrium constant of the reaction:

-AXIl

(a) Whatis equivalent conductivity and molar conductivity Cu(s) + 2Ag* (ag)> Cu** (aq) + 2Ag (s)
of an electrolyte in solution? (Given : E°,.4, = 0.46 V)
(6) Write the Nernst equation and calculate emf of the (6) State Faraday's first law of electrolysis. What is the
following cell at 298K. quantity of electricity in coulombs needed to reduce
Cu(s) |Cu?*(0.130 M) ||Ag*(1.0 x 10-*M) |Ag(s) 1 mol of Cr,02- ion for the following reaction ?
Given : E°(Cu?*| Cu) = +0.34 V, E°(Agt| Ag) = +0.80 V Cr,07+ 14 Ht + 6e° —> 2Cr** + 7H,O
(Mizoram S.B. 2015) (Given : 1F = 96,500 C mol)
5. (a) Define specific conductivity and molar conductivity for (c) Whydoes mercury cell give a constant voltage throughout
the solution of an electrolyte. How do they vary with its life?
dilution? Or
(6) Calculate A” for NH,OH given that the values of A* for (d) Asolution of CuSO, is electrolyzed for 10 minutes with
Ba(OH),, BaCl, and NH,Cl are 623.28, 280.0 and 129.8 a current of 1.5 amperes. What is the mass of copper
5S cm? mol! respectively. (Meghalaya S.B. 2015) deposited at the cathode? (Given : Atomic mass of
6. (a) State Faraday’s first and second law of electrolysis. Cu =68 g mol", 1F = 96500 C mol)
(6) Calculate the number of coulombs required to deposit (e) The molar conductivity of 0.025 mol L~ methanoic acid
40.5 g of Al when the electrode reaction is : is 46.1S cm* mol. Calculate the degree of dissociation.
Al5++ 3e- ——> Al(s) Given :
Or A° + = 349.65 cm? mol
(a) Whatis electro chemical series ? Write one application of (eee ed. S cm? mol
electrochemical series. Calculate the standard electrode (f) What are secondary cells? (Meghalaya S.B. 2017)
potential of Ni** |Ni electrode, ifthe cell potential of the 11. (a2) What is the standard electrode potential?
cell:
(b) The measured e.m_f. of the cell:
Ni |Ni**(0.01 M) ||Cu?*(0.1M) |Cu, is 0.69V. Pt(s)| H, a |H* (ag, 1M) || Cu?* (ag, 1M) |Cu(s) is
[Given E°(Cu?* | Cu)=0.34V] (Nagaland S.B. 2015) 0.34V.
7. (a2) What is a fuel cell? Write its one advantage over other What is the standard electrode potential of the half cell
ordinary cells. corresponding to the reaction ?
(6) Avoltaic cellis set up at 25°C with the given half cells:
Cu?* (ag, 1M) + 2e°-—> Cu(s)
Ag* (0.001M) |Ag and Cu** (0.10M)| Cu. (e Represent the cell in which the following reaction takes
ws

What would be the voltage of the cell (E°__,, = 0.46V)? place.

Or Me(s) + 2Ag* (0.01M)—> Mg** (0.1830M) + 2Ag(s)
(a) What is meant by 'molar conductivity’ of a solution?
Write the Nernst equation and calculate the emf of the
Describe how for weak and strong electrolytes, molar
cell at 298 K. Given E®_,, =3.17 V. (Assam S.B. 2018)
conductivity changes with concentration ofsolution. How
12. (a2) What are primary batteries ?
is such change explained?
(6) The cell potential of mercury cell is 1.35 V, and remain
(6) Themolar conductivity of 1.5 M solution ofan electrolyteis
constant during its life. Given reason.
foundtobe 138.9S. em? mol. Calculate the conductivity
of this solution. (Tripura $.B. 2016) (c) Write the equations of the reactions involved at each
electrode in a H, — O, fuel cell. (Kerala S.B. 2018)
8. (a) Represent the galvanic cell based on the cell reaction
given below:
Cu(s) + 2Ag* (aq) —> Cu** (ag) + 2Ag(s) >»: CBSE QUESTIONS <4
(6) Write the half cell reactions of the above cell. 13. (a) State two advantages of H,—O, fuel cell over ordinary
(c) A for NaCl, HCl and NaAc are 126.4, 425.9 and 91.0 cell.
S cm? mol? respectively. Calculate A for HAc. (6) Silver is electrodeposited on a metallic vessel of total
(Kerala S.B. 2016)
surface area 900 cm” by passing a current of 0.5 amp for
9, (1) Explain how salt-bridge maintains the electrical two hours. Calculate the thickness of silver deposited.
neutrality ofthetwo halfcell solutions in a galvanic cell. (Given density of silver = 10.6 gem, atomic mass of
(11) The molar conductivities at infinite dilution for silver = 108 amu, F = 96500 C mol")
CH,COONa, HCI and NaCl are 91.0, 425.9 and 126.4
Or
5 cm? mol?! respectively at 298 K. Calculate the molar
(a) Give reason for the following:
conductivities of CH,COOH at infinite dilution.
Or (t) Rusting of iron is quicker in saline water than in
ordinary water.
(1) What is the difference between strong electrolytes and
weak electrolytes? Give examples. (21) Aluminium metal cannot be produced by electrolysis
(11) Calculate the equilibrium constant for the reaction at of aqueous solution of aluminium salt.
298 K: (6) Resistance of a conductivity cell filled with 0.1M KCl
Cu(s) + 2Ag* (ag) —> Cu** (ag) + 2Ag(s) solution is 100 ohm. If the resistance of same cell
(Given: E when filled with 0.02 M KCl is 520 ohms, calculate
(Ag’ |Ag) = 0.80 V, FE ou2t \Cu) = 0.34 V) the conductivity and molar conductivity of 0.02 M
(Mizoram S.B. 2017)
ELECTROCHEMISTRY

KCI solution. Conductivity of 0.1 M KCl solution is Calculate the e.m.f. of the cell.
eo ie (A.f.S.B. 2006) [log 10° =—n]
14. (a) Write the anode and cathode reactions and the overall (6) Define fuel cell and write its two advantages.
reaction occurring in a lead storage battery. (A.IS.B. 2018)
(6) A copper silver cell is set up. The copper ion
concentration is 0.10 M. The concentration of silver ion
is not Known. The cell potential when measured was
»> NUS
Trey Vil 7-Yo)- a1) ae <q
0.422 V. Determine the concentration of silver ions in At equimolar concentration of Fe** and Fe**, what must
the cell. be the [Ag*] so that the voltage of the galvanic cell made
[Given : E®
(Ag*|Ag)_ + 0.80 V, E°
(Cu®+|Cu) = + 9-84 VI from Ag*|Ag and Fe**|Fe** electrodes equals zero? The
(A.S.B. 2010) cell reaction is
15. (a) What type of battery is lead storage battery? Write Fe** + Ag¥ “Qa ——tte* + Ag
the anode and cathode reactions and the overall cell [Ans. 0.335 M]
reaction occurring in the operation of a lead storage During the discharge of a lead storage battery, the density of
battery. sulphuric acid fell down from 1.294 to 1.139 g/ml. Sulphuric
(6) Calculate the potential for half cell containing 0.1 M acid of density 1.294 g/mlis 39% H,SO, by weight and that of
K,Cr,O, (aq), 0.20 M Cr** (aq) and 1.0 x 10*MH* (aq). density 1.139 g/ml is 20% H,SO, by weight. The battery holds
The half cell reaction is 3.6 L of acid and the volume remains practically constant
Cr,O? (aq) + 14 H* (ag) + 6e° —> 2Cr** (aq) + TH, OC) during discharge. Calculate the number of ampere-hours
and the standard electrode potential 1s given as : for which the battery must have been used. The charging
ee eet (A.L.S.B. 2017) and discharging reactions are :
16. (a) How many moles of mercury will be produced by Pb?* +50,277> === PbSO, + 2e (Charging)
electrolysing 1.0 M Hg(NO,), solution with a current PbO, + 4H* + SO,2- + 2e° ———_ PbSO, + 2H,O
of 2.00 A for 3 hours? [Hg(NO,), = 200.6 g mol]. (Discharging)
(6) Avoltaic cell is set up at 26°C with the following half [Ans. 264.9 amp-hr]
cells : A current of 4 amp was passed for 1.5 hours through
Al** (0.001 M) and Ni?* (0.50 M). a solution of copper sulphate when 3.2 g of copper was
Write an equation for the reaction that occurs when the cell deposited. Calculate the current efficiency. [Ans. 45.1%]
generates an electric current and determine the cell potential.
Calculate equilibrium constant for reaction :
[Given : He i? |ND =— 0.25 V, at) Al)=— 1.66 V] Fe(s) + Cd**(ag) —> Fe**(aqg) + Cd(s)
(A..S.B. 2011)
Given : E*(442+)ag)= —0-40V, E®(9+)re)= —0-44V
17. (a) Calculate E° _,,for the following reaction at 298 K:
(D.S.B. 2009) [Ans. 22.7]
2Cr(s) + 3Fe** (0.01 M) —> 2Cr** (0.01 M) + 8F e(s)
A voltaic cell is set up at 25°C with the following half cells:
Given : E_.1, = 0.261 V
Al | Al?* (0.001M) and Ni | Ni** (0.60M)
(6) Using the E° values of A and B, predict which one is
Calculate the cell voltage
better for coating the surface of iron [E” (Fe**| Fe) =
—0.44 V] to prevent corrosion and why? aoa 4

Given : HY (ane|ay =~ 2-37 V2 EB go, )p) =—0-14V

(D.S.B. 2009, AI.S.B. 2009) [Ans. 1.463 V]
(a) Theconductivity of 0.001 mol L “solution of CH,COOH
is 3.905 x 10° Sem. Calculate its molar conductivity Calculate AG and E..,, for the cell
and degree of dissociation (c). Al|A15+(0.01 M) || Fe2* (0.02 M) |Fe
Given 4° (H*) = 349.65 em? mol and Given that E*, a13+| an = 1-66 V and
i°(CH,COO_) = 40.9 5 em? mol. E*(7e2t| Fe) = 0.44 V (Pb.S.B. 2013)
(b) Define electrochemical cell. What happens if external
Calculate emf of the following cell at 25°C:
potential applied becomes greater than E°®__,, of
electrochemical cell? (A.L.S.B. 2016) Fe |Fe2+ (0.001 M) || H* (0.01 M) |H,(g) (1 bar) | Pt(s)
18. (a) Write the cell reaction and calculate the e.m.f. of the E°(Fe** |Fe) = 0.44 V, E°(H* |H,) = 0.00V
following cell at 298 K: (D.S.B. 2015) (Ans. 0.41065]
Sn(s) | Sn?* (0.004 M) ||H* (0.020 M) |H,(g)(1 bar) |Pt(s) A current of 0.5 ampere is passed for 30 minutes through
(Given : E®,,2+\Sn =—0-14 V) avoltmeter containing copper sulphate solution. Calculate
(b) Givereasons: the mass of copper deposited at the cathode. (At. mass of
(2) On the basis of E” values, O, gas should be liberated Cu = 63.0 amu) (Assam S.B. 2016)
at anode but it is Cl, gas which is liberated in the Calculate e.m.f of the following cell at 298 K:
electrolysis of aqueous NaCl. 2Cr (s) + 8Fe** (0.1M)
—> 2Cr** (0.01M) + 3 Fe(s)
(1t) Conductivity of CH,COOH decreases on dilution.
Given E° (Cr** |Cr) = -0.74 V, E” (Fe?*| Fe) = — 0.44 V
Or
(D.S.B. 2016)
(a) For the reaction
10. Calculate the emf of the following cell at 298 K:
2AgC\(s) + H, (g) (1 atm)—- 2Ag (s) + 2H* (0.1 M) +
2CI (0.1 M), Cr(s) |Cr** (0.1 M)| | Fe?- (0.01 M)| Fe(s)
AG® =— 43600 J at 26°C [Given : Ez. =0.80V] (C.B.S.E. Sample Paper 2017-18)
ae
11. The conductivity of 10° mol / L acetic acid at 25°C is
MODERN'S abe + OF CHEMISTRY
-AIl

Zn(s) + Cu** (ag) ——> Zn** (aq) +Cu(s)

4.1 x 10° 5S em'!. Calculate its degree of dissociation, if
(1 F = 96500 C mol?) (A.J. S.B. 2013) (Ans. —212.3 kJ]
A, for acetic acid at 26°C is 390.5 S em* mol’.
15. Calculate the emf of the following cell at 25°C:
(C_LB.S.E. Sample Paper 2017-18)
Ap(s) | Ag* (10M) || Cu2+ (10M) | Cu(s)
»> CBSE QUESTIONS ‘<4 Given E® eel! = + 0.46V and log 10" =n (A.L.S.B. 2013)
[Ans. 0.3125 V]
12. Acopper-silver cellis setup. The copper ion concentration in it
16. The conductivity of 0.20M solution of KCl at 298K is
is 0.10 M. The concentration ofsilverionis not known. The cell
0.025 S em. Calculate its molar conductivity.
potential measured is 0.422 V. Determine the concentration
of silver 10n in the cell. (ALL S.B. 2013, D.S.B.2013) |Ans. 125]
17. Calculate emf of the following cell at 25°C:
Given : Bae ae = +0.80V, ee pes = +0.34 V.
Sn |Sn2*(0.001 M) || H* (0.01 M) |H,(g)(1 bar) |Pt(s)
(A..S.B.E. 2009) [Ans. 0.0718 M]
E°(Sn** | Sn) =—0.14 V, E°(H* |H,) = 0.00V
13. Calculate the emf of the following cell at 298 K:
(A.[S.B. 2015) (Ans. 0.11056V]
Fe(s) |Fe+ (0.001 M) ||H*(1M) |H,(g), 1 bar, Pt(s) 18. The cell in which the following reaction occurs:
(Given | ae =+0.44Y) (A.S.B. 2012) |Ans. 0.5286 V]
2Fe** (aq) + 21 (aq) —> 2Fe**(aq) + 1,(s)
14. The standard electrode potential (E) for Daniell cell is has E® _,, 0.236 V at 298 K. Calculate the standard Gibbs
+ 1.1V. Calculate AG® for the reaction: energy of the cell reaction. (Given : 1F = 96500 C/mol™)
(isst. 2077)

Hints & Answers

for Revision Exercises
¢ 2. The charging and discharging reactions are :
Pb + 80,2 —> PbSO, + 2e7
2.303RT
[Al* ; PbO, + 4H* + 50,2 + 2e° ——> PbSO, + 2H,O
1. Beet aa E* on = 6F og (FEe a+ ie Net reaction : Pb + PbO, + 2H,SO, —~> 2PbS0,
+ 2H,O0
5. No 6. Fe,O,.xH,O
The reaction indicates that 2 mol of e- are transferred
8. Concentration decreases 9. 3x 96500C
for the consumption of 2 mol of H,SO,,.
11. Because acidic NH,Cl corrodes the zinc container.
12. Chemical energy ofthe fuelis converted to electrical energy. 2 mol of H,S5O, required electric charge = 2 x 96500 C.
13. H,—O, cell. 14. ohm! cm? mol Calculation of moles of H,S5O, in 3.6 L solution of density
16. A KX 1000
1.294 g cm?
_ M Mass of H,SO, in 1 em® =
39
1294x222
Cell constant
100°
17. Conductivity =
Resistance
Mass of H,s0O, in 3.6 L 1,294 x a x 3.5 x 1000 ¢g
18. Fuel cell 19. 3x 96500C
20. Decreasing conc. of the electrolytic solution 1.294 x 39 x 3.5 x 1000
21. 2x96500C Moles of H,SO, in 3.6 L
100 x 98
22. Hydrogen electrode
23. Molar conductivity increases 26. propane = 18.02 mol
30. (a) 31.(a) 32. (a) 33. (6) 384. (c) 35. (d) Calculation of moles of H,SO, in 3.6 L of density
36. (c) 37.(a) 38.(6) 39. (a) 40. (c) AL. (a) 1.139 g cm?
Numerical Problems /
Mass of H,SO, in 1 em’ = 1/8? %20
¢ 1. Fe** + Ag =—
100
Fe** + Ag
E = E® _ 0.059 log Xe
a+
] Mass of H,SO, in 3.6L = ne eee
1 [Fe ][Ag*]
oO = H.SO,.
1.189 x 20 x 3.5 x 1000
= ——_
Moles of
= ee agtlap ~ E* (pe8+ | Fe2+)
—_—s 4 100 x 98
= 0.799 — 0.771 = 0.028 V
= 8.136 mol
For E? = 0, [Fe**] = [Fe**]
Moles of H,5O, consumed during discharging
0.059 1 = 18.02 — 8.316 = 9.884 mol
0 = 0.028 -——
1”lo [Agt] Now, 2 moles of H,SO, correspond to = 2 x 96500C
9.884 mol of H,SO, correspond to
ELECTROCHEMISTRY

AG =—nFE
2 eee
oe — x 9-854 _ 953806 C
= — 6 x 96500 x 1.23
1 Coulomb = 1 amp. sec. = — 712170 J mol? = 712.17 ke) mol
3600 Coulmb = 1 amp. hr. ¢ 7. Fe(s) + 2H*(ag) ——-> Fe**(aq) + H,(g)
|
63806 CC = ——
953806 3600 x© 953806
°° 6 == 264.9
: amp.hr
. E cet! = 0.0 — (0.44) = 0.44 V
¢ 3. Quantity of electricity passed = 4 x 1.5 x 60 en weg oto [Fe** |]
=| cell = (Ht?
= 21600 C
Cu** + 2e°- —> Cu 0.059. (0.001)
= 44 Fa Io
2 x 96500 C of electricity deposit Cu = 63.5 g 2 50.01"
21600 C of electricity will deposit Cu EK = 0.44 — 0.0295 = 0.4105 V

_ 35
—63.5 _ 91600 _ ¢ 8. Cu** 2e —~> Cu
= 2x96500 <9 = 718 Quantity of electricity = 0.5 x 30 x 60
Amount of copper deposited = 3.2 g = 900 C
2 x 96600 C of electricity deposit Cu = 63.0g
3.2
Efficiency = ~, x 100 = 45.1%
v1 900 C of electricity will deposit Cu = 08-0900
2x 96500
+ 4, KF? = E°(Cd?*
| Cd) — E°(Fe?*
| Fe) = 0.294 g
K° 1) = —0.40 — (0.44) = 0.04V
55. B = Be 0:059 [CrP
d+ 72

6 [Fe™* |"
log K. = n Beet at 26°C
0.059 E* = -0.44 — (0.74) = 0.30 V
_ 2x 0.04 - 1.356 0.059. [0.017
EK = 0.30—- —— log
0.059 (0.1P
K_c = 22.7 _ 0.30 _ 0.059 log 0.1
¢ 5. Al| Al°*(0.001M) || Ni?*(0.60M) | Ni
= 0.30 — 0.01 (-1) = 0.81 V
2Al(s) + 3Ni7*(ag) ——> 2Al** (aq) + 3Ni(s)
¢ 10. 2Cr(s) + 3Fe** (ag) —> 3 Fe(s) + 2Cr** (aq)

E = E® _ 0.059,
7 [Al]
sical E = E°
— 0.059,
6
O
[Cr**P
[Fe*P
— 0,30 —2:959 toe o.1" 2

ER? =— E* ayiz+| Ni) > EB (013+) an 6 (0.01)

= —0.25 — (-1.66) = 1.41V
~ 0.30 — x4 - 0.26V
_ 141 0.059, log
(0.001)
ae 6 (0.50) ‘aa: |
C
0.059
= Aled= log8x 10° _ 41x10 —5 1000 Wa eatieaciel
107
— ].41 + 0.063 = 1.468 V
AC 4]
¢ 6. 2A + 3Fe ———=; 2Al + 3Fe** _ Am ~ ——_ _ 0,105
2 a 2
"9 ~ 390.5
KY = E (Fe-t |Fe) K (Al5+ | Aly
¢ 12, Cu(s) + 2Ag*(ag) —> Cu?*(aq) + 2Ag(s)
— —).44 — (- 1.66) = 1.22 V
The Nernst equation is

E — Ee
0.059, log [Re
We 1 E = po_0.059), [Cu
Cc 2+

6° al?
[Ag*|
0.059 4
— 1.29 — 20? jog (0.02) E® = E°(Ag*t|Ag) — E°(Cu2*|
Cu)
6 (0.01) 0.80 — 0.54 = 0.46V
0.059
= 122 - ——— log 0.08 0.422 = 9. 4¢_2:052 (0.1)
log ,
9
1.22 — (-0.01) = 1.28 [Ae]
ae MODERN'S abe + OF CHEMISTRY
-AXIl

0.059 (107+)
0.422 — 0.46 = —e = AGP ee = 0.3125 V
2 - (1077)
- [Ast| + 18 fs. 42 «x x 1000
M
ic _ a= = 1.2881
[af °
0.025 x 1000
— ———_ = 125 S em* mol!
0.20

¢ 17. Sn + 2H* (aq) —> Sn** + H,

ae 91Fs 2 _ 19.413
[Sn?*]
|As* | Bett oa Ben -s Be? log
[H*}F
0.1 n = 2, [Sn**] = 0.001 M, [H*] =0.01
gt]? — = 5.15x107
al Ag)’ = 79 413 “
i” il = ERO E*.
or [Ag*] = 0.0718 M = 0.00 —(-0.14) = 0.14
¢ 13. Refer Solved Example 52 (11) (page 41-42).
(a gig SF” lop ee
¢ 14, AG® = —-nFE° 2 (0.01)
= —2 x 96600 x 1.1 = -212.3 kJ
= 0.14- ~~ log 10
¢ 15. Cu(s) + 2Ag* (ag) —> Cu**(ag) + 2Ag(s)
= 0.14— 0.0295 x 1=0.1105 V
0.059 : [(Cu2*]
EK = E® ¢ 18. Refer Solved Example 48 (page 50).
2 ° TAgtP

Competition Filo Additional Useful Information and Objective Questions

eS
(ee >

ADDITIONAL USEFUL INFORMATION

O TYPES OF ELECTRODES Other examples are Cl-|Cl,(g), p atm)| Pt,
Some common types of electrodes and their reduction
potentials are:
= Cl, (g) + e°—> Ck (aq)
A. Metal-metal ion electrodes. These electrodes consist of OH |0,(g), p atm) |Pt
a pure metal (M) in contact with a solution of its cations (M™*).
It is represented as M®*|M(s) e.g., Zn?*| Zn, Cu**| Cu, ete. Its
O, (g) + H,O() + 2e- —» 20H (aq)
electrode reaction is D. Amalgam electrodes. These consist of metal amalgams
M**(aq) + ne-—>M(s) e.g., Zn** (ag) + 2e~ —> Zn(s) dipping in a solution of their ions. For example, lead amalgam
dipping in a solution of Pb** ions. It is represented as
and E(M=2*|M) = E°(M**|M)-— eg log a Pb(Hg) |Pb?*. The reaction is
n [M?*]
B. Metal-metal insoluble salt electrodes. These are Pb2* + 2e- —-> Pb (in Hg)
prepared by coating a piece of metal with an insoluble salt of
the same metal dipped in a solution containing the anion of EK = E°- ee oe
2 [Pb** ]
the insoluble salt. For example, silver is coated with AgCl and
dipped in a solution containing Cl ions. It is represented as : Other example is zinc amalgam electrode; Zn(Hg) |Zn?*.
Cl-| AgC1| Ag. The electrode reaction is E. Oxidation-reduction electrodes. These types of
AgCl(s) + e —+ Agis) + CI and electrodes are made by using an inert metal (e.g. Pt) immersed
0.059 in a solution which contain two ions of the same element in
E(CI |AgCl| Ag) = E°(CI-| AgCl |Ag) - > log [CI]
different oxidation states. For example, Fe**(aq) |Fe**(aq) |Pt,
C. Gas electrodes. These consist of an inert metal (usually
MnO; (ag) |Mn**(aq), H*(aq) |Pt. The reaction is
Au or Pt)in contact with a gas bubbling into a solution containing
corresponding anion. For example, the common hydrogen Fe**(ag) + e- ——> Fe**(aq)
electrode in which H, gas is bubbled over platinized platinum | , . 0.059, [Fe™*]
electrode dipped in an acid solution. It is represented as E(Fe** | Fe?*) = E (Fe?* |Fe?) — qe Fe? *]
H*|(H,, p atm)| Pt. The reaction is
and
H*(aq) + e- —> : H, (g)
MnO aq) + 8H*(aqg) + 5e- —> Mn?*(aq) + 4H,O (Z)

E = E° _ 0.059, (pH, EK = E°-

0.059
og —————_
[Mn?*]
1 [A 5 (MnO; ][H"1
ELECTROCHEMISTRY

oO SOLUBILITY PRODUCT FROM EMF DATA the conductance increases sharply due to excess Na* and OH
In a saturated solution of a sparingly soluble salt such as ions.
AgCl, equilibrium is represented as
AgCl(s) =~ Ag*(aq) + Cl'(aq)
K,, = [Ag*] [Cr]
Since solubility product is the equilibrium constant, it
must be related to e.m.f. of the selected cell having an overall I
reaction as above. For example, for determining solubility |
product of AgCl, the cell is Conductance ' end point
Ag|Ag*Cr (sat.), AgCl(s) |Ag
Atanode: Ag(s)—> Agt+e Volume of NH,OH
At cathode : AgCl(s) + e- —> Ag+ CI Fig. (b)
Overall reaction: AgCl(s) === Ag* + Cl
C. Titration of strong acid vs weak base
o

Bon
—

=
2088? joe tae Cl (e.g., HC] + NH,OH)
nk
2.303 RT H* +Cr + NH,OH —-+> NH,*t + Cl + H,O
= log K,, The conductance decreases initially because of the
replacement of fast moving H* ions by slow moving NH} ions
Knowing E° 1 can be calculated.
(Fig. c). After neutralization, the further addition of NH,OH does
oO CONDUCTOMETRIC TITRATIONS not make much change.
The principle of conductometric titrations is that during
the titration, one of the ions is replaced by the other. Since the
ions differ in their ionic conductances, the conductance of the
solution will vary during the course of the titration. The end
point may be detected by the break in the titration curves. Let
us illustrate by taking some examples : |
|
A. Titration of a strong acid vs strong base |

(e.g., HCl + NaOH). Conductance |I" end p point

H* + Cl + Na* + OH —-> Na*+ Cl + H,O
Volume of NaOH
In the beginning H* ions are replaced by slow moving Nat
ions and therefore, conductance decreases (Fig. a). After the end Fig. (c)
point, Na* and OH ions increase and hence the conductance D. Titration of silver nitrate vs halide ion
increases. (e.g., AZNO, + KCI).
Agt + NO; + K* + Cl —-+ K* + NO; + AgCl
Initially conductance remains almost constant because
Ag* ions are replaced by K* ions and both have almost the same
| mobility. After the end point, it increases because of the addition
|
of more K* and CI ions.
Conductance |
v end point

Volume of NaOH
Fig. (a)
B. Titration of weak acid vs strong base
(e.g.. CH, COOH + NaOH) |
|
CH,COOH + Na* + OH-——-> CH,COO- + Nat + H,O |
Conductance || end
id poin
point
After an initial decrease due to the titration of free H* ions,
the conductance increases because of the net gain of CH,COO- Volume of KC]
and Na* ions (as neutralization proceeds). After neutralization,
Fig. (d)
——_|sntoo MODERN'S abe + OF CHEMISTRY-AXIl

C. Q.
(a) 0.10 (6) 0.02
(c) 0.15 (d) 0.03
AQ. The values of limiting ionic conductance of H* and HCOO-
Electrolytic Conductance ions are respectively 347 and 63 S cm? mol! at 298 K. If
the molar conductance of 0.025 M methanoic acid at 298 K
Al. If the conductivity and conductance of a solution is same is 40 S em? mol, the dissociation constant of methanoic
then its cell constant 1s equal to:
acid at 298 Kis
(a) 1 (b) 0
(c) 10 (d) 1000. (a) 1x 10° (b) 2x10°
The units of conductivity are: (c) 1.65x10~+ (d) 2.6104
(a) ohm (6) ohm? em} Al10. The ionization constant of a weak electrolyte is 2.5 x 10°
(c) ohm“ cm? equiv! (d) ohm 'cm?. and molar conductance of its 0.01 M solution is 19.6
AS. The resistance of 0.1 N solution of acetic acid is S em? mol!. The molar conductance at infinite dilution
250 ohm, when measured in a cell of cell constant (S em? mol) is
1.15 cm}. The equivalent conductance (in ohm! cm? (a) 402 (6) 392
equivalent—+) of 0.1 N acetic acid is (c) 306 (d) 39.2
(a) 18.4 (6) 0.028
(c) 46 (d) 9.2 Electrochemical Cells
AA, In infinite dilution of aqueous solution of BaCl,, molar All. Which of the following statements is incorrect about
conductivity of Ba** and CI ions are = 127.325 cm?/mol and electrochemical cell ?
76.348 cm2/mol respectively. Whatis A,,, for BaCl, atsame (a) Electrons are released at anode.
dilution ?
(6) Chemical energy is converted into electrical energy.
(a) 280 S cm? mol} (6) 330.98 S em? mol
(c) Salt bridge maintains the electrical neutrality of the
(c) 90.98Sem?mol? (d) 203.6Scm? mol?
electrolytes.
The specific conductance of 0.1 M NaCl solution is 1.06 x 10-7
(d) Cell can work indefinitely.
ohm™ cm“. Its molar conductance in ohm™ cm? molt is
Al12. Point out the correct statement 1n a cell of zinc and copper :
(a) 1.06 x 102 (b) 1.06 x 10°
(a) Zine acts as cathode and copper as anode.
(c) 1.06 x 10+ (d) 53
(6) Zine acts as anode and copper as cathode.
AG. The limiting molar conductivities A° for NaCl, KBr and KCl
(c) The standard reduction potential of zinc is more than
are 126, 152 and 1650 S cm? mol” respectively. The A° for
that of copper.
NaBr is
(d) The flow of electrons is from copper to zinc.
(a) 2785 cm? mol + (6) 9765 cm? mol
(c) 1285 cm? mol (d) 3025 em? mol} Al13. The standard electrode potentials for Pb** | Pb and
Zn** | Zn are—0.126 V and—0.763 V respectively. Thee.m.f.
AZ. i. (CICH,COONa) = 224 ohm™ em* gm eq*,(NaCl) = 38.2
of the cell
ohm! em? gm eq?.AHCI) = 203 ohm? cm? gm eq +, whatis
the value of A(CICH,COOH)? Zn |Zn** (0.1 M) ||Pb?* (0.1 M)| Pbis:
(a) 288.6 ohm! cm*gmeq? (6) 289.6 ohm cm? gm eq+ (a) 0.637 V (b) <0.637V
(c) 388.8 ohm em*gmeq? (d) 59.6 ohm? cm*gmeq? (c) >0.637 V (d) 0.889 V.
The limiting molar conductivities of HCl, CH,COONa and Al4, Azinc electrode is placedin 0.1 M solution of ZnSO, at 26°C.
NaClarerespectively 425, 90 and 1265 mhocm? mol? at 26°C. Assuming that the salt is dissociated to an extent of 20% at
The molar conductivity of 0.1 MCH,COOH solution is 7.8 mho this dilution, the potential of this electrode is (E° = —0.76V)
em? mol atthe same temperature. The degree of dissociation (a) —0.81V (6b) —0.79V
of 0.1 M acetic acid solution at the same temperature is
(c) 0.81V (d) 0.79V

Araswies
Al. (a) AZ. (bd) As. (c) AA. (a) A5. (a) A6. (c) AZ. (c) A8. (bd) AQ. (d) Al0. (0)
All. (d) Al12. (5) Al13. (a) Al4, (a)
ELECTROCHEMISTRY

A15. For the electrode reaction A22. Aluminium displaces hydrogen from acids, but copper does
M"*(agq) + ne~ —> M(s) not. A galvanic cell prepared by combining Cu] Cu** and
Nernst equation is Al| Al®*+hasanemfof2.0 V at 298 K. Ifthe potential ofcopper
electrode is + 0.34 V, that of aluminium electrode is
(a) o, A
KB=E°+ OF log lt1
vas (a) -2.3V (b) 4+2.34V
(c) -1.66V (d) 1.66V
(b) E° = E° + RT ln [M™] . Standard electrode potentials are :

RT
Fe2+ |Fe (E° =—0.44 V), Fe+| Fe2+ (E° = 0.77 V)
(c) E= E° + — In [M™] Fe*t, Fe** and Fe blocks are kept together, then
nk
(a) Fe** increases (6b) Fe** decreases
(d) Be gee in [M**] (c) Fe?* |Fe** remains unchanged
r ao * (d) Fe**+ decreased
Al6. E*__,, and AG° are related as :
. Thestandard reduction potentials for two reactions are given
(a) AG® =nF EP (6) AG=—nF Ey, below:
(c) AG° =-nF E? (dq) AG? =nF E® _,,=0.
AgCl(s) + e- ———} Ag(s) + Cl(aq) K° = 0.22 V
Al7. Which of the following will decrease the voltage of the cell ?
Sn(s) + 2Ag* (ag)> Sn** (aq) + 2 Ag(s) Ag*(aq) +@ ———> Ag(s) E° =0.80 V
(a) increase in the size of silver rod The solubility product of AgCl under standard conditions of
(6) increase in the concentration of Sn** ions temperature (298 K) 1s given by
(c) increase in the concentration of Ag* ions (a) 16x 10° (b) 16x10
(d) None of the above. told e x 101° (d) 1.6x10-7°
A18. In the diagram given below, the value of x is . The e.m.f. of the following Daniell cell at 298 K is E,.
o _ 3 Zn | ZnSO, (0.01 M) | |CuSO, (1.0) | Cu
eg OY cg BHO ay When concentration of AnSO F is 1.0 M and that of CuSO riis
0.01 M, the e.m.f. changed to E,. What is the relationship
between E,, and E,?
Ee =x (a) E,>E, (b) E,<E,
(a) 0.86 V (b) 0.65 V (c) E,=E, (d) E,=04E,
(c) 0.825V (d) —0.65V ‘ gee = 0.54 V and E*,. = —0.76 V. A Daniell cell contains
Al19. By how much will the potential of a zinc electrode change if 0.1 M ZnSO, solution and 0.01 M CuSO, solution at its
the solution of ZnSO, in which it is immersed is diluted to electrodes. The EMF ofthe cell is
10 times at 298 K? (a) 1.10V (6) 1.04V
(a) Decreasesby30mV (5) Increases by 30 mV
(c) 1.16V (d) LO7V
(c) Increasesby60mV (d) Decreases by 60 mV
. Consider the following E® values
. The e.m.f. of the cell :
Cu(s) | Cu?* (1M) ||Ag* (1M) |Ag E® (Fe3* | Fe?+)=+0.77V, E® (Sn? | Sn) =-0.14V
is 0.46 V. The standard reduction potential of Agt |Ag is Under standard conditions, the potential for the reaction :
0.80 V. The standard reduction potential of Cu** |Cuis Sn(s) + 2Fe**(aq)
—> 2Fe**(aq) + Sn**(aq) is
(a) —0.34V (b) 1.26V (a) 0.91V (6) 1.40V
(c) -1.26V (d) 0.34V (c) 1.68V (d) 0.68V
A21. Saturated solution of KNO, 1sused tomakesalt bridge because
A28
.If E° 2+) 7.) = —0.441 V and Hee pet | Fe24) — 0.771V, the
(a) velocity of K* is greater than that of NO,~
standard E.M.F. of the reaction :
(6) velocity of NO, 1s greater than that of K*
Fe + 2F'e** ———-> 3Fe** will be
(c) velocity of both K* and NO, are nearly the same (a) 1.6638 (6) 1.212V
(d) KNO, 1s highly soluble in water. (ce) 0.111 (d) 0.380V
(C_B.S_E. P.M.T. 2006)

Areswers
A115. (c) <A16. (c) A177. (5) Al18. (c) Al19. (a) A20. (d@) AZ. (c) A222. (c) AZ. (6) Ad. (ed)
A25. (a) A226. (d) A27. (a) A28. (5)
—— farto2 MODERN'S abe + OF CHEMISTRY
-AXIl

Electrolysis Batteries and Corrosion

A29. Number of coulombs required to deposit 90 g of Al when the A37. When lead storage battery discharges
electrode reaction
(a) SO, 1s evolved (6) PbSO, is consumed
AP +82 — > Alis:
(c) Lead is formed (d) H,SO, is consumed.
(a) 9.65 x 10+ (b) 8.685 x 10°
(c) 9.65 x 10° (d) 6.966. A38s. In a Leclanche dry cell, anode is :
. 10800 C of electricity through the electrolyte deposited (a) Graphite rod (6) FeO and Fe(OH),
2.977 g of metal with atomic mass 106.4 a.m.u. The valency (c) Zinc container (d) MnO, +C.
of metal cation is:
A39. Rust is a mixture of
(a) 4 (b) 3
(a) FeO and Fe(OH), (6) FeO and Fe(OH),
{c) 2 (d) 1
. The charge on 1 gram mole ion of N* is
(c) Fe,O, andFe(OH), (d) Fe,O, and Fe(OH),.
(a) 6.00 x 10°C (b) 2.89x 10°C A40. Which of the following will be formed when lead storage
(c) 3.98 x 10°C (dq) 4.89x10°C battery is charged?
. Acurrent of 3A was passed through a solution of AuC1, ions (a) Sulphuric acidis consumed
using gold electrodes and it caused deposition of 1.234 g of Au
(b) leadis consumed
(Atomic mass of Au = 197). The time for which the current
Was passed is (c) sulphuric acid is formed
(a) 20 min 8s (6) 30min 12s (d) lead sulphate is formed.
(c) 10 min 4s (d) 10min 40s A4]1. ForaH,—O, fuel cell, the theoretical voltage has been found
. An electric current is passed through silver voltameter to be 1.23V and AH to be—-285 kJ molt. The efficiency of the
connected to a water voltameter. The cathode of silver fuel cellis
voltameter weighed 0.108 g more at the end of electrolysis.
The volume of i, at STP evolved is
(a) 76% (6) 83%

(a) 6.6 em® (b) 550 cm? (c) 89% (d) 72%
(c) 22.4 em? (d@) 11.2 em? A42. Which of the following reaction occurs at cathode in H,—O,
fuel cell ?
. Same amount of electric current is passed through solution
of AgNO, and HCl. If 1.08 g of silver 1s obtained in the first (2) H' +OH —-+H,0
case, the amount ofhydrogen liberated atS.T.P.in thesecond (6) O, + 2H,O + 4e°-—— 4 OH
case 1s:
(c) 2H, + O, —> 2H,O
(a) 112 cm? (6b) 22400 cm?
(d) H, + 20H —-> 2H,0 + 2e
(c) 224 em? (d) 1.008¢
A43. Which of the following reaction occurs at anode during the
. 4.6 g of aluminium (at. mass = 27. a.m.u) is deposited at
cathode from Al** solution by certain quantity of electric recharging of lead storage battery ?
charge. The volume of hydrogen produced at STP from H* (a) PbSO, +2H,O—-> PbO, + 80," +4H* + 2e7
ions in solution by the same quantity of electric charge willbe
(6) Pb+S0,? ——> PbSO, + 2e-
(a) 44.8L (b) 22.4L
(c) PbSO, + 2e-—— Pb+S0,7°
(c) 11.2L (d) 6.6L
. The quantity of electricity needed to separately electrolyse (d) PbO, +4H*+S0O,* + 2e°-——> PbSO, + 2H,O
1 Msolution of ZnSO,, AICI, and AgNO, completely isin the A44, In nickel-cadmium storage cell, the electrolyte is
ratio of (a) moist KOH (6) dilH,SO,
(a) Bee 1 (Teas.: 1
(c) aqueous NH,Cl (d) Ni(OH), (aq)
(co) 2:1:3 fm £:2:1

ASH
A29. (c) A380. (a) <ASl. (6) ABZ (c) ABs. (a) A384, (a) A385. (d) ASG. (a) ABZ. (d) ABs. (c)
A389. (c) A400. (c) Ad4l. (6) A42. (5) Ad4B. (a) A44, (a)
ELECTROCHEMISTRY

Bi. Standard electrode potential of three metals X, Y and Z

are —1.2 V,+0.5 V and—3.0 V respectively. The reducing
power of these metals will be
(a) Y>Z>X (6) Y>X>Z
AIPMT & Other State Boards’ (c)A>X>Y (d) X>Y>7
Medical Entrance (CBSE PMT 2011)
Bl. The efficiency of a fuel cell is given by : B8. Ifthe E?.,, for a given reaction has a negative value, then
which of the following gives the correct relationships for
AG AG the values of AG® and K, 3 ?
(a) AS () an (a) AG’ >0;K, > 1 (6) AG* <0; K,>1
(c) AG’ <0; K,, <1 (d) AG®>0;K,,<1
AS AH
(Cc) AG (dq) aq (C.B.S.E.P.M.T. 2007) (CBSE PMT 2011, NEET 2016)
B2. Standard free energies of formation (in kJ/mol) at 298 Kare B9. The electrode potentials for
—237.2,—394.4 and—8.2 for H,O(/), CO,(¢) and pentane (g), Cu** (aq) + e-—> Cut (ag)
respectively. The value of E° __,,for the pentane-oxygen fuel
and Cu*(aq) +e ——> Cu(s)
cellis:
are + 0.16 Vand+0.50 Vrespectively. The value of KE, Cu
(a) 2.0968 V (b) 1.0968 V Cu will be
(c) 0.0968 V (d) 1.968 V (a) 0.500V (6) 0.325 V
(C.B.S.E. P.M.T. 2008)
(c) 0.660V (d) 0.150V
Bs. Al,O, 1s reduced by electrolysis at low potentials and high (CBSE PMT 2011)
currents. If 4.0 x 10* amperes of current is passed through
B10. Standard electrode potential for 5n**/Sn** coupleis + 0.15V
molten Al,O, for 6 hours, what mass of aluminium is
and that for the Cr**/Cr couple is— 0.74 V. These two couples
produced? (Assume 100% current efficiency, atomic mass in their standard state are connected to make a cell. The
of Al = 27 g/mol) cell potential will be
(a) 8.1x10*¢ (b) 24x10°¢g (a) +1.19V (6b) +0.89V
(c) 13x 10*¢g (qd) 9.0x 10° 2g (c) +0.18V (d) +1.838V
(C_.B.S.E. PMT 2009) (CBSE PMT 2011)
BA, The equivalent conductance of M/32 solution of a weak
Bil. Limiting molar conductivity of NH,OH l[2.e. nes ] is
monobasic acid is 8 mho ecm? and at infinite dilution is 400
mbho em“. The dissociation constant of this acid is equal to

(a) 125x10° (b) 6.26107 (a) ase " AL Nac 7 A (NaOH)

(c) 1.25 x 10+ (dq) 1.25 x 10> (0) A aiNaOH ifA Nac)~ Anant sed
(C.B.S.E. PMT 2009) (c) A m(NH,OH) = ANH 4c A (HCl)
B5. For the reduction of silver ions with copper metal the
(d) Amgen tAmavaon ~Amnacy ALP.M.T 2012)
standard cell potential was found to be + 0.46V at
26°C. The value of standard Gibbs energy, AG*° will be B12. At 26°C, molar conductance of 0.1 molar aqueous solution of
(F = 96500 C mol): ammonium hydroxideis 9.540hm! cm? mol and atinfinite
dilution its molar conductance is 238 ohm™ cm? mol.
(a) —44.6 kJ (6b) —98.0 kJ
The degree of ionisation of ammonium hydroxide at the
(c) —89.0 kJ (d) —89.0J same concentration and temperature is
(C_.B.S.E. P.M.T. 2010) (a) 4.008% (b) 40.800%
B6. Anincreasein equivalent conductance ofa strong electrolyte (c) 2.080% (d) 20.800% (NEET 2013)
with dilution is mainly due to: B13. A button cell used in watches function as following.
(a) increase in bothi.e. number ofions and ionic mobility of Zn(s)+Ag,O(s)+H,O(@) —— 2Ag(s)+ Zn**(aq) + 20H (aq)
ions. Ifhalf cell potentials are
(6) imcrease in number of ions Zn** (aq) + 2e- —> 2Zn(s); E° =—0.76V
(c) increase 1n ionic mobility ofions Ag,O(s) + H,O() + 2e°-—-> 2Ag(s) + 20H (aq), E° = 0.34V
(ad) 100% ionization of electrolyte at normal dilution. The cell potential will be

ASH
(C_B.S.E. P.M.T. 2010) (a) 0.84V (b) 1.34V
(c) 1.10 V (d) 0.42V (NEET 2013)

Bl. (5) B2. (5) B38. (a) B4. (d) B5. (c) B6. (c) B7. (c) B8. (d) B9. (56) 510. (3)
Bll. (d) B12. (a) B13. (c)
—— far04 MODERN'S abe + OF CHEMISTRY
-AXIl

B14. Ahydrogen gas electrodeis made by dipping platinum wire (d) zinc has higher negative electrode potential than
in a solution of HCl of pH = 10 and by passing hydrogen iron
gas around the platinum wire at one atm pressure. The (NEET 2016)
oxidation potential of electrode would be? B23. In the electrochemical cell :
(a) 0.118V (b) 1.18V Zn | ZnSO ,(0.01 M)|| CuSO,(1.0 M)| Cu, the emf of this
(c) 0.059V (d) 0.59V (NEET 2013) Daniell cell is E,. When the concentration of ZnSO, is
B15. When 0.1 mol MnO? is oxidised, the quantity of electricity changed to 1.0 M and that CuSO, changed to 0.01 M,
required to completely oxidise MnO? to MnO; is the emf changes to E,. From the following, which one is
(a) 96500 C (b) 2x 96500 C the relationship between E, and E,?
(c) 9650 C (d) 96.60C (AIPMT 2014) (Given, RT/F = 0.059)
B16. The weight of silver (at. wt. = 108) displaced by a quantity
(a) E, <E, (b) E,>E,
of electricity which displaces 6600 mL of O, at STP will
be (c) E,=04E, (d) E,=E, (NEET 2017)
(a) 5.4 ¢ (6) 10.8 ¢g B24. Consider the change in oxidation state of bromine
(c) 564.0 ¢ (d) 108.0 ¢g (AIPMT 2014) corresponding to different emf values as shown in the
B17. A device that converts energy of combustion of fuels like diagram below :
hydrogen and methane, directly into electrical energy is +7
BrO, 1.82 ¥
+5
BrO3 L5V
+1
H BrO
known as
(a) dynamo (b) Ni-Cd cell 2
es
_ 0
Br 1.0652 V Bry 1.595 V
(c) fuel cell (d) electrolytic cell
(AIPMT 2015) Then the species undergoing disproportionation 1s:
B18. The pressure of H, required to make the potential of (a) BrO (6) BrO
H,—electrode zero in pure water at 298 Kis
(c) Br, (d) HBrO (NEET 2018)
(a) 10-7? atm (6) 10+ atm
B25. The equilibrium constant of the following redox reaction at
(c) 10°“ atm (dq) 10°" atm 298 Kis 1 x 108.
(NEET 2016) 2Fe5+(aq) + 21 (ag) == 2F e?*(aq) + 1,8)
B19. The molar conductivity ofa 0.6 mol dm™ solution of AgNO, If the standard reduction potential of 1odine becoming
with electrolytic conductivity of 5.76 x 10-7 S cm} at 298 K iodide is +0.64V, whatis the standard reduction potential
in S em? mol? is of Fe** |Fe**?
(a) 2.88 (b) 11.62 (a) + 1.006V (6b) —1.006V
(c) 0.086 (d) 28.8 (NEET 2016) (c) +0.77V (7d) —O.77V

B20. During the electrolysis of molten sodium chloride, the time (e) —0.662V (Kerala P.M.T. 2008)
required to produce 0.10 mol of chlorine gas using a current B26. A solution of nickel sulphate in which nickel rod is
of 3 amperes is dipped is diluted 10 times. The reduction potential of Ni at
(a) 66 min. (6) 110 min. 298 K
(c) 220 min. (d) 330 min. (a) Decreases by 60 mV (6) Decreases by 30 mV
(NEET 2016)
(c) Decreases by 30 V (d) Increases by 30 mV
B21. The number of electrons delivered at the cathode during
(e) Increases by 30 V (Kerala P.M.T. 2009)
electrolysis by a current of 1 ampere in 60 seconds is
(a) 6x 1079 (b) 6x 107° B27. When molten magnesium oxide was electrolysed for a
(c) 3.75 x 107° (d) 7.48 x 1078 certain period, 150 mg of Mg was deposited on the cathode.
(NEET 2016) The volume of oxygen gas in cm® at STP conditions
B22. Zinc can be coated oniron to produce galvanized iron but the liberated at the anode during the same period is (Atomic
reverse is not possible. Itis because mass of Mg = 24 g mol!)
(a) zine is lighter than iron (a) 140 (6) 280
(6) zinc has lower melting point than iron (c) 70 (d) 120
(c) zinc has lower negative electrode potential than (e) 240 (Kerala P.M.T. 2014)
iron

B14. (qd) B15. (c) B16. (d) B17. (c)~ B18. (ec) B19. (©) 520. (6) Bl. f&) 522. (dq) B23. ()
B24. (d) B25. (c) B26. (6) B27. (ce)
ELECTROCHEMISTRY

(6) p(H,) = 2 atm and [H*] = 2.0M

JEE (Main) & Other State Boards’
(c) p(H,) = 1 atm and [H*] = 2.0 M
Engineering Entrance
(d) p(H,) = 1 atm and [H*] =1.0M (A..LE.E.E. 2011)
B28. Given the data at 26°C: B35. Resistance of 0.2 M solution of an electrolyte is 50 Q. The
Ag+I —+ Agl+e E°=0.152V specific conductance of the solutionis 1.35 m1. Ifresistance
of the 0.4 M solution of the same electrolyte is 260 Q, its
Ag — Agt+e E°=-0.800V
molar conductivity is :
(2.303 RT/F = 0.059 V)
(a) 6.26 x 1075 m? mol (6) 626 x 10*S m? mol}
What is the value of log K. for AgI ?
(c) 62.65 m? mol (d) 62505 m2 molt
(a) +8.612 (b) —37.83 (AEB. 8077)
(c) -16.13 (d) —8.12 (A.LE.E.E. 2006)
B36. The standard reduction potentials for Zn** |Zn, Ni*| Ni,
B29. Resistance of a conductivity cell filled with a solution of an
and Fe** |Fe are—0.76, 0.23 and—0.44V respectively. The
electrolyte of concentration 0.1 Mis 100Q. The conductivity
reaction X + Y°*> X** + Y will be spontaneous when
of this solution is 1.29Sm“. Resistance ofthe same cell when
filled with 0.2 M of the same solution is 520 Q. The molar (a) X=Ni, Y = Zn (6) X= Fe, Y=4n
conductivity of 0.2 M solution of the electrolyte will be (c) X=Zn, Y=Ni (d) X= Ni, Y=Fe
(a) 1240x10*Sm?mol! (6) 1.24x10*S m? mol (A.LE.E_E 2012, Kerela P.E.T. 2016)
(c) 12.4 x 10+*S m? mol! (d) 124x10*Sm?mot? B37. Caven
(A.LE.E.E. 2006) E bia =-0.74V: Mn0q|Mn2* = 1.61V
B30. The cell Zn | Zn?*+ (1M) ||Cu?* (1M)| Cu 0 =1.33V; E°a,q =1.86V
ik Cry02—jCr3+
(E°7)= 1.10 V) was allowed to be completely discharged at Based on the data given above, strongest oxidising agent
[Zn** | will be
298 K. The relative concentration of Zn** to Cu2+ (ee is:
(a) MnO, (6) Cl
(a) 37.8 (6) 10978
(c) Cr3+ (dq) Mn*+ (JEE Main 2013)
(c) 9.65 x 10+ (d) antilog (24.08) B38. Given below are the half-cell reactions:
(A.LE.E.E. 2007)
Mn?* + 2e— + Mn ; E® =-1.18 V
B31. Given E° (Cr*+| Cr) =— 0.72 V and E°(Fe** |Fe) =— 0.42 V.
2(Mn** + e- — Mn**); E° = 4+ 1.51 V
The potential for the cell
Cr |Cr**(0.1M) || Fe?* (0.01 M) |Feis The E° for 3Mn** > Mn + 2Mn** will be
(a) —0.26 V (b) 0.26V (a) —0.33 V ; the reaction will occur
(6) —2.69 V : the reaction will not occur
(c) 0.339 V (d) —0.3389 V (A.LE_E_E. 2008)
B32. Given E° = —0.36 V, E°, = —0.439 V. Thevalue (c) —2.69 V ; the reaction will occur
Fe*+ [Fe e** IFe (dq) —0.33 V ; the reaction will not occur (JEE Main 2014)
of standard electrode potential for the change,
B39. . The equivalent conductance of NaCl at concentration C
Fe** + e ——> Fe** will be
and at infinite dilution are i, and i,, respectively. The
(a) —0.072V (b) 0.385 V
correct relationship between i, and A,, is given as (where,
(c) 0.770 V (dq) —0.270 V (AL_E.E.E. 2009)
the constant B 1s positive)
B33. The Gibbs energy for the decomposition of Al,O, at 500°C
is as follows: (a) 4,=1,+(B) VC (6) 4, =A, +(B)C
(c) A, =A, -(B)C (d) 4, =A, -(B) VC
23 ALO, —>~3 Al+ 20,
(JEE Main 2014)
The potential difference needed for electrolytic reduction
B40. Resistance of 0.2 M solution of an electrolyte is 50 Q.
of Al,O, at 500°C is at least
(a) 2.6V (b) 56.0V The specific conductance of the solution is 1.4 8S mt.
(c) 465 V (d) 3.0V (A.LE.E.E. 2010) The resistance of 0.5 M solution of the same electrolyte
B34, The reduction potential of hydrogen half-cell will be is 280 ©. The molar conductivity of 0.6 M solution of the
negative if: electrolyte in S m? mol is
(a) p(H,) = 2 atm and [H*] = 1.0M (a) 5 x 10? (6b) 6x10

ASH
(c) 5x 10° (qd) 656x109 (JEE Main 2014)

B28. (c) B29. (c) B30. (5) B31. (6) B32. (c) B33. (a) B84. (a) B35. (a) B86. (c) B37. (d)
B38. (5) B39. (d) B40. (5)
fates MODERN'S abe + OF CHEMISTRY-AXIl

B41. Two Faradays of electricity are passed through a solution Q = Cu**(0.1M)|Cu,,

of CuSO,. The mass of copper deposited at the cathode is R = Cu**(0.01 M)| Cu,,,
(at. mass of Cu = 63.5 amu) S = Cu** (0.001 M)|Cu,,,
(a) 2g (b) 127 ¢ If the standard reduction potential of Cu?*| Cu is + 0.34
(c) Og (d) 63.5 g (JEE Main 2015) V, the reduction potentials 1n volts of the above electrodes
B42. Galvanization is applying a coating of follow the order
(a) Pb (6) Cr (a)P>S>R>Q (ob) S>R>Q>P
(c) Cu (d) Zn (JhE Main 2016) (c)R>S>Q>P (dq) P>Q>R>58

B43. Given (e)Q>R>S8>P (Kerala P.E.T. 2010)

1yh
Cl,Ic
=1.36V,E°, Cr“ |\Cr
=-0.74V B48. The electrode potential of a hydrogen electrode at
pH = 10 is
o
=1.33 V,E°Sintra LV. (a) 0.59V (6) 0.00V
Cr,02-ICr*
(c)— 0.59 V (d) —0.059V
Among the following, the strongest reducing agent is (W. B. J_ELE. 2010)
(a) Cr (6) Mn** B49. E,, E, and E, are the emfs of the following three galvanic
(e)-cr* (d) Cl (J_B.E. Main 2017) cells respectively.
B44, How long (approximate) should water be electrolysed by (¢) Zn(s) | Zn?*(0.1 M) ||Cu2*(1M) | Cu(s)
passing through 100 amperes current so that the oxygen (tt) Zn(s) |Zn2*(1 M) ||Cu?*(1M) | Cu(s)
released can completely burn 27.66 g of diborane? (Atomic (iii) Zn(s) |Zn2*(1 M) ||Cu2*(0.1M) | Cu(s)
weight of B = 10.8 u)
Which one of the following is true ?
(a) 6.4 hours (6) 0.8 hours
(a) E, > HE, > E, (b) EH, >E,
> E,
(c) 3.2 hours (d) 1.6 hours
(J... Main 2018) (c) E, > E, > E, (d) E, > EK, > E,
(Karnataka CET 2011)
B45. An alloy of Pb-Ag weighing 1.08 g was dissolved in dilute
B50. The standard redox potentials for the reactions
HNO, and the volume made to 100 mL. A silver electrode
Mn** + 2e—- —-> Mn and Mn** + e—- —-> Mn** are — 1.18
was dipped in the solution and the e.m_f. of the cell set up
V and 1.51 V respectively. What is the redox potential for
Pt(s), H,(g) |H*(1M) ||Ag(aq)Ag(s) the reaction Mn** + 3e—- ——> Mn?
was 0.62 V. IfE°__,, = 0.80 V, what is the percentage of Agin
(a) 0.33 V (b) 1.69V
the alloy ?
(c) -0.28V (d) —0.865V
(At 26°C, 2.303RT/F = 0.06)
(e) 0.85 V (Kerala PET 2011)
(a) 26 (6) 2.60 B51. A current is passed through two cells connected in series.
(c) 10 (d) 1 The first cell contains X(NO,),(ag) and the second cell
(e) 5 (Kerala C.E.T. 2007) contains Y(NO,),(aq). The relative atomic masses of X
B46. One Faraday of electricity is passed through molten AL,O,, and Y are in the ratio 1 : 2. What is the ratio of liberated
mass ofX to that ofY ?
aqueous solution of CuSO, and molten NaCl taken 1n three
(a) 3:2 (b) 1:2
different electrolytic cells connected in series. The mole (c) 1:3 (d) 3:1
ratio of Al, Cu and Na deposited at the respective cathode (e) 2:1 (Kerala PET 2011)
18 B52. A weak electrolyte having the limiting equivalent
conductance of 400 5 cm? g. equivalent — at 298 K is 2 %
(a) 2:3:6 (b) 6:2:3
ionized in its 0.1 N solution. The resistance of this solution
(c)8:3:2 (d) 1:2:3 (in ohms) in an electrolytic cell of cell constant 0.4 em! at
(e)3:6:2 (Kerala P_E.T. 2010) this temperature is
B47. Consider the following four electrodes, (a) 200 (6) 300
P = Cu?*(0.0001 M)| Cu, (c) 400 (d) 600
(e) 600 (Kerala P.E.T. 2012)

AH
B41. (d) B42. (d) B43. (a) B44. (c) B45. (d) B46. (a) B47. (e) B48. (c) B49. (6) B50. (c)
B51. (c) B52. (d)
ELECTROCHEMISTRY

B53. Given that the standard reduction potentials for M*/M (a) 7x 10+*M (6) 7x 10° M
and N*/N electrodes at 298 K are 0.52 V and 0.25 V (c) 9x 10° M (dq) 9x 10*M (WB JEE 2014)
respectively. Which of the following is correct in respect
B59. The change in potential of the half-cell Cu?*|Cu, when
of the following electrochemical cell ?
aqueous Cu** solution is diluted 100 times at 298 K ?
M| M+ ||Nt|N
(a) Increases by 120 mV (b) Decreases by 120 mV
(a) The overall cell reaction is a spontaneous reaction.
(c) Increases by 60 mV (d) Decreases by 60 mV
(6) The standard EMF of the cell is —0.27 V.
(e) No change (Kerala PET 2014)
(c) The standard EMF of the cell is 0.77 V.
B60. Conductivity of a saturated solution of a sparingly soluble
(d) The standard EMF of the cell is —0.77 V.
salt AB at 298 Kis 1.85 x 10-°° 5 m!. Solubility product
(e) The standard EMF of the cell is 0.27 V.
of the salt AB at 298 K is
(Kerala P.E.T. 2012)
[Given A°_ (AB) = 140 x 10% S m? mol]
B54. 1M solution each of Cu(NO,),, AgNO,, Hg(NO,), and
(2) 5.7 x 1072 (6) 1.32 10-4
Mg(NO,), is electrolysed using Pt-electrodes. The
(c) 7.6 x 10-% (d) 1.74x 107!
values of standard reduction electrode potentials in
volts are: (Karnataka CET 2011)
Agt |Ag = +0.80V, Cu?* |Cu= +0.34V B61. For Cr,0,7 + 14H* + 6e° ——> 2Cr** + 7H,O
K° = 1.33 V. At [(Cr,O,7] = 4.5 millimole,
Hg,** |Hg = + 0.79 V, Mg** |Mg= -2.37V
[Cr**] = 15 millimole, E = 1.067 V. The pH of the solution
The sequence of deposition of metals on the cathode will be is nearly
(a) Mg, Ag, Cu (b) Mg, Cu, Ag (a) 2 (b) 3
(c) Ag, Hg, Cu (d) Cu, Hg, Ag it, (dq) 4 (Karnataka CET 2011)
(A.M.U. Engg. 2012) B62. In H,—O, fuel cell the reaction occurring at cathode is
B55. From the following data at 26°C (a) O,(g) + 2H,O@) + 4e7 —-+ 40H, a
Cr** (ag) + @ ——> Cr* (aq), H° =— 0.424V (6) H*(aqg) + OH (aq) —> H,O(Z)
Cr** (ag) + 2e0°- ——> Cris), E° =— 0.900V (c) 2H,(g) + O,(¢) ——- 2H,O(Z)
Find E° at 25° C for the reaction: (d) Ht+e- —> 5Hs (Karnataka CET 2015)
Cr** + 3e°- ——> Cris)
B63. In the lead - acid battery during charging, the cathode
(a) —0.741V (b) 1.824V reaction is
(c) -0.476 V (dq) +0.741V (A.M.U_ Engg. 2012) (a) formation of PbO,
B56. Equivalent conductivity at infinite dilution for sodium- (6) formation of PbSO,
potassium oxalate [(COO-),Na*K*] will be [given: (c) reduction of Pb?* to Pb
molar conductivities of oxalate, K* and Na®* ions at (d) decomposition of Pb at the anode. (A.M.U. Engg. 2015)
infinite dilution are 148.2, 60.1, 73.5 S em? mol, B64. What pressure of H, would be required to make emf of
respectively] the hydrogen electrode zero in pure water at 25°C ?
(a) 271.85 cm? eq (6) 67.955 em? eq+ (a) 10% atm (6) 10°* atm
(c) 643.65 em? eq? (dq) 136.95 em? eq (c) latm (d) 0.6 atm (A.M.U. Engg. 2015)
(W.B. JEE Engg. 2013) B65. How many Faradays are required to reduce 1 mol of
Cr,O, to Cr** in acid medium?
B57. A current strength of 9.65 amperes is passed through
(a) 2 (b) 3
excess fused AIC], for 56 hours. How many litres of
(c) 5 (d) 6 (W.B. J.ELE. 2017)
chlorine will be liberated at STP? (F = 96500 C)
B66. By passing electric current, NaClO, is converted into
(a) 2.016 (6) 1.008
NaClO, according to the following equation:
(c) 11.2 (d) 20.16
(e) 10.08 (Kerala P_E.T. 2013) NaClo, + H,O — > NaClO as ee

B58. At 25°C, the molar conductance of 0.007 M hydrofluoric How many moles of NaClO, will be formed when three
acid is 150 mho cm? mol“ and its A°, = 500 mho cm? mol*. Faradays of charge is passed through NaClO,?
The value of the dissociation constant of the acid at the (a) 0.75 (6) 3.0
given concentration at 25°C is (c) 1.5 (d) 1.0
(Karnataka C_E.T. 2017)

ASH
B53. (6) B54. (c) B55. (a) B56. (d) B57. (d) B58. (d) B59. (d) B60. (d) B61. (a) B62. (a)
B63. (c) B64. (c) B65. (d) B66. (c)
a: MODERN'S abe + OF CHEMISTRY-AXIl

B67. The standard reduction potential at 298 for

K the following B72. What amount of electricity can deposit 1 mol of Al metal
half cell reactions : at cathode when passed through molten AICI,?
Zn** (aq) +2e° ——>Zn(s); E° = -0.762 V (a) 0.8 F (6) 1F
(c) 3F (dq) V3F
Cr**(aq)+3e"° ——>Cr(s); E° = 0.740 V (WB J.E.E. 2018)
B73. Given the standard half-cell potentials (EK°) of the
2H" (aq)+ 2e° ——>H,(s); E° =0.0 V following as:
Zn — > Zn** + 2e(f Bie 76 iV
F, (g)+ 2e° ——>
2F (aq); K° = 2.87 V
Fe —> Fe** + 2e; E° = 0.41 V
Which of the following is the strongest reducing agent? Then, the standard e.m.f of the cell with the reaction
(a) Cr(s) (b) Zn(s) Fe** + Zn —+ Zn** + Feds
(c) H,(g) (d) F,(g) (a) —0.35 V (b) +0.35 V
(Karnataka C_E.T. 2017) (c) +1L.17V (dq) -1.17V
B68. Inthe electrolysis of aqueous sodium chloride solution, which (WB J.E.E. 2018)
of the half cell reaction will occur at anode ? B74. At a particular temperature, the ratio of molar
conductance to specific conductance of 0.01 M NaCl
(a) CI-(aq) —>5Cl, +e; Peon = 1.56 volts
solution is
(a) 10° cm? mol (b) 10° cm? mol
(b) 2H,O(l) —>0, +4H"* +4e7; E®,, = 1.23 volts (c) 10 em? mol? (d) 10° em? mol?
(Karnataka C.E.T. 2018)
(c) Na*(aqg)+e ——>Na,,; - E° = -2.71 volts
B75. For a cell involving two electron change, E°_,, = 0.3 V
at 26°C. The equilibrium constant of the reaction is
(d) H"(aqg)+e =H, EP 4,= 9-00 volts we ay1° (6) 3x 107
(c) 10 (d) 101°
(Karnataka C_E.T. 2017)
(Karnataka C.E.T. 2018)
B69. Consider a fuel cell supplied with 1 mole of H, gas and
B76. The charge required for the reduction of 1 mol of
10 moles of O, gas. If fuel cell is operated at 96.6 mA
MnO, to MnO, is
current, how long will it deliver power?
(a) 1F (6) 3F
(Assume 1 F = 96500 C/mol of electrons)
(a) 1x 10%s (b) 0.6x10%s
(c) 5F (d) 7F
(Karnataka C.E.T. 2018)
(c) 2x10%s (qd) 4x10%s
B77. Consider the electrochemical reaction between Ag(s)
(e) 5x 10®%s (Kerala P_E.T. 2013)
and Cl,(g) electrodes in 1 litre of 0.1 M KCI aqueous
B70. Which of the following statements is/are true for an
electrochemical cell?
solution. Solubility product of AgCl is 1.8 x 10-'° and
(a) Oxidation occurs at the anode only F = 96500 C/mol. At 1 wA current, calculate the time
(6) Reduction occurs at the anode only required to start observing the AgCl precipitation in
(c) Oxidation occurs at both the anode and cathode the galvanic cell.
(d@) Reduction occurs at both the anode and cathode. (a) 17388 (6) 346s
(JK. C_B.T. 2018) (c) 1.256x10%s (dq) 1256x105
B71. What will be the E__,, for the given cell ? (e) 101s (Kerala P_E.T. 2018)
Zn |Zn** (0. 1M)|| Cu2* (0.01 M)| Cu B78. The voltage of the cell consisting of Li(s) and F,(g)
Given : Ent |Zn = 0.76 V and Be out] Cu = 0.34 V. electrodes is 5.92 V at standard condition at 298 K.
What is the voltage if the electrolyte consists of 2 M
Also predict whether the reaction is spontaneous or
LiF. (In 2 = 0.693, R = 8.314 J K? mol"? and F = 96600
non-spontaneous.
C mol?)
(a) 1.07 V and spontaneous (a) 5.90V (b) 56.9387 V
(6) —1.18 V and non-spontaneous (c) 5.88V (d) 49V
(c) —1.07 V and non-spontaneous (e) 48 V (Kerala P_E.T. 2018)
(d) 1.18 V and spontaneous (JK. C_E.T. 2018)

Araswies
B67. (5) B68. (a) B69. (c) B70. (a) B71. (a) B72. (c) B73. (6) B74. (a) B75. (cd) B76. (8)
B77. (a) B78. (a)
ELECTROCHEMISTRY

B79. Consider the galvanic cell, B84. AgNO, (aq) was added to an aqueous KCI solution gradually
Pt(s)|H, (1 bar) | HCl (aq) (1 M)|Cl (1 bar)| Pt(s). and the conductivity of the solution was measured. The plot
After running the cell for sometime, the concentration of conductance (A) versus the volume of AgNO, is
of the electrolyte is automatically raised to 3 M HCl.
Molar conductivity of the 3 M HC1 is about 240 S em? mol
and limiting molar conductivity of HCl is about
420 S cm? mol”. If K, of water is 0.62 K kg mol",
calculate the boiling point of the electrolyte at the end (a), (6) A
of the experiment.
(a) 376.6 K folk Shak
(c) 378.1 K (d) 380.3K
(e) 381.6 K (Kerala P_.E.T. 2018) Volume Volume

JEE (Advance) for ITT Entrance

on (d) A
B80. The e.m.f. of the cell:
| |
Zn |Zn** (0.01 M) ||Fe** (0.001 M) | Fe at 298 K
is 0.2905. |
|
|
The value of equilibrium constant for the reaction is
(a) @l-32/0.0295 (b) 109.320.0295 Volume Volume
(LET. 2011)
(c) 1099-26/0.0295 (d) 1099.32/0.0591 (I.iy 2004)

B81. The rusting of iron takes place as follows : B85. For the following electrochemical cell at 298 K,
1
2H* + 2e7 + 3 O, ——> H,O() B° = + 1.23V
Pt(s) |H,(g), (1 bar) ||H%.,, (1 M)|M*,,,,, M’,,,, |Pt(s)
Fe** + 2e-———_> F e(s) E° =— 0.44V | |Me» |+= |
Mi
E.1, = 0-092 V when 10°. Given : E®,,4+,72+ = 0-161 V;
Calculate AG® for the net process
(a) —322 kJ mol“ (6b) —161kJ mol
2.303 “ = 0.069 V. The value ofx is
(c) —152 kJ mol (dq) —76kJmol+ (LT. 2005)
B82. Electrolysis of dilute aqueous NaCl solution was carried (a) -2 (b) —1
out by passing 10 milliampere current. The time required (c) 1 (d) 2 (JEE Advance 2016)
to liberate 0.01 mol of H, gas at the cathode is (1 Faraday
B86. For the following cell,
= 96500 C mol)
Zn(s) |ZnSO,(aq) || CuSO, (aq) |Cu(s)
(a) 9.65 x 10* sec (b) 19.3.x 10* sec
(c) 28.95 x 104 sec (d) 38.6 x 10*sec (LT. 2008) when the concentrations of Zn** is 10 times the

B83. Consider the following cell reaction concentration of Cu**, the expression for AG (in J mol) is
2Fe(s) + O,(g) + 4H*(aq)
—> 2F e**(aq) + 2H,O (2) E° = 1.67 V [Fis Faraday constant; Kis gas constant; Tis temperature;

At [Fe**] = 10° M,p(O,) =0.1 atm and and pH = 3, the cell K? 21 = 1.1 VI
potential at 25°C is (a) 2.303 RT-2.2 F (6) -2.2F
(a) 1.47V (b) L.77V (c) 2.303 RT+1.1F (d) 1.1F
(c) 1.87V (d) 1.57V (.L.T. 2011) (JAW. Advance 2017)

B79. (a) B80. (6) B8l. (a) B82. (6) B83. (d) B84. (d) B85. (d) B86. (a)
 MODERN'S abe + OF CHEMISTRY
-AXIl

(c) Dry cell can easily be charged.

(d) Graphite rod acts as cathode
with more than one correct answers C7. Given E° values (inV) as:
C1. Which of the following relations are not correct ? Zn** | Zn = —0.76, Ni®*| Ni | 0.25, Ag* | Ag = 0.80 and
Cu** | Cu = 0.34. Which of the following reactions under
| kK x 1000 re i a standard conditions will take place in the specific direction?
tay A= a (b) K=Cx j
(a) Cu(s) + 2Ag*(ag) ———> Cu** (aq) + 2Ag(s)

(2) k= p—
l (d)
l
— (cell constant) =«x —
1 (6) Zn(s) + Ni**(ag) ———> Zn** (aq) + Ni(s)
a a R (c) Cu(s) + Ni**(ag) ———> Cu** (aq) + Ni(s)
C2. Which of the folowing statements are not true? (d) Cu(s) + 2H*(ag) ———> Cu** (aq) + Hg)
(a) Molar conductivity of weak electrolytes is low as C8. Which of the following reactions are not correct ?
compared to that of strong electrolytes.
(6) Molar conductance of an electrolyte increases with (a) E,,,, = log aio logK Cc

increase in concentration of electrolyte.

(b) AG® = nFE®
(c) Conductivity of an electrolyte increases with decrease
in temperature.
(c) AG = WE
(d) Conductivity of an electrolyte increases with increase nE® at
in concentration of electrolyte. (d) log
K. = 0.059 at 298K.
C3. In which of the following pairs, the first can reduce the
C9. In a galvanic cell, the salt bridge
second ?
(a) does not participate chemically in the cell reaction
(a) Zn** |Zn, Ni** |Ni (6) Sn?*|Sn, Mg?*|Mg
(6) stops the diffusion of ions from one electrode to another
(c) Cu**|Cu,Ag**|Ag (d) Fe?*| Fe, Ale*| Al
C4, For the cell, Tl | TI* (0.001 M) | |Cu®* (0.1M) |Cu, E__,, at (c) 1s necessary for the occurrence of the cell reaction
26° Cis 0.826 V. The EMF can be increased (d) ensures mixing of the two electrolytic solution.
(a) byincreasing [Tl*] (5) by decreasing [TI] (JEE Advance 2014)
(c) by increasing [Cu2*] (d) by decreasing [Cu**] C10. During electrolysis of molten NaCl, some water is added,
C5. Which of the following increases with dilution ? what will happen?
(a) Conductance (6) Specific conductance (a) Electrolysis will stop.
(c) Molar conductance (d) None ofthese (6) Hydrogen will be evolved.
C6. Which ofthe following statements are correct regarding dry (c) Some amount of caustic soda will be formed.
cell?
(dq) A fire is likely. (WB. J_E.E. 2017)
(a) Zine container acts as anode.
(6) Zine container is in touch with a paste of MnO, and
carbon.

Areswers
Ci th ta) ez. (b),(c) Ce. (a), (c) C4, (b),(c) C5. (a), (c) C6. (a), (d)
C7. (a), () C8. (b),(c) C9. (a), (0), (ce) C10. (5), (c), (d)

The following electrode reactions occur :

based on the given passage/comprehension At anode : 2H, (g) + 40H (aq)-——-> 4H, O(Z) + 4e-
At cathode: O, (g) + 2H,O (2) + 4e7-——> 40H (aq)
Passage I.
Overall reaction : 2H,(g) + O,(¢)
> 2H, O(/)
Fuel cells convert the energy produced during the combustion
In this cell, the gaseous materials are consumed and
of fuels directly into electrical energy. Probably the most
continuously supplied. The thermodynamic properties of
successful fuel cell so faris hydrogen- oxygen fuel cell, which
has been used in spacecraft. The electrodes consist of porous fuel cell reaction at 25° C are:
screens of titanium coated with a layer of platinum catalyst. AH°=—285.8 kJ mol, AG° = —237.2 kJ mol, E°= 1.23 V
Concentrated KOH or NaOH solution is placed between Answer the following questions :
the electrodes to serve as electrolyte. Hydrogen and oxygen
D1. The value of AS® for the fuel cell reaction at 26° Cis
gases are bubbled through the porous electrodes into the
electrolyte solution. (a) 1944 JK" (6) —163 JK"
(c) —1630 JK"! (d) 1.944k JK

Areswets
Passage I. D1. (6)
ELECTROCHEMISTRY

D2. If the potential of the half cell reaction at cathode is, Passage III.
E° = 0.41V, then E* for the half cell reaction at anode is
The concentration of potassium ions inside a biological
(a) 1.64V (6) 0.82V cell is at least twenty times higher than the outside. The
(c) —0.82 V (dq) —1.64V resulting potential difference across the cell is important
D3. The volume of H, when combined with excess O, in the fuel in several processes such as transmission of nerve impulses
cell at 26° C and 1 atm needed to produce 47.4 kJ of work and maintaining the ion balance. A simple model for sucha
under ideal conditions is concentration cell involving a metal M is
(a) 4.89L (6b) 2.45 L M(s) |M*(aq; 0.06 molar) | |M*(aq; 1 molar) |M(s)
(c) 7.36.1. (dq) 2.0L For the above electrolytic cell the magnitude of the cell
D4. Ifthe concentrations of OH ions in the cell are doubled, the potential |E__,,| =70 mV.
cell potential will
(a) become double (6) be reduced to 1/2 Answer the following questions:
(c) become fourtimes (d) remain unchanged D9. For the above cell
D5. The thermodynamic efficiency of H,—O, fuel cell 1s (a) Ey <9; AG > 0 (6) Ey > 0; AG <0
(a) 9.5% (b) 89% (c) Ea, <0; AG® > 0 (d) Ey > 0; AG? <0
(c) 83% (d) 95%
(LLT.S ELE. 2010)
Passage II.
D10. Ifthe 0.05 molar solution of M*is replaced by 20.0025 molar
Tollen’s testis given by aldehydes
M* solution, then the magnitude of the cell potential would
eee eed 0 ete E°_.,=+ 0.800 V be
CHO boo CO + 2s Ze
(a) 36 mV (6) 7OmV
EK? = —0.05 V
[Ag(NH,),]* +@ —>Ag + 2NH, EK? gq= + 0.873V (c) 140 mV (dq) 700mV (LLT.S.E.E. 2010)

F Passage IV.
use (sr 38.9V
The electrochemical cell shown below is a concentration cell.
M | M** (saturated solution of a sparingly soluble salt,
Answer the following questions:
MX,) | |M?*(0.001 mol dm~) | M
D6. Calculate (In K) for
The emf of the cell depends on the difference in
C,.H,.0, + 2Ag* + H,O——> C,H,.0, + 2H* + 2Ag concentrations of M** ions at the two electrodes. The emf of
(a) 56.6 (b) 29.6 the cell at 298 Kis 0.059 V.
(c) 66 (d) 68.36
D7. On adding NH,, pH of the solution increases to 11 then Answer the following questions:
identify the effect on potential of half cell. D11.The value of AG (kJ mol!) for the given cell is
(a) E, increased by E°, by 0.65 V (take 1F = 96500 C mol)
(6) EB, decreased by E”, by 0.65 V
(a)—6.7 (6) 6.7
(c) E.__, increased by E°__, by 0.65 V
(c) 11.4 (dq) -114 (LIT. J.E.E. 2012)
(d) E,,,; decreased by E°__, by 0.65 V
D12. The solubility product (K, mol’ dm~*) of MX, at 298 K
Ds. NH, 1isusedin this reaction rather than any other base. What
based on the information available forthe given concentration
is the correct reason for this ?
cell is
(a) [Ag(NH,),]* is a weaker oxidising agent than Ag*.
(6) NH, prevents the decomposition of gluconic acid. (take 2.3038 x KR x 298/F = 0.059 V)
(c) Ag precipitates gluconic acid as its silver salt. (a)1x10-% (6) 4x10
(d) NH, changes the standard reduction potential of (c)1lx10-¥ (qd) 4x10 (LT. J.E_E. 2012)
[Ag(NH5),]*

Areswets
Passage I. D2. (c) D3. (a) D4. (d) D5. {(e)
Passage II. D6. (d) D7. (a) D8. (a)
Passage III. D9. (6) D110. (c)
Passage IV. D11. (d) D12. (5)
fant MODERN'S abe + OF CHEMISTRY
-AXIl

. Assertion : Zinc can liberate H, from aqueous solution of

Assertion Reason Type Questions HCL.
Reason : Zinc has +ve reduction potential.
The questions given below consist of an Assertion and a . Assertion : Copper sulphate solution can be kept in a zinc
Reason. Use the following key to choose the appropriate answer. vessel.
(a) Ifboth assertion and reason are CORRECT and reasonis Reason : The position of zinc is higher than copper in
the CORRECT explanation of the assertion. the electrochemical series.
(6) Ifboth assertion and reason are CORRECT, but reasonis . Assertion : For CH,COOH, the molar conductance of
0.1M CH, COOH and equivalent conductance
NOT THE CORRECT explanation of the assertion.
of 0.1 N CH,COOH is same.
(c) Ifassertion is CORRECT but reason is INCORRECT.
Reason : These do not depend upon concentration.
(dq) Ifassertionis INCORRECT but reason is CORRECT. . Assertion : 0.1 M NH,OH at 25°C has more conductance
(e) Ifboth assertion and reason are INCORRECT. than at 60°C.
Reason : Conductance of a weak electrolyte decreases
1. Assertion : Equivalent conductance of all electrolytes with increase in temperature.
decreases with increasing concentration. . Assertion : E° for Mn**|Mn** is more positive than
Reason : Lesser number of ions are available per gram Cr3+ |Cr2+,
equivalent at higher concentration. Reason : The third ionisation energy of Mn is larger
2. Assertion : Iron is protected from corrosion by connecting than that of Cr. (A.LM.S. 2006)
magnesium metal with it. . Assertion : According to Kohlrausch law the molar
Reason : Iron acts as a cathode and magnesium as conductivity of a strong electrolyte at infinite
anode which gradually disappears. dilution is sum of molar conductivities of its
3. Assertion : Chromium is used for coating iron. ions.
Reason : The current carried by cation and anion is
Reason : Chromium is non-corroding metal which forms
always equal. (A.LLM.S. 2007)

Asi
a protective layer on iron.

Poe) 2. (a) a 16) 4, (c) 5. (d) ag G. (c) 7. (e) 8.(6) 9. (c)

Column I Column II
Matrix Match Type Questions
(A) can liberate H, from dil HCl (p) Mg
Each question contains statements given in two columns, (B) cannot liberate H, from dil HCl ig) Al
which have to be matched. Statements in Column I are labelled (C) metals more active than zinc (r) Cu
as A, B, C and D whereas statements in Column II are labelled (D) metals less reactive than zinc (s) Fe
as p,g,r ands. Match the entries of Column I with appropriate
2. Match the type of cell in Column I with the electrolyte
entries of Column IJ. Each entry in Column I may have one or used in the cell listed in Column II.
more than one correct option from
qoesrs Column I Column II

NO
Column II. The answers to these
(A) Lead storage cell (p) Potassium hydroxide
questions have to be appropriately
(B) Nickel-cadmium cell (q) Ammonium chloride
bubbled as illustrated in the following
(C) Fuel cell (r) Aqueous H,SO,
example.

-|® @@®@
(D) Dry cell (s) Zine chloride
If the correct matches are A-g,
3. Match the units in Column I with the quantity given

»|® @O©
A-r, B-p, B-s, C-r, C-s and D-g, then
the correctly bubbled matrix will look in Column II.
like the following: Column IT

1. Match the electrochemical behaviour of metals in Column (A) m? (p) Molar conductivity
I with the examples listed in Column II. (B) S m? mol (q) 5
We Sire (r) Cell constant

Areswets (D) Conductance (s) Conductivity

(1) : (A) —@) (q)(s) (B) -—(r) (C) —(p) (q) (D) —(r)(s)
(2) : (A)—(r) (B) —(p) (C) —(p) (D) —(q)(s)
(sb) 7 (A}—(r) (B) —(p) (C) —(s) (D) —(q)
ELECTROCHEMISTRY

Match E®° of the redox pair in List I with the values given
Matching Type Questions in List Il and select the correct answer using the code
given below the lists:
Each question has matching lists. The codes for the lists
have the choices (a), (6), (c) and (d) out of which only one is
correct.
E°(Fe**, Fe)
The standard reduction potential data at 26°C is given
E°(4H,0 =—— 4H* + 40H)
1.

below.
E(Cut* + Cu > 2G)
E\(Fe*, Fe**) = + 0.77 V: E*(Fe*'; Fe) = — 0.44V eer Cr")
E°(Cu2t, Cu) = + 0.34 V; E(Cut, Cu) = + 0.62V
E°[O,,,, 2(g) + 4H* + 4e- —> 2H,O] = + 1.28V;
K° lO) + 2H,O + 4e- —-+ 40H] = + 0.40V
E°(Cr**, Cr) = — 0.74V; E° (Cr**, Cr) = — 0.91V
(JHE Advance 2013)

Areswets
1. (d)

is 0.46 V. The e.m.f. for the cell reaction :

Integer type or Numerical Value Type Questions
3Cu + 6GAg*(ag) ——> 3Cu** + 6Ag is
Integer Types: The answer to each of the following 0.46y V. The value of y is
question is a single-digit-integer ranging from 0 to 9. A cell consists of two hydrogen electrodes. The negative
electrode is in contact with a solution having pH = 6.
1. ies pe of metals which can liberate H, from The positive electrode is in contact with a solution of
dil HCl is : pH = x. Calculate the value of x if the e.m.f. of the
Zn, Cu, K, Al, Hg, Na, Ni, Ag, Au cell is found to be 0.118 V at 298 K.
2 The emf of the cell The molar conductivity of a solution of a weak
7" 7" £ acid HX (0.01 M) is 10 times smaller than the
Mg(s)|Mg” (0.1 M) || Cu’* (1 x 10%M) |Cu molar conductivity of a solution of a weak acid HY
is 2.651 V. The standard e.m.f. of the cell is 2.71 V. (0.10 M). If A°,- = A°y-, the difference in their pK
The value of x is values, pK (HX) — pK (HY), is (consider degree of
3. The number of Faradays of electricity required to ionization of both acids to be << 1)
deposit 81 g of Al from electrolysis of AICI, is (JEE Advance 2015)
4, Inanelectrolysis of acidulated water, 4.48 Lofhydrogen The conductance of a 0.0016 M ow solution of
was produced by passing a current of 2.14 A. How a weak monobasic acid was determined by using a
many hours, the current was passed? conductivity cell consisting of platinized Pt electrodes.
5. Two litres of 0.6 M KMnO, solution have to be eee pene a wang ae en ae
: ie . an area of cross-section of 1 cm*. The conductance of
completely reduced in acidic medium. The number of =
Faradaya of eldet@tmefuired will be this solution was found to be 5 x 10°‘ S. The pH of the
| solution is 4. The value of limiting molar conductivity
6. The e.m-f. of the cell (A°_) of this weak monobasic acid in aqueous solution
Cu|Cu?* (aq) ||Ag* (aq) |Ag is Z x 107 S cm? mol". The value of Z is
(JEE Advance 2017)

Areswets
1. 5. 2. 3. 3. 9. 4, 5. oD. 6 6.
fata MODERN'S abe + OF CHEMISTRY
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Numerical Value Type: Give the correct numerical 11. Consider an electrochemical cell:
value (in decimal notation truncated/rounded off to the A(s)|A™* (ag, 2M)| |B22* (ag, 1M) B(s). the value of
second decimal place) AH?® for the cell reaction is twice that of AG° at 300 K.
If the emf of the cell is zero, AS° (in JK mol)
10. For the electrochemical cell,
of the cell reaction per mole of B formed at 3500 K
Mg(s) |Mg* (ag,1 M) || Cu?* (ag, 1 M) |Cu(s)
the standard emf of the cell is 2.70 V at 300 K. When
(Given : In(2) = 0.7, R (universal gas constant) =
the concentration of Mg** is changed to x M, the cell
potential changes to 2.67 V at 300 K. The value of x 8.3 J K+ mol. H, 5 and G are enthalpy, entropy and
1B coves: Gibbs energy, respectively).

(Given, = = 11600 K Vt, where F is the Faraday (JEE Advance 2018)

constant and RK is the gas constant, In(10) = 2.30)

(JEE Advance 2018)

Arswets
10. 10.00 11. —11.62

NCERT Exemplar Problems //

Objective Questions
»» Multiple Choice Questions (Type-H) <@ (a) (b)
1. Which cell will measure standard electrode potential of 1) T
copper electrode?
2 =
(a) Pt(s)|H, (g,0.1 bar) |H* (aq.,1 M) ||Cu2*(ag..1M)| Cu A. +

(b) Pt(s)|H, (g,1 bar)| H+ (aq.,1 M) ||Cu2+ (ag.,2 M) |Cu

(c) Pt(s)|H,(g, 1 bar) |H* (aq.,1 M)||Cu2* (aq.,1 M)|Cu
log [Mg**] — log [Mg?*] +
(d) Pt(s)|H,(g, 1 bar)|H* (aq.,0.1 M) ||Cu?* (aq.,1 M)|Cu
(ec) (d)
2. Electrode potential for Mg electrode varies according to
» Which of the following statement is correct?
the equation
(a) Ea. and A.G of cell reaction both are extensive
e 0.059 1 properties.
BE lag = Eve” | Me = a log [Mg?" |. The graph of
(6) Ea, and A.G of cell reaction both are intensive
properties.
KA 2|Mg vs log [Mg*"] is (c) £..7 18 an intensive property while A_G of cell reaction
is an extensive property.
ih T (d) Eo. 18 an extensive property while A_G of cell reaction
y
EI *y
2 is an intensive property.
. The difference between the electrode potentials of two
x ss electrodes when no current is drawn through the cell is
called :
log [Mg?*] + log [Mg?*] > (a) Cell potential (6) Cell emf
(c) Potential difference (d) Cell voltage

Areswets
1. (c) mee) 3. (c) A, (5)
ELECTROCHEMISTRY

5. Which of the following statement is not correct about an 13. The quantity of charge required to obtain one mole of
inert electrode in a cell? aluminium from AlL,O, is
(a) It does not participate in the cell reaction. (a) 1F (b) 6F (c) 3F (d) 2F
(6) It provides surface either for oxidation or for reduc- 14, The cell constant of a conductivity cell
tion reaction. (a) changes with change of electrolyte.
(c) It provides surface for conduction of electrons. (6) changes with change of concentration of electrolyte.
(d) It provides surface for redox reaction. (c) changes with temperature of electrolyte.
6. An electrochemical cell can behave like an electrolytic cell
(d) remains constant for a cell.
when
15. While charging the lead storage battery
(a) Ey = 0 (6) Bun > Eee
(a) PbSO, anode is reduced to Pb.
(e) HS By (7) Eo = Ee
7. Which of the statements about solutions of electrolytes is (6) PbSO, cathode is reduced to Pb.
not. correct? (c) PbSO, cathode is oxidised to Pb.
(a) Conductivity of solution depends upon size of ions. (d) PbSO, anode is oxidised to PbO,.
(6) Conductivity depends upon viscosity of solution. 16. A°(NH,OH) is equal to
(c) Conductivity does not depend upon solvation of ions (of) a?m(NH 40H) + A°m(NH4C1) _ A°m(HCl)
present in solution.
(0) A avecy + Amoraom- Amavacty
(d) Conductivity of solution increases with temperature.
(c) Macy + Mmavacy- “mataoH)
8. Using the data given below find out the strongest reducing
(d) None of these
agent.
17. In the electrolysis of aqueous sodium chloride solution
:
Cr,07-/Cr* = 1-99 Vv £E.ci,/cr = 1-86 V
which of the half cell reaction will occur at anode?
(a) Na" (ag) + e ——-> Na (s); Een = —2.71V
1 +
Eo; [Mn** = 1.61V Bn ge =— 0.74V
(6) 2H,O (2) —-+ O, (g) + 4H* (aq) + 4e- ;
(a) Cl (b) Cr i). Ce (d) Mn?* ray
9. Use the data given in Q.8 and find out which of the following
Eo) = 1.23V
(c) H+ (ag) + e —~+ —H,
1 (g); EYcell_ 0.00 V
is the strongest oxidising agent.
(a) Cl (6) Mn?* = (c) MnO; (d) Cr** 2
10. Using the data given in Q.8 find out in which option the = 1 =
(d) Cl (ag) —> 2 Cl, (g) +e ; Ke = 1.36 V
order of reducing power is correct.
(a) Cr* < Cl < Mn** < Cr
(b) Mn?** < Cl < Cr** < Cr
(c) Cr** < Cl < Cr,O7 < MnO,
»>
Note : In the following questions two or more than two options
(a). Mac? < Ce? <2 Cr = Ce may be correct.
18. The positive value of the standard electrode potential of
11. Use the data given in Q.8 and find out the most stable 10on
Cu**/Cu indicates that
in its reduced form. (a) this redox couple is a stronger reducing agent than the
(a) Cl (b) Cr¥ (c) Cr (dq) Mn** H /H, couple.
12. Use the data of @.8 and find out the most stable oxidised (6) this redox couple is a stronger oxidising agent than
species. H /H,.
(c) Cu can displace H, from acid.
fa) Cre (6) MnO, (ec) Cr,O2- (d) Mn**
(d) Cu cannot displace H, from acid.

Ase
5. (cd) 6. (c) fe Ce 8. (b) ee) 10. (b) 11. (d) 12. (a) 13. (c) 14. (d)
15. (a) 16. (5) 17. (&) 18. (5), (d)
iante MODERN'S abe + OF CHEMISTRY
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(c) power of AC source.

19. Ee for some half cell reactions are given below. On the
(d) distance between the electrodes.
basis of these mark the correct answer. 22. AY H,0 1s equal to
1 e 0 0 0
(i) H’ (ag) + e@ —> 9 he (g); Ket = 0.00 V (a) A cHcyt AN (NaOH) — A n(Nacl)
(6) A’amo,)t Minav
a 0
ano,) ~ “mav
p
aoz
(it) 2H,0 (tj) i). (gf) + AH’ (aq) + 4e- ; . a
(c) A cano,t Amaraom 7 “myNan
oO
0
o,)
Ee) = 1.23 V (d) AN n(HIN,OH)* MnCl) 7 AN n(NH,Ch
(iit) 2502" (aq) —~> 5,07 (aq) + 2e ;
23. What will happen during the electrolysis of aqueous solution
Eo 2196 V of CuSO, by using platinum electrodes?
(a) In dilute sulphuric acid solution, hydrogen will be (a) Copper will deposit at cathode.
reduced at cathode. (6) Copper will deposit at anode.
(6) In concentrated sulphuric acid solution, water will be
(c) Oxygen will be released at anode.
oxidised at anode.
(d) Copper will dissolve at anode.
(c) In dilute sulphuric acid solution, water will be oxidised
at anode. 24, What will happen during the electrolysis of aqueous solution
(d) In dilute sulphuric acid solution, SO? ion will be of CuSO, in the presence of Cu electrodes?
oxidised to tetrathionate ion at anode. (a) Copper will deposit at cathode.
(6) Copper will dissolve at anode.
20. Eon = 1.1V for Daniel cell. Which of the following
(c) Oxygen will be released at anode.
expressions are correct description of state of equilibrium
(d) Copper will deposit at anode.
in this cell?
25. Conductivity, 1s equal to
(a) 11=K, (b) 2:303RT jogK = 1.1
; 2F
ORs
1 (d) R
Ge tc} AL (d) a
(c) log K, = 0.059 (d) log K.= 1.1
26. Molar conductivity of ionic solution depends on ;
21. Conductivity of an electrolytic solution depends on (a) temperature (6) distance between electrodes
(c) concentration of electrolytes in solution
(a) nature of electrolyte. (d) surface area of electrodes
(6) concentration of electrolyte. 27. For the given cell, Mg|Mg"*|| Cu2*|Cu
(a) Mg is cathode (6) Cu is cathode
(c) The cell reaction is Mg + ee Mg* + Cu

pao (d) Cu is the oxidising agent

19. (a), (c) 20. (Dd), (c) 21. (a), (6) 22. (a), (6) 23. (a), (c) 24, (a), (0)
25. (a), (0) 26. (a), (c) 27. (5), (c)

» Matching Type Questions

<q cn (1) intensive property
Note: Match the items of Column I and Column IT in the
following questions: (db) Een (11) depends on number of
28. Match the terms given in Column | with the units given ions / volume
in Column II. (ce) G (111) extensive property
A) A, Gran (iv) increases with dilution
@) Sem 350. Match the items of Column I and Column II.
(ei aris
(iit) S em? mol
(a) Lead storage battery (z) maximum efficiency
(iv) V
(6) Mercury cell (it) prevented by galvanisation
29. Match the terms given in Column I with the items given
(c) Fuel cell (iit) gives steady potential

Asset
in Column II.
(d) Rusting (tv) Pb is anode, PbO, 1s cathode

28. (a)— (ait); (6) — (zu); (c) —(); (d) — Gu). 29. (a)
— (tv); (6)
—(2); (e)
— (24); (2)
— (ait).
30. (a)— (iv); (6) — (azz); (©) — (a); (d) — (12).
ELECTROCHEMISTRY 3/117 —

94. Match the.items of Column I and Column IL 33. Match the items of Column I and Column IJ on the basis
of data given below:

FE qujAu =LAV, Ep,Br = 1.09V

la) F, (1) metal is the strongest reducing agent

(6) La (12) metal ion which is the weakest oxidising
agent
(c) Au** | (tit) mon metal which is the best oxidising
agent
te) Br (iv) unreactive metal
(a) Lechlanche cell} (z) cell reaction 2H, + O, — 2H,O (e) Au (v) anion that can be oxidised by Au®+
(6) Ni-Cd cell (11) does not involve any ion in Cae Le (vi) anion which is the weakest reducing
solution and is used in hearing agent
aids. (¢) FO (viz) metal ion which is an oxidising agent
(c) Fuel cell (111) rechargeable
(dq) Mercury cell | (iv) reaction at anode,Zn—> Zn** + Qe-
(v) converts energy of combustion
into electrical energy

Psu31. (a) — (iv); (6)

— (zz); (ec)
— G1); (d) —@). 32. (a) — (iv); (6)— (az); (c)
— @, v); (@)
— (2).
33. (a) — (uz); (6)
— (@); (c)
— (vit); (d) —(v); (e)
— Gv); () — (a2); (@) — (011,01).

, F Ts: mati 37. Assertion: A_ for weak electrolytes shows a sharp increase
issertion and Reason Type Questions a when the electrolytic solution 1s diluted.
Note: In the following questions a statement of assertion Reason: For weak electrolytes degree of dissociation
followed by a statement of reason is given. Choose the increases with dilution of solution.
correct answer out of the following choices. 38. Assertion : Mercury cell does not give steady potential.
(a) Both assertion and reason are true
, and the reason ts Reason: In the cell reaction, ions are not involved in
the correct explanation
j
of assertion. | solution.
(b) Both assertion and reason are true and the reason 1s 39
. Assertion : Electrolysis of NaCl solution gives chlorine at
not the correct explanation of assertion.
oS anode instead of O,.
(c) Assertion is true but the reason is false.
Reason : Formation of oxygen
Ys at anode requires
q
(d) Both assertion and reason are false.
= overvoltage.
(e) Assertion is false but reason is true.
| : 40, Assertion : For measuring resistance of an ionic solution
34, Assertion : Cu is less reactive than hydrogen.
an AC source is used.
Reason : Egy Cu is negative. Reason : Concentration of ionic solution will change if DC
source is used.
35. Assertion : E,.,, should have a positive value for the cell Al
. Assertion : Current stops flowing when E,,, = 0.
to function.
Reason : Equilibrium of the cell reaction is attained.
Reason: FE. athode < i
anode 42. Assertion: E Ag+ |a, increases with increasein concentration
36. Assertion : Conductivity of all electrolytes decreases on of Ag* ions.

eaeen Reason
| | : E
‘ + has a positive value .
Reason : On dilution number of ions per unit volume Ag’ |Ag P
decreases.
43. Assertion : Copper sulphate can be stored in zinc vessel.
Reason : Zinc is less reactive than copper.

Areswers
34, (c) 35. (c) 36. (a) 37. (a) 38. (e) 39. (a) 40. (a) Al. (a) AZ. (bd) 43. (d)
iante MODERN'’S abe + OF CHEMISTRY
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. atio ns for
Hints & Explan Difficult Objective Type Questions
A. Topicwise multiple choice questions 5

V 0.01
ak
Al. (a) : «=Conductance x cell constant g =
Since kK = Conductance
.. Cell constant = 1. AY
or A> — a 19.6 _ 399
AS. fe) : K = = x Cellconstant eS 5x10"
y A pe _ 0.059 Fi.
_ [Zn** at
|
ALS: te)
= — x 1.15 2 [Pb?*]
2900
x = Kk x 1000 iy 1.151000 | ye e oe
46.
7 ~ 250 0.1 | — —(0.126—(—0.763) = 0.637 V
A4, (a) : A* (BaCl,) = A~ (Ba**)+2A~ (Cr)
_ 0.059 (0.1)
= 127.5242 x 76.34 E = 0.637—
—— log ——
2 (0.1)
= 280 S cm? mol!
— 0.637 V.
Kk x 1000
AS. (a) : A. = — Al4, (a) : The electrode reaction is:
m M
Zn**(aq) + 2e-— Zn(s)
1.06 x10 x 1000
0.059 1
0.1 E = E°———log—{—
2 ign]
= 1.06 x 107 ohm cm? mol
20
AG. (c) : A°CNaBr) A°(NaCl) + A°(KBr) — A°( KCI) [Zn2*] = 0.1x—— =0.02M, E°=--0.76V
100
= 126 + 152-150
= 128 S em? mol}. BE = 9.762ie —*
AZ. (c) : A(CICH,COOH) 2 F002
= A(CICH,COONAa) + ACHCI) — ACNaC]l) 0.059
= -0.76- log 50
— 2944 208—-36.2
— 388.8 ohm! cm? equiv.
= -—0.76- — x1.70
A8. (6) : A°%CH,COOH)
= —0.76—0.05 =-0.81 V
= (A;CH,coo- * Mnat) - Cen + Rae) ms sat + hea-)

Al7. (5) : E=E*- 3

0.059, [Sn**]
log [Ag P
= 90 + 425 —- 125 = 390 mho cm* mol!
Ac 7.8 Increase in conc. of Sn** will decrease E.
Degree of dissociation = —s0p 90 = 0.02.
A18. (c) This can be obtained
1n terms of Gibbs free energies
AS. (d) = A°n arcooms ethane = 847 + 58 Cu?+ + e-—> Cut BE, =+0.165V
= 400 5 em? mol} oa AG, =—-l1xFx0.15V=—0.165F
AS nun=40S em? mol; C=0.026M
Cu* +e —>Cu E,° =+0.60V
Nv 40 0,
-. AG,? =-1 x F x 0.60 =—0.60F
~ A2 400 7
Now Cu** + 2e°-—> Cu |
a
K, = £© =co .. AG,? =-2x F x EY =-2E3 F
. 1-a@
Now .. AG,% =AG,® + AG,
= 0.026
x (0.1)? =2.5 x 10+.
—2E,°F =— 0.15 F-0.60 F=-0.65 F
Al0. (6) : K = co”
= CO” 0.65
: i= —Q = 0.325 V.
1-a
2.5x10° = 0.01 a?
ELECTROCHEMISTRY

0.059 1.0
Al1S. (a) : KE,1 = Ee- B03 log [Zn**],
. K,= EY- 9 8501 = H° —0.059
9
On dilution
- E> E,
B, — Eo 9059
OF yg 11 9.
2 [Zn | ~ te = E = £e—.9.059 log Zn"
0.059 1 2 [Cu**]
2” 0.1 [Zn], i = BY out) cu) ~ EY zn2+ | 20)
0.059 1
E,-E, = ——— log——_.— E* = 0.34-(—0.76)=1.10V
on 2 0.1 [Zn"*],
0.059 0.1
0.059 1 FE = 1.10— 9 log Do]
+ log ——.
2 [Zin],
1.10 — 0.295 = 1.0705 V.
0.059
— 9 log 0.1 be 2 Ee @= EO edt] Fe2h = E sn2+ |En)
= 0.77 —(— 0.14) = 0.91 V.
0.059 |
= 5 x (—1)
=— 0.0295 . (bf: Fe*++2e —> Fe E°, =—0.414V
or - -30mV Fe*+ +e° ——>Fe*+ E*, =0.771V
A20. (d)
The required equation can be obtained as :
Ee 6211 7 Beagt|Ag) = (cu2+| Cu)
0.46 = 0.80—E Gy) cu) Fe —> Fe**+2¢
Fou2+| cu) = 0.80 -—0.46 =0.34V 2Fe** +2e —> 2Fe*

Al |Al?* |] Cu2*] Cu
EB?oy = ES-ES =0.771-(—0.441)
= 1.212V
Boel = Eicu2+| Cu) ~ 43+) aL
» ic) 96500 x 3 coulomb ofelectricity
is required to deposit
2.00 = 0.34—B*a)34)41 27 g of Al
”. E°(Al*| Al) = 0.84- 2.0 =-1.66V No. of coulombs required to deposit 90 g of Al
A238. (b) : For e.m.f. to be positive, the following half cell
reactions will occur :
_ 369008 90 - 965000
ar
Fe ——-> Fe**+2e E° =+0.44V or = 9.65 x 10°C.
Fe" +2e° ——_> 2¥Fe** E°=+0.77V
s kia)= 2.977 gofmetalrequire = 10800C
Overall reaction :
| , 10800
Fe +2Fe** ——> 3Fe** E°=41.21V 106.4 gofmetalrequire = x 106.4
2.977
”. Fe** will decrease.
= 3.86x10°C
A24, (d) : Subtracting eqn. (11) from eqn (2)
3.86 x 10°
AgCl(s) —— Ag*(ag) + Cl(aq) E° =—0.68V
meee "96500
Rm po pl:059 [Ag* ][Cl] A3l. (b) : 96500 x 3 = 289500 = 2.89 x 10° C
1 '°8 TAgCls) A382. (ce) Au** + 3e°-—> Au
At equilibrium, E = 0 and [AgCl(s)] = 1 197 g of Au is obtained by charge = 96500 x 3 C
E° = 0.069 log [Ag*] [CI] 1.234 g of Au is obtained by charge

= 0.069 log ‘.. _ 96500 x3 x 1.234

7 197
0.059 log Kk. =— 0.58
= 1815.4C
log Kk. = —9.881 Now Axft = C
K,, = 1.48 x 107°. oxt = 1813.4

A25. (a) : For the given cell, Zn + Cu** —> Zn** + Cu or f = ee — 604s

E = E® —-——
0.059 log x
2+ = 10min4s.
~ [Cu™] Wt. of Ag deposited 108
A33. (a) :
Wt. of O, produced 8
EB = Bo“ tog 201 ~E° +0.059
0.108 108
— fan20 MODERN'S abe + OF CHEMISTRY
-AXIl

= 6(—394.4) + 6(—-237.2)—(—8.2)-8x0
Wt.ofO, = —_
—1972 — 1423.24 38.2—-0
= 8x10°¢
= — 3387 kJ mol“)
Vol.of O, = HON eh 105 AG® = —nFTE®

= 5.6cm*, or E° = _AG® where

n = 32
nk
Eq. wt. of Ag Mass of Ag
AS4. (a) :
Eq. wt. of H, ~ Mass of H, hy = _
™
—3387 x10"
a
— 1.0968 V.
32 x 96500
108 7 1.08
1 ~=6 Mass of H, B4. id) = gy Opp 9x107
A. 400
Mass of H, = ee 10° ¢g Dissociation constant, K ~ Ca”
108
2 g of H, occupies at STP = 22400 cm® 1 < (2x10 -9\*
K = 35 _
~1,25x10 5
10~*gof H, occupies at STP = 112 cm*.
B5. (e) Cu+ 2Ag*——> Cu" + 2Ag
A35. (d) : Gram equivalents of H* = Gram equivalents of Al**
AG® = —nFE° =—2 x 96500 x 0.46
4.5
No. of gm equivalents of Al** = 97 0.5 — —88780J =-89 kJ.
No. of gm equivalents of Ht = No. of mol of Ht B6. (e) In strong electrolytes, number of ions remain
Mass
of Ht=0.6x1 = 05g constant, so equivalent conductance increases due
Now, 2gofH,atSTP = 2241 to increase in ionic mobility.

0.6 gofH, at STP = maxes B7. (ce) Higher the reduction potential, loweristhereducing
power. Therefore, correct order is Z>X> Y.
= 5.6L
B8. ee AG® = —nFE°
ASG. (a): Zn?*(1M) + 2e- ——> Zn charge required = 2F
E° <0,AG° = —RT In K,,.
Al**(1M) + 8e-——>Al charge required =3F
AG® > Oand K,, <1.
Ag*t(1M) + e ——+> Ag charge required =1F
B9. (ob) = Cu2t + e-—> Cut Ey avin .. Ai)
Therefore, charge required for ZnSO,, AICI, and
AgNO, solutions is 2F, 3F and 1F respectively. AGG = —nFE) =-1xFx0.15
Thus, the ratio is 2:3:1.
Cut+e—>Cu Ej =0.50V .. (11)
AAI. (a): AG = —-nFE*_4
= (—2)x (96500 C) x (1.23 V) AGS = —nF E§ =-1xFx 0.60
= —237390.J mol
Adding eqn. (z) and (zz)
or = —287.390 kJ mol+
Cu** + 9e- —_> Cu
Efficiency (yn) = =
AH x 100
AG? = —nFE° =-—2 x FE®
—237.390 —2xExE° = —-1xFx0.164+(—1x
Fx 0.50)
= —s—7— «100 = 83%
285.8

B from competitive examinations ge — 9:15+0.50 _ 9 395 v.

Bl. (5) : Efficiency of a fuel cell (yn) = AG/AH B10. (5) : Erell = E(Sn**|Sn?*)—
E(Cr** |Cr)
= 0.16—(—0.74)=0.89 V.
B2. (5): C.H,.+80, —~5 CO, +6H,O
Bll. (d) : AS (NH,OH)
AG® = 5AG°(CO,) o 6A,G°(H, 0)

= AG° (C,H, 4) — 8AG°(O,) ~ A® (NH,Cl) + A°, (NaOH) - A°, (NaCl)

ELECTROCHEMISTRY

9.54 x 100 Now, quantity of electricity Q =I x t

B12. (a) : Degree of ionization = Am x 100 = — 3a 19300 C=3 xt
19300
= 4,008% = 6435.3 5
B13. (c) Bett osMe eatiesie = EY aa = 107.2 min. = 110 min.
= 0.34—-(-0.76)=1.10V B21. (e) Q=Ixt=1x60=60C
B14. (d) : 2Ht+2e ——> H, Charge on le =1.6 x 10-9C
0.059 1 1.6 x 10°19C =1 electron
E(H, =H) = K°- ——~ log
[H+] 1G=
1.6x1
09 electrons
0.059 1
= 0—-_—_ log ——-— 60 C= @ | @
ig x 60 electrons
- (i072?) Po
= 3.75 x 107° electrons
yee x 20 =—0.59V
B23. (b) : Zn| ZnSO, (0.01 M)|| CuSO, (1.0 M)| Cu
Oxidation potential =0.59V
E, - E, _ 0.059 1, 0.01
B15. (c) Change in oxidation number from MnO?toMnO;
2 17
is from +6 to +7. Therefore, 1 electron is lost in the
- E,- 0.059 ioe 1
process.
2 100
Charge required by 1 mol MnO,7 = 1F
= E, + 0.069
Charge required by 0.1 mol MnO,?7' = 0.1F
When concentrations are changed
= 9650 C 0.059 1
B16. (d) : AtSTP, 22,400 mL of oxygen = 32 g EK, = E, -—— =
ee a
Saniant it 325600 _
= Ky “= log 100
TN OF CAVES = "99,400
= EF, — 0.069
.. Weight of O, deposited = 8 g
E, > E,
According to Faraday’s second law,
Wt. of O, deposited — Equivalent wt. of oxygen B24 +7 lee +1
(7) : BrO,; —— BrO,7 —°" 5H BrO
Wt. of Ag deposited Equivalent wt. of silver °
= 0
8B Br’ < 1.0652 V Bry 1.595 V
cl Wt. of Ag deposited 108
HBrO undergoes oxidation as well as reduction and e.m_f.
or Wt. of silver deposited = 108 ¢g of the cell is + ve.
B18. (c) For a hydrogen electrode +1 0
2H* (aq) + 2e°- ——> H,(g) HBrO—— Br2 E°=1.595 V

E_—Fe_ oo0.059 tog Pe +1 +5

2 HBrO ——> BrOs3 E° = -1.50 V
[H"
water at 298K, [H*] = 107°
2HBrO ——> Br, + BrOy”
In pure

B= 0- LOR pe _ 9.059 j HB cell =1.595-—1.50 = 0.095 V

se
p(H,)

a>
.. E will be zero when p(H,) = 10-* atm
iG*
Since E° _,,15 positive, the reactionisspontaneous.

B25. (c) Be = 8n og Kw 2 =2
« x1000 5.76 x10 = 1000
B19. (6) : A, =————-=
Molarity 0.5 EK?on = edd log1 x 108
= 11.52 S cm? mol!
B20. (5) 2Nat* +2 Cl ——> 2Na+Cl, 2 eee x 8=0.236V
Amount of Cl, produced = 0.1 x 71=7.1¢g 2
71 g of Cl, is produced by electricity = 2 x 96500C E*_, = E® (Fe**| Fe) —E° (1, |)
2x 96500 0.236 = Ee (Fe**|Fe)—0.54
7.1 g of CL, is produced by electricity = x 7.1
71 E® (Fe**| Fe) —0.236 + 0.54
= 19300 C — 0.776 V.
— fan2e MODERN'S abe + OF CHEMISTRY
-AXIl

B26. (5) : Applying Nernst equation, 0x2

log [zn2+] _ 1.1 = 37.3
ICu?*| 0.059
E = Fe_ 9.059 log =<
2 [Ni™*]
IZu*| — 1027-4
After dilution
Icu?*|
E - po _ 9-059 log’. a B3sl. (5): 2 Cr + 8Fe** (aq) —> 2Cr** (ag) + 3 Fe(s)
2 [Ni**]/10 E®_, = E® (Fe*| Fe)—E® (Cr**| Cr)
— —0.42 —(—0.72)=0.30V
0.059 1 0.059
= K°-———] ——— log 10
9.059 jg" [or]J
q °° (Ni2*] 2 °°
Bo,
0.059 1
= k°-——log —.—- 0.0295
2° INA 6 [Fe**|
2
Hence, reduction potential decreases by
= 0.30— 0.059 log (0.1)5
0.0295 V=29.5mV=30mV. 6 (0.01)
B27. (c) According to Faraday’s second law
~ 0.30— 9-059 x log 104
Weight of O, liberated | Equivalent weight of O, 6
Weight of Mg deposited Equivalent weight of Mg
= 0.30— 0.059 x4
x 8 6
or Se
0.150 12 = 0.30—0.039 = 0.26V.

or x _ = 8
—xX0,150 =0.1lg | B32. (ce) (1) Fe3+ + 3e-—— Fe, Kj = —0.036 V
13 AG? = -8 x F x (0.036)
At 8.T.P., volume of 32 g oxygan is 22,400 em? (11) Fe2+ + 2e-—_> Fe, Ky = —0.489 V
“. Volume of 0.1 g oxygen at 8.T.P. is AGS = -2 x F x (0.439)
22,400 Required reaction is
—___ 0.1 = 70cm?
32 Fe*+ +e—>Fe**, AGQ=-1xFx EK’,
B28. (c) : Applying Subtracting eqn. (11) from eqn (z) gives the required
E°(T-| AgI| Ag) = E*(Ag* | Ag)+.0.059 K,_(Ag]) equation so that
AG, = AG*,-AG,
log K,(Agl) = ET |Ag! |Ag) - E°(Ag* |Ag)
0.059 —-1xFxEg = —-3xFx(—0.036)—(-2 x Fx—0.489)
—Es = 0.108—0.878
_ - 0,152 fifi Wy 35 E°. a = —0.108 + 0.878
0.059
= 0.77 V.
Cell constant 2 48 4 0
B29. (c) : Conductivity = B38. (a): Pee or a yk 4 om
Resistance
Cell constant — 1.29x100-129m"!
No. of electrons involved = =(3 x 2y=4
Conductivity of 0.2 M solution = asa =0.248S m1
AG® = —nFE®
3
966 x 10° = —4 x 96500 x E°
Molar conductivity = a 3
Ee ee
— 12.4x10¢°S m? mol. 4x 96500
B30. Zn** +Cu Thus, minimum potential difference required = 2.50 V
(6b) : Zn+Cu**——>
When the cell is completely discharged, E__,, = 0 B34. (a) : Pt |H,(g) | H*(aq)

0=E
- _0.059 5, zn**]
cell — 9 og [cu2*] H* +e —> =Hele)

re _ Vloo [Zn?*]|
0.059 le, _[Zn*™* me Ee 02059... Pe) yy
or

= 2 : [cu?*| 1 (H"]
0.059 | [zn?*] V2
1.10 = E = pe 9 tog =-ve.
ICu?*|
ELECTROCHEMISTRY

B35. (a) : Kk = 1.35m1=1.3x10"7Senrc! For 0.5 M solution

1... 1
— = 2p
1fl kK = eet mee x 0.70
R A 280
Rla
- 25x10°Sem!
|Oe
Lgxio®
.
= ==
2(4)
A = Kx ay
= Molarity
4
(4) = 1.3x10°x60=65.0 x 107% em? x10),
2.5 x1000 —~5 Sem? mol
a 0.5
a K x 1000 —- 5x 107*S m?* mol!
M B41. (d): Cu** £ 2 —SSsA Cu
2F of electricity deposit 1 mol of Cu
1jfl 1 |
m2 21 les fh.0« 10 .. Mass of Cu deposited = 63.5 g
| aa
B43. (a): |E® for Cr®*| Cris minimum and therefore, it can be
1 65.0x10
x 1000 readily oxidised. Hence, it is a strongest reducing
A. = —————
” 260 0.4 agent.
= 6.26S mol? cm?
B44, (c): B,H, + 80, —- B,0O, + 2H,O
= 6.25x10+S mol" m*.
B36. (c) The element with high negative value of standard Moles of B,H, = — = ]1 mol
reduction potential 1s good reducing agent and can
1 mole of B,H, requires 3 mole of O, for complete
be easily oxidised. Therefore, X should have higher
burning
negative value of standard reduction potential than
Electrolysis of H,O
Y so that it will be oxidised to X** by reducing Y"+*
to Y. Therefore, 2H,O0—- O, + 2H,
X=Zn, Y = Ni 1 mole of O, is produced from 2 mole of H,O
Zn + Niz+ —> Zn*++Ni Amount of H,O required to produce 3 mole of O, =
6 mole
or Ee, = —0.23—(—0.76) =+0.63V
No. of Faradays required = 6 x 2-12 F
Since E°? _, 1s +ve, the reaction is spontaneous.
12 x 966500C=I xt
B37. (d) : Mn?*isthestrongest oxidising agent because ithas 12 x 96500 C= 100 xt
highest reduction potential value.
B38. (b) Mn** + 2e-—_> Mn; E°=-1.18V
ei aes
100
AG,° = —2F(-1.18) = 2.36 V At)
or ebaaae 3.21 hr
Mn*+* + e@#—> Mn": E°=+1.61V
3600
AG,° =— F(1.61) =-1.51F soltt) B45. (d): Cell reaction is
Eq. (1) — 2 x Eq. (zi)
H, + 2Ag* ——> 2Ag + 2H*
3Mn?2+—> Mn + 2Mn*+ 2
E Ke 2.303RT og (H"]
AG," = AG, /@egAGu i: a +72
2F [Ag I" Pup
= [2.86—2 x (-1.61)] F
= 5.38 F 0.06 1
0.62 = 0.80-
But AG,° = —2F E° 2°log ——
[Ag*P
. E° = —2.69 V
0.62 = 0.80+2 —_ log [Ag*]
Since E° value is negative, the reaction will not occur.
B39. (d) : According to Debye Huckel Onsager equation, 0.06 log [Agt] = 0.62—0.80=— 0.18
—0.18
A, = A,- AVC
log lAg"] = 06 =
+ eh ee

Here A =B
[Ag*] = 10°
f A, = A,- BJC -3
B40. (b) For 0.2 M solution Moles of Ag* in 100 mL = ee 10+
1000
1 / 1 /7
kK = R A or 1.4= 50 A Weight of Agt in 100 mL = 10+ x 108 = 0.0108 g
0.0108
or . = 60 x 1.4= 70 m?! = 0.70 em? % of Ag in 1.08
g alloy = ac Mien =1%
— fa24 MODERN'S abe + OF CHEMISTRY
-AIl

B46. (a) : Al®+ + 3e-—> Al B51. (c): The oxidation states of X and Y are X** and Y*+
Cut +326 —>Cu Atomic masses arein the ratio=1:2
Nat +e-——> Na Since equivalent mass = Atomic mass / Valency
1} 1 . 1 2
Thus, 1F ofelectricity will deposit 3 mol of Al, 3 molofCu Equivalent masses = 3 5 oF 1:3.

and 1 mol of Na. Hence, mole ratio of Al, Cu, Na deposited B52. (d) : g= Aw

at respected cathodes is: Aaa

An /2 @*K,, = — x 400
[am ?

1 + 4 999¢6. 100
3° 2 = 8.0 Sem? gequiv!
0.059 1 » - k x 1000
B47. (e) : EH= eS pe —_—_
n° (M**] C
Lower the concentration of M™*, lower is the reduction MP Kk x 1000
potential. 0.1
Thus, standard reduction potential is or « — 30x01 _ 9, 104 ohm em
Q>R>S>P 1000
B48. (c) H*t+2e—— >H Now K = > x Cell constant
0.059 1 L
EK =E* Cell constant
~~ n of [H*] or =
K
_0— 9-059 5H 0-0.059 x 10 =- 0.59V.
1 — a 0.4 ema

8 x 10-4 ohm em7!

a — 500 ohm
0

B49. (5) : Eo = Eby - —

0.059
log
(Zn**]
[Cu**] B53. (5) : Be = Coe ie See

(1) Zn(s) |Zn2*(0.1 M) ||Cu2* (1 M) | Cu(s) = 0.25-—0.62=-0.27V

0.059 Q.1 B54. (c) Metals get deposited on cathode after undergoing
KE, = Een _ —; ee (9)
reduction;
M"* +ne~— — > M(s)
0.059 Higher the reduction potential, moreis the tendency
to get reduced.
(21) An(s) |Zn?*(1 M) ||Cu** (1 M) | Cus) Hence, correct order Ag, Hg, Cu.
. 0.059 1.0 B55. (a) : Cr°**(aq) +e ———> Cr** (aq);
E, = cell qs i) AG? = —1xFx-—0.424-0.424F alt)
oO Cr**(aq) + 2e~- ——> Cris);
— cell .
AG? = —2x Fx (—0.9000)=1.8F ...(tt)
(z1t) An(s) Zn“*(1 M) | Cu2* (0.1 M) | Cu
Adding eq. (z) and (zz)
4 0.059 | 1.0 Crt +ae° —s Crs) AG® = 2.224 F
Ey = el 8 07 AG® = —nFE°
0.059 2,224 F
or = =—0.741V
8F
E, > E, > E,. B56. (d) : A* (COO), Na*K*] =A" (COO), +A" (Na*)
B50. (c) Mn?t + 2e——>3Mn +h” (K*)
AG? = -—nFE°=2.56F sucht) — 148.2 + 60.1+ 73.5 = 271.85 cm? mol!
Mn** +e —> Mn?* An
AG? = -—nFE°=—1.651F ltt) Total charge on cation or anion
Adding eq. (z) and (iz)
Mn** + 3e- —> Mn Aewwiy = 28 = 1356.95 em? mol
i 2
AG? = 2.36F4+(-—1.51F)=0.85F
AG? = —nFE® B57. (d) : Quantity of electricity = Ixt
0.865F = —3xFxE® 90.65
x 6 x 60 x 60
0.85 = 173,700C
or EK? = — —— =-0,.28V.
3
ELECTROCHEMISTRY

se
Faraday of electricity =
173,700
—7- =18F
B66. (c): NaCiO, +H,0 —>NaClO, +H,
96500 5 7
2Cl—2e——> Cl, or NaCiO ig — 28. —> NaClO P
1F ofelectricity liberates 36.5g or 11.2 LofCl, atS.T.P. 2 moles of electrons or 2 Faradays charge produce 1
mole of NaClO,.
.. Volume of CL, liberated by 1.8 F electricity
.. 3 Faradays of charge will produce = ="3
= 18x 11.2=20.16L
AS = 1.5 moles of NaClO,
B58.(d) : es ee,
A? 500 B67. (Ob): Lower the reduction potential, more easily it is
oxidised and stronger is the reducing agent. Thus,
ca” _ 0.007 (0.3)? zine having lowest reduction potential is the
l-a (1-03) strongest reducing agent.

0.007 x0.09 B68. (a): During electrolysis of aqueous NaCl, the reaction
= 97 = 9x10¢M
occurring at anode is
B59. (d) : Decreases by 60 mV Ch(aq)—> ;CL(g) +e
B60. (d) : Forasparingly soluble salt
« x 1000 B69. In H, — O, fuel cell, net reaction is
Solubility = A,° 2H,(g) + O,(g¢) —> 2H, O()
Since cellis supplied with 1 mole of H, and 10 moles
ct = 1.85 x 10° Sm? =1.85 x 10’ Sem?
of O,, H, is the limiting reagent. Therefore, 1 mole
A,
i]
= 140 x 10* Sm? mol = 1405 em? mol"
of H, will react with 0.5 mole of O,
1.851077 x 1000
Solubility =
140 2H (g) + ;0,(g) —> H,O() ;n = 26"
= 1.321 x 10° mol L“! Q=nF
For an electrolyte AB, andQ@=Ixt, [=96.6mA=96.5x10°7A
AB =At+B 2 x 96500 = 96.5 x 10° xt
If s is the solubility, then or - — =2x10°%s5s
96.5x107
K. = s?=(1.321 x 10°)?
sp B71. (a) : Zn |Zn?*(0.1 M)| |Cu** (0.01 M)|Cu
= 1.745 x 10°!" mol? L“

B61. (a): E = FE
_ 0.0591), [cr°*P Boa = ee a2 Cu Bo n2t |Zn
[Cr,02- [Ht }4 = 0.34—(—0.76)=1.10 V

1.067 = 1,33-
0.0591), 5x 10°) 2+
6 (4.510 °)[H* }4 0.059 Zn
EK = E°—- — log | -
i 1.33 — 0.0098 log
50x 107 [cu** |
[Ht}*
501072 1.33 — 1.067 = 0.263 V
0.0098 log TH,
a = 2 (0.01)
1.0—0.0295 =1.07 V
= 50x107 0.263
= 26.83
0.0098 Since, E of the cell is positive, the reaction is
[Ht }*
spontaneous.
log(50 x 10-*)—log[H*]* = 26.83
— 1.3 —- 14 log[H*] 26.83 B72. (c) Al** + 3e-—>Al
—14 log[H*] = 26.83 + 1.3 = 28.13 For depositing 1 mole of Al, electricity required =
or — log[H*]
28.13 = 2.01 oF
14
pH = 2 B73. (5) : E® = E®,,, (cathode) —E° __, (anode)
B62. (c) 7 During charging, Pb** ions of PbSO, are reduced = & Fe“t |Fe
a = BK?

Zn=* |Zn
to Pb on cathode:
—0.41—(-0.76) = 0.35 V
PbSO,(s) + 2e° ——> Pb(s) + 5O,* (aq)
B65. (d): In acidic medium _ « (Specific conductance) x 1000
B74. (a) :
Cr,0,* + 14H* + 6e—> 2Cr** + 7H,O “ M
A 1000
Reduction of 1 mol of Cr,O,?- to Cr** require = 6F or — = — 10° ecm? mol"!
K 0.01
— ian26 MODERN'S abe + OF CHEMISTRY
-AXIl

B75. (d) : MEE

logK = ——cll PE cen qa = = = —
2.303RT 0.059 n-l 2-1 21
2x08
ibe oa
= — +] = —
0.0591
ZL 21
K = 101° AT, =k, m
+7 +4 33
B76. (5) : MnO, +3e —— MnO, ™ mya) <8 = 2-45 K

Charge required for reduction of 1 mol of MnO ,~ Boiling point of solution = 373.15 + 2.45
= $75.6K
= 3F
B80. (6b) : Zn+Fe**+——>
Zn** + Fe
BTi ta) - Ifx 1s the solubility of AgCl
Ba Ee 9.959 jog Zn?)
2
AgCl = Agt+Cr
2 [Fe**]
a a
KCl —> K' +Cr , 0.059 10°
= fe
2 § 103
0.1 0.1 0.059
[Ag*] =x, [CH =x+0.1=0.1(-: x<<0.1) 0.2905 = EE? — —
a
For precipitation to start 059

K,, = [Ag*] [CH

E® = 0.2906+ 9 = 0.52

1.8x107°=xx 0.1 Now Ee = = logK

1.8x 10719 0.382 =

0.059
logK
= — =-18x10°
a
0.1
Mass of AgCl = 1.8 x 10° x 143.5 0.32
logK = 0.0295
= 2.58 x 10“g - K = 19 0-32/0.0205

Quantity of electricity required to deposit B81. (a) : Fe(s) ——-+ Fe** (aq)
+ 2e7, AG,°
2.68 x 10-7 g AgCl
1 mol or 143.5 g of AgClis deposited by 96500C 2Ht42e + 50, ==> Jy); AG
2.68 x 10 gof AgCl is deposited by =
1
96500 x 2.58 x 1077 Fe(s) + 2H* + 3 O, ———> Fe**(aq)+ H,OW, AG,°
143.5
Applying AG,* + AG,° = AG,®
Now, 7
@ = Iltort= (a AG,* —- —3F x 0.44 + (-2F x 1.23)
96500 x 2.58
x 10
7 = — 2 x 96600 x 0.44 -2
or f = st ae = 173.48.
143.5 x1x10 x 96600x 1.23
B78. (a) : 21a(s) + F,(¢) —> 2LiF(aq) = — 322310 J
or AG,? = —322.3kJ
KE? 4) = 5.92V
B82. (6) : NaCl(ag+—-+Nat+ Cl
0.059 H,O — > H*+0OH™
fee ff i log [LiF]?
Ht+e — > 5H,
~ 5.92- —< 10g(2)
0.6 mol of H, is liberated by 96500 C
= 6.92—- 0.069 x 2 log?
0.01 mol of H, will be liberated by
= 6.92—0.069 x 0.3010 =5.90 V
_ 96500
, 9.01 =1930 C
Am 0.5
B79. (a) : a=
A
c
Q = Ixt
or .. QL 1930 C
_ 240 12
I 10x10°A
420 21
= 193000 sec = 19.3 x 104s
ELECTROCHEMISTRY

2+ 2 D3. (a) : Under ideal conditions, electrical work

B83. (d) - i = we 288) eT = AG=—237.2kJ mol
4 pO, x[H*}
4-32
Moles of H, needed
- 167 —4.7.4
4 0.1x (10) = pee =O
0.059 Vol. of H, needed at 25°C and 1 atm.
1.67 ———
4 log10°
5
nRT
1.67 —0.10 = 1.57.
p
B85. (d): Pt(s)|H,(@)(1 bar) |H*(aq), (1M) ||M**(aq), 0.2* 0.082 x 298
M?*(aq) |Pt(s) 1
The cell reaction is: H, + M** (aq)——> 2H* (aq) + M?* (aq) —- 4.89L

ca
_ 0.059, [H* FIM** (aq) D4. ta) = Since the cell reaction does not involve OH ions
Been =E cell concentration, E~ cet) Will remain unchanged.
n Py, [M™ (aq)
D5. (c) Thermodynamic efficiency
Foo = Eeygte
yee —E?yt), = 0-151-0 = 0.151V AG -nFE

[H*] = 1, E,.,, =0.092V, Pu, = 1 bar, x =2

AH AH
—2 x 96500 x 1.23
0.092 =0.151 -9-958), FIM tag) -285.8 x 10°
2 34 ,

2° IM (aq)] = (838 or 83%

2+ D6. (d) : E* on — ales ae
0.092—0.151 -— 2:0" UM aq) = 0.8—0.05
[M”* (aq)]
= 0.75V
2+
-0.059 =" Jo asin AG?4 = —2FE*4
2 [M*" (aq)]
2+
= —RTinK
or log (Mag) _9 2F
[M**(aq)] ——
RT * x().75
a+
UA (ag)! _ 40810
or +*=2 = 2x 38.9 x 0.75
[M""(aq)] = §8.35
B86. (a) : Zn(s)+Cu** (ag) —> Zn** (ag) + Cu(s) RT
D7. (a) : E = EY_-— infH*?
AG = AG° + RT In Q op (TlH
AG = AG® + 2.303 RT log Q
= he 2 In[H*]
_ [Zn?*] 10 38.9x2
~ (Cu2*] 1 pe , 2-303
AG? =-nF EY 4,=-2 *F x 1.1 38.9
10
AG =—2 x F x 1.14 2.303 RT log a or E = ieee ao x11
— 9 303,.RT+2.°oF
38.9
= E% +0.65
D. mcq based on passage/comprehension E-E* = 0.65 V.
D1. (5) : AG = AH—-TAS D8. (a) - Because E® Ag*||Ag >E? [Ag(NHg)9]"
|Ag
or AS = AH — AG D9. (5) > Mt — > M*
T (1M) (0.05M)

7 —285.8 —(—237.2) _ —48.6 Applying Nernst equation

7 298 298 0.05
EK = E® a log
—- —0.163kJ K-! mol! 1 1
—- -163J K" mol. _ 0.059
log (5x 10°) ~ 0.076
D2. (c) Ke = Fe" cathode) ~ # (anode)
©1238 = 0.41-E'node +ve
or > 0, AG =—ve or < 0
— ian2e MODERN'S abe + OF CHEMISTRY
-AXIl

EK, log 0.05 Q: 2H,O—> 0,+4H*+4e™ ; E° =— 1.23V

m2AOs) $22. % EB, log 0.0025 O,+2H,O + 4e° —-> 40H ; E° = + 0.40V

4H,O—> 4H*+40H- ; E° =— 0.83 V

E, log5 x 10° “jn 4
E, log25x10. 26 2 Re Guot*402-—+ Cn : B° =+0.34V

Now E, = 70(given) 2Cu —> 2Cut+ 2er é E° =— 0.52V

Cn + Ot en, : E° =—0.18V
Mm 4g E, =70x2=140mV
E, 2
S: Ort = @r** = Cr
Dil. (d) : AG = —-nFE.y
= —2~x 965600 x 0.059 AG?
= —11387J mol —0.74V, A=2
or = —11.4kJ mol
AG, = AG 3 AGS
D12. (db) M | M** (aq) (saturated solution)
—3F
x 0.74 = 1F x x + 2F x (—0.91)
|| M?* (aq) (0.001 M)| 1M
x = —2.929+1.82
Anode: M —> M** (aq) + 2e-
or — -0.40V
2+ a ,
Cathode: ee Integer Type or Numerical Value Type Questions
M (4q) cathode ——> M* (4) anode
1. (5) : Zn, K, Al, Na, Ni
E = Re- 0.059 log IM @Mlanode_
T ot
2 [M** (aq)leathode 2, (3): E _ reo_ 0-059 og ME |
2 [Cu**]
2+
0.059 = o— 9-099 log ME (eM Janode
2.661 = a pe
2 10-3 2 (1.0x10™)
2) log EM“ (@a@)lanode
2.651-—2.71 = a PL
103 2 (1.0x10)
—2 = 8log [M**(aq)]
oa.
or 107 = 10° [M** (aq)I node
§0.059 = -0:05% gq 0.1
2 (1.0x10™)
10-2 2 = log0.1—log(1.0
x 10~)
”[M**(aqgonae= —a = 10°
e108 2 = —1-log(1.0x
10™)
For MX,, MX, = M** + 2X" log(1.0x 10“) = —8
If's is the solubility, then log 1.0—xlog10 = —38
—x = —-—3
[M**] =s, [X] =2s
or =o
K [M?*] DC}?
sp 3. (9) : Alt*+3e ——> Al
s x (2s =4s?
Fordepositing 1molor27 gAl,electricityrequired=3F
Ax (10°)? =4x 10°" dm”? mol®
For depositing 81 g, electricity required = —_
Matching Type Questions
—9F
Dp. ago1 ty "2s AGS 4, (6) : 2H*+2e ——> H,
1. (d) P: Fe** 0.77V,n=1 Fe*+ —paiv,n=a Fe
AGS oa
22.4 LofH, is produced by = 2x 96500C

xV,n=3
;
4.48 LofH, is produced by =
2x 96500 x 4.48
Sa ee
22.4
Ga AGS + AGS
= 38600C
oxxk 1x0.77xF +2(-0.44)xF Now 38600C = 2.14Ax f(s)
Ox 0.77 —0.88
t = assed = 180375
2.14
= = —0.037 = -—0.04 V
18037
or r= =
3600
ELECTROCHEMISTRY 3/129 =

5. (6) : 2Lof0.6 M KMn0O, solution will contain 2 x 0.5 = 9. (6) : Refer Advanced Level Problems, Problem 2.
1.0 mol of KMnO, . Reduction of KMn0O, is (page 21)
MnO, + 8H* + 5e —-> Mn* + 4H,0 10. (10): Refer Advanced Level Problems, Problem 8
Thus, 1 mol of MnO; requires 5F of electricity. (page 45).
6. (1) : Electrode potential does not change with changein 11. (—11.62): Refer Advanced Level Problems, Problem 11
stoichiometric coefficients of electrode reactions. (page 51).
7. (4) : The cell may be represented as NCERT Exemplar Problems : MCQs Type-I
H, |Ht (10°M) || M*(M,) |H
a: [EL | MED Hp 1. (c) : Pt(s)|H,(g, 1 bar) |H* (ag, 1M) || Cu2* (ag, 1M)|Cu
0.059 0 glBoe represents correct cell for measuring standard
E = E°-——log—_—o+* :
1 i:ky ees electrode potential of copper.
a. (by) = Eg? | Mg) increases with increase in log [Mg**] and
011g 6
— 9—2:959 oe ae) ) = 0, the value is
at log [Mg**] . equal to E ° (Mtg?*[Mg)
1 M, 3. (c) : E18 anintensive property and A Gis an extensive

lo
(10)
M =
TaEa
0.118 Se ge
5. (d) : It provides surface either for oxidation or for
. a.
. , reduction reaction and not for a redox reaction.
10% = 6. (c) : When E,., becomes larger than E,..,,, the
M, =a electrochemical cell behaves as an electrolytic cell.
“* 7. (ce) Conductivity also depends upon the extent of
M, = as -10*M solvation of ions in the solution.
10° 8. (6): Cr°*|Cr has the least reduction potential and
re 4 therefore, it can be easily oxidised. Hence Cr acts
8. (3) : eatin A = MY | as strongest reducing agent.
Adding /°,,+ on both sides 9. (c) : MnOjcan be easily reduced to Mn** and therefore,
Ay tae = ALA MnO; acts as the strongest oxidising agent.
or ax = fae WO 11. (d): Mn** is most stable ion in reduced form because
Degree of dissociation is given as MnO; acts as the strongest oxidising agent.
Ac AS 12. (a): Cr** is most stable oxidised species because Cr
Oy = —i% and 0... = ih. acts as the strongest reducing agent.
HE si 13. (c) : Al** + 3e ———> Al
(iss No Me Sao ae - Quantity of charge required for one mole = 3F
ial Qhiry
= A Ye HY A a HX A HY
(Zi) 15. (a): While charging the leadCh
storage battery,
2PbSO,(s) + 2H,O ——=* Pb(s) + PbO,(s) +
But AS. = 5 A’, SOrL ATS 2H,SO, at anode
17. (6) : At anode, the standard reduction potential of water
Orgy = 0.1 Oey is slightly less than that of Cl (aq) and therefore, it
2 has more chances of getting oxidised.
col Hx
Now Ko, = Jf ee “gt A | |
1-Qyx NCERT Exemplar Problems : MCQs Type-II
= 0.01 x (0.10,,,)° ...(L1L)
K 9 0.1(0...)2 _2.3038RT ,_ ?

Dividing eq. (111) by eq. (tv)

loo K = nE° — 2x1.1
Kaa) _ 0.01x0.0107py
2
_ 6s 5 0.059 0.059
Kacy) 0.1 Oay 22. (a), (6): because A°_(H,O) = A, (H*) + A° (OH>
Taking log 1]
log K, (3x) — log K, ay = 3 25. (a), (6) : Conductivity, « = —

-PK, ay t PK) = —3 1
aa PR ax PK = 3 ork= 7. G", where G" is cell constant and is equal to L
a

DIO)
a, 30 MODERN’S abe + OF CHEMISTRY-XII

y UnitPractice Test g
Examination

Time allowed : 2 Ars. Maximum Marks : 85

1. Give the units of conductivity and molar conductivity. (1)

2. Write the overall cell reaction for lead storage battery. (1)
3. Define Faraday’s second law of electrolysis. (1)
4. What is the role of ZnCl, in a dry cell ? (1)
5. Out of copper and zinc vessels, which vessel would be suitable for storing 1M HCI? (1)
6. Predict the products of electrolysis in each of the following : (2)
(_) An aqueous solution of AgNO, with silver electrode.
(i) A dilute solution of H,SO, with platinum electrodes.
How much electricity is required in Coulombs to produce 40 g of Al from molten Al,O,? (2)
Conductivity of 0.00241 M acetic acid is 7.896 x 10° S em’. Caleulate its molar conductivity. If A_° for acetic acid is
390.65 S em? mol, what would be its dissociation constant? (2)
Write cell reactions which occur in lead storage battery
(1) When battery is in use
(it) When the battery is on charging. (2)
10. Give two points of differences between emf and potential difference . (2)
11. Write the Nernst equation and calculate e.m.f. of the following cell at 298 K:
Sn(s) |Sn?* (0.060M) || H* (0.020 M) | H, (1 atm) Pt. (3)
12. Explain the following :
(1) Electrical protection for preventing rusting of iron pipes in underground water.
(11) Can you store copper sulphate solution in a zinc pot or not?
(111) Effect of dilution on molar conductivity. (3)
13. Write the chemical equations for all the steps involved in the rusting of iron. Explain why does alkaline medium inhibits the
rusting of iron. (3)
14, State Kohlrausch law of independent migration of ions. Mention one application of the law. (3)
15. List main differences between electrochemical cells and electrolytic cells ? (3)

16. (a) The cell in which the following reaction occurs :

2Fe™* (aq) + 21- (aq) —> 2Fe™* (aq) + 1,
has E° _,, = 0.236 V at 298 K. Calculate the standard Gibbs energy and the equilibrium constant of the cell
reaction.
(6) What are fuel cells ? Give one example.
(c) Give the units of cell constant. (5)

To check your performance, see HINTS AND SOLUTIONS TO SOME QUESTIONS at the end of
Part I of the book.
SI
/|4 \CHEMICAL KINETICS¢
(0359) 0 Od MAYA DS) lan, “VG
Building on..... Assessing..... Preparing for Competition.....
@ Understanding Text 1 @ Quick Memory Test with @ Additional Useful Information 94
Conceptual Questions 22, 66 Answers 83 @ Topicwise MCQs 96
@ Advanced Level Problems 22,48, @ HOTS & Advanced Level @ Gikpetitive E ‘nation @s
60, 65 Questions with Answer 84
SOLUTION FILE REVISION EXERCISES » AIPMT & Other State Boards
¢@ Hints & Solutions for Practice (with Previous Years’ CBSE Qs Medical Entrance 100
Problems 68 & Other State Boards Qs) 86 >» JEE (Main) & Other State
CHAPTER SUMMARY & QUICK @ Hints & Answers for Revision Boards’ Engineering Entrance 103
CHAPTER ROUND UP ia Exercises 92 > JEE (Advance) for IIT Entrance 107

2 SR Gs awn eo ¢ NCERT Exemplar Problems

@ Intext Qs & Exercises with (Objective Questions) 112
Solutions 75 :
¢ NCERT Exemplar Problems with of Hine co Beg eae
Answers & Solutions (Subjective) 81 UNIT PRACTICE TEST 129 Difficult Questions 118

W. have learnt some aspects of chemical reactions. The feasibility of a

reaction under the given experimental conditions can be predicted on
the basis of decrease in Gibbs energy (AG < 0). The extent to which
x a reaction proceeds can be explained with the help of equilibrium
: constant of the reaction. The third important aspect of the chemical
x reactions is the speed with which the reactions proceed. Although
thermodynamics answer the first two aspects satisfactorily, it cannot
\ answer this important question; how fast a reaction can occur ?
\ The branch of chemistry which deals with the rates of chemical
reactions and the factors which influence the rates of reactions
| and the mechanisms by which the reactions proceed is called
/ chemical kinetics.
The word kinetics is derived from the Greek word 'kinesis’
meaning movement. The kinetic studies not only help us to know
; the speed or rate of a chemical reaction but also describe the
/ conditions by which the reaction rates may be altered. The study
of the rates of reactions also helps us to understand the pathways
from reactants to products called mechanism of the reaction.

RATE OF A CHEMICAL REACTION

Everyday experience tells us that chemical reactions take place in widely varying rates. Some reactions are so
rapid that they occur as soon as the reactants are mixed. For example, the reactions involving lonic species (known
as ionic reactions) are very fast. For example, the precipitation of silver chloride occurs very quicky on mixing
the solutions of silver nitrate and sodium chloride. Similarly, the neutralisation of an acid by a base occurs as soon
as the two substances are mixed.
AgNO,(aq) + NaCl(aqg) ———> AgCl(s) + NaNO.(aq)
NaOH(aq) + HCl(aq) M+ NaCl(ag) + H,O)
BaCl, (aq) + H,50,(aq) ——— BasO, (s) + 2HCl(aq)
a
 MODERN'S abc + OF CHEMISTRY-All

It may be noted that these reactions involve only the tons and no bonds are
broken. Therefore, they occur very fast. These reactions occur in about 10-%
to 10-!® seconds. On the other hand, there are certain reactions which occur
at an extremely slow speed. For example, rusting of iron occurs so slowly
that one could be misled into thinking that no reaction is taking place at all.
However, there are some reactions which occur in a conveniently measurable
Reactions involving ionic species
time and their rates can be measured easily in the laboratory.
(known as ionic reactions) are very
Some common examples of such reactions are :
fast reactions. These generally
(1) Hydrolysis of an ester in the presence of sodium hydroxide
occur in 10°? to 10-'® seconds.
CH,COOC,H. + NaOH ——-—> CH,COONa + C,H,OH
Ethyl acetate Sodium acetate Ethanol
(i1) Decomposition of hydrogen peroxide
2H,O, (aq) ———> 2H,O(/) + O,(g)
(111) Inversion of cane sugar to give glucose and fructose
C15H,.0,, r HO , aa CoH,,0, v C.H,.0,
Sucrose Glucose Fructose
(iv) Decomposition of nitrogen (V) oxide
2N,0, ——> 4NO, + O,
These are the reactions which are focus of attention for us.
You must be knowing that speed of an automobile is expressed in terms
of change in position of distance covered by it in a certain period of time.
Similarly, the rate of a chemical reaction is a measure of the speed with which
the reactants are converted into products.
Rate of reaction may be defined as
the change in any one of the reactants or products per unit time.
This may be obtained by dividing the change in concentration of a reactant
or a product by the time interval over which the change occurs.
Consider a hypothetical reaction:
R —~— P
in which one mole of the reactant 'R' produces one mole of the product 'P'. The
rate of the reaction may be expressed in either of the following two ways :
(t) The rate of disappearance or decrease in concentration of R (reactants):
Rate of reaction = Decrease in concentration of R
Time taken
(it) The rate of increase tn concentration of P (products) :
Increase in concentration of P
Significance of negative sign. ——
Rat&ot reaction = —_$__._______—_
Time taken
The significance of negative sign
in the case of expressing rate of If [R], and [P], are the concentrations of R and P respectively at time ¢,
reaction in terms of reactants may and [R]., and [P], are their respective concentrations at time ¢,, then
be understood. The concentration At = t,-¢,
of reactants is decreasing as time AIR] = [R],-—[R], and A[P] = [P], — [PI],
passes and, therefore, AR, (z.e., final where the square brackets express the molar concentrations and A[R] and A[P]
concentration—initial concentration) are the changes in concentrations of R and P during time interval At. Then
will be negative. rate of the reaction may be obtained by dividing the change in concentration
This makes the expression a
[R] of a reactant or a product by the time interval over which the change occurs.
This is expressed as a:

(reaction rate) negative. But we know Rate of reaction = aS ...(1)

that rate is always positive, as also
obtained from the rate of formation or Rate of reaction = “ AD)
of products. Therefore, minus sign ft
where A[R] gives the decrease in concentration of R and A[P] represents
A[R]
is put before ava so that the rate increase in concentration of P. The square brackets around the substances
are used to express the molar concentration (mol/litre). It may be noted that
1s positive [(—) x (—) = +ve]. Thus, in the case of concentration of reactants minus sign is used. This implies that
AIR] _= ———
Rate of reaction = — ——
ALP] the concentration of reactants is decreasing with time.
The above rate is also called average rate of the reaction. It has the
At At
dimensions of concentration/time. The units of concentration and time are
chosen according to the convenience.
CHEMICAL KINETICS

In the above example, the stoichiometric coefficients for the reactants

and products are same. Therefore, the rate at which the concentration of
R decreases will be the same as the rate at which the concentration of P
increases. Therefore, the rates expressed by the Eq. (1) and Eq. (2) are same.
For example, for the reaction :
PCI. (g) ——+ PC], (g) + Cl, (g)
Rate may be expressed as :
Raine A[PCl, ] _ A[PCl,] A[Cl,]
At At ~ At
Similarly, for the reaction :
Hg (2) + Cl, (g) ——+ HgCl, (s)
Rate may be expressed as :
_ AlHg] _ AICI,] | AL[HgCl,|
Rate =
At At At
Reactions Involving Different Stoichiometric Coefficients of Reactants
and Products
Consider the reaction
A+B —>2C
In this case, one mole of A reacts with one mole of B to form 2 moles of C.
This means that the rates of disappearance of A and B are same but the rate
of appearance of C must be twice the rate of disappearance of A and B. Thus,
2 Rate of disappearance of A= 2 Rate of disappearance of B
= Rate of appearance of C
To get unique value of the reaction rate (independent of the concentration
Average rate concept and
terms chosen), we divide the rate of reaction defined with any of the reactants
mechanical speed. The concept
or products by the stoichiometric coefficient of that reactant or product involved
of average rate is similar to
in the reaction. Thus, for the above reaction,
mechanical speed. For example,
Rate of reaction =
ALA] AB] _ 1 AIC) the average speed of a car can be
At AP Ara easily calculated by knowing the
For example, for the decomposition of gaseous nitrogen pentoxide (N,O,) as: distance covered by it in a given
2N,0.(¢) ——— 4NO,(g) + O,(g) time. If the car covers 250 km
in 5 hours, its average speed is
1 A[IN,O;] — 1 ALNO,] — A[O,]
Rate of reaction = = 250 km/5 hr = 50 km/hr. However,
At 4 At “\ Af during the journey, the driver can
Similarly, for the reaction :
look from the speedometer that
2HIi(g¢) —_—— H,f(g) + Lf)
the speed keeps on changing
rate may be expressed as :
depending upon the conditions of
1A[HI] AlH,] Ally] the road, weather, traffic density
Rate of reaction = 0 4 Sime 4
etc. The needle of the speedometer
For a gaseous reaction at constant temperature, concentration is directly indicating speed may vary from
proportional to the partial pressure of a species and hence, rate can also be as low as 10 km/hr to 120 km/hr.
expressed as rate of change in partial pressure of the reactant or the product. For a chemical reaction also,
the average rate depends on the
Average Rate and Instantaneous Rate
values of ¢, and ¢, chosen. Like
The rate expressions given so far give the average rate of reactions over the
speed of the car, the rate also
time interval (At). This may be expressed as :
changes. This is due to the fact
a Change in concentration _ Ax that in case of reactions, the rate
Time interval At depends upon the concentration
However, it may be noted that average rate cannot be used to predict of the reactants. As the reaction
the rate of a reaction at a particular instant because the rate is generally proceeds, the concentration of the
not constant throughout the reaction. This is because rate of a reaction reactants keeps on decreasing.
depends upon the molar concentration of reactants which keep on decreasing Thus, the rate of a reaction may
with the passage of time (while those of the products keep on increasing). not be constant in the time interval
Therefore, to express the rate at a particular moment of time, we determine which we measure.
the instantaneous rate. Thus, instantaneous rate of a reaction may be
defined as
the rate of change of concentration of any one of the reactants or
products at a particular moment of time.
a 4/4 MODERN'S abc + OF CHEMISTRY-All

To express instantaneous rate of reaction, the time interval Af is made

as small as possible so that rate of reaction remains almost constant during
that time interval.

Mathematically* instantaneous rates may be represented by — a or on

REMEMBER A[P
instead of _ ALR] oO aed respectively. Here d[R] or d[P] represents
@ Symbol Ais used for larger change At A
..e for average rate. infinitesimally small changes in concentration of Ror P in infinitesimally small
@ Symbol 'd' is used for smaller interval of time, dt. Thus, the average rate approaches the instantaneous rate
change i.e. for instantaneous rate. as At becomes smaller and smaller 1.e.,

(Ae
—| ——
d[R]
=——— and
(2)
|—— a
d{P]
a ee dt 7 /a a |
d|R| dP
Thus, fee = Oe or = dt

In general, if dx represents very small (infinitesimally small) change in

concentration of any species during the very small (infinitesimally small)
change of time, dt, the rate of the reaction may be expressed as :

Rate of reaction = —
dt
If the rate is expressed in terms of concentration of any one of the reactants,
which obviously, keeps on decreasing, the negative sign is used, as already
discussed.
For a general reaction,
aA
+ OB eC +dD
the rate of the reaction is defined as :

1ld[A]_ 1 d{B]
Rate of reaction
-adt 6b dt
1a{C)_1
c dt
aD)
d dt
Let us write the instantaneous rate expressions for some reactions :
(1) 2N,0, —— 4NO, + O,

Rate of reaction =
_1d{N,05] _ 1d[NO,1
2 dt 4 dt

d{Oy]
dt

* In differential calculas, when At becomes very small and approaches zero, the ratio A[R] may be replaced by the derivative,
At

aR] That is,

In general, for change in concentration of any species

Limit Ax _ dx
Af—-+0) At dt

where dx is the infinitesimally small change in concentration corresponding to infinitesimally small change in time, dt.
CHEMICAL KINETICS

(ii) Ho 1, = 2
: | 1 aH
Rate of reaction = —72! _ _ al] _ 2 tH REMEMBER
ie we a -? @ Th te of of a reaction
The rate ti can b be
(vit) N, + 3H, 2NH, expressed in terms of any reactant
d[N_ | 1 a[H, | or product.
. - 27 _ 2
Rate of reaction = — dt 3 dt @ As concentration of reactant
decreases, anegative sign is used
= 1 d{NH,| to express the rate of reaction in
2 dt terms of reactants.
-_ = _ i , | rr @ As concentration of products
(wv) 5Br (aq) + BrO; (aq) + 6H*(aq) 3Br,(aq) + 3H,O(W) : As ae
increases, a positive sign is used
1 d| Br” | d| BrO5 | 1 d| H* | to express the rate of reaction in
Rate of reachon = ——_—>__* — -.._*
__ +. * terms of products.
5 dt dt 6 dt @ Tomake the different expressions
4 d|[Br, | 1 d[H,0]| for the rate of reaction to be
= +-———_ > = + —- equivalent, the rate expressions
3 dt 3 dt are divided by the stoichiometric
EXPERIMENTAL MEASUREMENT OF REACTION RATE coefficients of that reactant or
product in the balanced chemical
In order to measure the rate of a reaction, we have to monitor the Sqineieco
concentration of the reactant (or product) as a function of time. The most
common practice to do so is to withdraw a known small amount of the reaction
mixture (1 to 2 mL) at different intervals of time, cool it down immediately to
nearly O°C to arrest the reaction and then measure the concentration of the
reactant (or the product) by some suitable method. The most common method
used is the titration of the solution against a suitable reagent. However, more
convenient techniques have been developed that can continuously measure
the changes in some physical property which is related to the concentration of
one of the species, at different intervals of time without stopping the reaction.
For example, if a gaseous reaction involves a change in number of molecules,
the pressure of the system changes when the volume and the temperature are
kept constant. By measuring the pressure changes as the reaction proceeds,
we can measure the rate of the reaction. Some other commonly measurable
properties are volume change, change in thermal or electrical conductivity,
change in optical rotation, change in colour, pH or refractive index etc.
Calculation of average rate of reaction
As already studied, the average rate of reaction can be determined by
calculating the change in concentration of a reactant or a product in a given
interval of time. For example, if the concentration of a reactant decreases from
C, to C, in a time from ?, to ¢,, then average rate of the reaction is

Average rate = 2-1

to —h
However, rate of reaction can be conveniently calculated by graphical
method. A graph is plotted between the concentration of a reactant and time
as shown in Fig. 1(a@) ahead.
The average rate of reaction is determined by noting the concentration of
reactants at two different times. In Fig. 1 (a), x, and x, are the concentrations
in the time interval between ¢, and ¢,. Then average rate is :

Average rate of reaction = — Alx] ae aaa

At mde
It is clear that the concentration of reactant decreases with time making
(x, —x,) a negative quantity. Thus, the minus sign makes the rate as a positive
quantity. For example, from Fig. 1(a), it is clear that the concentration of the
reactant at time 10 min is 0.10 mol L“? and it decreases to 0.07 mol L7 at time
20 min. The average rate over this time interval is
 MODERN'S abc + OF CHEMISTRY-All

Average rate = _9.07- 0.10

20-10
= = 0.003 mol L7 min
= Similarly, it can be calculated at other time intervals.
E
£ Calculation of instantaneous rate of reaction
a : : , pais ‘
E Since reaction rate is constantly changing, it is more appropriate to measure
8 the instantaneous rate. The instantaneous rate gives the rate at any specific
Ko instant of time during a chemical reaction. It can be determined graphically
E 10 20 30 40 50 60 70 by plotting concentrations of a reactant or a product against time. Then a
Time (in min) ————> tangent is drawn to the curve at time at which the rate of reaction is to be
(a) Calculation of average rate of reaction.|_ determined. Then the slope of this tangent gives the instantaneous rate of the
i 0,12 reaction at that time. The slope can be determined by extending the tangent
7. 0.10 to intersect both the axes. Fig. 1 (b) shows the variation of the concentration
:a of a reactant with time and tangent at a time corresponding to point P. The
we tangent is shown extended to intersect both the axes. The distance OA along
2 se the ordinates gives the change in concentration, Ax, while the distance along
3 0. the abscissa OB gives the corresponding change in time, Af.
3 0.02 Ax
ck? —}+—_—_—"‘w The ratio — or —— gives the slope of the tangent. Thus,
Oo O° “490 20 30 40 50B 60 70 OB At
Time (in min) —> OA
(6) Calculation of instantaneous rate of Instantaneous rate of reaction = ——
reaction. OB
Fig. 1. Measurement of (a) average Ax
rate and (b) instantaneous rate of a or = AE
reaction from the plot of conc. of a a ;
pales een eee Saeer } For example from Fig. 1(0), it 1s clear that for tangent at point P
corresponding to 20 min, the OA and OB distances are 0.115
Significance of negative and positive) ol I and 52.5 min respectively. The instantaneous rate is
slopes and rates of reactions. 0.115 mol It
It may be noted from Fig. 1 that in the plot of Instantaneous rate
concentration of reactant vs time, the tangent 52.5 min
at any instant of time has a negative slope 0.0022 mol L*! min“!
whereas in the plot of concentration of product The instantaneous rate at any other time can be determined
vs time (Fig. 2), the near has a positive) in a similar manner. It is clear from Fig. 1 that the concentration
slope. Hence, we have : of reactant does not change linearly with time. Consequently, the
a= _ aR]
rs =_ — slope of tangent
slope of the curve and, thus, rate of the reaction keeps on changing
ee dee.

Sale = slope of tangent

Calculation of rate of reaction from plot of concentration
of a product versus time
If concentration of one of the products is plotted against time, a
curve as shown in Fig. 2 is obtained. The average rate of reaction
between times ¢, and f, is calculated by noting the concentrations
[P,] and [P,] corresponding to these times as:
AP _ [P,]-[P,]
_—
1
=
Average rate =
a
=
At Bok
=
—
a
_ AP _ (IFIP Similarly, the rate of reaction at any instant of time, f 1.e.,
—
=) to—t, instantaneous rate is calculated from the slope of the tangent at
Se
‘i
(1.
—
that point as
[ais

=|
=
|
ia dt OB
10 4 20 - 4050. 60 70
Time {in min) ———-?+
Slope of the tangent
Fig. 2. Calculation of average and instantaneous It is clear from the figure that the graph is not linear. This
rate of a reaction from the plot of conc. of products | supports the observation that rate of the reaction is not constant
vs time. ' with time.
CHEMICAL KINETICS
a7]
= SOLVED EXAMPLES
L) Example 1 during different intervals of time.
Express the rate of the following reactions : t(s) C,H,Cl(mol L-4) t(s) C,H,Cl(mol L-4)
(1) 4PH.—— P,.+6H, 0 0.100 300 0.0549
(tt) 2NO,——> 2NO0 +0, 50 0.0905 400 0.0439
interms of the concentration of reactants and products. 100 0.0820 500 0.0835
Solution: 150 0.0741 700 0.0210
(1) For the reaction, 200 0.0671 800 0.017
4PH, ———> P, + 6H,

Rate of reaction = _1d{PHs] us alP | = 1 dH, | Solution : Average rate of reaction in the interval £, to ¢,
can be calculated as:
4 dt dt 6 dt
(it) For the reaction, I[CyHgCl] ,-[CyHgCl] , |
2NO, ——-> 2NO + O,
Att=0 [C,H,Cl] = 0.100 mol L*+,
Rate of reaction = _1aiNOg! Att=50s [C,H,Cl] = 0.0905 mol L*
2 dt
0.0905 — 0.100
r_,(in time interval 0 — 50s) =
_ 1d{NO] 7 d[QOz | (50-0)
~2 dt ~~ dt 1.90 x 10-4 mol Ls?
4 Example2 Att = 50 s [C,H,Cl] = 0.0905 mol L*7,
The concentrations ofareactantR at different times are At t= 100s [C,H,Cl] = 0.0820 mol L™
given below: r,,4n time interval 50 — 100s) = (0.0820 — 0.0905)
t(s) [R] (mol L~) t(s) [R] (mol L-) 100-50
0 160x107 5 80 x 10% 1.70 x 104 mol L? s?

10 40x10° 20 10x 10 Att = 100s [C,H,Cl] = 0.0820 mol L”,

Att = 150s [C,H,Cl] = 0.0741 mol L*
30 25x10"
r_(in time interval 100 — 150s) = —{0-0741— 0.0520)
Calculate the average rate of reaction, R——> Pduring 150-100
different tntervals oftime. = 1.58 mol L's"
Solution : The average rate of reaction can be calculated Att = 150s [C,H,Cl] = 0.0741 mol L+,
Aas: At ¢ = 200s [C,H,Cl] = 0.0671 mol L+
_ _[R}, -[R} 1~ 0.0741)
r,,(in time interval 150-200s) = —{0-067200-15
a At 0
1.40 mol L*? s!
IR,] [Rj #4, # r,, (mol L* s*)
Similarly, we can calculate in other time intervals
x10°% x10° s s
_ (80—160)x 10° = 16x 10° r,,(200 — 300s) = 1.22 x 10*molL*s*
160 80 0 5 r,,(800 — 400s) = 1.10 x 10*molL‘*s*
5—0
40— 80)x10-? r,.400 — 500s) = 1.04 x 10* mol Ls?
80 40 #5 10 pee XP _ 5. 103 r,(000 — 700s) = 0.625 x 10% mol Ls?
105
—3 r_,(700 — 800s) = 0.4 x 10~* mol L* s*
40 10 10 20 eS x10 _ 3103 It is clear that the average rate of reaction decreases
10 from
2.5—10)x107?
10 25 20 30 _ $25—10)x10 _ 9.75 x108 1.90 x 10°* mol L*! s“! to 0.4 x 10°* mol Ls".
30—20 Example4
It can be seen that the average rate decreases from Ammonia and oxygen react at hightemperature as:
16 x 10° to 0.75 x 10°? mol L“! s! during the time interval 0
to 30 s.
4NH.(g) +50,(g) ——> 4NO(g) + 6H,,0 (g)
In an experiment, rate of formation of NO is
1 Example 3 3.6 x 10% mol L-1 s!. Calculate (i) rate of disappear-
From the concentration of C,H,Cl (butyl chloride) at ance ofammonzia, (tt) rate of formation of water.
different times given below, calculate the average rate of (Pb.S.B. 2009, Assam. S.B. 2012)
reaction: Solution : For the reaction,
C,H,Cl + H,0 —~> C,H,OH + HCI 4NH,(g) + 50,(g) —> 4NO(g) + 6H,O @g)
 MODERN'S abc + OF CHEMISTRY-All

Rate = ma
4 dt 5 dt 4 At
1 d{NO] _ 1 d{H,0] AINDD) = 4x Rate
4 dt 6 dt At
(t) Rate of disappearance of ammonia = 4x 6.79 x 10°* mol L“! min"!

Rate of disappearance of NH, = Rate of appearance of NO = 2,72 x 10° mol L" mir.
= 3.6 x 10° mol L? s1. Example 6.
(11) Rate of formation of water Dinitrogen pentoxide decomposes at 475K as:
Rate of formation of H,O = d\H,01
From rate equation, ; N,Os@) —>N,0,@) + 50,(@)
1d{H,0] _ 1d{NO] Ifthe tnitial pressure ts 125 mm and after 30 minutes
6 at 4 dt of the reaction, total pressure of the gaseous mixture 1s
148 mm, calculate the average rate of reaction in
d[H,0] _ —6 x 3.6x 10% =5.4 x 10° mol L's,
(i) atm min Giymol L-? st,
dt 4
Solution: (z) Let p is the decrease in pressure of N,O, in
4 Example 5.
30 minutes then i
The decomposition of N,O in CCL, solution at 318 K has
N,O,(g¢) —> N,O,(g) + 9 O,(g)
been studied by monitoring the concentration of NO,
in the solution. Initially, the concentration of N,O, is Initial pressure 125 mm 0 0
2.33 M and after 184 minutes, it 1s reduced to 2.08 M. 1
After 30 min 125—p p 3p
The reaction takes place according to the equation:
2N,0,—_> 4NO, + O, Total pressure = 125 -p+p+sp = 148
Calculate the average rate of this reaction in terms of
or 125 += p = 148
hours, minutesand seconds. Whatisthe rate ofproduction
of NO, during this period ? or =P = 148-125
= 23 mm
Solution: Rate of reaction
or p= 2x 23mm =46 mm
_ 1AIN,O;] ; ; 46
- 2 At .. Decrease 1n pressure in 30 min = 46 mm = 769 2m

1 (2.08—2.33) mol L7* Average rate of reaction =

46/760 atm
~ 2 184 min 30 min
= 2.02 x 10° atm min“!
= 6.79 x 10-* mol L-! min"!
(it) Applying pV = nRT
Iftime = 184 min = 3.067 hr
or eo ..¥.
Rate =
_ 1(2.08~2.33) mol L™ V RT
Decrease in molar concentration
2 3.067hr _ 46 /760 atm
= 4.07 x 10 mol L-? hr? ~ 0.0821 Latm K~! mol”! x 475K
Iftime = 184 x60=11040s = 0.001552 mol L“?
_1(2.08— 2.33)mol L* .. Average rate of reaction
Rate =
2 11040s 0.001552
= 8.62x 10-7 mol L's"!
~ 30x60
1.13 x 10° mol Ls"!

1. How can we express the rates of following reactions in terms of concentration of

reactants and products ?
= Answers to Practice Problems — (i)
20, —— 30,
2. (4) 1.2 x 104 mol L's. (11) 2NO+Br, =—— 2NOBr
(iz) 3.6 x 10-* mol L? st. (iit) 2ICl(g) + Hg) ——> _ L(g) + 2HCl(g)
2. For the reaction,
Hints & Solutions on page 68
N,+3H, ———> 2NH,
CHEMICAL KINETICS

the rate of reaction measured as ALNHs | was found to be 2.4 x 10-* mol L-?! st.
fl
Calculate the rate of reaction expressed in terms of (i) N, and (iz) H,.
(Pb.S.B.2011)
3. For the reaction :
2N,0,(g¢) ——> 4NO, (g) + O, (g),
the rate of formation of NO, (g)1s 2.8 10° Ms. Calculate the rate of disappearance
of N,O,(g). (A.LS.B. 2018)
4, Areaction, 3X —-> 2Y + Z proceeds in a closed vessel. The rate of disappearance
of X, — A[X]/At is found to be 0.072 mol L s"!. Calculate

ALY] end AZ]

b.8.B. 2009
At At - j

5. Consider the reaction:

ANO,(g) + O,(g¢) ——> 2N,0,(g¢)
In an experiment, rate of reaction of O, is 0.024 mol Ls. Calculate (z) the rate = Answers to Practice Problems =
disappearance of NO, and (iz) rate of formation of N,O.. 3 pete 1S ee
6. The concentration of a reactant changes from 0.03 M to 0.02 M in 25 minutes.
4 . 0.048, 0.024.
Calculate the average rate of reaction using units of time both in minutes and
seconds. +)» (1) 0.096 (zz) 0.048.
7. For an elementary reaction : 6 2 4s 1 mol bmn
2A +B—=+3C
6.6 x 10° mol L7! s1.
the rate of appearance of C at time f is 1.3 x 10-* mol Ls". Calculate at this
. (t) 4.33 x 10° mol Ls
time
(i) rateofreaction (ii) rate of disappearance of A. (iz} 8.67 x 107 mol Ls.
(C_B.S.E. Sample Paper 2008) Hints & Solutions on page 68

FACTORS INFLUENCING RATES OF CHEMICAL REACTIONS

There are a number of factors which influence the rate of a reaction. Some
of the important factors are :
1. Concentration of the reacting species.
Temperature of the system.
Nature of the reactants and products.
Presence of a catalyst.
Surface area.
bh
©
Fe
oo Exposure to radiation.
Let us briefly discuss these factors.

1. Concentration of the reactants

The rate of a reaction ts directly proportional to the concentration of the
reactants. If the concentration of the reactants is large, the rate of reaction is
large. As the concentration of the reactants decreases, the rate of the reaction
also decreases. For example, the rate of burning of wood depends upon the
concentration of oxygen. A piece of wood burns slowly in air (containing about
20% oxygen) but burns rapidly in pure oxygen (i.e., 100% oxygen) because the
concentration of oxygen 1n air is less (only about 1/5th of the concentration
of pure oxygen).

2. Temperature of the system

In general, an increase in the temperature tncreases the rate of almost all
chemical reactions. On the other hand, a decrease in temperature decreases the
rate. This effect is observed for exothermic as well as for endothermic reactions.
A general approximate rule for the effect of temperature on reaction rates
is that the reaction rate for most of the chemical reactions becomes almost
double, for every 10°C rise in temperature.
 MODERN'S abc + OF CHEMISTRY-All

3. Nature of reactants and the products

R U Curious... S32)
Rates of reactions are influenced by the nature of reactants and products.
A chemical reaction involves the breaking of old bonds and formation of new
) Pieces of wood burn faster bonds. The reactivity of a substance can, therefore, be related to the ease with
than a log of wood of the which the specific bonds are broken or formed and the number of such bonds
same mass. involved. For example, the oxidation of nitric oxide to nitrogen dioxide takes
» The total surface area of the place fairly rapidly while oxidation of carbon monoxide to carbon dioxide
wooden pieces is larger than takes place slowly :
log of wood of the same mass.
Greater the surface area, faster
2NO + O, ——> 2NO; (Fast)
is the reaction. 2cO + O, ——>/a2Go, (Slow)
In these two reactions, the reacting species appear to be very similar to
The reactions which are initiated each other, still they differ in reaction rates.
by the absorption of radiation 4, Presence of catalyst
are called photochemical A catalyst is a substance which influences the rate of a reaction without
reactions. undergoing any chemical change itself. It has been observed that many reactions
are made to proceed at an increased rate by the presence of certain catalysts.
For example, a mixture of H, and O, does not react at room temperature.
However, in the presence of a catalyst such as finely divided platinum, the
R U Curious... DN reaction becomes quite vigorous.
5. Surface area
1 Generally ultraviolet or
The larger the surface area of the reactants, the faster is rate of reaction. It has
visible radiations are
been observed that if one of the reactants is a solid, then the rate of the reaction
used for carrying out
depends upon the state of sub-division of the solid. This fact is supported by the
photochemical reactions. general observation that finely divided solids react faster than massive substances.
But infra-red radiations For example, a log of wood burns slowly but if it is cut into small wooden chips,
cannot be used. the burning takes place rapidly. This is due to the fact that the total surface area
This is because the photons of of the smaller particles is greater than that of large particles and this permits
ultraviolet or visible radiations more molecules of the reactants to come in contact and form products.
possess energies approximately 6. Exposure to radiation
of the order of 420 kJ per In some cases, the rate of a chemical reaction is considerably increased by the
mol which is comparable to use of certain radiations. The photons of these radiations having frequencies (v)
most of the bond energies. possess sufficient energies (K = fv) to break certain bonds in reactants.
Therefore, ultraviolet or For example, reaction of hydrogen and chlorine takes place very slowly in the absence
visible radiation energies are of light. However, in the presence of light, the reaction takes place very rapidly.
capable of breaking the bonds. H, + Cl, —#**.. 2HCI
On the other hand, infra-red
radiations are generally not DEPENDENCE OF REACTION RATES ON CONCENTRATION : RATE
used because their photons LAW EXPRESSION
possess energy of the order of When a chemical reaction proceeds, the reactants get converted into the
60 kJ per mol which is quite products. As a result, the concentration of reactants decreases while that of
less for breaking the bonds. products increases. The general behaviour of the concentration of the reactants
and the products is shown in Fig. 3.
From the figure, the following observations can be made :
Increasing concentration (t) In the beginning of the reaction (i.e., when time = 0), only reactants
of products are present so that the concentration of the products is zero. As the reaction
progresses, the concentration of the reactants decreases while the concentration
of the products increases.
‘\ ¢ Decreasing concentration (it) The change in concentration of the various species takes place rapidly
‘ of reactants
in the beginning but very slowly as the reaction approaches the final stage.
From the above observations, it can be concluded that at the start of the
reaction, the rate of the reaction is large and it decreases with passage of
L-1)——p>
Concentration(mo!
Time (Min) ie time. This means that the rate of a reaction is directly proportional to the
concentration of the reactants. In the gas phase reaction, the Increase in
Fig. 3. The concentration of reac- pressure of the reactant gases increases the rate of the reaction. With increase
tants decreases while concentration in pressure, the number of molecules per unit volume increases and, therefore,
of products increases with time. rate of reaction increases.
CHEMICAL KINETICS

Law of Mass Action

The quantitative relationship between the rate of a reaction and the
molar concentration of the reacting substances was given by two Norwegian
chemists, Guldberg and Waage in 1867. This relationship is known as law
of mass action. According to this law :
at a given temperature the rate of a chemical reaction is directly
proportional to the product of the molar concentrations of the
reactants.
The molar concentration of the reactant is also called active mass.
Let us consider a simple reaction of the type
A + B——> 2AB
According to law of mass action, rate of the reaction may be written as :
Rate = & [A][B]
where [A] and [B] are the molar concentrations of reactants, k is constant of
proportionality and is called rate constant. The rate constant is also called
velocity constant and is a measure of rate of the reaction.
Now, if concentration of each of the reactants involved in the reaction is unity,
i.e. [A] = [B] = 1, then substituting these values in above expression, we get
Rate of reaction = Rx1x1=k
Thus, the rate constant of a reaction at a given temperature may be
defined as
rate of the reaction when the molar concentration of each of the
reactants is unity.
That is why the rate constant is also called specific reaction rate.
Characteristics of Rate Constant
Some of the characteristics of rate constant are :
(.) Rate constant ts a measure of the rate of the reaction. Larger the value
of k, faster is the reaction. Similarly, smaller value of k indicates
slow reaction.
(it) Different reactions have different values of Rk.
(iit) Ata fixed temperature, the value of k is constant and is characteristic
of the reaction. However, it changes with temperature.
(iv) For a particular reaction, the value of rate constant is independent
of concentration.
Differences between Rate of Reaction and Reaction Rate Constant
Let us sum up the differences between rate of reaction and reaction rate
constant.
Rate of reaction Reaction rate constant

1. It is the speed with which reactants | It is the proportionality constant in

are converted into products. It is] the rate law and is defined as the
measured as the rate of decrease in | rate of reaction when the concentra-
concentration of reactants or increase | tion of the reactants is unity.
in concentration of products with time.
2. It depends upon the initial concentra-|It is independent of the initial
tion of the reactants. concentration of the reactants.
3. Its units are always mol L“! time"!. |Its units depends upon the order
of reaction.

Rate Law Expression

To express the rate of a reaction as a function of the concentration of the
reactants, it is essential to measure experimentally the actual dependence of
the concentration of the reacting species. For example, consider the reaction
between NO, and F, to form NO,F :
2NO,(g) + Fg) ——> 2NO,F(g)
 MODERN'S abc + OF CHEMISTRY-All

Experimental observations reveal that the rate of the reaction 1s proportional

to the product of the concentrations of nitrogen peroxide and fluorine. Therefore,
the rate of the reaction may be expressed as
Rate = 2 [NO,]IF,]
This expression is called rate law or rate equation.
Similarly, consider the decomposition of dinitrogen pentoxide :
2N,0.(g¢) ———> 4NO,(g) + O,@)
Experimental studies have shown that the rate of this reaction is proportional
to the [N,O.] and not to [W,,0.1*. Therefore, the rate law is :
Rate = k [N,O.]
This expression is called rate law or rate equation.
Consider a general reaction,
aA + 6B + eC ——> Products
where A, Band C are the reactants and a, 0 andc are stoichiometric coefficients
of the balanced equation.
From the kinetic study of the reaction, the dependence of the concentration
of reactants on the rate of the reaction have been found to be
Rate = & [A]? [B]? [C]” ...(3)
where p, g and r are constant numbers or the powers of the concentrations of
the reactants A, B and C respectively on which the rate of the reaction depends.
It may be noted that the values of p, g andr are determined experimentally
and may or may not be equal to a, b and ¢ coefficients in the reaction. The
expression (3) is the rate law or rate equation. It may be defined as
the mathematical expression which denotes the rate of a reaction
in terms of molar concentrations of reactants with each term raised
fo some power which may or may not be same as the stoichiometric
coefficient of the reacting species in a balanced chemical equation.
The power of concentration terms corresponds to experimentally observed
rate of reaction.

R U Curious... §

Differences between rate law expression and law of mass action

The rate law gives the experimentally observed dependence of rate on the concentration of reactants.
The powers of concentrations of reactants in rate law expression may or may not be same as the coefficients of
reactants in balanced chemical equation. On the other hand, the law of mass action gives the rate expression on
the basis of stoichiometry of overall balanced equation for the reaction :
Consider for example, a general reaction :
aA + bB ——> cC + dD
where a, b, c and d are stoichiometric coefficients.
According to law of mass action:
Rate = k [A]® [B]?
The rate law expression is
Rate = & [A]* [Bl’
where x and y are experimentally determined values. These may or may not be equal to the stoichiometric
coefficients (a and b) of the reactants.
For example, for the reaction,
2NO,(g) + F,(¢) ———> 2NO,F
rate law expression
Rate = & [NO,] [F,] and
rate expression according to law of mass action
[erie She (IeLO = Me
Similarly, for the reaction :
5Br- (aq) + BrO, (aq) + 6H*(aqg) ——_> 3Br,(aq) + 3H,O()
The experimentally observed rate law is
Rate — 2 Br) (eres ae
As evident, the rate law does not correspond to stoichiometric coefficients in the balanced chemical equations.
Thus, rate law for any reaction cannot be predicted by merely looking at the balanced chemical
equation i.e., theoretically but must be determined experimentally.
CHEMICAL KINETICS

It may be noted that generally the rate law expressions are not simple.
These may differ even for the same reaction depending upon the conditions of
the reaction. For example, for the reaction :
H,(g) + L(g) ——— 2HI)
Rate = R [H,] el

However, for a similar type of reaction :

H, (2) + Br, i) 2HBr
The rate expression is
k, [H, [Br]?
Rate =
1+, ({HBr]/[Brz }}
Here k, and k, are constants which depend upon the temperature of the
reaction. It can be seen that in the absence of HBr, the initial rate of reaction
may be given as :
Rate = , [H,] [Br,]”
Rate law expressions for some other reactions are :
CE eet Ot ae
Rate = k [CHCI,] [Cl,]”
CH,COOC,H,. + H,O ——__> CH,COOH + C, HAI
Rate = k [CH,COOC,H,] [H,O]°
The rate expression becomes more complicated especially when a number
of parallel reactions take place simultaneously. It may have more than one term
on the right hand side.

ORDER OF A REACTION
The dependence of the reaction rates on concentration may be expressed
in terms of order of a reaction. To calculate the order of a reaction, we must
carry out the experiments to find out the dependence of reaction rate on the
concentration of each individual reactant at a given temperature. Moreover,
the concentration dependence of various reactants, as we have seen, is given
by the rate law. Thus, the order of a reaction is defined as :
the sum of the powers to which the concentration terms are raised
in the rate law equation to express the observed rate of the reaction.
The power of the concentration of a particular reactant in the rate law is
called the order of the reaction with respect to that reactant.
Thus, if the rate of a reaction,
aA + bB + eC ——> Products
is given by the rate law as :
Rate = — - = R{A} [B]? [C]’
then, the order of the reaction, 7, is :
m=pt+gqtr
where p, g and r are the orders with respect to individual reactants and overall
order of the reaction is sum of these exponents, i.e., p +g +7.
When n = 1, the reaction is said to be first order reaction, if nm = 2, the
reaction is said to be second order reaction and so on.
Some Examples of Reactions of Different Orders
Some common examples of reactions of different orders are given below :
(a) Reactions of first order
(1) Decomposition of nitrogen pentoxide (N,O,)

N,O, (g) ——> 2NO, (g) + 5 2 (g)

Rate = & [N,O,]
4 MODERN'S abc + OF CHEMISTRY-All

(11) Decomposition of ammonium nitrite in aqueous solution

NH, NO, ——> N, + 2H,O
Rate = 2k [NH, NO,]
(tit) Decomposition of H,O, in the presence of I" ions
10; —* + HjO+ 50 =
Rate = k [H,0,]
(tv) Decomposition of SO,Cl, :
SsO,CL —— 50, 7201
Rate = k [SO,Cl,]
(b) Reactions of second order
(4) Decomposition of nitrogen peroxide
2NO, ——~> 2NO+0,
Rate = k [NO,]?
(11) Reaction between H, and I, to give HI
H+l, Ae— eo
Rate = 2 [H,] [1,]
(tit) Reaction between NO and O, :
NO /@= ~f NO, +0,
Rate = k [NO][O,]
(c) Reactions of third order
(i) Reaction between nitric oxide and oxygen
2NO +O, —— > 2NO,
Rate = 2 [NO]? [O,]
(11) Reaction between nitric oxide and Cl,
2NO + Cl, ——~+> 2NOCI
Rate = & [NO]? [Cl,]
(d) Reactions of fractional order
(i) Decomposition of acetaldehyde is a fractional order reaction
CH,CHO ~———+ CH,+CO
Rate = k [CH,CHO]*” ; Order = 3/2 or 1.5
(it) The reaction between hydrogen and bromine to form hydrogen
bromide is a fractional order reaction
H,(g) + Br.(g) ———> 2HBr
Rate = (H,] [Br,]"?; Order = 145 = 15 or 15
(zit) Dissociation of COCI, :
cocl, ——> CO+Cl,
Rate = & [COCI,]®2, Order = 2
(e) Zero order reaction a
A number of zero order reactions are known in which the rate of the
reaction is independent of the concentration of the reactants. For example,
the decomposition of ammonia at the surface of metals like gold, platinum
etc., 1s a zero order reaction.
Platinum
2NH; —yigo. 7” No + 3H
It has been observed that the rate of the reaction is independent of the
concentration of ammonia, i.e.,
Rate = = =p [NH,]° or Rate=k
Order = 0
In this reaction, platinum metal acts as a catalyst. At sufficiently
high pressure of ammonia, the metal surface gets fully saturated with gas
molecules. On further increasing the concentration of NH,, the amount of
NH, on the surface of the catalyst does not change. Therefore, the rate of
CHEMICAL KINETICS 4/15 ee

reaction becomes independent of the concentration and hence becomes zero

order reaction. Similarly, thermal decomposition of HI on gold surface is also
a zero order reaction :
Gold
2HI ae «Cz + I,
Many enzyme catalysed reactions and photochemical reactions (e.g.,
formation of HC] from H, and Cl,) are also examples of zero order reactions.
Units of reaction rate constants
Units of rate. The rate is the change 1n concentration with time. Therefore,
the rate of reaction 1s expressed by concentration units divided by time units.
If the concentrations are expressed in moles/litre and time in seconds, then
the units for rate of a reaction are mol litre: s7 as :
Concentration 7 molL*
Rate = = mol L7! s1,
Time
Units of rate constant. The units of rate constants of different orders
are different. This can be easily illustrated as :
(4) Units of rate constant for zero order reaction
For zero order reaction, rate may be expressed as
Rate = & [AJ® or=k
molL +
=i
5

or k = mol Ls?
The units of rate constant of zero order reaction are mol LL s~1,
(41) Units of rate constant for first order reaction
For first order reaction, rate may be expressed as :
Rate = & [A]
=
mol” | % (mol 1)
S

or k=sl
The units of rate constant of first order reaction are s™.
(zit) Units of rate constant for second order reaction
For second order reaction, the rate may be expressed as
Rate = R[A]?
=
moll _ % (mol L?
Ss

1 L. mol? s1.
molL‘s
The units of rate constant for second order reaction are L mol s“!.
(jv) Units of rate constant for third order reaction
For third order reaction, rate may be expressed as : In general, the units for rate
Rate = [A]® constant for the reaction of nth
a,| order are :
ma = k (mol L- Rate = R[A]”
S
=
or c= = L? mol? s meek (mol L™)*
mol* L>*s Ss
or k =(molL-5!"' =,
The units of rate constant for third order reaction are L? mol? s™.
Units of Rate Constants for Gaseous Reactions
In case of gaseous reactions, the concentrations are expressed in terms of
pressure in the units of atmosphere. Therefore, the rate has the units of atm
per second. Thus, the unit of different rate constants would be :
 MODERN'S abc + OF CHEMISTRY-All

(1) Zero order reaction : atm s7!

(11) First order reaction se
(tii) Second order reaction : atm! s"!
(tv) Third order reaction - atm s7! so on.
The units of rate constants for some reactions are summed up below :

Units
Reaction Solution Gaseous reactions

Zero order reaction mol L-1 s-1 atm st

First order reaction sl gl
In general, jor the gaseous reaction Second order reaction L molt s7 atm?! st
of nth order, the units of rate Third order reaction L? mol? st atm st
constant are (atm)! s 1 nth order (mol L-)! s7 (atm)! st

MOLECULARITY OF A REACTION
According to ‘collision theory, for a chemical reaction to occur, the reacting
molecules must collide with each other.
The number of reacting species (molecules, atoms or tons) which
collide simultaneously to bring about a chemical reaction is called
molecularity of a reaction.
If a reaction involves the decomposition of only a single species, the
molecularity is one or it is called unimolecular reaction. For example,
the decomposition of hydrogen peroxide involves single species which
undergoes the change to form the products. Hence, it is a unimolecular
reaction.
mO@s— H,O + 1 O, unimolecular reaction

Decomposition of ammonium nitrite is also unimolecular reaction because

it involves only one reacting species :
NH,NO, ——\> N, + 2H,0
Similarly, if the reaction involves the collision of two species, it is
bimolecular and if three species take part in a collision leading to the
formation of the products, it is called trimolecular and so on. The examples
of bimolecular and trimolecular reactions are given below :
(i) Dissociation of hydrogen iodide is a bimolecular reaction because two
molecules collide to bring about the reaction.
2HI(g) —- Hg) + L©@ bimolecular reaction
(11) Combination of NO and O, is a bimolecular reaction :
NO) + O,(g) ——>NO,g) + O,)
(iit) The reaction of nitric oxide and oxygen is a trimolecular reaction
because it involves collision of three reacting molecules.
2NO(g) + O,(g) ——~> 2NO,(g) trimolecular reaction
In a similar way, we can expect reactions which involve the collisions of four
or more molecules. However, it has been observed that reactions involving three
or more molecules are uncommon. The reason for this is that the occurrence of
such reactions requires the simultaneous collision of three or more than three
molecules. In other words, simultaneous collision of three molecules means that
the third molecule must collide the other two molecules at the same time when
they are in the process of collision. The chances of the occurrence of such
collisions are very small. On this basis, we can say that reactions involving
three or more than three reacting particles should be slow. However, it has
been observed that some reactions involving more than three molecules are
quite fast. For example, consider the reaction of bromide ions with bromate
ions in the presence of an acid :
5Br- (aq) + BrO, (aq) + 6H* (aq) ——-> 3Br, (aq) + 3H,O (J)
CHEMICAL KINETICS

The experimentally measured rate law for this reaction is given as :

Rate = k[Br] [BrO,] [H*]?
Therefore, this rate is first order with respect to Br’ and BrO, ion and
second order with respect to H* ions and the overall order of the reaction is
1+1+2=4. However, from the above equation, it is clear that if the reaction
were to take place in a single step, the 12 particles (5 Br ions, 1 BrO, ion
and 6 H* ions) would have to collide simultaneously.
But chances of such events are extremely small, so much so that a reaction
which takes place by such collision will not occur at all. However, the reaction
is found to be quite fast. This means that even though the balanced equation
involves a large number of molecules, yet the reaction does not proceed by
simultaneous collision of all these reacting particles. In other words, it involves
simultaneous collision of two or at the most three molecules. Such type of
reactions which take place through a sequence of two or more consecutive steps
are called complex reactions. The detailed description of various steps by which
reactants change into the products is called mechanism of the reaction. The
steps which contribute to the overall reaction are called elementary processes.
Mechanism and Rate Law
In case of multi-step reactions, since each elementary step involves quite different
type of reactions, so each step will occur at its own distinctive rate. Some of the
steps will be very fast while others will be slow. If one step takes place much more
slowly then all other steps, it will definitely control the overall reaction rate. This
means that all the steps have to wait for the occurrence of this step and the rate of
the reaction cannot be less than the rate of this slowest step. But once this slowest
step has occurred, the other steps will take place to form the products.
Slowest step as rate determining
Thus, the rate of the reaction is step
the rate of the reaction which is determined by the slowest step in
the sequence. The slowest step is called rate determining step in the This can be easily understood
proposed mechanism. in terms of a simple analogy.
Let us consider reaction between NO, and F, to form NO,F : Suppose a cycle factory manu-
2NO,(g) + Fg) ——> 2NO,F(@g) factures different parts like
handles, paddles, rims, seats,
The experimental observations reveal that the rate of the reaction is
brakes parts etc. at the rate of
proportional to the product of the concentrations of nitrogen peroxide and
500, 600, 50, 800, 400 pieces per
fluorine. This indicates that the rate determining step in the mechanism of this
day respectively. The overall rate
reaction must be the reaction between NO, and F, only. Keeping this in mind,
of cycle production cannot be more
a mechanism of this reaction may be suggested as :
than 50 per day, which depends
NO, + F, ym
/, + iF Slow step upon the slowest working section
NO, + F ~~[—_ me YO.F Fast step of the factory (i.e., production of
rims).
2NO, + F,»——-, 2NO,F Net reaction
Although the above reaction proceeds through two steps but the rate of the
overall reaction is determined by the first step which is the slower of the two
steps. Each of the steps is called an elementary process. Elementary processes It may be noted that the
are almost always either unimolecular or bimolecular. Occassionally, they may mechanism of a reaction may
be trimolecular. involve the formation of certain
All the steps taken together give the mechanism of the reaction. The sum molecules in one step which are
of the equations for the separate consecutive steps give the overall reaction. later used up in the subsequent
Accordingly, the experimentally observed rate of the reaction is given by
steps. These molecules are
the expression :
dx termed intermediates and
Rate = — riko R[NO,] [FI donot appear in the overall
This is the rate law for the reaction. reaction.
Let us consider some more examples :
(i) Reaction between NO, and CO to form CO, and NO
NO,(g) + CO@) ——> NOw) + CO,g)
The experimental observations reveal that the rate of the reaction is
proportional to the square of the concentration of nitrogen peroxide. This
 MODERN'S abc + OF CHEMISTRY-All

indicates that the rate determining step in the mechanism of this reaction must
be independent of the concentration of CO. Keeping this in mind, a mechanism
of the reaction may be suggested as :
Step 1. NO, + NO, ——> NO + NO, _ Slow step
Step 2. NO, + CO ——> CO, + NO, Fast step
NO, + COQ —» CO, + NO Net reaction
Although the above reaction proceeds through two steps but the rate of the
overall reaction is determined by the first step which is the slower of the steps.
Accordingly, the experimentally observed rate of the reaction is given by the
expression :
Rate = k[NO,]?
This is the rate law for the reaction.
(ii) Thermal decomposition of dinitrogen pentoxide,
2N,0.(g) —>—> 4NO,(g) + O,&)
It has been found experimentally that
Rate of reaction = k [N,O,].
If the reaction were to take place by the collisions of two N,O, molecules
as Indicated by the balanced equation, it would be a second order reaction as
Rate = k[N,O,]*
But the observed rate law suggests that it is a first order reaction.
This means that the reaction is a complex reaction and proceeds by two or
more successive steps.
The probable mechanism of the reaction is as follows :
Step 1. Mas. =——», INO, - INO. Slow
Step 2. N,O. + NO. ——> »sNO, + UO, Fast
2N,0, ——> 4NO, + O,
Hence, the above reaction is unimolecular reaction or reaction of first order.
(iii) Reaction of NO and H, as:
2NO(g) + 2Hg) —— N,fg) + 2H,0f%)
It has been observed experimentally that
Rate of reaction = k[NO]? [H,]
The rate law expression suggests that it is a complex reaction and is
believed to proceed by two step mechanism in which the first step is the rate
determining step as :
Step 1. 2NOw) + H,(g) —— Ng) + H,0, Slow
Step 2.H,0.(g) + H,(g) —— > 2H,0 (g) Fast
Since the first step is slow and rate determining, the rate law is
The rate of a reaction may depend Rate = k[NO]? [H,]
not only on the reactants but also (jv) Reaction of decomposition of hypochlorite (C1O-)
on the substances present as
3sClO- ——> ClO, + 2CI
catalyst. For example, the
decomposition of hydrogen The various steps are :
peroxide is catalysed by I ion ClO7 + ClO — > ClO, + Cr Slow
inan alkaline medium and the clo, + ClO” ——> ClO, + Cr Fast
reaction rate depends upon the
The first step is slow and hence rate determining. Thus, the rate law is
concentration of both H,O,andT-.
Rate = k [ClO-}?
(v) Reaction of decomposition of hydrogen peroxide
The decomposition of HO, is catalysed by iodide ion in an alkaline medium:
2H,0, 7
alkaline medium
2H,O + O,
CHEMICAL KINETICS

It has been found experimentally that

Rate = Rk [H,0,] [I-]
The reaction is first order with respect to both H,O, and I. This means
that the reaction is a complex reaction and proceeds by two or more successive
steps. The probable mechanism for the reaction is as :
Ho, + Fs’ .HO + IO
H,O, + Io _fst., HO + FTF + O,
Both the steps are bimolecular elementary reactions. Species IO~ is called
as an intermediate because it is formed during the course of the reaction but
not in the overall balanced equation. Since the first step is slow, it is rate
determining. Thus, the rate of formation of intermediate (IO-) will determine
the rate of this reaction.
Let us sum up the important points of distinction between order and
molecularity.
Molecularity
. Molecularity is the number of reacting species undergoing| Order is the sum of the powers of the concentration terms
simultaneous collision in the elementary or simple reaction. in the rate law expression.
. Molecularity is applicable only for elementary reactions. For | Orderis applicableto elementary as well as complex reactions.
complex reactions, molecularity has no meaning.
. Molecularity is a theoretical concept. Order of a reaction is determined experimentally.
. Molecularity has whole number values only z.e., 1, 2, 3, etc. It} Order of a reaction need not be a whole number 2.e., 1t can
cannot be a non-integer. have fractional values also.
. Molecularity of a reaction cannot be zero. Order of a reaction can be zero.
. For complex reactions, molecularity is given for elementary steps. |For complex reactions, order is given by slowest step.
Molecularity of the slowest step is same as the order of the reaction.

= SOLVED EXAMPLES &

4 Example7 Solution :
(a) Calculate the overall order ofa reaction, which has (a) For the reaction,
the rate expression : A+B ——> AB
(i) Rate=k[Af!'’27[BP” (ii) Rate=k[AP'? [BP
Rate = &[A] [B]
(b) The reaction A+B—>C has zero order. aa
Write rate equation. N .C.E.R.T, mol dm™ = % (mol dm-*) (mol dm)
min
Solution:
(a) (1) Rate = [A]? [B]?? or k = (mol dm“)* (min) = mol" dm? min“.
(6) For zero order reaction, the rate is independent of the
Order of reaction = f BaF concentration :
bo
| 2
i.é., second order. Rate R
(ii) Rate = & [A]? [B]*+ LE
. Unitsofkare: R Rate = = =molL! s1,
Order of reaction = °+(—D= ;
Example 9
i.e., half order.
(6) For zero order reaction, Write the units of the rate constant for a nth order
A+B——sC reaction. Deduce from this the units of rate constant
Rate equation is : for a (i) half or der reaction (11) 3/2th order reaction
Rate = R[A]® [B]® (tit) third order reaction.
Examples Solution : The units of the rate constant for nth order
reaction are:
(a) Ifconcentrations of Aand B are expressed in terms
Rate = R[A]*
of mol dm~ and time in min, calculate the units for the
rate constant for the following reaction: molL!
= k[mol L-!]" or & = (mol L7)'* ="!
A+B ——> AB
(6b) What are the units for a zero order reaction ?
(concentrations are expressed in mol L~! and time in : 1 .
(1) n= —, the units are: mol!” L151,
seconds).
 MODERN'S abc + OF CHEMISTRY-All

Example 13
i) n= ~Mi cctenneesi aie A reaction is second order with respect toa reactant. How
(iii) n=38, the units are: mol L?s1. is the rate of reaction affected ifthe concentration of the
reactant 1s
LY Example 10
(1) doubled
Identify the reaction order from each of the following
(it) reduced to half ?
rate constants.
Solution : Rate = R[A]?
Gh=2310" Lima's
(D.S.B. 2009, A._S.B. 2012, Hr. S.B.2013)
(ie =o e100 Ss
(4) When concentration of reactant is doubled, the rate
Solution : Order of a reaction can be predicted from the becomes 4 times.
units of rate constant. (it) When concentration is reduced to 1/2, the rate becomes
() The unit of second order rate constant is L mol! s and 1/4 times.
therefore, k = 2.3 x 10° L mol s* represents a second order
Example 14
reaction.
The decomposition of hydrogen peroxide inthe presence
(it) The unit of a first order rate constant is s—! and therefore,
k =3.2 x 10*s7 represents a first order reaction. of iodide ion has been found to be first order in H,O,:

LY Example 11. 2H,0,(aq) 1‘ , 2H,O() + O,@)

The rate law fora reaction of A, B and C has been found The rate constant has been found to be 1.01 x 10° min-t.
to berate =k[A][B][C]*. How would the rate of reaction Calculate the rate of the reaction, when
change when (a) [H,O,] = 0.4 mol L™ (6) [H,O,] = 0.15 mol L™
(i) concentration of Cis doubled (c) What concentration of [H,O,/ would give rate of
(it) concentration of Ais halved 1.12 x 107 mol L~ min-1? (Pb.S.B. 2011, 20185)
(111) concentration of both B and C are doubled Solution : The reaction is of first order in H,O, so that
(tv) concentration of each of A, B and C are tripled ? Rate = k[H,0,]
Solution: Suppose the initial concentrations are: (a) k = 1.01 x 10°? min’, [H,O,] = 0.4 mol L*
[A] =a mol L“!, [B]= 6 mol L“4, [C] =c mol L"! ”. Rate = (1.01 x 10 min“!) x (0.4 mol L7)
Rate = k abc? = 4,04 x 10° mol L min.
(6) When [H,O,] = 0.15 mol L*
(1) New [C] = 2c
Rate = (1.01 x 10°? min“) x (0.15 mol L“)
Rate =k ab(2c)? = 4kabc? ”, 4times
= 15x10? mol L' mint.
(ii) New [A] = ©2 (c) To obtain concentration of H,O, when rate
1.12 x 107 min L7! min"!
Rate = k 5 oe ~ :kabe2 ~—S . 1/2 times Rate 1.12x 10-? mol L! min™!
[H,0,] = k=: 1,01x 10-? min!
(tit) New [B] = 20, [C] = 2c
Rate = kxax 2bx(2c)= 8 kabc? .. 8 times = 1.11 mol Lt.
(iv) New [A] = 3a, [B] =30, [C] =3ce Example 15
Rate = k x 3a x 3b x (3c)? = 81 kabec? ”. 81 times For the reaction
L) Example 12. 2A+B+C— >A, B+C
The rate of a gaseous reaction becomes halfwhen volume The rate law has been found to be
of the vesselis dowbled. Whatis the order ofthe reaction ? Rate = k[A] [BF with k = 2.0 x 10° mol L? s-1
Solution: For the gaseous reaction; A——> Products For this reaction, determine the initial rate of reaction
Suppose the order of reaction is 72, so that with [A] = 0.1 mol L-!, [B] = 0.2 mol L-!, [C] = 0.8
rate = k[A]" mol L-1. Determine the rate after 0.04 mol L~ of A has
or r= k(a)* AL) been reacted.
When volume of vessel becomes double, molar concentration Solution : Rate law is:
becomes half. Since rate becomes half, therefore, Rate = &[A][B]?
where k=20x10* mol? L?s1
a HS) .(ZL) Initial concentration,
2 2
[A] = 0.1 mol L-!, [B] = 0.2 mol L~!, [C] = 0.8 mol L“!
Dividing eq. (1) by eq. (iz), 2 = 2” ”. Rate = (2.0 x 10° mol L? s*) (0.1 mol L) (0.2 mol L“*)”
or = 2 =8x10°%molL?s!
nm=1 Conc. of A after 0.04 mol L~! of A has been reacted
Order = 1 [A] = 0.1 — 0.04 = 0.06 mol L-1
CHEMICAL KINETICS

Now, we know that when 2 moles of A are consumed then Solution: Before the volume of the reaction vesselis changed,
one mole of B gets consumed. Therefore, moles of B consumed the rate of reaction is expressed as :
when 0.04 moles of A have been consumed = 0.04 x 42=0.02 mole
rate = k[NO}]?[0O,] re
[B] = 0.2 — 0.02 = 0.18 mol L“!
Rate = (2.0 x 10° mol? L? s”) x (0.06 mol L) x , i :
(0.18 mol L?)? When the volume 1s reduced to — , the concentration of each
3.89 x 10° mol L? s1. reactant is increased by 3 times. Therefore, we may write
Example 16 rate’ = k[3NO}?[80,] ltd)
Following reaction takes place in one step: = 27 k[NO}?[0,]
2NO(g) + O,(g) ——> 2NO,(g)
How will the rate of the above reaction change if the rate’ 97
volume of the reaction vessel ts diminished to one-third rate
of its original volume ? Will there be any change in the . Rate will become 27 times.
order of the reaction with reduced volume ? It is clear from eqn. (ii) that the order of reaction remains
(A.L.S.B. 2004) the same.

=rca ibe
8. The rate of formation of a second order dimerisation reaction is 5.8 x 10-®
mol L7! s-! at 0.01 mol L~! monomer concentration. Calculate the rate constant.
9. The gas phase decomposition of COCI,,
COCL,(g) —— > CO(g)+ CL)
follows the rate law : rate = k[COCI,]*”
What are the units of its rate constant ?
10. Identify the reaction order for each of the following rate constants :
(a) k=7.6 x 10* mol liter+ s+ (6) R=5.6 x 107 mol litres?
(c) R=7.1x10°s? (dq) R=1.25 x 107? mol litre? s!
(e—) R=5.0x10°% atm'!s?
11. For a reaction : A + B ——> Products,
the rate is given as &[A]* [B]*. What are the units of its rate constant ?
12. The rate law for a reaction is found to be:
Rate = k [NO, ][T][H*}?
How would the rate of reaction change when
(1) concentration of I- is halved
(12) concentration of H+ is doubled
(112) concentration of each of NO,, F and H' are tripled ?
13. For the reaction : 2A ——-> A,,
the rate of reaction becomes 27 times when the concentration of A is increased — Answers to Practice Problems
three times. What is the order of the reaction ?
poe) 8. 5.8 x 107 mol Ls?
14, For a reaction X ———> Y, the rate of reaction increases by a factor of 1.857 when
the concentration of X is increased by 1.5 times. What is the order of reaction with 9. atm”? s*
respect of X ? 10. (a) zero (b) second (c) first
15. The decomposition of N,O, in carbon tetrachloride solution has been found to be (d) third (e) second.
first order with respect to N,O, with rate constant, k = 6.2 x 10*s?
11. mol-*? L*3 <1,
N,O, (solution) ———> 2NO, (solution) + 42 O,(g)
12. (2) halved (ii) 4 times (ziz) 81 times.
Calculate the rate of the reaction when
(z) [N,O,] = 2.50 mol L7* 13. 3.
(1) [N,O,] = 0.50 mol L+ 14, 1.5.
(zit)What concentration of N,O, would give a rate of 4.2 x 10° mol Lt s?? 15. (i) 1.55 x 10% mol L?s74,
16. The rate of a reaction : (PO.S.B. 2011, 2015) (it) 20 be es aim] ee
2A +B ——> A,B (iit) 6.77 mol Lt.
has the rate law : rate = R[A]? , with rate constant equal to 0.50 molt Ls?. 16. (@) 0.18 mol L*s”
Calculate the rate of the reaction when (7x) 0:11 mol Lt s+.
(i) [A] =0.60 mol L*, [B] = 0.05 mol L™ and
(it) when concentration of A and B have been reduced to 1/4. (Pb.S.B. 2015) Hints & Solutions on page 68
| area MODERN’S abc + OF CHEMISTRY-XII

NA OAIWEE a : Accelerate Your Potential

i eevee ff PROBLEM S (for JEE Advance)

Ammonia decomposes as: Ratecn. = 1d [ NHg | 3 d|N,| oe. d|H,|

2NH,(g) —— N,(2) + 3H, (2) ee 2 at dt 3 dt
The rate of reaction can be expressed as: Substituting the given values,
| 1. 1
es = k,[NH,], aa =k, [NH,] and gt LNHs] = 2, INH] = 3% NH]
IE ] =
d(H, k,[NH,]
1 i.
or 5M = k, = a3
di
Derive relationship between k,, k, and k, 9 = 1,thenk,=2andk,=3

fa ido he enlien wikee Us : :

Conceptual uestions
Q. 1. Is there any reaction for which reaction rate does not decrease with time ?
HHH i

Ans. For a zero order reaction, the reaction rate does not decrease with time because it is independent of concentration
of the reactants.
Q. 2. How will rate of a reaction change when [A], is doubled and tripled for
(4) zero order reaction
(it) second order reaction ?
. When [A], is doubled
(i) the rate of zero order reaction remains unchanged.
(ii) the rate of second order reaction becomes four times.
When [A], is tripled.
(1) the rate of zero order reaction remains unchanged
(it) the rate of second order reaction becomes 9 times.
Q. 3. Why is the use of instantaneous rate of reaction preferred over average rate of reaction ?
Ans. The rate of reaction continuously decreases with time (except for zero order reaction) and therefore, average rate
has no significance for the reaction.
Q. 4. What is the order of a reaction whose rate constant has same units as the rate of the reaction ?
Ans. Zero order reaction. (H.P.S.B. 2010)
Q. 5. State the order with respect to each reactant and overall order for the following reaction:
2NOBr(g) — 2NO (g) + Br, (g)
Rate = k [NOBr/?
What are the units of rate constant? (Pb.S.B. 2016)
Ans. Order w.r.t. NOBr = 2
Overall order = 2
Units of rate constant = mol? Ls
Q. 6. A reaction is found to be zero order. Will its molecularity be zero ? (H.P.S.B. 2010)
Ans. No, molecularity of a reaction cannot be zero.
Q. 7. The rate of a reaction is equal to rate constant of the reaction. Mention the order of the reaction.
(Assam S.B. 2016)
Ans. Zero order reaction.
Q. 8. How is rate constant related to concentration of the reactants ?
Ans. Rate constant does not depend upon the concentration of the reactants.
Q. 9. For a reaction : 2NH,(g) rt, N,(g) + 3H,(g)
Rate =F
(1) Write the order and molecularity of this reaction.
(ii) Write the unit of k. (A.LS.B. 2016, D.S.B 2016)
Ans. 2NH,(g) —*> N,(g) + 3H,(g)
Rate =k
(1) Order of reaction : Zero order
Molecularity = 2 (bimolecular)
(iz) Unitofk =mol Ls oratms?
CHEMICAL KINETICS 4/23 »»

Q. 10. Identify the order of a reaction from each of the following rate constants: (H.P.S.B. 2010)
(1) k=2.3 x 10° Lmol' s? (ii) R=3.1 x 10757 (iz) k=9.38 x 10+ mol L's!
Ans. Order can be predicted by the inspection of units of rate constant
(x) second order reaction (11) first order reaction (tii) zero order reaction
Q. 11. For the reaction : Ester + H* ——> Acid + Alcohol, rate = & [Ester] [H*]®. Find the order of reaction.
(Pb. S.B. 2005)
Ans. Order = 1
Q. 12. For the assumed reaction : X, + 2Y, —— 2XY,, write the rate equation in terms of the rate of
disappearance of Y,,.

Ans. 1di¥ol
nae opp XS] jy,[¥QN"5 =AY!
2 = 2k IX, ILY,].
. For the reaction: Cl,(g) + 2NO (g) ——-> 2NOCI(g)
The rate law is expressed as rate = k[NO]? [C1,]
What is the overall order of the reaction ? (D.S.B. 2007)
Ans. Overall order = 1+ 2 =3.
Q. 14, Express the rate of the following reaction in terms of disappearance of hydrogen in the following
reaction : 3H,(g) +N,(¢) ——— 2NH,(g) (ALL SB. 2007)
1d[H,|
Ans. Rate =— 3 dt
Q. 15. The decomposition reaction of ammonia gas on platinum surface has a rate constant,
k =2.5 x 10+ mol L's, What is the order of the reaction ? (C_.B.S.E. Sample Paper 2007)
Ans. According to units of rate constant; it 1s a zero order reaction.
Q. 16. What is the molecularity of the reaction:
1
Cl——-> — Cl,(g)? (C.B.S.E. Sample Paper 2007)
Ans. Unimolecular. 2
Q. 17. The decomposition of NH, on platinum surface, 2NH, (g) ses N,(g) + 3H,(g) is a zero order reaction
with k = 2.5 x 10-* Ms'. What are the rates of production of N, and H, ? (D.S.B. 2007; 2008)

Rate = —2 SNH! _ aINe] _1

FB LVe Se A0 Met
2 dt dt 3. dt
. of N,
Rate of production dlNo| 2.5 x 10* 4\Wet
Ms

1 dl H,]
38 de» =2.5x10*Ms*
Rate of production of H, os. = 3x25x104=7.5 x 10* Ms?

. If the concentration be expressed in mol L! units and time in seconds, what would be units for rate
constant, & (7) for a zero order reaction (i7) for a first order reaction (D.S.B. 2008)
. (1) Fora zero order reaction,Rate = k[A]®
mol! L'
: =kxl or k=molL?s1

(zz) For a first order reaction, Rate = &[A]

-1
mol L™ = k mol L“! or k=sl
s
. Identify the order of a reaction if the units of its rate constant are:
(i) L-* mol st (ii) L mols (A.f.S.B6.2011)
. (t) Zero order (it) Second order
. A reaction is of second order with respect to a reactant. How is the rate of reaction affected if the
concentration of the reactant is reduced to half? What is the unit of rate constant for such a reaction ?
(A.LS.B. 2011)
. For a second order reaction, Rate = R[A]?
If the concentration of A is reduced to half, rate will become 1/4 of the original value.
Units of k
mol L?
Rk (mol L-)?
5

k= = =mol!L s1
mol Ls
a 4/24 MODERN'S abc + OF CHEMISTRY-All

Q ml. In the
th reaction
i A+ 6B —- products;
:aA+ d 1fif concentration
i of f A is
Ais doubled
double (k eeping
ing B6b constant),), the
th
initial rate becomes four times and if 5B is doubled (keeping A constant), the rate becomes double.
What is the rate law equation and order of the reaction? (Manipur S.B. 2012)
Ans. Rate = &[A]? [B], Order = 1 + 2 =3.
Q. 22. The rate constant of a reaction is 3 x 107 min“!. What is the order of reaction ? (Assamn. S.B. 2012)
Ans. Order = 1 (from units of rate constant).
Q. 23. For a reaction : A + B ——-; P, the rate law is given by, r= [A]“ [BI?.
What is the order of reaction ? (A.LS.B.2013)
1 1
Ans. Order= 3 +23=2 3 or h.

Q.24. For a reaction, rate law is give as rate = k[A] [B]'”.

Can the reaction be an elementary reaction ? Explain. (Pb.S.B. 2009)
Ans. For an elementary reaction, order of a reaction should be equal to molecularity of the reaction and molecularity
should be integral. For the given reaction, order of reaction is AR+ ;]. Since molecularity cannot be fractional,

therefore, for the given reaction, order is not equal to molecularity. Hence, given reaction cannot be elementary

reaction.
Q.25. The rate of formation of a dimer in a second order reaction is 9.5 x 10° mol L! s* at 0.01 mol L!
monomer concentration. Calculate the rate constant.
Ans. Ifthe monomer is represented by X. Then,
2X ——> (X),
Since the reaction is of second order, the rate of reaction will be given by:
Rate = k[X]?

Rate = a — AX | =95x105 molL?s1!

2 dt dt
9.5x10°molLts? = &(0.01 mol L?)
9.5x107°
k = ———,— =0.95 Lmol™ s™.
(0.01)
INTEGRATED RATE EXPRESSION
We have learnt that for a general reaction:
aA + bB—>cC + dD
rate may be expressed as :
Rate = R[A]P [B]49
This form of equation is called differential rate equation. It is not always
convenient to measure the instantaneous rate because it 1s measured by
determination of slope of the tangent at point 7’ in the concentration versus
time graph. Therefore, it is difficult to determine the rate law and hence
order of the reaction. In order to solve this problem, we can integrate the rate
equation and obtain integrated rate equation which gives a relation between
directly measured experimental quantities i.e., concentrations at different times
and rate constant. The integrated rate equations are different for reactions
of different orders.
The integrated rate equations for different order reactions can be derived
as given below :
Zero order reaction
A reaction is said to be of zero order, if its rate does not depend on the
concentration of any of the reactants. Consider the general zero order reaction :
R ——> Product
Let [R] be the concentration of the reactant R and & is the rate constant
for the zero order reaction. For the zero order reaction, the rate of the reaction
is proportional to zero power of the concentration of R. Thus,
a{R|
Rate = 7 =k [RJ!=kx1 ( [RJ®° = 1)

or d{R] = —-2.dt ...(4)

CHEMICAL KINETICS 4/25 ee

Integrating both sides, we get

faRl = -k fd
[IR] = —kt+I]1 ...(5)
where I is the constant of integration. The value of I can be calculated from
the initial concentration. For example, the initial concentration of R be [R], at
t = 0. Then equation becomes
[IR], = -kxO0+!I
or I = [Rl,
Substituting the value of I in Eqn. (5), we get
[R] = —¢ + [Rl], ...(6)
Further simplifying the above equation, we get the rate constant, & as
kt = [RI], — [BI
ae [RJ], —([R]
i
where [R], is the initial concentration of R, [R] is the concentration at time f.
From this, rate constant, k can be calculated.
Alternatively, if the initial concentration of R is ‘a’ moles per litre and let
x moles of reactants get changed to products in time ¢. Then, concentration
of R left after time ¢ be (a — x).
R ——-> Products Time taken for a zero order
reaction to complete
a 0
When the reaction is complete,
a-x s
[R] =
[R], = a, [R] =a —~x so that
——
[R], -[R] = a-(a-x)=x
Thus, Eq. 6 becomes
k= ; or x =A

The above equation is integrated rate equation for zero order reactions.
The amount of the substance reacted is proportional to the time.
Graphical representation of zero order reactions
(4) The differential rate law for zero order reaction is given as

rate = —
d{R]_
dt ‘
The plot of rate versus [R] at different times is a horizontal straight line as
shown in Fig. 4.

(it) The integrated rate law for zero order reaction is given by Eqn. 6 as:
[R] = — At + IRI,
The equation has the form of linear equation, y = mx + c. The plot of [R] versus
time (t) is a straight line as shown in Fig. 5. The slope of the straight line
is equal to -k and intercept on [R] axis is [R]p.

In general, the rate of decomposition of ammonia is given as :

Rate «=e
—MUNHs! oe,
1+h,[NHs]
[R] ——>
where k, and 2, are constants. When [NH,] is very low, k,[NH,] can be
neglected in comparison to unity so that the above equation becomes : Fig. 4. Plot of rate versus [R] at
Rate = k, [NH] different times for a zero order
reaction.
This reaction is first order in ammonia.
 MODERN'S abc + OF CHEMISTRY-All

[R], (intercept) At higher concentration of ammonia (high pressure), we may neglect 1

as compared to [NH,] so that the equation 7 becomes :
NH
slope of the line = —& Rate = SENS)
| 3! = Be =
oc kg[NH3] ke
or & = — slope of the line
=
2 ae Rate = R [NH,]°
o
= This means that rate becomes constant and independent of [NH,] and
=
g= therefore, becomes zero order reaction.
o
O

First order reaction

Time — Consider the general first order reaction
Fig. 5. Variation of concentration of R —-> Products
a reactant with time for a zero order
Let [R] is the concentration of the reactant R and & is the rate constant
reaction.
for the first order reaction. For the first order reaction, the rate of the reaction
is directly proportional to the concentration of the reactant R. Thus,

Rate = — aR] = k[R] ...(8)

dt
This form of rate law is known as differential rate equation. Rearranging
the above equation :
AR! _ _pai (9)
[R]
Integrating the above equation, we get
d[{R] |
——- = —k :
[Rl ja
in [R] = —kt +1 ...(10)
where I is the constant of integration. The value of I can be calculated from
the initial concentration. For example, the initial concentration of R be [R], at
t= 0. Then Eq. (10) becomes
in [R], = -—kxO+1]
ce I = In [Rly
Substituting the value of I in Eqn. (10), we get
In [R] = —kt + in [RI], ..(11)
Rearranging,
In [R], —¢n [R] = Rt

or in Llp = kt
[R]

or | =, Lo ...(12)
f [R]
Eqn. (12) is integrated rate expression for the first order reaction.
Changing the above expression to log base 10 (/n x = 2.303 log x), we get

2.303 [R]p
R= log 7 ...(13)
t [R]
If we perform the experiment at two different times ¢, and ¢, having
concentrations [R], and [R], respectively, then from equation (11)
CHEMICAL KINETICS

In [R], = — kt, + In [RI],

in |Rl, = —t, + in IR,
Subtracting we get

In [R], —?n [R], = — kt, -(— Rt.) =k (t, -t,)

[R]
Ina = Blt ty |
or k= . ln LR
(t—t,) [Ro

or k= 2.303 lo LR hi _..(14)
(t, a ty ) [R lo

The equation (12) may also be written in the exponential form as :

In Blo = kt
LR]
Taking antilog of both sides
TR]
[Rl
[R]

The equation (13) may also be written in an alternate form. Let the
initial concentration of R is 'a' moles per litre. Suppose in time ¢, x moles
of reactants get changed to products. Then the concentration of R left after
time ¢ is a — x. Therefore,
[R], = a and [R] =a-x
Thus, Eq. (13) becomes
2.303
k log 2
t ef 4

Significance of Integrated Rate Equation

The integrated rate equation can be used in the following ways :
(4) Order of reaction. All reactions of first order obey the following
equation :
2.303 [RJ
k= log ...(16)
t
[R]
Starting with the known concentration of R, the concentration of the
reactant [R], at different intervals of time (¢) may be measured. The values
of [R] at different time intervals are substituted in the above equation. If the
value of & comes out to be constant, then the reaction is of first order.
(zz) Caleulation of rate constant. The integrated rate equation can be
used to calculate the rate constant of a reaction. If the reaction is known to
be of first order, then by substituting the initital concentration of reactant
[R], and concentrations at different times (¢) in Eq. 13, the value of k can be
calculated.
The rate constant can also be calculated graphically. The Eq. (13) may
be written as
kt _= 1 [RJ ..(17)
2.503 [R]
kt
= log [R], — log [R]
2.303 =
k
or log [R] = — t + log([R] ...(18)
2.303
a 4/28 MODERN'S abc + OF CHEMISTRY-All

. This equation is comparable to equation of a straight line (y = mx + c).

log [R] (intercept) When a graph is plotted between log [R] and time ¢ at different intervals of
time we get a straight line. This is shown in Fig. 6.
slope = — Rk The slope of this line is equal to
ae OK

From this, rate constant k, can be calculated.

Alternatively, if we write the equation (17) as
1 [Flo kt
oe =
° TR] ~ 2,303
The plot of log LR Io vs ¢ will give a straight line with slope = a
Time, t (s) —» [R] 2.903
Fig. 6. Plot of ¢ versus log [R] to
This is shown in Fig. 7.
calculate rate constant for the first ; :
alee Gana. Hydrogenation of ethene is an example of first order reaction.
C,H,(g) + Hg) ———_ C,H,(g)
Rate = k [C,H,]
Decomposition of N,O. and N,O also follow first order kinetics.

Integrated Rate Equation for a Typical First Order Gas Phase Reaction
Let us consider a typical first order reaction in gaseous phase :
A (g) —— Big) + Cig)
Let p, be the initial pressure of A and p, be the total pressure at time f.
Integrated rate equation may be written as :

a ai log Pe he)
A
where p, is the partial pressure of A at time ¢. The partial pressure of A
Time (t) > can be derived as follows :
Total pressure, p, will be
Fig. 7. Plot of log [R],/[R] vs ¢ for a
P; = PatPptPec
first order reaction.
where p,, Pp and pv, are the partial pressures of A, B and C respectively.
For the second order rate law, Let the pressure of A decreases by x atm after time ¢. Since one mole of
there are two cases : B and C are formed from 1 mole of A, then increase in pressure of B and
(i) The reaction is second order C will also be x atm each as :
in only one reactant : A(g) ——> Big) + Cig)
rate = k [A]? Att =0 p, atm 0 0
(it) The reaction is first order in At time t (p, — x) atm x atm x atm
two different species : Now, Dp, = (p,-x)+xt+x=p,+x
rate = & [A][B] or x = D,-p,
In second order reactions with Now, at time f, DS hse pS 0,= 6) Ses,
only one reactant, the integrated Substituting in Eqn. (19) we get
rate law is 2 203 DP;
ep = log
_ ee
"TRIy 2D; — Pt
Knowing the values of p, and p,, 2 can be calculated. However, it may
= Mtok Met!
1 be noted that the relation will depend upon the reaction.
et [R] [Rly

SOLVED EXAMPLES
LU) Example 17. k = 0.0030 mol L7!s"!
The rate constant for a reaction of zero order in A is [A]. = 0.10 M, [A] = 0.075 M
0.0030 mol L~*st. How long will it take for the initial ° [Al -[A]
concentration of A to fall from 0.10 M to 0.075 M ky = ——

PB IO) [Ah -[A]_ 0.10-0.075

Solution : For a zero order reaction, t = om en 8.33 s.
CHEMICAL KINETICS

LU) Example 18 S.No. Time (s) Total pressure (atm)

The decomposition of N,O, at 318 K according to the ‘2 0 0.5
following equation follows first order reaction : 2: 100 0.512
1
N,O(g) ——_~> 2NO,(g) + 3 O,(g) Calculate the rate constant. N.C.E.R.T,
Solution : Let the pressure of N,O, decreases by 2x atm.
The initial concentration of N,O, was 1.24 x 107 mol
Since 2 moles of N,O, decompose to give 2 moles of N,O, and
L- and that after 60 minutes was 0.20 x 10° mol L-1.
1 mole of O,, then the pressure of N,O,(g) increases by 2x atm
Calculate the rate constant of the reaction at 318 K.
and that of O,(g) increases by x atm.
N.C.E.R.T., (Meghalaya S.B. 2015) 2N,0,(¢) ——> 2N,0,(g) + O,(g)
Solution : For a first order reaction Attime,t=0 0.5 atm 0 0
jas 2.303 log [RJ At time (100s) (0.5-2x)atm 2x atm x atm
k [R] Total pressure, p, = (0.6-—2x)+2v+x=0.5+x
or x = p,-0.5
¢ = 60 min. [R], = 1.24 x 107 mol Lt,
t = 100s, p,=0.512 atm
[R] = 0.20 x 10 mol L7! or x = p,-0.5 = 0.512 —0.5 = 0.012 atm
2.303 1.24107? mol L7! Now, p(N,O,) = 0.6-2x=0.5—2 x 0.012 =0.476 atm
k = pn
> log SNES OP,
60 0.20x10°7 mol L For a first order reaction,
2.303
= oes log 6.2 =——— x 0.7924 p= 2303, p(N2O5)o _ 2.303, 0.5 atm
60 60 t p(N,O;), 100 ~ 0.476atm
= 0.0304 min!
2.30 2.303
LU) Example 19. = po log 1.0504 = x 0.0214
100 |
The decomposition of a compound is found to follow = 4,93 x 104 s"!
first order rate law. If it takes 15 minutes for 20 per O Example 21
cent of original material to react, calculate The following data were obtained during the first order
(i) the specific rate constant thermal decomposition of SO,Cl, at constant volume.
(it) thettmeat which 10 percent ofthe original material
SO,Cl, (g) ——> SO, (g) + Cl, @
remains unreacted
(tit) the time tt takes for the next 20 per cent of the Experiment Times/s Total pressure/atm
reactant left to react after first 15 minutes. 1 O 0.5
(D.S.B. 2002)
2 100 0.6
Solution : (i) For the first order reaction :
2.308 [Al Calculate the rate of reaction when total pressure 1s
- ioe
. t [Al 0.65 atm. (CBSE Sample Paper 2011)
Let [A], = 100, [A] = 100 —- 20 = 80 Solution: For the decomposition of SO,Cl,
= 2.308 log
SO,Cl,(g) —> SO,(g) + ClL,(g)
15 80
Att=0 Pp atm 0 0
= — x 0.0969 = 0.0149 min Attimet (p,—x)atm oa .
DP, = Pg-X4X4+X =pPytx
(iz) If [A], = 100, and [A] = 10, then
or x = DP.-Dy
2.303 lo [Alo
{= Now at time ¢, p(SOCI,) = p, — x = Ppyp—(P, — Pp) = 2 Py —D;
k Jas) b= 2.303 his Do
= 2 YS log 100 = 154.6 min 2Py — Pt
0.0149 10
when t= 100s
80 x 20 - 64
(zit) If [A], = 80, [A] = 80 —
100
pe ge log 1.25
100 2x0.5-0.6 100
2.303 80
t = ——— log — = 2.2316 x 10%s7%
0.0149 64
When p, = 0.65 atm 1.e. py + p = 0.65 atm
=2. 90149
= x 0.0969
0. == 15.0
15.0 min.
mi
p = 0.65 — p, = 0.65 — 0.50 = 0.15 atm
) Example 20 Pressure of SO,Cl, at time t = 0.50 — 0.15
The following data were obtained during the first order = 0.35 atm
thermal decomposition of N,O,(g) at constant volume, Rate = 2.2316 x 10°? x 0.35
2N,0,(g) ——> 2N.0,@) + O,@) 7.8 x 10° atm s?
a 4/30 MODERN'S abc + OF CHEMISTRY-All

For a first order reaction HALF LIFE PERIOD OF A REACTION

Half life period of a reaction is defined as
the time during which the concentration of a reactant is reduced
Att=0 [Alo to half of its initial concentration.
In other words, it may also be stated as the time in which half of a reaction
is completed. It is generally denoted as ¢,,,. The half life period for different
order reactions may be calculated as given below :
Half life period for zero order reaction
For a zero order reaction,
Ati= typ
A —> Products
one half life .
the rate constant is given as

Now, half life period corresponds to time during which the initial
1 TAlo concentration, [A], is reduced to half, ie.,
At t= 2t,» at Att=t,,, [A] = [A],/2
two half lives = ra — [Alp —[A]y/2 _ [A]
= bye 2t1/9

= [Alp
Ios
7
or LL,Ve = =>
ab

=e It is clear that ¢,, for a zero order reaction is directly proportional to the
initial concentration of the reactants and inversely proportional to the
rate constant.
Attent IAlo Half life period for first order reaction
nhalt ives, 2" The first order rate equation for the reaction :
A ——~ Products is:
REMEMBER
kt = 2.303 log LAlo
Thus, the time required to reach ]
the concentration values [A],/2,
- ' = 2.303 | LA],
[A],/4, [AI,/8, [A],/16, [A],/32 —— log
pe es k [A]
ALE Cy), Alyjo, Blyjo, Ahyjo, Obyjo / . ; ; ; —
respectively Now, half life period corresponds to time during which the initial
: concentration, [A], 1s reduced to half z.e.,
REMEMBER [A] = [A],/2 at f=#,,
It is clear from the above illustration , 7
that for a first order reaction: eee
The amount of substance left after n P _ 2,308 1 [Alo — 2.303 los 2
half life periods is given as : V2 kB °8 [Aly /2 — f 8

ea)
me cman ee
eee
[A],
a:
AFB or taj =
2.303 x 0.3010
=
0.693
> [.. log 2 = 0.3010]
e.g., if half life period of a substance
is 10 min, then time taken to reduce ete 0.693 (20)
its concentration to 1/16 of its original on : b an
value can be calculated as :
= : . Thus, half life period of a first order reaction is independent of the
G 2 et G = B orn =4| initial concentration of the reactant. Further, it is also clear from the
2 16 2 2 relation that halflife period for the first order reaction 1s inversely proportional
1.e., 4 half life periods. to the rate constant.
“. Time REEL = Hl min. Similarly, the relation for the time required to reduce the concentration
semithin ahh oe em of the reactant to any fraction of the initial concentration can be
ae ogee area eae! calculated. For example, for the first order reaction:
min. 1.e., 4 half life periods, then aie, _
AN ae oH (1) ttme required to complete 1/3 of the reaction will be given as :
ml -(3] al [A], = a, A]=a-a/3 =2/3a
[Alp \2) 16 ; . . _ 2803; 4 _ 2.303), 3
i.., its concentration is reduced to — th its We k . 2/3a =k : 2
of its original value. 16
CHEMICAL KINETICS 4/31 —

(it) tume required to complete 3/4 of the reaction will be

[IA], = a, l[AJ=a-34a=1/4a
_ 2.303 a _ 2.308
es gp ee
3/4 Reve pat per ee
In general, the time required to complete mth fraction of the first order reaction
will be
[A] o
a, [A] =a-—-

Half life period for a second order reaction

The rate equation for second order reaction is
pe =
[A] [Al
For half life period, ¢,,, = [A] = [A],/2
2 1 1
kt = _ =
i [Al [Al [Al
f ia 1
Lf falAly

These are summed up below:

Type of reaction Rate equation vd

Zero order Rate = k[A]° se

First order Rate = [A] —

1
Second order Rate == k[A] 2 a
RIA],

These results give very interesting observation that only the half life of
first order reactions are independent of the concentrations. The half life vs
concentration [A], or 1/[A], plots are shown below:

ero order First order Second order

Thus we have observed that

For a zero order reaction, ¢,,. « [Al,
For a first order reaction, f,,. < [A]
For a second order reaction, ¢,,. « [A]
In general, for a nth order reaction,
In general, for a nth order reaction,
hy ee (es an or
a 4/32 MODERN'S abc + OF CHEMISTRY-All

Rate of Radioactive Decay

All natural and artificial radioactive decay of unstable nuclei take place
by first order kinetics. For example, radium decays as :
299 4
= Ra —_3,, Hn+ {He
Rate = Rk[ Ral]

Since radioactive decay follows first order kinetics, this means that rate
of disintegration is directly proportional to the number of atoms present
in the sample at that time.
Suppose a radioactive element A disintegrates to form B,
A—B
Let N, be the number of atoms present in the beginning, at ¢ = 0 and
N be the number of atoms present at time ¢, then
, _ 2.303, _N,
@ Competition Plus A= ere
ener wee - Samuel where 2 is a constant known as decay constant or disintegration
eee (eeeer ye ane constant. Its value depends upon the nature of the decaying element.
developed by Willard Libby to find Half life period for radioactive decay is
the age of archaeological object (wood 0.693
plants or animal fossils). For detail, _= 27
refer Compitition File (Page 94) r
The halflife period of a radioactive element gives idea about its stability.
If the half life period is small, it means that the element is extremely
unstable and will decay in a short period. On the other hand, longer half
life periods indicate stability of the radioactive element. For example, the
half life period of Ra-224 is 3.64 days, while the half life period of Ra-228
is 6—7 years and the half life period of Ra-226 is 1596 years. This means
that Ra-226 is most stable among the three isotopes of radium while
Ra-224 is least stable.
It may be noted that in case of a radioactive substance, the whole of
the substance never disintegrates. In other words, the time required for
complete disintegration is infinity. Therefore, the term average life is
used. As faster is the disintegration, smaller is the average life, therefore,
average life (expressed as T, tau) is taken as reciprocal of disintegration
constant, A, le

—— SOLVED EXAMPLES
LJ Example 22 0.693 :
cae uw. = 900 = 3.465 x 10 s.
Calculate the half life period of a first order reaction
where the specific rate constant is (0) k= 2mm!
(a) 200 s+ (b) 2 min (c) 4 year+ ty = — ~ 0.3465 min.
Solution : For the first order reaction, ;
0.693 (c) k = 4 year”
— = é
a R “ js 0.698 = 0.1732 year.
(a) k = 200s 4
CHEMICAL KINETICS

LJ Example 28.
For 3/4 of a reaction to take place, ¢ =¢,,,, [A] = [A], —- ;[Alo
A first order reaction ts found to have a rate constant, Rk
1
=§.5x 107 s. Find the halflife period of the reaction. ‘;[A],
N.C.E.RD.(A.1.S.B. 2018) 2.003 [Alp 2.003 _
— log4 ---(t)
Solution : For the first order reaction, Thus, ta = 1/4[A], = lo k
_—_— a Now, for half of a reaction to take place,
1 1
_ 193
0.693 -~ 1.26 x 10" . p= A] == [A],
[A] [A], -— —3 [A],
[A], = —[A
9 [Al],

Example 24.
paxle "a" This, t= 2.30
2.3035 [A Io ba
2.303 Ing 2 Ait)
For a first order reaction, calculate the ratio between [A], /2 k
the time taken to complete three-fourth of the reaction Dividing eq. (i) by eq. (it)
and the time taken to complete half of the reaction. t log 4 0.6020 _
Solution : For first order reaction, 4
1/2 log 2 0.3010 —
2.303, [Aly
= —— log Thus, the time required for 3/4 th of the reaction to
k [A] occur is two times that required for half of the reaction.

17. During the decomposition of N,O, dissolved in carbon tetrachloride at 303 K, the
following results were obtained :
Time (min) 0 AQ 80 120 160 co
Vol. of O,
collected (cc) 0 15.6 298.6 38.6 46.8 84.6
Show that the reaction is of first order. Also calculate the rate constant.
18. Diazobenzene chloride decomposes as :
C,H;N, Cl——> C,H,Cl + N,
The volume of N, evolved at different times was measured and following results
were obtained :
Time (min) 0 20 f S
Vol. of Ih (ml) 0 10 ood 162

Calculate the (z) order of the reaction and (iz) rate constant.
19. The rate constant for the decomposition of N,O, is 6.0 x 10s. At what time will
the initial concentration of 1 M be reduced to 0.2 M if the reaction is of first order ?
20. For the reaction, N,O, (g) ——- 2NO,(g) + 5O,(g), the initial concentration of
N,O, was 1.24 x 10°? mol L™ at 318 K. The concentration of N,O, after 60 minutes
was 0.20 x 10°? mol L"1. Calculate the rate constant of the reaction at 318 K.
(Meghalaya S.B. 2013)
21. The decomposition of N,O, in CCl, solution follows the first order rate law. The - Answers to Practice Problems
concentration of N,O, measured at different time intervals are given below :
17. k is almost constant therefore,
Time in seconds (f) 0 80 160 410 600 1130 #81720
reaction 1s of first order.
[N,O,] mol/L 5a 5.0 AS AO o.4 2A 1.6
k = 5.08 x 10? min?.
Calculate the rate constant at ¢ = 410 s and ¢ = 1130 s. What do these results 18. (z) order = 1 (iz) 3.21 x 10°? min!.
show ? 19. 2683 s.
22. The decomposition of N,O, in CCl, at 45°C
20. 3.04 x 10? min"!
2N,O, —“4 . 4NO, +O, Sie Poo ii se ls i
is first order reaction with k = 6.32 x 10+ s+. Calculate the concentration of N,O, 22. 0.041 mol L7!, 89.75 %
remaining after one hour when the initial concentration of N,O, was 0.40 mol L”.
What percentage of N,O, has reacted ? Hints & Solutions on page 68
| 434 MODERN'S abc + OF CHEMISTRY-All

EXPERIMENTAL DETERMINATION OF ORDER OF A REACTION

There are a number of methods for determining rate law or order of a
reaction. The following methods are commonly used :
1. Graphical Method
This method is used when there is only one reactant. It involves the
following steps :
1. The concentrations of the reactants are measured by some suitable
method.
2. A graph is plotted between concentration and time.
3. The instantaneous rates of the reaction at different times are calculated
by finding out the slopes of the tangents corresponding to different times.
4. The rate of reaction (calculated above step 3) is plotted versus
concentration, [R] or (concentration)?, [R]? and so on.
(a) If rate of reaction remains constant in rate versus concentration graph,
it means that the rate is independent of the concentration of the reactant, i.e,.
Rate =k [RJ2 =k
Therefore, the reaction is of zero order.
(6) If a straight line is obtained in rate versus concentration graph, it
means that the rate is directly proportional to concentration of the reactant 1.e.,
Rate = R[R]
Therefore, the reaction is of first order.
(c) If a straight line is obtained in rate versus (concentration)? graph, it
means that
Rate = R[R]?
Therefore, the order of the reaction is two.
(d) Similarly, if we get straight line in rate versus (concentration)® graph,
then
Rate = k[R]?
and the order of reaction is 3.
In general, if we get straight line by plotting graph of rate versus
(concentration)”, where n = 1, 2, 3 .... so on, then
Rate = k[R]”
and the order of reaction is 7.
These graphs are given below :

First order Second order Third order

Let us illustrate the above method by taking the example of the

decomposition of nitrogen pentoxide.
2N,0.(¢) ———> 4NO,(g) + O,@)
This reaction involves the gaseous reactants and products. Therefore, the
reaction can be easily studied by measuring the increase in pressure of the
gaseous mixture at different intervals of time. From the measured values of
CHEMICAL KINETICS

total pressure, the partial pressure of N,O, at different times can be calculated.
From this, the concentration of N,O, in moles per litre can be calculated.
The molar concentrations of N,O, obtained are plotted against time. The
rates at different times are obtained by measuring the slopes of the tangents
corresponding to these times.
The rate of this reaction at different concentration of N,O, is given in
Table 1. The table indicates that the rate of the reaction is proportional to
the concentration of N,O. and it may be expressed as :
Rate [N,O.]" or Rate = k[N,O,]”
Table 1. Rate of reaction corresponding to different concentrations
of N,O..

1.13 x 10 34x 10*

0.84 x 10° 2.5 x 10+
0.62 x 10° 1.1 x 10+
0.46 x 10° 1.3 x 10+
0.35 x 10° 1.0 x 10+
0.26 x 10° 0.8 x 10+

Now, different graphs are drawn by plotting rate versus [N,O,], rate versus
[N,O.]*, etc. These are given in Fig. 8 and Fig. 9 respectively. We observe in
c
that the plot of rate versus [N,O,] is a straight line (Fig. 8). This means that E
the rate of the reaction is directly proportional to the [N,O.]. Therefore, the ey
3
rate law is : E
Rate = R[N,O,] 2
id
an)

However, we do not get straight line by plotting rate of reaction against

[N,O.]*. This means that the reaction is not of second order. 0.002 0.004 0.006 0.008 0.010
[N,O,] mol L~1
Thus, the correct rate law for this reaction is :
Fig. 8. Rate of decomposition of N,O,
Rate = — o = RIN,O-] as a function of [N,O,].
and order of the reaction is 1.

From the above discussion, we notice that the

coefficient of N,O, in the balanced equation is 2 while
the exponent in the rate law is 1. Thus, the order of the
reaction is not same as the coefficient in the balanced
chemical equation.
min‘)
L-?
(mol
Rate
Calculation of Rate Constant
2x 10° 4x 10°6x10" 8x 10> 10x 10> 12x 10°
The rate constant can be calculated by substituting
[N,O,]? mol? L-2
the values of rate and concentration of N,O- in the rate
law expression Fig. 9. Rate of decomposition of N,O, as a function of
Rate = k[N,O,] [N,O,]2.
For example, when

[N,O.] = 1.13 x 10-7 mol L and

rate = 3.4 x 10* mol L* min"!
_ Rate _ 3.4x 10+ mol L? min
[N,O,] 1.13 x10 mol L-
= 3.0 x 10°? min!
2. Use of integrated rate equation
This method is also known as method of trial and error. The kinetic data
is fitted to different integrated rate equation. Wherever the data fit with the
a 4/36 MODERN'S abc + OF CHEMISTRY-All

equation for the correct order of the reaction, it will give constant value of rate
constant for all data points (concentrations at different times). Alternatively,
graphical method can also be applied for integrated rate equation. In the
method, appropriate function of concentration is plotted against time. The
resulting curve will be straight line only for the case in which the appropriate
integrated equations has been used. For a general reaction :
A —-> Products
the integrated rate equation for zero, first and second order reactions are
given below :

Type of reaction Equation corresponding Linear plot Intercept

to y=mx+e

“ero order [A] = — At + [A], [Al vst

(rate = 2)

First order log [A] =—- - a + log [A], log [A] vs ¢

(rate = R[A]) 2.303
Second order nS ee = i vs t
(rate = R[A]?) [A] [A] [A]

It is clear from the above relations that the straight lines are obtained for a
plot of [A] versus ¢ for a zero order reaction, of log [A] versus ¢ for a first order
- reaction and of 1/[A] versus ¢ above for second order reaction as shown below:
The plot of in [A] against ¢ for a first
order reaction is a straight line with Zero order First order Second order
slope =— k. Intercept Intercept
[Al :

slope =—k

<— Intercept = zal

(Al,

These curves also help to calculate the value of & from the slope of the
straight line.

ee ee

4 Example 25 b
2.303 lo Vo
Pi : or = =<
The rate of decomposition of hydrogen peroxide at a t 7 V;
particular temperature was measured by titrating tts Here V, = 22.8 and the value of & can be calculted by sub-
solution with acidicKMnO, solution. Kollowingresults _ stituting the concentration of V, at different times.
were obtained : t= 10min, V,=13.8
Time, t (min) O 10 20

i 1(KMnO,)
ti Aa22.8 13.8 8.3 Z b= 22°?
10 tog =2*
13.8 = 0.05022 min
(i) Show that the reaction is of first order. t = 20min, V,=8.3
(it) Calculate the rate constant. | 2.303. 22.8 |
Solution : Volume of KMnO, used is proportional to the = k= 20 log 83 7 0.05053 min
amount of H,0, present. If the reaction is of first order, 1t must (i: Sine tip valuc-ol econiee cnt ta bealnoa constant the
obey the equation, ; :
reaction therefore, is of first order.
k= 2.3038 log
0 LAI (it) The mean value of & = 0.05037 min“.
t [A]
CHEMICAL KINETICS 4/37 =

UO) Example 26. (vt) Calculate the half-life period from k and compare
The following results were obtained for the decomposition utwith (6). oe
pata : Solution. (i) The plot of [N,O.] versus time is shown below:
of nitrogen peroxide in an inert solvent : 205

t (s) 0 300 +600 900 oo

Vol. of O,
evolved (cm®) O o42 650 8.95 $84.78

Show that the reaction is of first order and also calculate

the rate constant.
Solution : The reaction will be of first order, ifitobeysthe OO, ,ag f----- a a 0.815 x 10°M
equation, 102
[N,O,]
x
2.303 1a Ae
a—x
In this reaction, oxygen 1s liberated and collected at different
times. The total volume of oxygen collected at the end of reaction 0.2
(after infinite time, tf =>° )gtves a measure of the total concentration
of nitrogen peroxide taken initially 1.e., a. If V, is the volume 0
400 800 1200 1600 2000 2400 2800 3200
collected after time t and V,, is the total volume collected at the
Time(s) ——>
end of the reaction, then the concentration of nitrogen peroxide
at any time ¢ i.e., (a — x) is V,, — V,. Thus,
(ii) Initial cone. of N,O, = 1.63 x 10° M
V.. = a, V,«<xand a-x=V_,-V:
Thus, the above equation becomes Half of initial cone. = 1 63x 10-2 x z=
2.303 V. 4
k = —_ loss ~V = 0.815
x 10?M
Substituting the values, so Time corresponding to half of initial cone. (¢,,.) from the
plot = 1440s
t = 300s, V_, = 34.75, Vi = 3.42
(iit) Plot of log{N,O,] vs time
2.303 og 34.75 |
k =
300 34,75 — 3,42
= 0.000345
t = 600s, V_ = 34.75, Vi = 6.30
2.303 34.75
k= —“log—""" — = 0.000333
600 ~~ 34.75—6.30
t = 900 sec, V_, = 34.75, Vi = 8.95

k= “28
900
tog 34.75
9 — 8.95_ = 0.000381
logiNO,]
Since the value of & is almost constant, the reaction is of
first order. The average value of rate constant is 0.000336.
4 Example 27.
f . 400 800 1200 1600 2000 2400 2800 3200
The experimental data for decomposition of N,O, Time (s)
2N,0,—> 4NO, + O,
(tv) Since the graph between log[N,O,] vs time is a straight
in gas phase at 318K are given below:
line, the reaction is of first order.

[0 [a | | | 9 me
Rate equation :

mol Li .
(v) Slope of the line = — =o
(i) Plot [N,O,/ against t. 4.208
(ii) Find the half-life period for the reaction. Slope = — 2.10 x ane graph)
(iii) Draw a graph between log [N,O,J and t. = k = —2.10 x x (—2.303)
(iv) What is the rate law? = 484x 10s
(v) Calculate the rate constant. (vi) i= a 1432 s
k 4,84x 10-4
 MODERN'S abc + OF CHEMISTRY-All

3. Initial Rate Method

The graphical methods cannot be applied for the reactions which involve
more than one reactants. The rates of such reactions can be determined by
initial rate method. This method involves the following steps :
1. The initial rate of the reaction i.e., the rate at the beginning of the
reaction 1s measured. This may be taken as the rate over an initial time
interval that is short enough so that concentrations of the reactants do not
change appreciably from their initial values. This corresponds to slope of the
tangent to the concentration versus time graph at ¢ = 0.
2. The initial concentration of only one reactant is changed (keeping other
concentrations constant) and the rate is determined again. From this the order
with respect to that particular reactant is calculated.
3. The procedure is repeated with respect to each reactant until the overall
rate law is fully determined.
4. The sum of the individual orders with respect to each reactant gives
the order of the reaction.
This method can be illustrated by taking a hypothetical reaction :
2A + 2B ——— Products
The order of this reaction can be experimentally determined by studying
the concentration dependence of reactants A and B. Let us assume that we
start with 0.01 M concentration of both A and B and the initial rate of the
reaction is 0.005 (say). This has been listed in Table 2 in experiment I. In
second experiment when the initial concentration of A is doubled (from 0.01 M
to 0.02 M), keeping concentration of B constant, the rate becomes four times
(i.e., changes from 0.005 to 0.020). This means that the rate of the reaction
is proportional to the square of the concentration of A,
Rate of reaction « [A]?
In other words, order of the reaction with respect to A is two.
Table 2. Data for the hypothetical reaction,
2A + 2B ——} Product.

Experiment Concentration(M) Rate of reaction

[A] [B]

Similarly, the comparison of results of experiments II and III shows that

when the concentration of B is tripled (from 0.01 M to 0.03 M) keeping the
concentration of A constant, rate becomes triple (from 0.020 to 0.060). The
rate of reaction is, therefore,proportional to the concentration of B i.e.,
Rate « B
In other words, order of the reaction with respect to B is one.
The overall rate law equation may be written as :
Rate = &[A]?[B].
Thus, the overall order of reaction is 2 + 1 = 3. Obviously, the powers of the
reactants in rate law expression are different than the coefficients in the
overall chemical equation.
Alternative Method
In some cases, it is not easy to compare the rates by simple inspection.
Then an alternative mathematical method is used as given below :
Consider a general reaction :
aA + bB + eC —-> Products
The general form of the rate law may be written as :
Rate = R[A]’ [B]? [C]’ .--(t)
CHEMICAL KINETICS

Then initial rate of the reaction may be given as :

ry = Rate =k [A],’ [B],’ [Cl
If [B] and [C] are kept constant, then
r, =, [Aly where &, = AI[B],’ (Cl,
The value of p can be determined by inspecting the rate at different values
of [A]. Alternatively, if we know the initial rates at two different concentrations
of A, we have :
Te = eyplAdg tine (it)
(Tp). = Ry [AgI.” ... (HE)
where (7,), and (7,), are the initial rates of reaction when the initial concentration
of A are [A,], and [A,], respectively. Dividing eqn. (ii) by Eq. (iii) we get

(mr _ at |
(2 — [LAole
Taking log on both sides we get
(7) [Aol
lo = p log ——
Be [Aol
_ log (74 i (r% Jo }
P= Jog (Agh /TAgle!
Therefore, the order of reaction with respect to A can be determined. In the
same manner, the order of reaction with respect to other reactants can also be
determined. The overall order of the reaction is the sum of all the exponents
in equation (7) as
m=ptgqtr.
This may be illustrated by considering the above reaction :
2A + 2B —> Product
The general form of the rate law may be written as :
Rate = R[A]’ [B]?
Then, the expression for the initial rate is
(Rate), = RAJ,” [Bl,’
where subscript zero denotes initial values. The problem involves the
determination of p and g.
Consider the experiments I and II (Table 3) and substituting the values
we get,
(Rate), = R(0.01)° (0.01)? = 0.005 (i)
(Rate), = 2(0.02)° (0.01)? = 0.020 ..(ii)
Dividing Eq. (iz) by Eq (2) we get
(0.02) _ 0.020
(0.01)? | 9.005
(ay = 4 or (2)? = 2 S poe
Similarly, comparing experiments IT and III
(Rate), = k(0.02)° (0.01)? = 0.020 .. (itt)
(Rate); = 2(0.02)’ (0.03) = 0.060 (iv)
Dividing Eq. (iii) by Eq. (iv), we get :

(0.03)' _ 0.060
0.01" 9-020
37 =3 or g=1
Therefore, the order with respect to A is 2 and the order with respect to
B is 1. Thus, the rate law may be written as :
Rate = R[A]*[B]
| 40 MODERN'S abc + OF CHEMISTRY-All

| SOLVED EXAMPLES
LJ Example 28. Solution : Let the initial rate be :

The following data were obtained for the reaction: ry = RIA?

2NO(g) + Br,(g) ——— 2NOBr(g) (To), _ JlAoh i
(To [Agls
Initial conc. Initial rate
Experiment [NO] [Br,] (mol Lt min™) or gos log {(75)4 / (Ty ot

I 0.10 0.10 13x IO? log {[Ao]; /TAg]s}

IT 0.20 0.10 52 10° _ (2.40%10°4/0,60%
loglog (2 x 107° /1x 107°)104) _ log 4_
log 2
fil 0.20 0.50 1.56% 10°
Determine (t) the orders with respect to NO and Br, ”. The order of reaction = 2
(iu) the rate law and Now, Rate = k[A/?
(iii) rate constant. a Rate s 2.4x10°* mol L's"!
or
Solution : The rate law may be written as : TAP (2x10? mol L)?
Rate = k[NO}’[Br,]*
= 0.6 x 107 mol Ls.
The initial rate becomes
(Rate), = k[NO}’[Br,]? Example 30.
Comparing experiment I and II, we get The following data were obtained for the reaction:
(Rate), = k(0.1)°(0.1I)7=1.3%x10% — ...(i) 2NO,(g) + F.(g¢) ———> 2NO,F
(Rate), = k(0.2)°(0.1)?=5.2x 10% — ...(ii)
Dividing Eq. (ii) by Eq. (2) Experiment Initial conc. Initial rate
[NO,/, [FJ], mol L4 min
(Rate), _ #(0.2)(0.1)" 5.210
1 0.20 0.05 6.0 x i0°
(Rate), —-R(0.1)"0.)"_—-1.8x10 ° 2 0.40 0.05 12107
or (2? =4 or (2/ =2? 3 0.80 0.10 48x 10°
: p=2

Thus, order with respect to NO is 2. Determine (1) order of reaction

(it) rate law
Comparing experiments IJ and III
(iti) rate of reaction when [NO,] = 0.50 mol L*
(Rate), = k(0.2)°(0.1)? =5.2 x 10% ....ait) and [FJ = 0.60 mol L".
(Rate), = k(0.2)°(0.3)? = 1.56 x 10> ....(iv) Solution : The initial rate expression may be written as :
Dividing Eq. (ziz) by Eq. (iv) , we get : (Rate), = k[NO,}’IF,]?
Comparing experiments 1 and 2, we get
k(0.2)"(0.3)7 _ 1.56x10~° (Rate), = k(0.2)2 (0.05)? =6.0 x 10% ...(z)
h0.2)°(0.)% «52x 107° (Rate), = k(0.4)% (0.05)? = 1.2 x 10°? ...(iz)
or ay =o Dividing Eq. (iz) by Eq. (7)
or g=1 (Rate), _ (0.4)’(0.05)" _ 1.2x10~
Thus, order with respect to Br, is 1. (Rate), — (0.2)°(0.05)" 60x10
(it) The rate law for the reaction or (QP =2
Rate = k[NO]” [Br,] = p=1
(iit) Rate constant can be calculated by substituting the Thus, order with respect to NO, is 1.
values of rate, [NO] and [Br,] for any experiment Comparing experiments 2 and 3,
Rate 13x10” (Rate), = k(0.4)°(0.05)? = 1.2 x 10°? ...(iiz)
kw ee (Rate), = k(0.8)"(0.10)? = 4.8 x 10°? ...(iv)
[NOT [Br,] (0.1) (0.1)
Dividing Eq. (iv) by Eq. (iit), we get :
1.3 x 10°? mol? L? s1.
k(0.8)°(0.10) _ 4.8x10~
LJ Example 29 k(0.4)?(0.05) «1.2 10?
The rates of a reaction starting with initial concentrations
(2) ig = A
2x 107% M and 1 x 10% M are equal to 2.40 x 107 M s1
Now, we have obtained p = 1 for the reaction, so that
and 0.60 x 10 M s+ respectively. Calculate the order
(2 (2)%=4 or (2))=2 or g=l
of the reaction with respect to the reactant and also the
Thus, order w.r.t. F, is 1
rate constant.
(z) Order of reaction = 1+1=2
CHEMICAL KINETICS
at)
(11) Rate law for the reaction 1s : Dividing eqn. (vit) by eqn. (vi), we get
Rate = k[NO,][F,] (Rate), _ (0.04)° 8.32x1073 _
(zit) Rate of reaction, when [NO,] = 0.50 mol L™ and (Rate), (0.02) 2.08x1073
[F,] = 0.60 mol L*
Let us first calculate, & from first run.
or oe =
cH 2
Rate = k[NO,][F,]
Therefore, the order of the reaction with respect to A, B
6.0 x 10-3 mol L7! min“! = &(0.20 mol L~*) x (0.05 mol L*)
and C are 1, 1 and 2 respectively and overall order of reaction
_ 6.0x10° =1+1+2=4
or = 0.6 mol L min?
~ 0,20 x 0.05
Rate = [A] [B] [C}
Substituting the values of k, [NO,] and [F,]
Substituting the values from expt. 1, we get
Rate = 0.6 x (0.5) x (0.60)
= 0.18 mol L* min". 2.08x 10° = k& x 0.02 x 0.02 x (0.02)
_3 7 ay
L} Example 31 = 2.08 as _ 2.08 x at Se ee
(0.02) 16x10
The initial rate of reaction :
Rate of reaction when concentration of all reactants = 0.01 M
A + 5B + 60 >> 3L + 3M
has been determined by measuring the rate of disap- Rate = 1.3 x 10+ x (0.01) x (0.01) x (0.01)?
pearance of A under the following conditions : = 13x10*Mmr!.
Expt. [A], [Bl], [Cl/, Initial rate According to the reaction,
No. M M M M/min— dA] 1d{[B)_ 1d{C)
i. 0.02 0.02 0.02 2.08 x 10% Rat a 5 dt 6 dt
2. 0.01 0.02 0.02 1.04 x 10%
_ 1 a[C] _ s d{M]|
a. 0.02 0.04 0.02 4.16 x 107 - 3 dt 3 dt
4, 0.02 0.02 0.04 8.82 x 107
Determine the order of reaction with respect to each Now, Rate = _1d{B)
5 dt
reactant and overall order of the reaction. What is the
rate constant ? or a = —5x Rate=-5x13x10+*Mmin!?
Calculate the initial rate of the reaction when the
= -6.5 x 10*M min".
concentration of all the reactants ts 0.01 M. Calculate
Similarly,
the initial rate of change in concentration of B and L.
Solution : Rate law may be written as: Rate = 1d)
3 dt
(Rate) = k[A]*[B]°[C]°
The initial rate becomes (Rate), = k[A,]" [B,]°1C,I° At) or a: = 3x Rate=3x1.3x10*Mmnm!
t
Comparing experiments 1 and 2
= §8.9x10+?M min".
(Rate), = &(0.02)* (0.02)’ (0.02) = 2.08 x 103 ._-(ti) Example 32
(Rate), = k(0.01)* (0.02)” (0.02) = 1.04 x 10-3 (iii) Nitrogen pentoxide decomposes according to equation :
Dividing Eq. (ii) by Eq. (ii) we get
2N,0,(g) —> 4NO, (g) + O,(g)
(Rate), _ (0.02)7 2.08x10° _ This first order reaction was allowed to proceed at 40°C
(Rate), (0.01) 1.04x107° and the data below were collected :
or o" = 2
- a= | [N,O,] M) Time (min)
Comparing experiment 3 and 1, we get 0.400 0.00
(Rate), = k (0.02) (0.02)° (0.02) = 2.08 x 103 ...(iv) 0.289 20.0
(Rate), = k (0.02) (0.04) (0.02) =4.16x 10 ...(v) 0.209 40.0
Dividing Egn. (v) by Eqn. (iv), 0.151 60.0
(0.04) = 4.16x107° | 0.109 80.0
(0.02) = -2.08x 107? | (a) Calculate the rate constant. Include units with your
2” = 2 answer.
b= 1 (b) What will be the concentration of N,O, after 100
Comparing experiment 1 and 4, we get minutes ?
(Rate), = k(0.02)° (0.02)° (0.02) =2.08x 103 _.(vi) (c) Calculate the initial rate of reaction. (D.S.B. 2011)
(Rate), = k(0.02)” (0.02)° (0.04) =8.32x 103 ...(viz)
a 4/42 MODERN'S abc + OF CHEMISTRY-All

Solution : (a) Since it is a first order reaction. at ¢ = 80 min

2.903 0.400
PS = lb
— = log = 80 0.109
= 2.808 x 0.565
Rk can be calculated as:

ae =ees = 0.01626 min“

ce 2.303 is 0.400 The average value of rate constant,
20 0.289 k = 0.01624 min“ or = 1.624 x 10 min“.
= — iat (6) Concentration of [N,O,] at ¢ = 100 min

| 2.303 0.400
== 0.01624) min
in72 0.01624 = —100 lo 4 [N,O;]

at ¢t= 40 min
0.01624 0.400
2.303 0.400 —— x 100 = log
k = —— log —— 2.303 LN,O;]
40 0.209
0.400
or log = (2/052
2 = 0.282 © TN,Os]
0.400 . .
== 0.01624: min
| :
[NOs] = antilog (0.7052) = 5.072

at t = 60 min ; [N,O,] = 0.400 _ 0.0789 M

p= 2:303 |, 0.400 5.072
~ 60 5 0.151 (c) Initial rate of reaction,
rate = k[N,O-]
= 2.908 0.428 =
60 = 0.01624 x 0.400 = 6.496 x 10°
= 0.01624 min?

=Pract teae
23. The following rate data were obtained for the reaction :
2NO(g) + O,(g) ——> 2NO,(g)
Experiment Concentration (mol L~) Rate of reaction
[NO] [O,| mol L? s+
J 0.30 0.30 0.096
Il 0.60 0.30 0.384
IT 0.30 0.60 ale
IV 0.60 0.60 0.768
Determine the rate law expression and order of the reaction.

24, For the reaction :

2ZNO(g) + Cl(g) ——~> 2NOCI(g)
the following data were collected. All the measurements were taken at 263 K.
Experiment Initial Initial Initial rate of disappearance
No [NO] (M) [Cl] (MD) of Cl, (M/min)
i 0.15 0.15 0.60
2 0.15 0.30 1.20
Answers to Practice Problems 3 0.30 0.15 2.40
4 0.25 0.25 ?
23. Rate = k[NOJ [O,], order = 3
(a) Write the expression for rate law.
24, (a) Rate = k[NO}’[Cl,]
(b) 177.8 M2 min"! (6) Calculate the value of rate constant and specify its units.
| Soe (c) What is the initial rate of disappearance of C/, in exp. 4 ? (D.S.B. 2012)
eee 25. Fill in the blanks in the following table which treats a reaction of a compound A
with a compound B, that is the first order with respect to A and zero order with
respect to B.
CHEMICAL KINETICS 4/43 —

Experiment [A] [B] Initial rate

mol L7! mol L7!
I 0.1 0.1 2.0 x 10°? mol L7! min“!
II — 0.2 4.0 x 10°? mol L“! min“!
Ill 0.4 0.4 =—

IV mi 0.2 2.0 x 10° mol L™* min™ — Answers to Practice Problems =

26. In a reaction between A and B, the initial rate of reaction was measured for a ; 9
different initial concentrations of A and B as given below : cli LC
oc/, L-!
SW.mir, <04th line 0.1.
A (M) 0.20 0.20 0.40
0.10 0.05 fn, =Sian,. = 0.
B (M) 0.30
r(Ms*) 893x10% 893x10° 2.53 x 10+
What is the order of reaction with respect to A and B ?

4. Ostwald isolation method

This method was introduced by Ostwald in 1902 and is used to find the
order of a reaction with respect to one reactant at a time. The total order of
the reaction is then equal to the sum of the orders of reaction for individual
reactants. This method is based on the principle that if the concentrations of
all but one reactant are taken 1n excess, then during the course of the reaction,
the concentration of those reactants taken in excess will remain almost constant
and hence variation in rate will correspond to the concentration of that reactant
whose concentration is small. This process is repeated with other reactants one
by one and order with respect to each reactant is determined. The overall order
will be the sum of all these orders. For example, consider the general reaction:
aA + 6B + cC ——> Products
Suppose we isolate A by taking B and C in large excess and get order of
reaction with respect to A (say p). Similarly, we isolate B by taking A and C in
excess and isolate C by taking A and B in excess and get order with respect
to B and (say q) and C (say r) respectively.
Overall order of reaction n =p +q +r.
5. Half Life Period Method
The order of a reaction can also be determined by half life period method.
This method is based on the principle that if a reaction is of the nth order
in a reactant, then half life is inversely proportional to (n—1)th power of its
initial concentration.
For example, if initial concentration of a reactant is C, and half life period
is (¢,/.),, 1f initial concentration of a reactant is C, and half life period is (¢,,,),
| A
(ty,3 hae (F }
then
(t1)9 )o C; 4

log(t,)2)4 YW (ta) = (n-l)logC,/C,

nal

_— log(t1/2), /(tv2)y
_
log C, /C,
From this, 7 can be calculated.

ESOLVED EXANIELES 7
Ul Example 33. Concentrations were measured as a function of time
The reaction : and are given as :

ean a So ee eee ee. mun.

paar gu
[CH.COF] (M) a"min gli (MD
[H,O] f
has been studied under the following initial conditions: 0 0.01000 0 0.02000
Experiment I Experiment I 10 0.00857 10 0.0176
[H,O], = 1.00 M [H,O], = 0.02 M 20 0.007385 20 0.0156
[CH,COF], = 0.01 M [CH,COF], = 0.80 M 40 0.00540 40 0.0122
 MODERN’S abc + OF CHEMISTRY-—AXIl

Calculate the order ofthe reaction and the rate constant

(t1/2),
for the reaction.
(t/a), Ell
Solution : Let rate of reaction is 1152 _ (oz)
Rate = k[CH,COF|* [H,0]’ 568 0.1
In the first case, [H,O] >> [CH,COF]. Therefore, we can 2.02 = (2)r-1
determine rate with respect to CH,COF according to Ostwald or n-l=l1
isolation method. Since rate of reaction changes with time, n= 2
the reaction is not of zero order. We can now apply first order Thus, order of reaction is 2.
equation as : Alternatively, applying the formula

k=
2.303, [CH,COF',
log ——>—__* _ log (t1/2), /(t1/2)>
t [(CH,COF] log C, /C,
log 152/568 _ |, 0.3071
t [CH,COF] —&[H,0]? = 2-393jog]!CHsCOF log 0.2/0.1 0.3010
| | | [CH,COF]
(min) (M) (min? al fa = 2
0 0.0100 =

10 0.00857 0.0154 MISCELLANEOUS

20 0.00735 0.0154 ——— re Ve Ne
40 0.00540 0.0154 LJ EKxample 35
“. k (H,O] = 0.0154 min A first order reaction has a rate constant of 0.0051
min. If we begin with 0.10 M concentration of the
.. Order of reaction with respect to CH,COF is 1.
reactant, what concentration of reactant will remain
Now let us determine order of reaction with respect to H,O. in. solution after 3 hours ?(D.S.B. 2009; AI.S.B. 2009)
Since the concentration of water changes, it 1s not of zero order. Solution : For first order reaction,
We now apply first order equation as :
2.303 lo [Alp
2 2.303 [H,0]
t [HO] k[(CH,COF]? = ; log fH,O] EO
[A],
=0.10 M, & = 0.0051 min“, t=3x 60 = 180 min, [A] =?
(min) (M‘*) (min)
180 = 2303. 0.10
log ne!
0 0.0200 ~
0.0051.” [Al
10 0.0176 0.0128
20 0.0156 0.0124
0.10 = JEUx0,000!
og tt? 180x0.0051 _ 9 g0n6
40 0.0122 0.0124 “ [A] 2.303
The value of & is almost constant and mean value = 0.0125 7 = 2504
min.
.. Thereactionis first orderin H,O andwe have k[CH,COF] b a] = 22°
2.504 - oo41m
= 0.0125 min}.
LI Example 36
The rate constant can be calculated as:
What will be the initial rate of a reaction if its rate
Incasel, k =
k{H,O? — 0.0154 min~ 1 =0.0154M-! min?! constant is 10% min! and the concentration of the
[HO] 1.0M reactant is 0.2 mol dm~? ? How much of the reactant
a a, | will be converted into the products in 200 minutes ?
In case II,k = RICH,COF! _ 0.0125 min ~
[CH,COF] 0.80M Solution : Rate constant, k=10? min},
Initial rate = [A]
= 0.0156 M* min
(10-3 min“?) x (0.2 mol dm-)
”. Rate constant = 0.0155 M-! min}, = 2x 10%* mol dm? min!
Ll Example 34 Now, the integrated rate equation for the first order
The half life period for the conversion of ammonium reaction Is :
cl
cyanate into urea at 803 K, at initial concentrations kt 2.303 log
of ammonium cyanate of 0.1 mol L-1 and 0.2 mol L~4 ai —x

are 1152 and 568 min respectively. What is the order or log —“— = 2 *3
a—xX
of the reaction ? =) Il 200 min, & = 10°? min“! so that
Solution : For C, = 0.1 mol L*, (¢,,,)* = 1152 min
a _ 10°x200 = 8.68 x 10°
For C, = 0.2 - L*, (¢,5). = 568 min
~ - 2.303
Since ba © qc! or = 1.22 (antilog 8.68 x 10-7 = 1.22)
CHEMICAL KINETICS

or a= 1.2294 -—1.22x Solution : For a first order reaction,

us)
or 1.29% = 1.22a —a = 0.22a 2.303 l [A] 0

or [=
0.22
7 = 0.18a
kk” [Al
Le k = 60s14, [A] = [A],/10
0.18 100 2.303 ” [A], _ 2.303
% conversion = ee ee Now, Ps log 10
60 [A], /10 60
LU) Example 37.
= 0.0388sor3.8 x10" 5s.
A first order reaction takes 20 minutes for 25% decom-
Example 40
position. Calculate the time when 75% of the reaction
will be completed. (A.LLS.B. 2017)
The haif life period for radioactive decay of 14C is 5730
year. An archaeological artefact contained wood had
Solution : For the first order reaction :
only 80% the 1C found in a living tree. Estimate the
b= :
2.303 A
log [Alp age of the sample.
t [A] (A.P.S.B. 2010, Mizoram S.B.2014)
ax 25 ;
If [A],
=a, [A] = a—- =0.75a,¢=
20 mm 0.693
100 Solution : Decay constant, k = a
b= 2.303 \oz a ty = 0730 year —
20 0.75 a 0.693
7 = 1.209 x 10+ year+
2.303 . 5730y
= x 0.1249 = 0.0144 min!
: 20 ax 75 : Since the rate of counts 1s proportional to the number of 4C
In second case, if [A], =a, [A] =a— wa 0.25 a and time, atoms in the sample,
i=. N, = 100, N = 80
; Al 2.303
Now, t = a og Lb = log : 2.303 N
k [A] 0.0144 0.254 Now,
Ow t = ——log—?
b 4 N

2.303 100
=ea
Aida x 0.6021
0. = 96.3
96.3 min.
mi
1.209 x 10 80
LJ Example 38.
= a x 0.0969
A first order reaction takes 23.1 minutes for 509% 1.209 x 1074
completion. Calculate the time required for 75% comple- = 1846 year.
tion of this reaction. (log2 = 0.301, log3 = 0.4771, log4
Example 41
= 0.6021) (A.LS.B. 2015)
Calculate two-third life of a first order reaction having
Solution: For a first order reaction,
k=5.48x104s+. (H.P.S.B. 2010, Pb. S.B. 2018)
k= 2.308 1, [Aly Solution : For two-third of a reaction,
t [A]
[A], = a, [A] =a-2/8a=a/3
If [A], = a, then [A] = a— 2X28 = 0.50 a, ¢t = 23.1 min
2,303 [A]
ae cee |5 (Al0
2.303 a 23 h
= ——log ——
23.1 ° 0.5a _ 2.303 log a 2,303 log 3
_ 2.303 log 2 k a/3 k
23.1 fo = ee log 3 = 2.01 x 103° s.
2.000 : 9.48 x 107
; x 0.301 = 0.030 min-! Example 42
Now, if [A], = a, and [A] =a
ax _
0.25 a The reaction: SO,Cl, —*—+ SO, + Cl,
is a first order reaction with half life 3.15 x 10%s at
, = 2308), [Alo 575 K. What percentage of SO,Cl, would be decomposed
k [A] on heating at 575 K for 90 minutes? (AJ.S.B. 2003)
2.303 a
t = ———log Solution : For the first order reaction :
0.030 0.25a
2.303 lo [Al
t= 2.303 log4
0.0350
TAI
Now, tj = 3.15 x 10*s*
t= 2.308
0.030
9.6021 = 46.2 min
p = 9:693__0.698_ 99 9554
LU) Example 39. to 3.15x10
time, t = 90 min = 90 x 60 = 5400s
The rate constant for a first order reaction is 60s! . How
much time will tt take to reduce the concentration of the 22%105 = 2308 log [Alo
reactant to 1/ 10th of its tnitial value ? 9400 [A]
(A.ILS.B. 2007, H.P.S.B. 2012, —5
or log [Alo = 2.2x10 * x5400 = 0.0516
Pb. S.B. 2018, 2016, Mizoram S.B. 2013)
[A] 2.303
| 46 MODERN'S abc + OF CHEMISTRY-All

or [Alp = 1.126 = =o
=—
2.303
108
a
[A] 8.13 x 10 0.40a

or tAl = 0.888 2.303

[Aly = ———_.
8.13 x 10
x 0.3979
Amount of SO,Cl, decomposed = 1 — 0.888 = 0.112
0.112 112.7 min.
Percentage of SO,Cl, decomposed = x 100 = 11.2%.
Example 45
Example 438 Show that in case of a first order reaction, the time
The rate of decomposition of N,O, in CCL, solution taken for completion of 99.9% reaction is ten times the
has been measured at 318 K and the following results time required for halfchange of the reaction.
were obtained : Solution : When 99.9% reaction is completed,
t(min) 0 135 339 689 1680 99.9
c (M) 2.08 1.91 1.67 1.85 0.57 [R] = [Rlp-F5p
(lo =0.001 IRI,
Find the order of reaction and calculate its rate constant.
What ts its half life period ? Mas f \Al
99 9%) = w fh eval
Solution: Itis clear that the rate of reaction does not remain
constant with time and therefore, it 1s not a zero order reaction. 2.303
We try integrated rate equation for first order reaction as: ey? og __lRly = ——— log 103
Rk 0.001[R],, R
k= bin Lo) 2.303 x3
t (C) ee saeat aaa (Lt)
t C k= gene icp 0 min?
t (C) When half of the reaction is completed
(min) (M)
2.08 = [R] = [R],-0.5 [R],=0.5 (Rl,
2.303, 2.08 — 2.303, [Rlp = 2.303 nee
135 1.91 ——— log ——- = 6.32 x 10-4
135 1.91 k 051k], #&
339 ~—«-1.68 EO Ge 1
339° 1.68 — a
2.303 * 0.3010 .
...(it)
k
683 1.35 2.308 jog 2-08 _ 6 33 x 10-4 Dividing eq. (i) by eq. (zz)
683. 1.35
1680 0.72 2,803 1, 2-08 _ 6.31 440-4 fi99.9%)
ts = 3
Feo ang
10 times.
1680” 0.72
Since value of & remains to be constant, the reaction is of L Example 46
first order.
The decomposition of phosphine, PH,, proceeds
k =6.315 x 10-* min“!
according to the following equation :
0.695 _ 0.693
Now, i.1f = 4PH, (g) ———+P, (g) + 6H, (g)
k
~ 6.315 10-4 min7! lt is found that the reaction follows the following rate
= 1.097 x 10° min. equation :
lL] Example 44 Rate = k{PH,].
A first order reaction is 15% complete in 20 minutes. The half-life of PH, is 37.9 s at 120° C.
How long will it take to complete GO% ? (i) How much time is required for 3/4 of PH, to
(P0.S.B.2010, H.P.S.B, 2012, Mizoram S.B. 2018) decompose?
Solution : For the first order reaction :
(it) What fraction of the original sample of PH,
2.303 [Alp remains behind after 1 minute? (AJ.S.B. 2010)
g = log ——+
Ra, A) Solution : Half life period, ¢,,, = a
a 2el5
If [A], =a, [A] =a—- = 0.85 a, t = 20 min
100
or = a = hehe = 0.0183 s+
—_
=
2.303
—— lo
a to 37.95
20 . 0.85 a
Now t
2 2.303,
a log (Al
[Al 0
2.303
x 0.0706
20 (i) For 3/4" of a reaction to decompose,

In second case, if [A], = a, [A]

8.13 x 10 min“!

=a — sai = 0.40 a and

T= [al,-2[a},
Sra)
= 2A
=e
time,t =? _ 2.303 log |A , _ 2.308 ie
Now, i=
2.303, [Al 0.0183 “1/47 ~ 0.0183
k [A] 4 0
CHEMICAL KINETICS
a7]
If initial cone. of Ais a, then
= —2.909 x 0.6020 = 75.76s
0.0183 [A] = guy = ho
4 A
(ii) p = 2:308),, [Alo kR=2Ax10%s1
t [A]
For t = 1min.=60s
ag pe _ ae" aan
2.4x10% "a/4 2.4x10°
0.0183 = 2,308 1,5 [Alo
60 [A]
or oglAlo = 9.0188x60 _ 9 76g L} Kxample 49.
[A] 2.303 Starting from 10g of a radioactive element, 0.25 g was
or [Alo = 2.585
left after 5 years. Calculate
[A] (i) Rate constant for the decay of the radioactive element.
(it) The amount left after one year.
IA] - 033
(iit) The time required for half ofthe element to decay.
[Alo
(iv) Average life of the element. (A.LLS.B. 2011)
LJ Example 47.
Solution:(1)
2.303) log
& = ae
[Alb
Sucrose decomposes in acid solution into glucose and
k [A]
fructose according to the first order rate law witht, ;.=
[A], = 10g, [A] =0.25g¢, t= 5 years
3 hrs. Calculate the fraction of sucrose which remains
after 8 hrs. (CBSE Sample Paper 2011) k 2.303 10

Solution : = ala nee = 0.231 hr

tio hr
A (zt) Amount left after 1 year
Now, k= 2.303 log [A],
t [A] t=1lyear, [A],=10g, [A] =?
2.303 , _—_——4
[Al
0.231 = — I
Shr — [Al p = 2303), [Al
; [A]
log [A], = 9:231%8 _ 9 soo4 0.7379
:
2.303,
==——lo log
10
[A | 2.303

[A], log10 = ~2**"

0.7379x1 _ 9.3904
Ta] = 6.345 ETA] 2.303
[A]
10 = Antilog (0.3204) = 2.09
IA] = 0.158 [A]
[A],
LJ Example 48. [Al =
2.09
= 4,785 ¢
The thermal decomposition of HCO,H ts a first order (tit) Time for decay of half of the element
reaction with a rate constant of 2.4 x 10% sata
certain temperature. Calculate how long will it take 0.693 0.693
= — = = 0.9392
for three-fourths of initial quantity of HCO,H to 12 ~ 2 * 0.7379 —
decompose. (log 0.25 = — 0.6021). (A.LS.B. 2011) (iv) Average life,

Solution : t =
2.3034» [Alp
——log t= = = : = 1.5552 year
k [A] k 0.73879

= Pal Glew
27. An acidic solution of sugar was hydrolysed to the extent of 57% after 66 min-
utes. Assuming the reaction to be of first order, calculate the time taken for
75% hydrolysis. — Answers to Practice Problems —
28. A first order reaction is 20% complete in 10 minutes. Calculate the time taken for
the reaction to go to 80% completion. (Ar.S.B. 2017) 27. 108.4 min.
29. A first order decomposition reaction takes 40 minutes for 30% decomposition. 28. 72.12 min.
Calculate its t,,, value. (D.S.B. 2008, 2013) 29. 77.69 min.
30. A first order reaction is 20% complete in 10 minutes. Calculate the time for 75% 30. 62.15 min
completion of the reaction. Hints & Solutions on page 68
(Pb.S.B. 2010, H.P.S.B. 2011, 2012, Hr. S.B. 2017)
| 48 MODERN'S abc + OF CHEMISTRY-All

ol. The three-fourth of a first order reaction is completed in 32 minutes. What is the half
life period of the reaction ? (J_.K.S.B. 2000, H.P.S.B. 2011, Mizoram S.B. 2017)
OZ. The half life period for a reaction of first order 1s 2.31 x 10° min. How long will it
take for 1/5 of the reactant to be left behind ? (Pb. S.B. 2013)
oo. A reaction is first order with respect to reactant P having rate constant 6 min.
If we start with [P] = 0.5 mol L-!, when would [P] reach the value of 0.05 mol
L+ ? Calculate half life period of the reaction. (Pb. S.B. 2013)
34. For a first order reaction half life period is 100 seconds. How long will it take the
ol. 16 min. reaction to complete 75%? (Uttarakhand S.B. 2013)
o2. 5.36 x 10° min. OO. The rate constant for a first order reaction is 80 s +. How much time will it take
oo. 0.383 min, 0.1155 min. to reduce the concentration of the reactant to 1/18th of its initial value?
a4, 200 min. (Pb. S.B. 2016)
oo. 3.61 x 107s. 36. The pressure of a gas decomoposing at the surface of a solid catalyst has been
36. Order = 0, =5 Pas, t,,. = 400s. measured at different times and the results are given below :
ov. “ero order. t(s) 0 100 200 300
38. 399 min. p(Pa) 4.00 x 10? 3.50 x 10° 3.00 x 10? 2.5 x 10?
39. 161 min. Determine the order of reaction, its rate constant and half life period.
of. The half life period of a substance is 60 min at a certain initial concentration.
Hints & Solutions on page 68 When the concentration is reduced to one half of the initial concentration, the
half life period is found to be 30 min. Calculate the order of the reaction.
oo. The thermal decomposition of a compound is of first order. If 50% of the compound
1s decomposed in 120 minutes, how long will it take for 90% of the compound to
decompose ? (H.P.S.5. 2011, Nagaland S.B. 2018)
39. A first order reaction takes 69.3 minutes for 50% completion. Calculate the time
required for 80% completion of this reaction. (D.S.B. 2005)

r-S The half life time of a first

2 PROBLEMS
order
Accelerate Your Potential
(for JEE Advance)

Now, 1 mole of N,O (g) at S.T.P. = 22.4 L

0.099 mole of N,O (g) at 8.T.P. = 22.4 x 0.099
decomposition of nitramide is 2.1 hour at 15°C.
= 2.218 litres.
NH,NO, (aq) —> N,0 (g) + H,O ()
34) The decomposition of Cl,O, at 400 K in the
If 6.2 of NH,NO, 1s allowed to decompose, calculate gas phase to Cl, and O, is a first order reaction.
(z) time taken for NH,NO, to decompose 99% and (i) After 55 seconds at 400 K, the pressure of Cl,O,
(7) volume of dry N,O produced at this point measured falls from 0.062 to 0.044 atm. Calculate the rate constant.
at S.T.P. (it) Calculate the pressure of Cl1,O, after 100 s of
(:) For first order reaction. decomposition at this temperature.
For the first order reaction :
ae 0.693
2.303 a
tio = ]
‘ t 8 (a-zx)
Here ti = 2.1 hr (1) Here, a = 0.062 atm, (a —x) = 0.044 atm,f=55s

np = 299%
2A
0 Ts Fe Se ae WOE poe 1 a
55 0.044
(tt) To calculate (a —x) when ¢t = 100 s, a = 0.062 atm.
Now, t= pI log [Aly
k [A] 6.24103 = 2.003 lo 0.062
If Al, = a, [A Sf — —_
100
ved =0.0la 100 (a — x)
0.062 ey_ 6.24x10%x100
Sena a eed |
2.303 1 a 2.303 or log aaa) 2.303 0.2709
= — log — x 2=13.96hr
0.33 0.0la 0.33
(zi) 1 mole of NH,NO, decomposed to give = 1 mole of N,O or 0.062 = 1.866
(a — x)
Moles of NH,NO, taken = 9:2 = 0.1 mol (Molecular mass of
NH,NO, = 62) 62 or (a—x) = 0.033 atm.

0.1x 99 The gas phase decomposition of dimethyl

Moles of NH,NO, decomposed = = 0.099 mole
100 ether (CH,OCH,) follows first order kinetics.
Moles of N,O (g) produced = 0.099 mole
CH,OCH,(g) —> CH,(g) + H,(g) + CO(g)
CHEMICAL KINETICS
aso)
The reaction is carried out in a constant volume Let at time f, [A] = 3[B]
container at 775 K and has a half life of 14.5 min. Initially
only dimethyl ether is present at a pressure of 0.40 For A,k, = ee For B, k= ode
atmosphere. What is the total pressure of the system after
12 min? Assume ideal gas behaviour. For A after time f,
CH,OCH,(g) —> CH,(g) + H,(g) + COW)
Initial pressure 0.40 atm - - ~ = a X00 log 5 or cae ae (t)
Pressure after 12 min (0.40 — P) atm P 1 iE
For B after time f,
Since the reaction is of first order:
p = 2-303 log [R] 2 te x15 log ha (ii)
t [Rk]
For ideal behaviour, mole « pressure(at constant T and V) Nowt, =t,

[R], = 0.40 atm™, [R] = (0.40 — P) atm

a bea) = a st log =
0.693
k = ——— =0.0478 mn!
14.5
log st
0.0478 = 2:3038 peas a [B] _ logi—logiB!
ie (0.40 -—P) ig, == log 1—-log3[B]
0.40 0.0478 x 12
3[B]
pS
© (0.40—P) 2,303
Taking antilog

snes = L774 : log| B]

0.40 -—P
log3 + log|B|
0.40 = 1.774 x 0.40-—1.774 P
4 (log 3 + log[B]) = log[B]
1.774 P = 0.7096 — 0.40 = 0.3096
4(0.477 + log[B]) = log[B]
0.3096
Ee = 0.175 atm
1.774 1.908 + 4 log[B] = log[B]
.. Pressure of dimethyl ether decomposed = 0.175 atm or 3 log[B] =—1.908
Total pressure = 0.40-P+P+P+P=0.40+2P
or log[B] = —0.636
= 0.40 + 2 x 0.175 = 0.75 atm
[B] = antilog (—0.636) = 0.231 ...(ti1)
3) A flask contains a mixture of A and B. Both
the compounds decompose by first order kinetics. The Substituting the value of B in egn (iz)
half lives of A and B are 60 min and 15 min respectively. If 2.4003 X15 ]
t= ———— log ——_
the initial concentrations of A and B are equal, how long 0.693 0.231
will it take for the concentration of A to be three times
= 2.003 X15
that of B? x 0.636
0.693
Let the initial concentration of both A and B be 1M.
= 31.7 min
[A], = 1M, [5] (aM

PSEUDO CHEMICAL REACTIONS

Some reactions are first order each with respect to two different reactants /.e.,
A+ B ——— Products
Rate = [A] [B]
However, if one of the reactants is present in high concentration (solvent)
then there is very little change in its concentration. In other words, the
concentration of that reactant remains practically constant during the
reaction. For example, if [A] = 0.01 M and that of solvent water [B] = 55.5 M,
the concentration of B changes only from 55.50 to 55.49 M even after the
completion of the reaction. Under such conditions, we may write,
Rate = RIAI where Ro = RB]
The reaction, therefore, behaves as a first order reaction in A. Such
reactions are called pseudo first order reactions.
The reactions which are not truly of first order but under certain
conditions become reactions of first order are called pseudo first
order reactions.
a 4/50 MODERN'S abc + OF CHEMISTRY-All

Consider the hydrolysis of ethyl acetate :

CH,COOC,H. + H,O as’. CH,COOH + £C,H,OH
The molecularity of the reaction is two because it involves two reacting species,
namely ethyl acetate and water. However, the concentration of ethyl acetate
changes during the reaction while water is present in such a large excess
that its concentration remains practically unchanged. Therefore, the rate of
the reaction depends only on the concentration of ethyl acetate and hence the
order of the reaction is one.
Rate = k’ [CH,COOC,H.] [H,O]
[H,O] can be takes as constant so that
Rate = k [CH,COOC,H,]
where 2 = k’ [H,O]
Thus, the reaction appears to be second order but follows the first order
kinetics. Such reactions which appear to be of higher order but actually follow
lower order kinetics are called pseudo chemical reactions. For example,
the above reaction is called pseudo first order reaction. Another important
example is the hydrolysis of cane sugar or inversion of cane sugar to give
glucose and fructose :
C,5H,.9), + HO > C,.H,,0, + C,H,,0,
Sugar Excess Glucose Fructose
Rate = kIC,,H,,0,4]
In this case also molecularity is two while order is one.

i SOLVED EXAMPLES
LU) Example 50 ‘ 2.303 Cc. |
Hydrolysis of methyl acetate in aqueous solution has coin os — it 108 oo )
been studied by titrating the liberated acetic acid against 0 0.8500 _
sodium hydroxide. The concentraction of the ester at
different times ts given below :
; vinta bi a a6 4 30. 0.8004 a log ate = 2.004 x 10-3
c(molL) 0.8500 0.8004 0.7588 0.7096
Show that it follows a pseudo first order reaction as 60 0.7538 a log cee = 2.002 x 10°
the concentration of H,O remains nearly constant (55 ,
mol L-1) during the course of the reaction. What is the 90 0.7096 = lee> 35—~29 005x107

ia aaa area al — Since k[H,O] is constant, it is pseudo first order reaction.

rate = k' [CH,COOCH,] [HO] Ol = 9001240 Sake!
Solution: Forpseudo first order reaction, the reaction should (H,0} - 55M
be first order with respect to ester because [H,O] = constant onavi6
k = k'[H,O]. Let us calculate the value of & for the first order + p- SY =3.64 x 10° M min.
reaction : 99

COLLISION THEORY : ENERGY AND ORIENTATION BARRIERS TO

REACTIONS
We have learnt that the basic requirement for a reaction to occur is that
the reacting species (atoms, molecules or ions) must collide with one another.
This is also the basis of collision theory for reactions. This theory was put
forward by Max Trautz and William Lewis in 1916-18. It is based on kinetic
theory of gases. According to this theory, the reactant molecules are assumed
to be hard spheres and reaction is postulated to occur when molecules collide
with each other.
The number of collisions that take place per second per unit volume
of the reaction mixture is Rnown as collision frequency Z.
CHEMICAL KINETICS

The value of collision frequency is normally very high. For instance,

under ordinary conditions of temperature and pressure, in a gaseous system,
the collision frequency of binary collisions is of the order of 107° to 107°. If
all the collisions are effective in forming the products, the reactions must
be completed in a very short time. However, in actual practice, most of the
chemical reactions are slow and take much longer time for their completion.
This means that all the collisions among the reacting species at a given
temperature are not effective in bringing about the chemical reaction. The
collisions which actually produce the products and therefore, result in the
chemical reactions are called effective collisions.
There are two important barriers to a reaction namely
(1) energy barrier (it) orientation barrier.
(1) Energy barrier. For the reacting species to make effective collisions,
they should have sufficient energy to break the chemical bonds in the reacting
molecules. The minimum amount of energy which the colliding molecules
must possess is known as threshold energy. This means that only those
collisions of reactants will give products which possess energies greater than
threshold energy.
(it) Orientation barrier. The colliding molecules should also have proper
orientation so that the old bonds may break and new bonds are formed.
For example, consider the reaction :
NO, (g) + NO, (g) ——> N,0, (g)
During this reaction, the products are formed only when the colliding
molecules have proper orientation at the time of collisions. These are called
effective collisions [Fig. 10 (a)].
On the other hand, when the molecules do not have proper orientation at
the time of collision as shown in Fig. 10 (0), they result in ineffective collisions
and do not form the products.

Molecules a’ Bond
approach ‘ 7“ formation

Collision
(a) Properly oriented collisions form products

Molecules>
—_———— =EN | ) Molecules >
approach “) , separate

+ NO, Collision \ +
(b) Collisions not properly oriented No products

Fig. 10. Illustration of (a) effective and (0) ineffective collisions between
molecules for the reaction.
NO,(g) + NO,(g) ——_ N,0,(g)

Similarly, consider the reaction of bromomethane (CH,Br) with OH” ions

to form methanol. The OH- ion must attack the positively charged carbon to
form an intermediate which changes to product after elimination of Brion. If
OH does not get proper site for attack, reaction will not occur. It is observed
that in this reaction, first an intermediate is formed by the attack of OH” at
the site away form Br- and finally product is formed as shown below :
CH,Br + OH- ——> CH,OH + Br-
 MODERN'S abc + OF CHEMISTRY-All

ae -)C
Improper H-—C—Br’ ‘OH—— | No products
H<
orientation
H ce Repel

H—C—Br + OH
H attacking ion H H

Proper 6 [de
orientation

Intermediate Methanol

It is clear that proper orientation of reactants leads to the bond formation

whereas improper orientation simply makes them to bounce back and products
are not formed.
Thus, the collisions in which the colliding molecules do not possess the
minimum energy for effective collisions (threshold energy) or proper orientation
do not form products. In other words, the colliding species rebound unchanged
in such cases. Therefore, it follows that only a small fraction of collisions is
effective.
Thus, the main points of collision theory are summed up below :
(1) For a reaction to oceur, there must be collisions between the reacting
species.
(it) Only a certain fraction of the total number of collisions are effective
in forming the products.
(111) For effective collisions, the molecules should possess sufficient energy
as well as orientation.
The fraction of effective collisions, under ordinary conditions may vary
from nearly zero to about one for ordinary reactions.
Thus, the rate of reaction is proportional to
(a) the number of collisions per unit volume per second (collision frequency,
Z) between the reacting species,
(6) the fraction of effective collisions (properly oriented and possessing
sufficient energy), f:

1.e.., RAe - — & ieeae

dt

Table 3. Rate constant for N,O, at

DEPENDENCE OF REACTION RATES ON TEMPERATURE
different temperatures. Temperature has a great influence on reaction rates. In general, an
increase in temperature increases the rate of almost all reactions. On the other
Temperature (K) Rk (s7)
hand, a decrease in temperature decreases the rate. This effect is observed
71.81 for exothermic as well as for endothermic reactions. For example, the rate
3.56 x 10° constant for the decomposition of N,O, is 7.87 x 10~ s“ at 273 K but it becomes
4.98 x 10+ 3.56 x 10 s! at 298 K. This means that for a rise of 25° in temperature, the
4.87 x 10° rate constant is increased by about 45 times. Similarly, it has been observed
that the time taken for the decomposition of N,O, to half of its original
concentration is 10 days at 0°C, 5 hour at 25°C and 12 min at 50°C. You must
have observed in practicals that in a mixture of potassium permanganate
(KMn0O,) and oxalic acid (H,C,O,), potassium permanganate gets decolourised
faster at a higher temperature than at a lower temperature.
A general approximate rule for the effect of temperature on reaction rates
is that the rate of a reaction or rate constant becomes almost double for every
10° rise in temperature. This is also called temperature coefficient. It is the
ratio of rate constants of the reaction at two temperatures differing by 10°. Thus,
Rate constant (T + 10)°C
Temperature coefficient = :
Rate constant at TC
CHEMICAL KINETICS

Explanation for Increase in Rate of Reaction with Rise in

Temperature
According to collision theory of chemical reactions, we know that the rate
of a reaction depends upon collision frequency (Z) and fraction of the effective
collisions (f). Obviously, we may think that the increase in rate of a reaction
with temperature is brought about by either of the two or a combination of
both factors. These are discussed below :
(4) Increase in collision frequency. With the increase in temperature,
the average kinetic energy of the molecules increases and this leads to an
increase in number of collisions per unit time (Z). The average kinetic energy
of the molecules is directly proportional to the absolute temperature. This
increases only by 3% when the temperature rises from 300 K to 310 K.
This means that if the increase in the collision frequency is the only
reason for increase in rate of reaction with temperature, then the reaction
rate would have been increased by a factor of only 3%. This is very small in
comparison to the experimentally observed factor of 2 or even more in some
cases. Therefore, the increase in rate of a reaction its not simply due to the
increase in collision frequency.
(71) Effective collisions. According to the collision theory, only a small
fraction of collisions is effective in bringing about the chemical reaction and the
rest of the collisions are ineffective. For effective collision (to yield products) the
colliding molecules must have more than or equal to certain minimum amount Most probable
of energy called threshold energy. If the energy of the reacting molecules is kinetic energy Fraction of
| molecules
less than this value, collisions will be ineffective. Thus, the energy of collisions i
capable of
®
determines the possibility of a reaction. =
a effective collisions
2
Now let us consider as to why some collisions should be highly energetic &
E
while others are not so. Ludwig Boltzmann and James Clark Maxwell used
i
&
Cc
statistics to predict the behaviour of large number of molecules. 2
BD
We know that all the molecules in a substance do not possess the same hs
LL

kinetic energy. This is due to collisions between the moving molecules so that Energy __-_» Ee
their energies are transferred from one molecule to another. Thus, there is Fig. 11. Distribution of molecular
a distribution of kinetic energies among reacting molecules. If the energy of energies.
molecules are plotted against the corresponding fraction of molecules, N,/N,
with a given energy (where N, = number of molecules having kinetic energy
E and N, = total number of molecules), at a particular temperature, a curve
of the type shown in Fig. 11, is obtained. This is called Maxwell’s distribution
of energies. From the figure, it is evident that the fraction of molecules having
very low or very high energies is very small. Most of the molecules have
intermediate kinetic energies as shown by the peak in the graph. This peak
corresponds to most probable kinetic energy 1.e., kinetic energy of maximum
fraction of molecules. In the figure, E corresponds to minimum or threshold
energy required for effective collisions. The molecules having energy equal to
or greater than E will result in the formation of products and this fraction of
molecules capable of effective collisions is very small.
It may be noted that for reactions having low values of E, there will be larger
fraction of colliding molecules which produce effective collisions and hence, rate
of the reaction will be high. On the other hand, if the value of E for a particular
reaction is high, then only a few collisions will be sufficiently energetic to give
products while all other collisions will be ineffective. The reaction will proceed
very slowly.
Let us now consider the effect of increase in temperature on the number
of effective collisions. Fig. 12 shows the energy distribution of molecules at
two different temperatures T, and T,, where T, = T, + 10°.
| 454 MODERN'S abc + OF CHEMISTRY-All

From the figure, it is evident that the curve at higher temperature gets
shifted towards the right indicating that at higher temperature, the molecules
have higher energies. Further, the curve at higher temperature
is flatter than that at lower temperature which also indicates
—_— that the number of molecules with higher energy content
w
o
: Na get have increased.
2
=
OO The minimum energy required for the effective collisions
@
Oo is also shown in the diagram and the number of molecules
= Fraction of molecules
_
o _capable of effective
possessing energies equal to or greater than E, 1s proportional
=
collisions to area abcd at temperature T, and area abef at temperature
O
a) T,. In the figure, the area abef is roughly twice as large as
ie
LL
abcd. Since the rate of reaction depends upon the number
of molecules which possess energies larger than threshold
energy (for effective collisions), it may be interpreted that
Energy —————+ a
the fraction of molecules possessing threshold energy has
Fig. 12. Distribution of molecular energies at increased approximately two times and thereby, increases
temperatures T, and T,. the rate by two times for a rise of 10 degrees.
Thus, we may conclude that increase in the rate of reaction with the rise
in temperature is mainly due to the increase in number of effective collisions.
ARRHENIUS EQUATION AND CALCULATION OF ACTIVATION
ENERGY
Arrhenius proposed a quantitative relationship between rate constant
and temperature as :
k= Ag BdRT ...(21)
This equation is called Arrhenius equation in which constant A
is known as Arrhenius factor or frequency factor. It is also called
pre-exponential factor. It is a constant specific to a particular reaction.
This factor is related to how many successfully oriented collisions occur in a
particular reaction. E, 1s the activation energy which represents the minimum
energy that the reacting molecules must possess before undergoing a reaction.
Both A and E, are characteristic of the reaction. These are collectively called
Arrhenius parameters. The factor e=“®! corresponds to the fraction of
molecules that have energy greater than E,. T is the absolute temperature
and R is the gas constant.
Taking logarithm, Eqn. (21) may be written as
1
ee ee [ine = 1)
Rk T
Converting to common logarithm (/n X = 2.303 log X), we get
2.303 log k = 2.303 log A — =
Dividing each side by 2.3038, we get
InterceptlogA log k = log A- iT
...(22)
2.303 RT
It is clear that by increasing the temperature or decreasing the
activation energy will result in an increase in the rate of reaction.
Calculation of activation energy.
The activation energy can be calculated from Eqn. (22). As is clear the
equation is in the form y = mx + c which represents a straight line. When log k
1
is plotted against —, we get a straight line (Fig. 18). The intercept of this line is

equal to log A and slope is equal to __*a _

,77 —.
Therefore, Slope = — ——*— ...(23)
Fig. 13. Plot of log k versus 1/T to
calculate activation energy. Knowing the value of slope and gas constant R, activation energy can be
calculated as
CHEMICAL KINETICS 4/55 »»

E, = — 2.303 R x Slope
Alternatively, EK, and A can be determined by measuring the values of rate
constant at two different temperatures. Let 2, and zk, are the rate constants
for the reaction at two different temperatures T, and T, respectively. Then,

log
ne k, 1 == log
SS" A—-~ —4—
9303 RT, ..(24
aa
E
and log k, = log A-— —*—\ ...(25)
Ba = 8 “~ 9.303 RT,
Subtracting Eq. (24) from Egn. (25), we get

Ne © S21 = 9303R|T T,
or hie ae _ Ey Tid ...(26)
2.303 R|T, TT;
E =
or log oe eee
ky 2.303R |T, x T,

Collision Theory and Arrhenius Equation

Though Arrhenius equation is applicable under a wide range of
circumstances, collision theory provides a greater insight into the energetics
and mechanistic aspects of reactions. For a bimolecular elementary reaction:
A + B —-> Products
rate of reaction may be expressed as
Bate — 9 ...(27)
where Z,p represents the collision frequency of reactants A and B and
e Fa/RT yepresents the fraction of molecules with energies equal to or
greater than E.. Since rate of reaction is directly related to rate constant,
k, we can also write
ge A esale ...(28)
This equation predicts the values of rate constants fairly accurately for
reactions involving atomic species or simple molecules. However, if reactant
molecules are complex, significant deviations are observed. This is because,
even if the colliding molecules have energy greater than threshold energy,
they may not have proper orientation at the time of collision and therefore,
no breaking of bonds between reacting species and formation of new bonds
to form products may occur. In other words, besides the requirement of
sufficient energy, the molecules must be properly oriented in space also for
a collision to be successful resulting effective collisions.
To account for effective collisions, another factor P, called the orientation
factor or stearic factor or probability factor is introduced. Hence, eqn.
(28) may modified as 2s
k = PZ,,¢ °9/*" (29)
if we compare this equation with Arrhenius equation,
k= Ae Ea/RT

we observe that pre-exponential term, A in Arrhenius equation is

A = PZap
Thus, in collision theory, activation energy and proper orientation of the
molecules determine the criteria for an effective collision and hence the
rate of a chemical reaction.
It may be noted that collision theory has certain drawbacks. It considers
the atoms or molecules to be hard spheres and does not take into account
the structural aspects. Some other theories such as ‘transition state theory’
have been proposed to explain reaction rates. However, their discussion is
beyond the scope of present class.
| 4156 MODERN’S abc + OF CHEMISTRY-XII

Selucag Yuamertcalt Prtblems

FORMULAE AND UNITS
Arrhenius equation
log k log A 2 303 a RT

k = rate constant,
A = frequency factor
EK, Activation energy
R Gas constant
8.314 JK mol
For two different temperatures T, and T,,
bi fel
log
k, 2303001 ga
where 2, andz, are rate constants at temperatures T, and T, respectively.

me) AY >
LU) Example 51 ko
For a decomposition reaction, the values of rate ky E ; F
constant Rkat two different temperatures are given below: log 2 = eT ec a5 _ saa
k, = 2.15x10% s+ at 650 K ~~ i
and Re =2.89x 10% s1! at 700 K. 0.3010 = 2303x8314 mm 298 x 308
Calculate the activation energy for the reaction. :
(A.LS.B. 2009, Pb. S.B. 2014) he E = 0.3010 x 2.303 x 8.341 x 298 x 308
Solution : The Arrhenius equation is : :~ 10
Ry _ EK, At. = 52898 J mol!
°F}, 2.303R|T, 1, = 52.898 kJ mol-.
k,= 2.15x10%st T,=650K L} Example 53
= tol =
hy = oes lia SS The rate constant of a first order reaction becomes 5
Substituting the values,
times when the temperature ts raised from 350K to
ie 2.39x107 _ E, Ye 1 400K. Calculate the activation energy of the reaction.
2.15x10% 2.303 x 8.314 650 700 (R = 8.314 JK, log 5 = 0.69897).
(Nagaland S.B. 2018)
ae = EK, 700-650
2.303 x 8.314 |650 700 E [11
Solution : log ky = o i a
p= 1.046 2.303 8.314 x 650 x 700 hk, 2.808R/T, Ty
a
~ 19a 50
j, = 5 R=8.314JK*
hy = = —1
mol, —1 T, == 350K,
T,==400K
or = 182.254 kJ mol! E 1 1
log5 = ——#—__|___ —__
Example 52 2.303 x8.314 es ‘is
In general, it is observed that the rate of a chemical
reaction becomes double with every 10° rise in 0.69897 = E, . 400 — 350
temperature. If this generalization holds for a reaction , ~ 2.303x 8.314 |350~x 400
in the temperature range 298 to 308 K what would
; ; ; 0.69897 x 2.503 x 8.914 x 350 x 400
be the value of activation energy for this reaction ? a EE, = eEeEeFFe
(R = 8.814 JK mol) ”
(D.S.B. 2000, Pb. S.B. 2014) or = 37473.2 J mol = 37.473 kJ mol.
Solution : Arrhenius equation is:
hs F 1 1 LJ Example 54
logog — a
re = 2.303R|T,eae eee
a The rate constants of a reaction at 700 K and 760 K
are 0.011 s? and 0.105 s respectively. Calculate the
T, =298K,T, = 308 K, R=8.314 JK? mol values of Arrhenius parameters.
CHEMICAL KINETICS

: ko E, | 1 1 or log —
k = -
E:. ee —
Solution : log ~ = ee
k, 2.303R|T, T, A RT 2.303

k, = 0.011 s+, T, = 700 K, &, = 0.015 s+, T, = 760 K, Calculation of k

R = 8.314 JK-! mol 0.693 0.693
k = 26 _ UGO8! _ sage ges
tro 10x60
lor 0-005 § Bt
5 0.011 2.903
x 8.314/700 760 1155x107 _ 98.6 x 10°
E 760 —700
4x10% 8.314xTx 2.303
log 9545 = oJ
2.905 x 8.914 |700 x 760 | 98600
un ~ 16.54 = ~ 9374x2303 T
E 60
(ores oe or T= 98600 = $311.34 K.
2.903 x 8.314 x 700 x 760
8.314 x 2.303 x 16.54
FE = 0.9798 x 2.303 x 8.314 x 700 x 760 LJ EKxample 57
- 60 A first order reaction is 50% completed in 40 minutes
= 166.342 x 10° J mol? at 300 K and in 20 minutes at 320 K. Calculate the
= 166.342 kJ mol. activation energy of the reaction.
(Given : log 2 = 0.8010, log 4 = 0.6021, R = 8.314
Now, logk =- logA es ee
2.303 RT JK+ mol (A.I.S.B. 2018)
Solution : Let us first calculate 2, and &, at temperatures
or lop A = log k+ __ By 300 K and 320 K. We know that
ees 8 © 9 303 RT vw =
0.693 or k=
0.693
166.342 x 10° k tye
log A = log 0.011 +
2.303 x 8.314 x 700 0.693
= —1.9586 + 12.411
= 10.4524
A = 2.834 x 1019 5-1. At 320K, t,, = 20min hy =
hy E, [1 1
N log 2. =
2803R cereale
L) Example 55
The first order rate constant for the decomposition of ow BE 7, Ty
ethyl todide by the reaction: Substituting the values,
C,H,IJ(g¢) ——> C,H, () + HI @) 0.693, 40 _ E, 1 1
at 600 K is 1.60 x 10~° s. Its energy of activation is
°S 20 0.693 2.303x8.3141300 320
209 kJ mol. Calculate the rate constant of the reaction
at 700 K. N.C.E.R.TS (Kerala S.B. 2018) ss E, 320-300
Solution : E, = 209 kJ mol™ = 209 x 107 J mol °B* = 9 303x 8.314|300x 320
k, = 1.60 x 10% s, T, = 600 K
hy =? T, = 700K 0.3010 = Ey 20
2.903 x 8.314 * S00 x 320
Substituting the values
ho 209x 10° {700-600 or BK
0.35010 x 2.308 x 8.314 x 300 x 320
2oeoee
© G0x10
TT 2.303 x 8.314| 700x600 - 20
27663.8 J mol! or 27.66 kJ mol-!.
log 2Ro |
= _2.599
5 1.60x 10 LJ Example 58.
2 = 397.19 The values of rate constant for the decomposition of HI
1.60 x 10 into H,and I, at different temperatures are given below:
k9 397.19 x 1.60 x 10°
T(K) 633 667 710 738
6.36 x 10° s1,
k(s-1) 0.19 1.00 8.31 25.1
LJ Example 56
In the Arrhenius equation for a certain reaction, the Draw a graph between In k and 1/T and calculate the
values of Arrhenius parameters.
values of A and E,, are 4 x 10% s+ and 98.6 kJ mol
respectively. If the reaction ts of first order, at what Solution : The values of Jn & and 1/T at different tempera-
temperture will tts half life period be 10 min ? tures are :
(A.P.S.B. Sample paper) T(K) 633 667 710 738
Solution : Accroding to Arrhenius equation, I/T(K") 1.58x 10? 1.50x10% 141x107 1.36x107
f= Age
Ink — 10.87 —9.21 — 7.09 — 5.99
 MODERN'S abc + OF CHEMISTRY-All

The plot of in & against 1/T is shown below : a

ig deg ede ee 313

= — 1.708 + 15.621
= 13.913
A = antilog (13.913) = 8.185 x 104% s"!
Example 61
The rate constants of a reaction at 500 K and 700 K are
0.02 st and 0.07 s* respectively. Calculate the values
of Zand A. |N.C.E.R.T, (CBSE Sample Paper 2011,
Ar. S.B. 2012, Assam S.B. 2013)
Solution : According to Arrhenius equation,

log ky ff Eee
1534 14 13.5 15 1.6 AGM 2.308RA T,T;
(1/T x 10%) k, = 0.02 st, k, = 0.07 s+, T, = 500 K, T, = 700 K
The slope of the line is — 20.62 x 10° Substituting the values :
E, = —Slopex R log 297 = E, 700—500
= —(— 20.62 x 10° #) x 8.314 0.02. 2.303 x 8.314/700 x 500
= 171.4kJ mol E
0.544 = a zal
Now, we can calculate A from the value of & at 633 K 2.308 x 8.314 3500
E p= 0:544x 2.303 x 8.314 x 3500
InA = Ink+ RT
a 200
InA = -—10.87+ eee =-— 10.87 + 32.57
= 182281 J or 18.228 kJ
InA = 217 8.314 x 633 Calculation of A
kh = Ae-Ea/RT
A = 2.65 x 108s.
logk = logA- a
Example 59 ees 8 9303 RT
Rate constant 'k' ofa reaction varies with temperature Substituting the values at 500 K
'T' according to the equation:
E, 1
log 0.02 = log A— —__18728_
2.003 x 8.314 x 500
log k =logA- Sa53R = —1.699 = log A—1.904
where Eis the activation energy. When a graph is plotted log A = 1.904-—1.699 = 0.205
for log k vs. =. a straight line with a slope of — 4250 K is A = 1.603 s1.

Example 62
obtained. Calculate 'E.,' for the reaction (R = 8.314 JK+ mol)
The activation energy of a reaction is 75.2 kJ mol"
(D.S.B. 2013) in the absence of a catalyst and 50.14 kJ mol with
Esa a catalyst. How many times will the rate of reaction
Solution: Slope =—-
2303R grow in the presence of the catalyst if the reaction
EK, = — 2.303 x R x Slope proceeds at 25°C ? (R= 8.3814 JK? mol-»)
= —2.303 x 8.314 JK" mol x (—4250 K) (A.L.S.B. 2005)
= 81375.3 J mol or 81.375 kJ mol". Solution : According to Arrhenius equation,
Example 60. logk = log A- eos
kK,
er
The rate constant for a reaction is found to be 1.96 x
10° s7 at 318 K. The activation energy of the reaction For uncatalysed reaction, |
is 93.62 kJ mol-!. Calculate the frequency factor, A.
logk, = logA- eae sol)
2.303 RT
Solution: logk =-—- +logA For catalysed reaction,
2.303RT
logk, = log A- ae ii)
or log A = log k + 2 303
E
RT
A 1s equal for the same reaction.
k=1.96x10%s7?, E,=93.62 x 10? J mol Subtracting Egn. (z) from Eqn. (iz)
R = 8.314 JK! mol, T=313 K
CHEMICAL KINETICS

kg E,,(D—-E, (2) Solution : According to Arrhenius equation,

108 T= 5 303RT lek
oO = ine A—~—™
as| suit)
si | | 1 ieee 2.303 RT
. (75,.2—50.14) kJ mol The given equation is
2.5038 x 8.414 x 2985 4
1.0x10* K
log kp 4.39 loz k= 14.2 — —_—__- -- Abt)
hy Comparing eq. (z) and (iz)
ke = 2.45 x 104 _
By 9 X16
ky 2.303 R
. Rate of reaction increases by 2.45 x 10* times. K,, = 1.0 x 10* x 2.303 x 8.314
= 19.147 x 10+ J mol
LU) Example 68.
or = 191.47 k.J mol“!
The rate constant for the first-order decomposition of
HO, is given by the following equation: Now ty = a
log k = 14.2 — 1:9%10"x or
0.693
k-= yr
i
Calculate E_, for this reaction and rate constant R if tts ie
half-life period be 200 minutes. (Given : R= 8.814 JK _ _ 0.698
— 3.465107? min™
mol) (D.S.B. 2016, A.I.S.B 2016) ~ 200 min

The rate of a reaction becomes four times when the temperature changes from
293 K to 313 K. Calculate the energy of activation (E,)of the reaction assuming
that it does not change with temperature.
[R = 8.314 J K? mol", log 4 = 0.6021] (A..S.B. 2013)
41. The reaction, 2NO, —— > 2NO0+0,
has an activation energy of 110 kJ mol. At 400°C, the rate constant is
7.8 s-!. What is the value of rate constant at 430°C?
42. The rate constant for the decomposition of nitrogen pentoxide :
N,O, ——-> N,O, + ¥2 O, is 3.46 x 10° s7? at 25°C and 4.87 x 10° s* at 65°C.
Calculate the energy of activation for the reaction. (Pb.S.B. 2008)
43. The rate of a particular reaction triples when temperature changes from 50° C to
100°C. Calculate the activation energy of the reaction.
(log 3 = 0.4771, R= 8.314 JK mol) (D.S.B. 2006, H.P.S.B. 2010) — Answers to Practice Problems —
44, The rate of a reaction doubles when the temperature changes from 27°C to 37°C.
40). 52.86 kJ mol!
Calculate the energy of activation. (Pb S.B. 2006, Mizoram S.B. 2015)
41. 18.05 +
45. A first order reaction is 50% complete in 30 minutes at 27°C and in 10 minutes
at 47°C. Calculate the activation energy of the reaction. 42. 103.56 kJ
43. 22.012 x 10° kJ mol-!.
46. The rate constants for a reaction are 2.0 s! and 32.0 s+ at 700 K and 800 K
respectively. Calculate the energy of activation for the reaction. 44, 53.6 kJ mol}.
A7. The rate constant for a first order reaction becomes six times when the temperature 45. 43.8 kJ molt.
is raised from 350 to 400 K. Calculate the activation energy for the reaction. 46. 129.1 kJ mol.
(Gas constant R = 8.314 J K? mol") (Pb. S.B. 2014) AT. 41.7 kJ mol-1.
48. The rate constant for a reaction 1s 1.6 x 10° st and 6.36 x 10°? s+ at 600 K and 48. 209.01 kJ mol-!.
700 K respectively. Calculate the activation energy for the reaction. 49. A= 151 = 10™ min.
49. The rate constant for the decomposition of N,O, at various temperatures is given E, = 100.67 kJ mol,
below :
k (30°C) = 6.64 x 10° s+,
TCC) 0 20 AQ 60 80
eR DES F008BO [vec Se
10° x k (s+) 0.0787 1.70 20.7 178 2140
50. 44.1 kJ mol-1.
Draw a graph between In & and 1/T and calculate the values of A and E,. Predict
the rate constant at 30°C and 50°C. Hints & Solutions on page 68

50. The rate constant of a reaction is 1.2 x 10-3 st at 30°C and 2.1 x 10s at 40°C.
Calculate the energy of activation of the reaction. (Pb. S.B. 2004, 2006)
 MODERN'S abc + OF CHEMISTRY-All

ol. For the decomposition of ethyl iodide :

C,H.1 ——> C,H,+HI
the rate constants are 1.60 x 10° s? and 6.36 x 10°? s+ at 600 K and 700 K
respectively. Calculate the activation energy for the reaction.(Pb. S.B. 2004, 2008)
52. The specific rate constant for the combination of H, and I, to form HI
H, + 1, ——~ 2HI
is 2.34 x 10-3 s+ at 673 K and 7.50 x 10-7 s? at 773 K. Calculate the activation
energy for the reaction.
Da. Rate constant, & of a reaction varies with temperature as:
E
log & = Constant — ———?—_
2.303 RT
where E, is the activation energy. When agraphis plotted for loge vs 1/T, astraight
— Answers to Practice Problems line with a slope of -6670K is obtained. Calculate the energy of activation for this
reaction. (R = 8.314 JK? mol?) (D.S.B. 2011)
ol. 209.1 kJ mol}. a4, The activation energy of a first order reaction at 300 K is 60 kJ mol". In the
52. 15.1 kJ mol". presence of a catalyst, the activation energy gets lowered to 50 kJ mol at
Da. 127.7 kJ mol“. 300 K. How many times the reaction rate changes in the presence of a catalyst at
o4, 55.08 times the same temperature ?
5D. 24"; 5D. The decomposition of A into product has value of & as 4.5 x 10? s+ at 10°C and
activation energy is 60 kJ mol. Calculate the temperature at which the value of
Hints & Solutions on page 68 k be 1.5 x 10% 571. (CBSE Sample Paper 2011)

Adgven-t
tl
Accelerate Your Potential
td 540) 39 FW BO (for JEE Advance)

Two reactions of the same order have equal At 400 K, Rk = Ae Ealev/400R

pre-exponential factors but their activation energies pEal500R = 4-Bq(cV/400R
differ by 24.9 kJ mol". Calculate the ratio between the
rate constants of these reactions at 27°C. (Gas constant, pa E _ E,()
R = 8.3 JK"! mol"). 500R 400R
The Arrhenius equation is : or E ake) =
ri—E
BS
Poe Ae =a ‘RT
But E,-E,(c) = 20kJ
: : E,
Taking log on both sides, log k = logA — 9.303 RIE
E,-=E, = 8k) ae =E, = 20 kJ
For reaction (z), log k, = log A-
B, @) Ea = 20x5=100kJ mol".
2.303 RT

For reaction (zi) log k, = log A-—

E, (2) “i The time required for 10% completion of
2.303 RT a first order reaction at 298 K is equal to that required
Subtracting (z) from (7) log Ry = Ey) - E,(2) for its 25% completion at 308 K. If the value of A is
ky 2.303 RT 4x 10's", calculate k at 318 K and E,.
24.9 x 1000 For 10% completion of the reaction,
log fy = 4.342
2.303 x 8.3 x 300
hy
ko = 2.198 x 104. Feigea) atenl L)
t 90
ky
For 25% completion of reaction
cf A hydrogenation reaction is carried out at
500 K. If the same reaction is carried out in the presence 2.303, 100
of a catalyst at the same rate, the temperature required (
R(3808K) ) = ; logg ——
75
is K. Calculate the activation energy of the reaction if
the catalyst lowers the activation energy by 20 kJ mol". 2.303, 100
According to Arrhenius equation, R(308K) _ ¢ 8 75
k = Ap-Ba/RT Rope ete ee
t ~ 90
Let activation energy in the absence of catalyst be E, and
in the presence of catalyst be E,(c), then _ 9.1249 .
At 500 K, k = Ae Fa/500R 0.0458
CHEMICAL KINETICS

Now, ,
peach) ae! E ee jE
Z 1 = .
2.303 log , [A], 0
2(208K) 2.303R| T,T, t [A]
25 |
E Ine _ [A], =a (say), [A] =a-a X—— =0.754
(pees ee eee) 0 100
2.303 x 8.314 ~ 308x298 9-an8
= = * log—4— = 0.01439 min!
pes = EK, . 10 20 0.754
“~~: 2.303 x 8.314 ~ 308x298 Calculation of &,,.
B= 0-486 2.303 x 8.314 x 308 x 298 ‘oe Ee E, |1/@
3 10 ey, 2.303R| KT
= 76623 J mol = 76.623 kJ mol
= er = sso eal es |~ 0.5879
Now, log K = log A-——2 _ 0.01439 2.303x8.314L298 313
2.303 RT ho
or 0.01439 = 3.872 or Re = 0.0557 min!

76623 re
log K(318K)= log 4x 10)? — ——_ Calculation of percentage decomposition at 40°C
= °8 2.303 X 8.314 x 318
Let the percentage decompostion in this case = x
10.6020 — 12.5843
a= 100,a@-—x=100-x
log K (318) = — 1.9823
2.303 100
K (318)= 1.042 x 107 s+ k, = ——lo
ae oe 2~ 20° °100-x
“3 A first order reaction, A — B requires 0.0557 = 22203 ipo 100
activation energy of 70 kJ mol“. When a 20% solution of 20 100-x
A was kept at 25°C for 20 minutes, 25% decomposition 100
took place. What will be the per cent decomposition in the log 100—x = 0.4837
same time in a 30% solution maintained at 40°C? Assume
that activation energy remains constant in this range of 100, _so45 or y=67.15
temperature. 100-—x

Calculation of & at 25°C (say k,) Percentage decomposition = 67.15%

CONCEPT OF ACTIVATION ENERGY AND TRANSITION

R U Curious... @
STATE THEORY
We are quite familiar with chemical reactions such as burning of Combustion of fuels is highly exo-
coal gas in air or combustion of carbon or combination of hydrogen thermic reaction yet these can be safely
and oxygen gases, which do not occur unless some energy in one form stored in contact with oxygen or air.
or the other is supplied to reacting system. Thus, some extra energy (1 The stability of fuels is due to high
has to be supplied to the reactants to bring their energy equal to the activation energy of these combustion
threshold energy. reactions. As a result of high activation
The excess energy (over and above the average energy of the energy, these reactions do not occur
reactants) which must be supplied to the reactants to undergo chemical at ordinary conditions. When some
reactions is called activation energy, E,. It is equal to the difference extra energy (flame) is supplied to the
between the threshold energy needed for the reaction and the average fuel in the presence of air, a portion
kinetic energy of all the reacting molecules. That is, of reactants absorb energy (equal to
activation energy) and the reaction
Activation energy = Threshold energy — Average kinetic
gets initiated. The enormous amount of
energy of the reacting molecules
energy is released during the reaction
or E., = & (threshold) — E (reactants) because the reaction is exothermic. The
Kach reaction has definite value of E, and this decides the fraction released energy increases the energy of
of total collisions which are effective. If the activation energy for a other molecules in the remaining fuel
reaction is low, large number of molecules can have this energy and and therefore, the combustion continues.
the fraction of effective collisions, f, will be large. The reaction will Explosive reactions have also high
proceed at high rate. On the other hand, if the activation energy is activation energy and therefore, can
high, then fraction of effective collisions will be small and the reaction be safely stored for years inspite of
may be quite slow. Thus, the fact that they give enormous
amount of energy when they explode.
Low activation energies Fast reactions
The explosive reactions occur when
High activation energies Slow reactions
activation energy 1s supplied by heating
or mechanical energy.
 MODERN'S abc + OF CHEMISTRY-All

Activated Complex State

When the colliding molecules possess the kinetic energy equal to E_, the
atomic configuration of species formed at this stage is different from the reactants
as well as the products. This stage is called the activated state or transition
state and specific configuration of this state is called activated complex or
intermediate. For example, in the reaction between H,(g) and I,(g), activated
complex has configuration in which H—H and I—I bonds are breaking and H—I
bonds are forming as shown below :

Reactants Activated complex Products

This activated complex state is unstable transitions state of the reacting
system which is mid-way between the reactants and the products. It has a
very short life span (being highly unstable) and splits into the products to
acquire stable state of lower energy.
Progress of a Reaction
According to the concept of activation energy, the reactants do not change
directly into the products. The reactants first absorb energy equal to activation
energy and thereby form activated complex. At this state, the molecules have
energy at least equal to the threshold energy. This means that the reaction
involves some energy barrier which must be overcome before products are formed.
Threshold Activated complex
The energy barrier is known as activation energy barrier. In graphical
energy (E,) ra
representation of the reaction, the energy barrier is shown as an energy hump
Energy barner which has to be crossed before the reactants go to the products (Fig. 14).
(activation energy) As an illustration, consider the general reaction,
A(g) + B,(g) ———+AB(g) + B@&)
Energy of the
reaction
The reactants have the average energy, E, and the products have the energy
E,. The reaction involves the approach of an atom A to a molecule B,. The
AB + B (E,) reaction cannot occur until the colliding reactants A and B, possess sufficient
energy to reach the top of the energy barrier and form activated complex.
Progress of reaction —,»
The energy required to form activated complex is called the activation
Fig. 14. Progress of a reaction. energy. The activated complex formed [A....B] has a very short life span and
splits into the products. This may be shown as :
% to BaP eS Aare B..---------B — > A—B+B
Reactants Activated complex Products

Activation energy plays an important role in comparing the rates of

reactions. To illustrate this, consider the two reactions, oxidation of NO and
CO, which appear to be similar. As already discussed, the oxidation of NO is
a fast reaction whereas that of CO is a slow reaction.

NO@) + =| 0,¢) —> NO,e) Fast

CO(g) + = 0g) ——> CO0,g) Slow

In the oxidation of NO, the activation energy is small and only the small
increase in energy enables the reacting species to cross the energy barrier to
form NO,. Therefore, the reaction is fast at room temperature. However, in
the case of oxidation of CO, the activation energy is high, consequently large
amount of energy is needed by the reactants to cross the energy barrier. Such
a large amount of energy is not available at room temperature. Hence, the
reaction is slow at room temperature.
CHEMICAL KINETICS

Activation Energies and Reversible Reactions

Consider a reversible reaction : Exothermic reaction
A+B C+D
Just as activation energy is required for forward reaction, activation energy
is also required for backward reaction. During the progress of the reaction the
reactant molecules in the forward reaction and the product molecules in the
backward reaction follow the same path and form the same activated complex.
However, the activation energies of the two are different. These are represented
graphically in Fig. 15 (a) and (b) for exothermic and endothermic reactions. It is
clear from the figure that the reactant molecules in their forward reaction and
the product molecules in their backward reaction have to pass through the same
transition state even though the activation energies for the forward E_, (forward) Progress of reaction—_—»
and E, (backward) reactions are different. Mathematically, E, (forward) and (a)
E, (backward) are related to the overall energy change, AH, in the process as :
AH = E, (forward) — E, (backward) Endothermic reaction

As evident from Fig. 15 (a), for the exothermic reaction.

Activation energy for Activation energy for
<
the forward reaction the backward reaction
E,, (forward) < E, (backward)
Thus, AH = E, (forward) — E, (backward) = —ve
On the other hand, for the endothermic reaction.
Activation energy for Activation energy for
the forward reaction the backward reaction
Progress of reaction ———»
EK, (forward) > E, (backward)
(b)
Thus, AH = E, (forward) — E, (backward) = +ve
Fig.15. Activation energies for the
EFFECT OF A CATALYST ON REACTION RATES forward and backward reactions in
A eatalyst is a substance which increases the rate of a reaction case of (a) exothermic and
without itself undergoing any permanent chemical change. (6) endothermic reactions.
For example, manganese dioxide (MnO,), a black powder speeds up the
thermal decomposition of potassium chlorate.

2KCIO, (s) MnO»,

oncatalyst 2KCK(s) + 30,
The phenomenon of increasing the rate of a reaction by the use of catalyst
is called catalysis. It is observed that a catalyst is not consumed in the
reaction. Actually, what happens is that in a catalysed reaction the catalyst
is used in one step and is regenerated in a subsequent step and thus, it is
used up again and again without undergoing any permanent change.
The action of catalyst can be explained by intermediate complex
theory. According to this theory, a catalyst combines with reactants to form
an intermediate activated complex which is short lived. This decomposes to
form the products and regenerating the catalyst. The intermediate complex
formed has lower potential energy. This means that the activation energy
becomes lower for the catalysed reaction than that for uncatalysed reaction.
Consequently, the fraction of the total number of collisions possessing lower
activation energy is increased and hence, the rate of reaction also increases.
Consider a hypothetical reaction
A + B——> AB
The reaction proceeds through the formation of activated complex as :
A + B ——} [A.------B] ———> AB
Reactants Activated Product
complex
a 4/64 MODERN'S abc + OF CHEMISTRY-All

Addition of a catalyst C result into the formation of new activated complex

of lower activation energy.

Acoma Ts
A+ B + C —~ SU |> AB + C
Reactants Catalyst Cc watts

=e Activated
~~ Complex
Without Thus, a catalyst provides a new
catalyst pathway for the reaction of lower
—_"*__ #Lowering of activation energy than thatof the reaction
activation = in the absence of the catalyst. Because
z _| sw energy = for lorware Wcaiaysed of lower activation energy, the reaction
oe OT E.(b) = for backward uncatalysed becomes fast and the reactants are
> \ reaction converted to products quickly.
o
=
Reactants
With \\ E’,(f) = for forward catalysed Fig. 16 gives an energy diagram
catalyst eo ping for Backward calaived which depicts the effect ofa catalyst on
LL

Products reaction the energy of activation. The solid line

Progress of reaction ——> shows the path for uncatalysed reaction
and dotted line shows the path adopted
Fig. 16. Progress of an uncatalysed and catalysed reaction. Addition of a
catalyst provides a path of lower activation energy (shown dotted). by catalysed reaction.

Some Important Characteristics of Catalysts and Catalysed Reactions

(z) Only a small amount of catalyst can catalyse a large amount of reactants.
(it) A catalyst cannot initiate a reaction. It can only accelerate the rate of a
reaction. It other words, a catalyst cannot catalyse non spontaneous reactions.
It area Pra = It catalyses {4 only
spontaneou
‘ s reactions.
_—— .
may be no at some substances oe.
PAGECLCIEREe heen ine: dices (iit) Catalysts are highly specific in nature. A catalyst which can catalyse
Le ee e e ere one reaction may have no effect on another reaction even, if that reaction is
very similar.
(iv) A catalyst may undergo intermediate physical changes and it may
even form temporary chemical bonds with the reactants but it is recovered
unchanged in original form at the end of the reaction.
(v) The catalyst does not change AE (or AH) of the reaction. This is clear
from Fig. 16 that the addition of a catalyst does not change the energies of
reactants (E,) and products (Ep) so that AE (E,, — E,) remains same.
(vi) A catalyst does not change the free energy change (AG) of a reaction.
(vit) Although a catalyst speeds up the reaction but it does not shift the
position of equilibrium. This is due to the fact that the presence of a catalyst
reduces the height of barrier by providing an alternative path for the reaction
and lowers the activation energy. However, the lowering in activation energy
is to the same extent for the forward as well as for the backward reaction.
In the figure, it is clear that decrease in activation energy for the forward
reaction E, (forward) — E,’ (forward) is same as for backward reaction, E,
(backward) — E,’ (backward), where E,’ (forward) and Eq’ (backward) are the
activation energies for the catalysed reaction. As a result, the increase in the
rate of the forward and backward reactions is same and hence, the position
of equilibrium remains unaltered. However, by increasing the two rates, the
equilibrium is attained earlier.
Catalysts are very important for our existence. Catalysts are used in many
industrial processes. Many biochemical reactions occurring in living organisms
are catalysed by enzymes.
CHEMICAL KINETICS

SOLVED EXAMPLES
LJ Example 64
(a) Calculate AE for the rection.
An exothermic reaction A ———> B has an activation
energy of 17 kJ per mole of A. The heat of the reaction (b) Calculate the energy of activation for the forward
is 40 ke. Calculate the activation energy for the reverse and the backward reactions.
reaction B ———> A.
Solution : For the reaction A———> B. (c) The dotted curve is the reaction path in the presence
Activation energy, E, = 17 kJ of the catalyst ? What is the energy of activation for
Since the reaction 1s exothermic, the energy of the products the forward and backward reactions in the presence
is less than that of reactants. The potential energy diagram for of the catalyst ? What 1s the lowering in activation
such a reaction is given in Fig. 17. energy in the presence of a catalyst ?
From the figure, it 1s clear that the activation energy for the
reverse reaction, B——> Ais:
(d) Will the catalyst change the extent of the reaction ?
E, (reverse) E, (forward) + AE Solution : (a) It is clear from the figure that
17+ 40 =57 kJ
Energy of reactants (A, and B,) = 110 kJ mol
E_ (forward) + AE
== feveme) Energy of products (2AB) = 100 kJ mol
AE = E,-E,
= 100-110 =-10 kJ mol
.. Reaction is exothermic.
(6) Threshold energy = 140 kJ mol
Energy of reactants = 110 kJ mol
KE. (forward) = E, — E,

= 140-110
Progress of reaction —>
Fig. 17. = 30 kJ mol

LJ Example 65. Energy of products, E, = 100 kJ mol™

Consider the diagram (Fig. 18) for a reaction E, (backward) = E; - E,
A, +B, == 2AB
= 140-100 = 40 kJ mol"

(c) In the presence of catalyst, threshold energy becomes

120 k.J

E,.’ (forward) = 120-110 = 10k.J mol

E,’ (backward) = 120 -— 100 = 20 kJ mol“

Lowering in activation energy = E; (without catalyst) — E;

(with catalyst)
mol!)
(kJ
Energy
———-»
= 140-120 = 20 kJ mol"

(d) There will be no change in the extent of reaction because

activation energy for the forward reaction and the backward
Progress of reaction ——+
reaction have decreased equally.

AOAIVECED td 540) 3)BY

Accelerate Your Potential
(for JEE Ad
vance)

18) The rate constant of a reaction increases Let the rate constant at 300 K=2
by 7% when its temperature is raised from 300 K to 301 K
while its equilibrium constant increases by 3%. Calculate Increase in rate constant =k x 7 =0.07k
the activation energy of forward and reverse reaction.
”. Rate constant at 301 K=£+0.0072=1.072
 MODERN’S abc + OF CHEMISTRY-XIl

Equilibrium at 301 K= K+ 0.03 K= 1.03 K

ke E, > ba Now,
le ean nae 2
ky 2.303R|/T, Ty 1
K AH F 4
1L.07k E, |i...1 | Ky 2.303 R|T, T,
= eo
k Sy
2.303 x ees
ean
8.314|300 301
aan. Se aa
og 108K _ Aue ee
log 1.07 = E, _, 301-300 "8k ~ 2.303 x 8.34 [300 301
| 2.303 x 8.314 300x301 2
AH 01-30
0.02938
: = SSS FaSSS SSS !
2.303 x 8.314 300x301
0.01284 = /2 : Wasa «1314 ee
: x ae
E. = 0.02938 x 2.303 x 8.314 x 300 x 301 “i AH = 0.01284 x 8.314 x 2.308 x 300 x 301

= 50798 J = 50.8 kJ mol 22.19 k.J mol

This is activation energy for the forward reaction, i.e.,
Since A,H® is positive, the reaction is endothermic.
Ez fe oe= vo}—2
50.8 kJ mol Bat AH il gE! _E

Let equilibrium constant at 300 K= K me A Ef AH?

: eee 3
Increase 1n equilibrium constant = aa = 0.03 K = 50.8 — 22.19 = 27.61 kJ mol!

add on Concep UCSITIONS ZZ

22 =

The half life period of first order reaction is + and three-fourth of the same reaction is y. How are x
and y related to each other ?
y 1s twice of x because the time required for 3/4th of a reaction to occur is two times that required for half of the
reaction.
After five half life periods for a first order reaction what fraction of reactant remains ?
1
39°

For a first order reaction, time taken for half of the reaction to complete is ¢, and 3/4 of the reaction to
complete is f,. How are #, and ¢, related ?
t, = 2t, because for 3/4th of the reaction to complete, time required is equal to two half lives.

A reaction is first orderin reactant A and second order in reactant B.

(1) Write differential rate equation.
(72) How is the rate affected when concentration of B alone is increased to three times ?
(zz7) How is the rate affected when concentration of both A and B are doubled ? (D.S.B. 2010)
(1) Rate = R[A] [B]?
(11) Rate becomes (3)? = 9 times
(111) Rate becomes (2) (2)? = 8 times.
Express the relation between the halflife period of a reactant and its initial concentration for a reaction
of nth order. (A.LS.B. 20065)

- i k [A, |iis i.

(a) For the reaction

H* , |
C,, H,,0,, + H,O C,H,,0, + C,H,,0,
write :
(¢) Rate of reaction expression,
(74) Rate law equation,
CHEMICAL KINETICS 4/67 a

(411) Molecularity,
(iv) Order of reaction (CBSE Sample paper 2011)

Ans. (z) Rate = — @[CygH 011] = —alH0]

dt dt
_ d[C,H,,0,| _ d[C,H,,0.|
dt dt
(it) Rate law equation :
Rate = Rk[C,, H,, O,,]
(zi) Molecularity = 2
(1) Order = 1

Q.7. Consider the decomposition of hydrogen peroxide in alkaline medium which is catalysed by iodide ions.

1 ls Lg ee
This reaction takes place in two steps as given below:
Step-I H,O, + fT————~ H,0 + IO (slow)

Step-I H,O, + 1O— ———— H,O+T + O,( fast)

(a) Write the rate law expression and determine the order of reaction w.r.t. H,O,.
(6) What is the molecularity of each individual step? (CBSE Sample paper 2011)

(a) Rate = k[H,0O,] It]

Order w.r.t. H,O, = 1
(BD) Molecularity : Step l= 2, Step Il = 2

For a chemical reaction variation in rate with conc. is shown:

(a) What is the order of the reaction ?
(b) What are the units of rate constant Fk for the reaction ? Rate
(CBSE Sample paper 2012)
(a) Order of reaction is zero.
(6)Units of rate constant is mo] L“s7!. Conc. ——>
Can activation energy for reactions be zero ?
In the Arrhenius equation,
b= AewEa/RT

if EK, is zero then k = A

i.e., every collision between molecules leads to the chemical reaction. This is not true. Thus, E, cannot be zero.
Q.10. What value of k is predicted for the rate constant by Arrhenius equation if T — ~ ? Is this value physically
reasonable ?

Ans. From the equation, & = Aga" , if T >; k > Aso that E, = 0. This is not feasible.
Q.11. Why AG is positive for photochemical reactions ?
Ans. This is because a part of light energy absorbed by the reactants gets converted into free energy.
Q.12. What is the main difference between a photosensitizer and a catalyst ?
Ans. A catalyst only changes the speed of the reaction, while a photosensitizer only initiates the reaction.
Q.13. Give the damaging effect of photochemistry.
Ans. The colour of fabrics fades away on exposure to sunlight.
Q14. Why does equilibrium constant not change with the presence of a catalyst?
Ans. The catalyst increases the speed of forward and backward reaction to the same extent. Therefore, equilibrium is
attained quickly but the position of equilibrium does not change.
ace Q15. What is the fraction of molecules having energy equal to or greater than activation energy, E, ? What
MODERN'S abe + OF CHEMISTRY
-AXIl

is this quantity called ?

The fraction of molecules having energy equal to or greater than activation energy (E,)is equal to e*:"" at temperature
T. Itis called Boltzmann factor.
Q16. For a reaction: A + B —-; P, the rate law is given as:
Rate = k[A][B}*
(41) How is the rate of reaction affected when the concentration of B is doubled?
(74) What is the order of reaction if A is present in large excess. (A.LS.B. 2015)
(1) Rate becomes four times
(zz) Order = 2
Find out half life time of a first order reaction with rate constant, k = 2.31 x 10"*s! (Assam S. B. 2017)
i 0.693 _ 0.695 Sy ils
k —-2.31«107"*s
What is the effect of ctl a catalyst on
(z) Activation energy (E,) and
(74) Gibbs free energy (AG) of a reaction? (A.LS.B. 2017)
(1) Activation energy decreases
(11) No effect on AG because Gibbs free energies of products and reactants remain the same in the presence of
catalyst.
Q19. In the Arrhenius equation, what does the factor e Ea/Rt correspond to ?

= w
(CBSE Sample Paper 2017-18)

Ans. Pl corresponds to the fraction of molecules having kinetic energy greater than E..

rT _-_ = ——

\ / Hints & Solutions for

\ > _ Practice Problems
| 1 df 7
Oo 1. G) Rate —LH0s!_ 1a0)! AlZ), =: AY). =.
J
O48 = 1084 mal Te
2dt 3 dt At $4 ° 3

Gi) Rate — - 12 MNO]

dt
_ _ alBrp]
dt
_ 2f1rage)
dt
5. .
Rate . _LAINOs]__
a
AlO,]
iv
_ 12 At
AIN,O,!
ag L alICl] _ _ dl] _ dll, | a: d| HCl) i) -1 AINO,| : _ AO)
2: dt dt dt 2a fit 4 At At
3 2 AIN,] 1A[NH,] _ ly 2.4107 ae ree = 4x 0.024 = 0.096 mol L? s!
a = == = 5X

= 12x 10+ mol L's! ie - S

_ AIH]
_ 3 AINH3] © 3 v9.4
x104 us AIN305] _ ox —H0a! —~2»x 0.024
At 2 At At dt
Sto ¢ x A0-4 mol L's = 0.048 mol L? s}
| 1 A[N,O 1 AINO,] - 3
O 8. Rate= _ 21 AND
dt
es 1 6. Rate = — (0.02- 0.08) _ 4.9 . 104 mol L4¢min
4 dt 25 min
A[N,O;] 2 A(NO,] 1 3
—_— 4) = = —_* = _— x2.8x10 in-4 =
dt 4 dt 2 or = Se = 6.6 x 10° mol Ls?
= -14x 10° Ms? . ?
“ 7%. For the reaction,
. Rate of disappearance of N,O, 1e. (-ol 2A +B > 8C
a rate - —2@IA]__
@[B]_ 1d{C]
= 14x 10° Ms! 2 dt dt 3 dt
3 4 1 ALY] 1 AIX] (1) Rate of reaction = 1 d{C] = te 1.30107
2 At 3 At 3 dt 3
4.383 x 10° mol L's!

At 3
CHEMICAL KINETICS

(11) Rate of disappearance of A (it) 4.2: 10" mol Ds *=2 x 10% 2") [N,0,]
_ _@A)_ 2d[cl
dt 3 dt : - [N,O.] _,= 4.2x10°
6.2x104 6.77 mol L4
= 2131074
3 Rate = R[A]?
8.67 x 10° mol L-!1s"1 (i) Rate = (0.60 molt Ls) x (0.60 mol L)
5.8 x 10°A = 0.18 mol Ls
oO ae = R[A]* 2 or & Pe icc
8. Rate 0.01"
(ii) Rate = (0.60 mol?L s~) x (0.15 mol L“)?
= 5.8 x 10° mol L's"! = 0.11 mol L7 s?
Rate = k[COC1,]°”
: k= 2305 i
t a-x
oe (atm) k= atm! st Volume of O, liberated is collected at different time
sec intervals :
. The order can be predicted by the inspection of units Y= x= 9
of rate constants.
2.303 fox V..
moll _ (mel) (mel) t V..- V;
s 7 L L Substituting the values of V, and V_, & comes out to
k = mol L*#?% s1
be almost constant (k = 5.08 x 10°).
~ fl — a V.
. Let the initial concentrations are :
v..-V,
oo

[NO,] =a mol L*+, [T] = 6 mol L*+, [H*] =c mol L'?

rate = k abc?
Time V, V,— V, k
20 10 162-10 2303 jo, 162 _319 x 103 mint
(t) When [I-]= . rate’ = ka{ 5)
ro =<abe® i.@., rate
20.” 152
70 83 162-338
- 2.303,
“Slog 162
log =24
5 —=8.25x10-%min4
of reaction is halved.

(12) When [H*] = 2c (1) Since & is constant, it is a first order reaction.

rate” =k ab (2c)? = 4 k abc? 1.e., rate becomes 4 times. (ii) k (average) = 3.21 x 10? min“

(111) When [NO;] = 3a, [I] = 36 and [H*] = 8c

19, ¢- 2993 _19g +9 ~ cess5
rate’”’= k (8a) (3b) (3c)?= 81 kabc?1.e., rate becomes 6.0x104* ~~ 0.2
81 times. | 2.303 [A]
m 20. k= log 0
r = k[X]" ee t {Al
27 r = k[3X]" ... (il) ¢ = 60 min, [A], = 1.2 x 10° mol L?
Dividing eq. (11) by eq. (1), 27 = 3" orn =3 [A] = 0.20 x 10-7 mol Lt

. r=kxy
2.303, 1.24x107
at) k = —_ log —_—__y
60 0.20 x 10
1.837 r = k[1.6X]" ailtt)
= ae x 0.7924
Dividing eq. (11) by eq. (1), 1.887 = (1.5)" 60
Taking log on both sides = 3.04 x 10° min!
log 1.8387 = n log 1.6
mm 21. At 410s, k = —_ log —. 7.769 x 104s!
log 1.837 _ 410 4.0
= log 1.5 — eae
At 11380 s, k = Se igo a = 7.04 x 107+s1
Rate = k[N,O,] 1130 2.4
Since & is almost constant, it is first order reaction.
(iz) Rate = (6.2 x 10+ 5“) x (2.650 mol L“!)
1.55 x 107 mol Ls* 22, 6.32 x 10+ = 2-303), 0.40
3600 [A]
(iz) Rate = (6.2 x 10*s-) x (0.50 mol L“)
log Boi = (0.9879 or [A] = 0.041
= 3.1 x 107 mol L? s! [A]
 MODERN'S abe + OF CHEMISTRY
-AIl

Amount of NO reacted = 0.40 — 0.041 = 0.369 (6) According to experiment 1,

0.359
% N,O. reacted = ai x 100= 89.75%
89, [NO] 0.15.M ; [Cll = 0.15 M

The initial rate is Rate = 0.6 M /min

Rate = k[NO]? [Cl]
(Rate), = kINO],” (ealry

Comparing experiments I and IT and substituting the

0.6 M/min = & (0.15 M)?(0.15 M)
values we get k 177.8 M? min?
(Rate), = k(0.30)” (0.30)? = 0.096 A(T) ”. Units of k are M? min? or mol? L? min?
(Rate), = k(0.60)° (0.30)* = 0.384 ...(it) (c) In experiment 4, [NO] = 0.25 M [Cl,] = 0.25M
Dividing eq. (11) by eq. (1) we get k = 177.8.M? min“
(0.60)” 0.3584 Rate = k [NO]? [Cl,]
(0.30)? 0.096 = 177.8M? min? x (0.25 M)* x (0.25 M)
(QP =4 or (QP =2 3» p=2 = 2.78 M min“

Similarly, comparing experiments I and III and . Rate = R[A][B]°

substituting the values, we get 2.0 x 10° =& [0.1] ork = 0.2
(Rate), =k (0.30) (0.30)? = 0.096 A(T) 2nd line : 4.0 x 10 = 0.2 [A]
(Rate), = Rk (0.30) (0.60)? = 0.192 ...(Li1) or [A] = 0.2
Dividing eqn. (1i1) by (7), we get
ard line : Rate = 0.2 x 0.4 = 8.0 x 107
(0.60)? 0.192_ q_ Ath line : 2.0 x 10? = 0.2[A] or [A] = 0.1
(0.30)? m£7, - ==
Rate = k[A]’[B]?
Thus, the overall rate low expression is
Rate, = k(0.20) (0.30)? = 8.93 x 10%
Rate = RINO}]|* [O,]
Rate, = k(0.20) (0.10)? = 8.93 x 10
. Let the rate law may be expressed as :
Rate, _ (0.30) _ 4
rate = k[NO]’ [C1,]*
Rate, (0.10)?
The initial rate becomes
or 37 = 3° or g=0
(rate), = k [NO] [C1]?
Comparing experiment 1 and 2, we get Rate, = k(0.40)° (0.06)? = 2.58 x 10+
(rate), = &(0.16)° (0.15)* = 0.60 (i) Rate, = k(0.20)° (0.10)? = 8.93 x 10%
(rate), = k(0.15) (0.30)? = 1.20 silt)
Rate, _ te P (oa |
q
_ 983
Dividing Eq. (iz) by Eq. (2)
Rate, 0.20) (0.10
a
(rate), _ (0.30)" _ or 27 = 91 q=1 op({t) — 2.83
(rate), (0.15) 2
Thus, order with respect to Cl, 1s 1.

*(3)
+0
2.83
Comparing experiment 1 and 3, we get \2
(rate), = R(0.16)? (0.15)? = 0.60 ...(L11) 2” — 2.88
(rate), = k(0.30)" (0.15)? = 2.40 (tv) p log2 = log 2.83 = 0.452
Dividing eq. (iv) by eq. (zzz) p(0.3010) = 0.452

(0.30)? _
Pp = 1.5

(0.15)” Oo 27%. k= — log a = 0.01279 min!

or QP = 2 p=2
Thus, order w.r.t. NO is 2. When [A] = 100 — 75 = 25

(a) Rate law expression :

t = ane log [Alo = 108.4 min
Rate = k [NO]? [Cl] t [A]
CHEMICAL KINETICS AI71 —

2.303 a 2.303
o 28 k = — log — = 0.0223 min! = ——xlog18
80 08
10 6 0.8a _

_ 2303 1% _ 72.19 min _ 2.303 y 1 955 = 3.61 <x 107s

0.0223 0.2a 80
(3.50 — 4.00) x 10°
a a. Tata ane a f 36. Between 0 — 100 s, rate = — 400.

Conc. after 40 min = 0.70 a =5 Pas!

2.303 | a 0-3 mint Calculate rate between 100 — 200 s and 200 — 300 s, it
=a 69ig oe comes out to be 6 Pa s2,
0.693 Since rate remains constant, itis zero order reaction.
= a = 77.7 min. i
8.9210 4.00 10°Pa _
i = —7 400 5.
2.303 [Aly
2x5Pas!
._ A
oO 30. k= = log (Al 37. Let initial cone: is a, then

If [A], 9 == a,
4, [A] == a— tial
a“ 0.80 a,i=
a, ¢ = 10 min
mi “Te a
Foo ad) 7) min, when
; Ula = 0.

p= 280846
10
4 = 0.0225 min
0.80a
t wah, _ (012
/2\""
(t1/2), .
: ax75 a
In second case, if [A], = a, [A] = a — 100 = 0.25a 60 _ (=)
‘Al 30 2
te 2.303 log 0 WW
k [A] or 2= (=)
= 2.303 Ut
x log ——— .
= 62.18 min an 9 = gi-n
0.0223 0.254 tod
or -1l-n
2.303 a
31e- log —— = 0.0433 = n=1-1=0
a2 1/4a
0.693 ;
0.693 o 38 .. k= —— =5.77 x 10° min
(a aaaea = 16 min 120 min
0.0433 Now, for the first order reaction,
0.693 ee 2.303 [A]
“ 32. k =— ———
2.31x10° = 3.0 x 10 min 5 t=| Aw7 log fs.
Al

2.303 a If [A], = a, then [A] = a —a x 0.90 = 0.10a.

t = ————, log —— = 5.366 x 10° min.
3.0x107% © 1/5a } . ,_ 2303) a
2.303 , 0.5 - ~ 5.77x10-° 0.10
0.693
tho = —, 7 = 0.1155 min.
. ~ 5.77x10°
;
6 = 399 min. (-- log 10 = 1)
FSA typ = 1008 = -——»
0.693 = 6.98/« 10° o 39. k =
0.693 0.693
——=—— =0.01 min”
100 bie 69.3
If [A], = 4
For 75% completion, [A] =a —- ae 0.25 a Now ¢ — 2-308 1a [Alo
100 5 Ta
~ 2.503 log a For 80% completion, let initial cone. [A], = a
6.93x10°% ~ 0.25a ax 80
. then [A] = a- = 0.20 a
=200 min. 100

Oo 36. t = 2.303 1, [Alo t = oo log ¢_ 161 min.

k [A] 0.01 0.20a
[A] = [A],/18, k = 80 st
9 303 [Aly 2.303 x 8.314 |}293 313

80 [A], /18 E 313 — 293

: 0.6021 = a Parity
2.303 x 8.514 | 293x* 313
 MODERN'S abe + OF CHEMISTRY
-AXIl

2.903 x 8.314 x 0.6021 x 293 x 313 0.77892 = ___Ba 50

a 20 2.303 x 8.314 400 x 350
or — §2863.3 J mol — 52.86 kJ mol.

| lo78
g te ~_ 110x108 [1
0.7782 x 2.503 x 8.314 x 400 x 350
110 x 10° 1 1 or i. @eeass
= 50
oe 2.303 early st
= 41721 J mol = 41.7 kJ mol.
low B2. _ —110x 10?x(703 - 673)
78 ~ 2.303 x 8.314 x 673 x 703 og 0:36 X10 _ E, 700 - 600
kg5 =
log0g —2 = 0.3648
0. ky ees)2.31
or a:
aa ST6x10> 2.303 8.314| 600 x 700
or k, -931x«78=18 s1, EK, = 209.01 kJ mol".

4 42. 487x107 _ E, 338 — 298 . The plot of in & vs 1/T comes out be straight line with
3.46x10° 2.303 8.314| 338 x 298 slope = — 12.109 x 10°

E,, = 103.56 kJ mol! E

Slopeope = -—#
= a

O 43. kJ/k,=8
—_ E 373 — 323
log 3 = —___4____]log |—____ or EF =—( 12.109 x 10°) x 8.314 = 100.67 kJ mol
2.303X8.314 ~| 373x273
EK, = 22.012 x 10° kJ mol-! InA=Ink
ce
Rr

5 44, Bue
ky | = —10.98 +
100.67 x 10°
= 30.34
8.314 x 293
2.303 x 8.314 |300=310
or A = antilog (30.34) = 1.51 x 107° min
E. — 53.6 kJ mol-!
100.67 x 10°
4 45. tio = 0.693 Now, 30.34 = In k + ——__
ne 8314 x 303
or - 0.693 In In & = 30.34 — 39.96 = — 9.62
ty 9 k = 6.64 x 10° s?
At 27°C, #,. = 30 min; k, = oe 0.0231 Similarly at 50°C, k = 7.93 x 10+ s?
2.1x10° E ee - 4
At 4AT°C, ty, = 10min; k, = = = 0.0693 la
°8 72x10" = 2,303 x 8.314] 303x313
o 0.0693 E. 1 | KE, = 44.126 kJ mol".
0.0231 — 50 a
636x10o° 4,
_ ao
0.4771 — ___- Ba*20 60x10 2303x8314 ”\ 700 x 600
2.303 * 8.314 x 300 x 320
E. a = 209.1 kJ mol!
— 43.8 kJ mol.

4 46 ip E, 800 — 700 -s Ea 1
eee 1
A 52. log al
2.0 2.303
x 8.314] 700
x 800 9234x1073 2.303 R(673 773

E. = 129.1 kJ mol. E a = 1.61 x 10* J mol = 15.1 kJ mol".

I 47,
} 2 E, |T,-T . Slope of thedine = — "2 _ = — 6670 K
ie ky 27 1 2.303 R
hy 2.303R| T,T, |=
eS 2.303 x 8.314 (Jmol 1K”) x 6670 K

or Ba
hy = 6,6,1,=
T, = 350
| K, T,
9 = = 400K
| = 127711.4J mol? = 127.7 kJ mol"!

q 54. kh = Ae Eat
log6 = E, Poaaeel ky = Ae BacyRt
2.903 x 8.514 |400x350
CHEMICAL KINETICS Al7/3 =

E,—E 60x10° |T, — 283

foghy = tla
2.303 Pale)
RT loess . = eee _ eee
2.303x8.314| 283 T,
6000— 5000 |
log fa = 9303x8314x300 > L741 60x 10° T, — 283
hy 7 j x .

: 0.625 = 9 303x8.314|
— ANE Sine Hon i aera

283 T,
ae Tl)eee

Ry
— = 6b.08 |

. ably
T, — 283
a0
0.523 x 2.303 x 8.314

.. The reaction rate increases by 55.08 times.

ee T,—283 = 0.047T,
Ol 86: log 2 a ee |
Se or 0.953T, = 283
k, 2.303| 1,T,
T, -/ = Sof K
log 2:3*108 60x10° |T, — 283 0.953
& 4.5x10° 2.303x8.314| 283 T, or T, =, 297 —278 = 24°C

® Rate of a reaction. It is the change of concentration of any one of the reactants or products per unit time.
® Rate constant. It is the rate of a reaction when the molar concentration of each of the reactants is unity.
® Order of a reaction. The sum of the powers to which the concentration terms are raised in the rate law equation to
express the observed rate of the reaction.
@ Molecularity of a reaction. The number of reacting species (atoms, 10ns or molecules) which collide simultaneously to
bring about a chemical reaction.
@ Elementary steps. The reaction steps which contribute to the overall reaction.
@ Half life period or time. The time during which the concentration of a reactant is reduced to half of its initial concentration.
@ Pseudo first order reaction. The reaction which appears to be of higher order but actually follow lower order (first
order) kinetics.
@ Activation energy. The excess energy (over and above the average energy of reactants) which must be supplied to the
reactants to undergo a chemical reaction.
@ Law of mass action. The rate at which a substance reacts is proportional to its active mass and the rate of a chemical
reaction 1s directly proportional to the product of the active masses of the reactants.
@ Rate law: The mathematical expression which denotes the observed or actual rate of a reaction in terms of the molar
concentration of the reacting species which influences the rate of the reaction.
_ . _—_. "a

QUICK CHAPTER ROUND UP |)

Rate of reaction Dependence of rate of reaction on
For a reaction,
concentration for a reaction
aX + bB =a cC + dD aA + bB = cC+a4D
_1d{Al__Se
1d[BI
rate =
a dt b dt
_ 1d{C]_1d{D] Law of mass action Rate law expression
c dt d dt rate = k[A][B]? Tate = k[A}*[B]’

>» —ve sign is used for conc. of reactants. - -

=> x and y are expenmentally determined
=> x and y may or may not be equal to a and D
a AI7A MODERN'’S abc + OF CHEMISTRY-XII
Order of a reaction Molecularity
sun of the powers to which the conc. Number of reacting species which
terms are raised. collide simultaneously
can be fractional always whole number
can be zero cannot be zero
experimentally determined theoretical concept

Integrated rate equation Half life period

eet le EN [A] ,/2k Amount left after
half lives
kt 0,693
log [A] = =
2.303*lool°8lAl
A "sa
k
A
oa
1
Second | => |L mol-!s5s~!
[A],

For nth order

For nth order, units of
k = (mol L~!)!-" s“!
% [ARO

O Acatalyst speeds up a reaction

Arrhenius Equation usually by lowering the value
AH = E, (forward) — E,(backward)
k = Ae Ea/RT Low E, => Fast reactions of E.,.
E 1 High E, = Slow reactions A catalyst be recovered
log k,
2 = 2.303R|
=| T, E,a (catalysed) < E,a uncatalysed unchanged at the end of the
ee
A catalyst does not change AH
of a reaction.

Important Graphs

/ero order

Zero order First order Second order

Intercept Intercept
[Alp

slope =—k

¢— Intercept = a5
[Al,
CHEMICAL KINETICS Af7/5 =

1 ,
Lj ty, Vs COTLC. Di logk vs 7 for first order

/ero order First order peo ee

MINSSESN — Sobyed
In-text Questions TI

Q.1. For the reaction R ——-> P, the concentration of What is the order of the reaction?
a reactant changes from 0.03 M to 0.02 M in 25 1 5
minutes. Calculate the average rate of reaction Ans. Order = 3 te = 2.5
using units of time both in minutes and seconds.
AIR Q.4. The conversion of molecules X to Y follows second
Ans. Average rate = _ ALR] order kinetics. If concentration of X is increased
At three times how will it affect rate of formation of Y?

7 (0.02 — 0.03) mol E> Ans. Rate = RLA]? or ba?

25 min
When conc. of A is increased 3 times, then
= 4x 10+ mol L! min"
[A] = 3a
Time = 25 min = 25 x 60s
Rate = k (3a)? = k9a?

oe (0.02 — 0.03) mol L* Rate of formation will become nine times.

7 hae Q.5. A first order reaction has a rate constant

~ 6.67 x 10 mol L's 1.15 x 10° s". How long will 5g of this reactant
take to reduce to 3g? (Hr. S.B. 2017)
Q.2. In a reaction 2A —_> Products, the concentration
of A decreases from 0.5 mol L to 0.4 mol L7? in Ans. For a first order reaction:
10 minutes. Calculate the rate during this time 2.303 [Al,
interval. t= —_ |e Al

Ans. Rate = an [A], = 5g/M, [A] = 3g/M, k =1.15 x 10%s*

where M is molar mass

1 (0.4 —0.5) mol L?
2 fii t= 115x10° © 3M
—~ 5 x 10° mol L? min" 2.303 5
= a ae a og —

Q.3. For a reaction, A + B — Product, the rate is given 1.15 x10 3

by, 2.308
= 7 = * 0.2218 — 444 5
r= R[A}2{BP. 1.15 x10
 MODERN'S abe + OF CHEMISTRY
-AIl

Q.6. Time required to decompose SO,CIl, to half of its 1 E. 308 — 298

initial amount is 60 minutes. If the decomposition og 2 = ——_4____ x |——____
2.303 x 8.314 | 308 x 298
is a first order reaction. Calculate the rate constant
of the reaction. E, «40
Ans. tj. = 80 min = 60 x 60s
0.3010 = 5393x8314 298 x 308

0.693 0.693 BE _ 0.3010 x 2.303 x 8.314 x 298 x 308

k = = ———._ = 1,925 x 10*s1 =~ 10
Lie 60x 60s
= §2.898 kJ
Q.7. What will be the effect of temperature on rate
constant?
. The activation energy for the reaction
The rate constant of a reaction increases with increase
Ans.
in temperature. For detail refer Text, page 52.
2HI (g)—_> Hg) + L(@)
Q.8. The rate of the chemical reaction doubles for an is 209.5 kJ mol" at 581 K. Calculate the fraction
increase of 10 K in absolute temperature from of molecules of reactants having energy equal to
298 K. Calculate E.. or greater than activation energy.

Ans. The fraction of molecules having energy equal to or

Ans. greater than activation energy,
k, 2.303R| TT,
_ 209.6
x 1000

2 2,T, = 298 K, T, = 308 K, R= 8.314 J K mol

ae E,/RT _ e Bald» 581
Fraction of molecules
1
= e 4357 _ 1,461 x 10-9

Textbook Exercises [/
. From the rate expression for the following (zv) Order = 1
reactions, determine their order of reaction and Dimensions of Fk
the dimensions of the rate constants. mol Lis? = Rk (mol L“)
(i) 3NO(g) > N,O(g) Rate = k[NO}* k= g1
(it) H,O,(aq) + 381-(aq) + 2H* — 2H,O(D + I . For the reaction :
Rate = k[H,0O,] [T] 2A + B — A,B
(711) CH,CHO(g) — CH,(g) + CO(g) the rate = R[A][B]* with k = 2.0 x 10° mol? L? s1.
Rate = k[CH,CHO}*” Calculate the initial rate of the reaction when [A]
(iv) C,H,Cl(e) — C,H,(g) + HCI () = 0.1 mol L-, [B] = 0.2 mol L-!. Calculate the rate
of reaction after [A] is reduced to 0.06 mol L“.
Rate = k[C,H,Cl]
Ans. (1) Rate = k[A] [B]?
Ans. (z) Order = 2
When [A] = 0.1 mol L~, B = 0.2 mol L"
Dimensions of k
Rate = 2.0 x 10 x (0.1) x (0.2)"
mol L>} s+ = k. (mol L71)
—- 8.0 x 10° L mol's!
oe R= mol? L sl
(it) When [A] = 0.06 mol L7}
(i) Order =1+1=2
= A reacted = 0.1 — 0.06 = 0.04
Dimensions of k
B reacted = 0.02
mol Lt s7 = k (mol L-) (mol L7) [B] = 0.2 — 0.02 = 0.18 mol L“!
& k = mol” Isa Rate = 2.0 x 10° x (0.06) x (0.18)
(iit) Order = 3/2 = 3.89 x 10°L mol's!
Dimensions of k Q.3. The decomposition of NH, on platinum surface
mol L>}s7 = k (mol L71)" is zero order reaction. What are the rates of
k = mol [1 ="! production of N, andH, if & = 2.5 x 10+ mol" Ls".
(D.S.B. 2008)
CHEMICAL KINETICS
Ce
Ans. 2 NH, ——> N, + 3 H, Att=30s
2.303 0.55
1 diNH,| _ aN, ] _ 1d{H,|
Rate of reaction= > de ae se t+ 8031
For a zero order reaction = a x 0.249= 1.91 x 10751
Rate = k=2.6 x 104*M ss! Att=60s
Rate of production of N, = a
_ d{Nog] _
2.5 x10
4 2.303 | 0:55
60 50.17
- 2.5 x10¢*Ms!
d{H,] 2 a" x 0.5099 = 1.96 x 102s
Rate of production H, = =3x2.5x10* Att — 80 5
2.303 vg 0-58
-~7.5x10'?*Ms!
90 © 0.085
Q.4. The decomposition of dimethyl ether leads to the
formation of CH,, H, and CO and the reaction rate = iene x 0.8109 = 2.07 x 107 s?
is given by
Average value of k = 1.98 x 10-*s
Rate = k[(CH,OCH,]*?”
The rate of reaction is followed by increase in
Q.9. A reaction is first order in A and second order in
B.
pressure in a closed vessel, so the rate can also
(4) Write the differential rate equation
be expressed in terms of the partial pressure of
dimethyl ether, i.e., Rate = k(poyocn,)*” (14) How is the rate affected on increasing the
concentration of B three times ?
If the pressure is measured in bar and time in
(711) How is the rate affected when the concentrations
minutes, then what are the units of rate and rate
of both A and B are doubled ?
constants ?
b . (2) Rate = R[A] [BI]?
Ans. Rate = = = bar min= (71) Rate becomes 9 times
min
(zit) Rate becomes 8 times
Rate = k(pCH,OCH,)?”
Q.10. In a reaction between A and Bb, the initial rate of
bar min™! = k(bar)*" reaction (7,) was measured for different initial
_ bar min” ee concentrations of A and B as given below:
(ban ar“ mineee|

Q.5. Mention the factors that effect the rate of a chemical

AfmolL+ | 020 | 020 | 040 _
reaction. B/mol L-! 0.30 0.10 0.05

Ans. Refer Text Page 9. r,/mol L-'s | 5.07 x 10° | 5.07 x 10° | 1.43 x 10+
Q.6. A reaction is second order with respect to a What is the order of the reaction with respect to
reactant. How is the rate of reaction affected if A and B?
the concentration of the reactant is(A./.S.5. 2012) Ans. Rate = k[A]? [B]?
(7) doubled (it) reduced to half? Rate, = (0.20)? (0.30)? = 6.07 x 10° aaht)
Ans. Refer Solved Example 15 (page 20) Rate, = (0.20) (0.10)? = 6.07 x 10° ...(i)
Q.7. What is the effect of temperature on the rate constant
of reaction ? How can this temperature effect on (Rate), — (0.30)" _
rate constant be represented quantitatively? (Rate), (0.10)?
Ans. Refer Text Page 52 — 58. 33=1 or 37=3° .q=0
Q.8. In a pseudo first order hydrolysis of ester in water Rate, = (0.40 (0.05)? = 143 x 10 ...(iii)
the following results were obtained:
Dividing (iiz) by (cz)
Lve__(ha 0 {7a0| 60] 90 (Rate), (0.40)? 0.05)" _ 1.4310
|UesterV/mol L*] 0.55 | 0.81] 0.17) 0.085. (Rate), x 10
(0.20)? 0.10)" = 5.07
(4) Calculate the average rate of reaction between
the time interval 30 to 60 seconds. oP x + = 2.8
99

(it) Calculate the pseudo first order rate constant

Since g = 0
for the hydrolysis of ester.
2 x= = 2.8
Ans. (i); t=
=
0.17 -0.31
60 — 30
2
2 = 2.8
4.67 x 107 51
Taking log on both sides
(it) k = 2.303 LR),
p log 2 = log 2.8
t [R]
 MODERN’S abe + OF CHEMISTRY-XII

log 2.8 _ 0.45 Experiment | [A]/mol L [Bl/mol L-! Initial rate/

or p=
log 2 0. 3010 mol L7* min- 1

I 2.0 x 10°
Order of reaction w.r.t. A = 1.5,
Il 4.0 x 10°
order of reaction w.r.t. B = 0. iit
Q.11. The following results have been obtained during 2.0 x 10°
the kinetic studies of the reaction :
2A + B—> C+D Ans. Refer Solution of Practice Problem 25 (Page 70).
Q.13. Calculate the half-life of a first order reaction from
[Amol L-| [B/mol L Initial rate of
their rate constants given below:
formation of
(i) 200 s+ (iz) 2 min“ (477) 4 years
D/mol L-!min-!
Ans. Refer Solved Example 22. (Page 32)
I 0.1 0.1 6.0 x 10° Q.14. The half-life for radioactive decay of ‘*C is
5730 years. An archaeological artifact contained
7.2 x 10°
wood had only 80% of the *C found in a living
2.88 x 107 trees. Estimate the age of the sample.
Ans. Refer Solved Example 40. (Page 45)
2.40 x 10°
Q.15. The experimental data for decomposition of N,O,
Determine the rate law and the rate constant for 2N,0, —> 4NQ, + O,
the reaction. in gas phase at 318K are given below:

E74 @©
AEE
Te
Ke Kd
Ans. The initial rate is
(rate), = ALAI,? [B,I?

Comparing experiments I and IV and substituting the fs L1.

values we get
(z) Plot [N,O,] against f¢.
(rate), = R(0.1)? (0.1)9
(ii) Find the half-life period for the reaction.
= 6.0 x 10° A(T)
(i211) Draw a graph between log [N,O,] and ¢.
(rate), = k(0.4)? (0.1)2
(iv) What is the rate law?
= 2.40 x 10° ...(it) (v) Calculate the rate constant.
Dividing eq. (ii) by eq. (1), we get (vi) Calculate the half-life period from k and
compare it with (5).
(0.4)" — 2.40x107 Ans. Refer Solved Example 27. (Page 37)
(0.1) 6.0x107 Q.16. The rate constant for a first order reaction is
60 s'. How much time will it take to reduce
A4P — 4 or (4)!
the initial concentration of the reactant to its
or ped
1/16" value ? (Pb.S.B. 2016)
Similarly, comparing experiments II and III and
substituting the values we get Ans. Let initial concentration, [A], = a

(rate), = R(0.3 (0.2)2 1

Final concentration = [A] = os a
= 7.2 x 107 ...(LiL)
(rate), = R(0.3)? (0.4)?
= 2.88 x 107 ..(iv)
, 2303),
: [Aly
A
k [A]
Dividing eq. (zv) by eq.(ziz), we get
2.303 a
(0.4)? — 2.88x107' | 60 a/16
(0.2)? meio" _ 2,303 log 16
60
(Q=4,/or 2?
y= £ = ee x 1.204 = 0.046 sec
60
Thus the overall rate law expression is:
= 4,6 x 10° seconds.
rate = k [A] [B]?
Q.17. During nuclear explosion, one of the products is Sr
Substituting the values from (z), we get
with half-life of 28.1 years. If 1 pg of °°Sr was absorbed
6.0 x 10° = & (0.1) (0.1)? in the bones of anewly born baby instead of calcium.
6.0x10° How much of it will remain after 10 years and
or Ee eee 5 = 6.0 mol? L? min“.
(0.1)(0.1) 60 years if it is not lost metabolically ?
Q.12. The reaction between A and B is first order with ror b 0.693
respect to A and zero order with respect to B. Fill bye

in the blanks in the following table: tio = 28.1 years

CHEMICAL KINETICS

0.693 Let initial conc. = a

= — = 0.0247 years! 3
28.1 Cone.
one. after after 40
40minmin = a
=a-ax
— Se
77 = 70 a
p — 2308), [Aly 2.303 [A],
Now R
: [A] t [A]
Initial concentration of °°Sr = lug
2.303 a
Let concentration of °°Sr after 10 years = x ug = log
t 0.70a
0.0247 = _2:303_),,, LHS
10 years x We = BANS x 0.1549
1 F 40)
log— — 9:0247%10_ 9 1070 k =8.92 x 10% min!
x 2.303
Now, a ee
or . = 1.280
x
x =0.782 pg 0.693
I ————_—_———— — S764 min.

Concentration of °°Sr after 10 years = 0.782 ug 8.92 x 107 min

Let concentration of Sr after 60 years = y ug Q.20. For the decomposition of azoisopropane to hexane
2.303. log PS
0.0247 = = 1 and nitrogen at 543 K, the following data is obtained.
60 yug
log2= 2.024760 _ 9 435
7 2.303
or 1 _4 40
y
y =0.228 ug
Calculate the rate constant.
Concentration of °°Sr after 60 years = 0.228 ug.
. Let initial pressure of azoisopropane = p.
Q.18. Show that time required for 99% completion is
twice the time required for the completion of 90% Let x atm of azoisopropane decreases at time ¢ so that
reaction. (D.S.B. 2013, H.P.S.B. 2014) (CH,), CHNH = NHCH(CH,), —>+ N, + C,H,,
Ans. For a first order reaction Att =0 D; 0 0
2.303 [A] Attime=t (p,—x) atm xatm x atm
ft = ——lo :
k > [Al P,=p,-X+xX+4+x=p,+%
Let initial concentration, [A], = a or x = Pp, — D;
For 99% completion of reaction, p (azoisopropane) = p. — x = p. — (p, — p,) = 2p. — p,
ax 99 2.003 [A],
AJ] =a-
Al = 4-00 = 0.01
a k = log 7
t [A]
; _ 2,303 - a
_ 2.303 log P;
alias k af0.01la
t 2D; — P,
= ears log 100 At time 360 s
k
2.303 X2 : _ 2.303 ; 35.0
= wa(L)
k 360 © (2x 35.0 — 5d)
For 90% completion of reaction,
=_ 2.303 log 30.0
SN 2
360 16
[A] - A ian = 0.1la
100
= — x 0.33599
P 2.303 1 a
(90%) — = N 08 iis
= 2.17x 10%s1
2.303 " At time 720 s
- ;
—— x1 Pee (it)|
: = 2.903 og 35.0
Dividing equation (z) by (iz) 720 (2 x 35.0 — 63.0)
(99%) _ 9 2.303 30.0 2.9003
x 0.699
“90%) 720 7 720
2.94 x 10-871
Q.19. A first order reaction takes 40 min for 30% 2.17xX10°+2.24x107°
Mean value of k =
decomposition. Calculate t,,,. 2
(D.S.B. 2008, Mizoram S.B.2014, H.P.S.B. 2014) 2.20 x 10s"
ao
Q.21.
MODERN'S abe + OF CHEMISTRY
-AXIl

7 2.303, 1og [Ak

The following data were obtained during the first
order thermal decomposition of SO,CI, at a constant R ; A]
volume.
SO,Cl, (g) ——> SO,(g) + CL(g) |
20% 102 & 2303. 101.0

1 0
Total pressureatm g ag
log 9 = 2.0107 2 %100 _ 9 g6g
2 100
[A] 2.303
Caleulate the rate of the reaction when total
1.0 wp e7o
ONS
pressure is 0.65 atm. (CBSE Sample Paper 2010) [A]
[A] - —-—= 0.135 M.
Ans. k= 2.303 log oe (same as for Q@.20) 7.379
t (2p,— P,) Q.25. Sucrose decomposes in acid solution into glucose
2.303 0.5 2.303 0.5 and fructose according to the first order rate law,
—— log —————~ = —— log ——
100 (2 * 0.5 -— 0.6) 100 0. with t,,. = 3.00 hours. What fraction of sample of
sucrose remains after 8 hours ?
= 2.303 9.0969 = 2.93 x 10-351
100 0.693 0.693
Now, rate = p SO,Cl, Ans. k = = 7 0-281 br®
Pressure of SO,Cl, when total pressure = 0.65 atm by 2

pSO,Cl, = 2p,—p, Let initial conc. of sucrose = 1 M

= 2x 0.5 — 0.66 = 0.35 atm Cone. after 8 hr. = (1 — x) where x is the amount of
Rate = 2.23 x 10% x 0.35 sucrose decomposed.
= 7.805 x 10+ atm s+
h A
2.303 jog [A],
Q.22. The rate constant for the decomposition of N,O,
t [A]
eee
at various is given below :
(es Oca cyPP
8 1-x

log = ee 80
Draw a graph between In Ff and I1/T and calculate 1-<x 2.303
the values of A and E.. Predict the rate constant
at 30° and 50°C. : 6.346
l-x -
Ans. Please try yourself (similar to Solved Example 58
page 57) by plotting graph between In & vs 1/T. This will give 1 = 6.346 — 6.346 x
slope = — E,
Q.23. The rate constant for the decomposition of ea oo
6.345
he
hydrocarbons is 2.418 x 10° s? at 546 K. If the
energy of activation is 179.9 kJ/mol. What will be Cone. of sucrose left after 8 hr
the value of pre-exponential factor ? = 1-—0.842
E
——#= = 0.158 M
Ans. log k = log A —-
= ia 2.303 RT Q.26. The decomposition of hydrocarbon follows the
equation & = (4.5 x 101s "!)e28000K/T
E
log A = log & + ——#_ Calculate E_.
=. ° 2.303 RT
Ans. k = (4.5 x 1014¢-1)e48000K/T
a

= log 2.418 x 10° + __ BB XTO Comparing the equation with Arrhenius equation
2.303 X 8.314 x 546
Rk = A ge Ba/KT
= — 4.616 + 17.208
= 12.592
_% = —28000K
A = 3.90 x 10% 5"! R
Q.24. Consider a certain reaction A —> Products with KE = 28000 x 8.314
k = 2.0 x 10s", Calculate the concentration of A = 232792 J mol?
remaining after 100 s if the initial concentration = 232.792 k J mol!
of A is 1.0 mol Lt. Q.27. The rate constant for the first order decomposition
Ans. k = 20x10? of H,O, is given by the following equation:
t, = 0, [A], = 1.0M log k = 14.34 - 1.25 x 10*K/T
t, = 100s, [A] =? Calculate E, for this reaction and at what
temperature will its half-period be 256 minutes?
CHEMICAL KINETICS

Ans. According to Arrhenius equation, Q.28. The decomposition of A product has value of k as
E . 4.5 x 10° s! at 10°C and energy of activation 60 kJ
logk = log A— ——4#__ me 3
i 2.303 RT mol". At what temperature would & be 1.5 x 10* 51?
The given equation is, - he KE (Rat
| n4 ™ log ;, 2803R| Tx
loxk = 1434 a er
og 15x 10° 60x10" ~—|T,- 283
Comparing eqn. (z) and eq. (iz), 45x10° 2.303x8.314| 283xT,
_ EE
2303R ~~
1 5
*
104
log 3.338 = 3133.62| 12— 283
283 x Tl
E. — 1.25 x 10* x 2.303 x 8.314
— 23.934 x 104 J moll. 0.5228 = 3132.62| 12-253
(283 x Ty
or — 239.34 kJ mol
Half life period,
T,-283 _ 0.5228
0.693 283xT, 3132.62
tip = —— T, — 283, = 0.0472 T,
= b - 0.693 0.9628 T, = 283
T, = 283
hije = 297.02
0.9528
k= BLM =451x10°s+ = 297.02 — 273 = 24.02°C
256 min @.29. The time required for 10% completion of a first
Substituting the values in Eqn. (iz), order reaction at 298 K is equal to that required
for its 25% completion at 308 K. If the value of A is
125 10+
log 4.61x 10° = 14.34- — 4 x 10'°s', calculate k at 318 K and E,.
Ans. Advanced Level Problem 8 (Page 60)
4
Q@.30. The rate of reaction quadruples when the
4.34568 = 14.34— 129x107 temperature changes from 293 K to 313 K. Calculate
the energy of activation of the reaction assuming
125 x 10+ that it does not change with temperature.
pT. eX 669 K. (A.LS.B. 2013)
18.6858
Ans. Refer Solved Example 53 (page 56).

Exemplar Problems TI
Subjective Questions
4, For which type of reactions, order and molecularity
have the same value?
Ans. For elementary reaction, order and molecularity have the
same value.
1. State a condition under which a bimolecular 5. In a reaction if the concentration of reactant A is
reaction is kinetically first order reaction. tripled, the rate of reaction becomes twenty seven
Ans. Bimolecular reaction becomes kinetically first order when times. What is the order of the reaction?
one of the reactants is in excess. Ans. Order is 3 because
2. Write the rate equation for the reaction 2A + k = [A}®
B —-> C if the order of the reaction is zero. 6. Derive an expression to calculate time required
Ans. Rate =k [A]°([B]® or Rate =k for completion of zero order reaction.
3. How can you determine the rate law of the Ans. For a zero order reaction,
following reaction? R = [R], — Rt
2NO(g) + O,(g) —> 2NO, (g) For completion of the reaction, [R] = 0
Ans. The rate law can be determined by measuring the rate -. kt = [R],
of this reaction as a function of initial concentration by
or t= Ho
keeping the concentration of one of the reactants constant
and changing the concentration of other reactant or by 7. For a reaction A + B —-> Products, the rate law
changing the concentration of both the reactants. From is : Rate = k[A][B]?*.
the concentration dependance of rate, rate law can be
Can the reaction be an elementary reaction? Explain.
determined.
aa
Ans. The reaction is not elementary because order of the
MODERN'S abe + OF CHEMISTRY

15. Why does the rate of any reaction generally

-AXIl

reaction is fractional 1 + ~=2 decreases during the course of the reaction?

Ans. The rate of a reaction depends on the concentration of
8. For a certain reaction large fraction of molecules
reactants. As the reaction progresses, the concentration
has energy more than the threshold energy, yet
of reactant decreases because the reactants start getting
the rate of reaction is very slow. Why?
converted to products. Hence the rate decreases.
Ans. Though the reacting molecules may be having energy
more than threshold energy, yet they may not be effective 16. Thermodynamic feasibility of the reaction alone
due to lack of proper orientation. cannot decide the rate of the reaction. Explain
9. For a zero order reaction will the molecularity be with the help of one example.
equal to zero? Explain. Ans Thermodynamic feasibility (-ve AG) cannot alone decide
Ans. Molecularity can never be zero or a fractional number. the rate of reaction because the reaction may be feasible
but its rate may be very very slow because of very high
10. For a general reaction A —-; B, plot of concentra-
activation energy. For example, conversion of diamond to
tion of A vs time is given in figure below. Answer
graphite is highly feasible but this reaction is very slow
the following question on the basis of this graph.
because it has high activation energy.

17. Why in the redox titration of KMnO, vs oxalic

acid, we heat oxalic acid solution before starting
the titration?
The reaction between KMnO, and oxalic acid 1s very slow.
By raising the temperature we can increase the rate of
A—>
of
Conc. reaction.
18. Why can’t molecularity of any reaction be equal
t—> to zero?

(4) What is the order of the reaction? Ans Molecularity is the number of molecules taking part in
an elementary step. For this we require at least a single
(17) What is the slope of the curve?
Gii) What th ‘ta of rat tant? molecule leading to the value of minimum molecularity
Ut at are the units of rate constant?
of one.
Ans. (z) zero order reaction 19. Why molecularity is applicable only for elementary
(ii) [R] = [R,] — Rt reactions and order is applicable for elementary
Slope = —k as well as complex reactions?
mol =I L _ 0 _ 7 .ff Ans. A complex reaction occurs through several elementary
(111) = a Ve ee reactions. Numbers of molecules involved in each
elementary reaction may be different 1.e., the molecularity
11. The reaction between H,(g) and O,(g) is highly
of each step may be different. Therefore, the molecularity
feasible yet allowing the gases to stand at room
temperature in the same vessel does not lead to of overall complex reaction is meaningless. On the other
the formation of water. Explain. hand, order of a complex reaction is experimentally
Ans. This is because activation energy for the reaction is very determined by the slowest step in its mechanism and 1s
high at room temperature. therefore, applicable even in the case of complex reactions.
20. Why can we not determine the order of a reaction
12. Why d th te of tion i ith ri
eee . | Y ae by taking into consideration the balanced chemical
in temperature? ae
equation:
Ans. At higher temperatures, larger fraction of collidin
a 7 yoo ae Ans. Balanced chemical equation often leads to incorrect order
particles can cross the energy barrier (i.e. the activation
energy), which leads to faster rate. For detail refer text. or rate law. For example, the following reaction appears
to be a tenth order reaction.
13. Oxygen 1s available in plenty in air yet fuels do not
KCI1O, 4 6FesO, + 3H,SO, —> KCl + 3H,O +
burn by themselves at room temperature. Explain.
Ans. The activation energy for combustion reactions of fuels 3Fe(SO,),
is very high at room temperature therefore they do not However, this is actually a second order reaction. Actually
burn by themselves. the reaction is complex and occurs in several steps. The
14, Why is the probability of reaction with molecularity order of such reaction is determined by the slowest
higher than three very rare? step in the reaction mechanism. Order is determined
The probability of more than three molecules colliding experimentally and gives the actual dependence of
simultaneously is very small. Therefore, the possibility observed rate of reaction on the concentration of
of molecularity being three is very low. reactants.
CHEMICAL KINETICS 4/83 =

Memory TEST

i] Say True or False 6. The units of rate constant for a second order gaseous
reaction are ............. :
1. The units of rate constant of a zero order reaction are 7. The rate of a reaction when the concentration of each
same as the units of rate of a reaction. reactant is taken as unity is called .............
2 (BORA parhcali Ponrlebn, Hs tele cee
ih sae eneen 8. A catalyst provides a path of ............. activation energy.
of concentration.
3. In general, for nth order gaseous reaction, the units of 9. For a first order reaction, half life period is equal to
rate constant are(atm)*2 so 00 nts
4, The rate of a multistep reaction is determined by the 10. If the rate of reaction : N, + 3H, —-~ 2NH, measured
fastest step in the sequence. as A[NH,]/At was found to be 3.6 x 10~ mol L's“, then
5. For the second order reaction with respect to a reactant rate of reaction expressed as A[H,] / Af is .............
rate becomes 8 times ura its concentration 18 tripled. 11. The sum of powers to which concentration terms are
6. For Sn order reaction, rate becomes 1/2 times on raised in the rate law expression is called ............ of the
doubling its concentration. @ action
7. The halflife period for a first order reaction is independent
ae re ea ee ae 12. For a reaction : A + B—-> Products, the rate is given as
R[A]""B?. The units of its rate constant are ............. ;
8. If[A], is the initial concentrati f tant follow1
a ee eae 18. When the concentration of a reactant of a second order
first order reaction, then after three half lives its
[A] is tripled, then rate will become ............. times.
concentration becomes ——¢ . : o e
3? 14, Ifhalflife period of a first order reaction is 32 min, then
9. The molecularity of a reaction is always greater than the time taken for concentration to be reduced to 1/16
order of the reaction. ME ecbececens: ;
10. Higher the activation energy of a reaction, faster is the 15. Ifrate constant for a first order reaction has been found
reaction. to be 2.31 x 10-9 s1, then its half life period is ............. ;
11. Order of a reaction may be fractional but molecularity
is never fractional. @f5] Choose the correct alternative
12. For a first order reaction, plot of /n([A],/[A]) versus time
has a positive slope whose value is equal to the rate 1. For a zero order reaction, a plot of [A] vs ¢ 1s linear with
constant of the reaction. slope equal to —k/k.
13. The time taken for 3/4" of a first order reaction to 2. Half life period for a second order reaction is
complete is 1.5 times the half life period. beg ee ere OF Ds Ad
14, Fora zero order reaction, plot of [A] vs tis a horizontal line.
3. Average life time is more/less than half life time for a
15. Average life period for a first order reaction is equal to first order reaction.
reciprocal of disintegration constant.
fe. For fast reactions, activation energy is low/high.
I-38 Complete the missing links on. The molecularity of hydrolysis of cane sugar is two/one.

1. Rate constant and rate of a reaction have the same units 6. Increase in rate of reaction with rise in temperature is
for reactions of 4m. orate mainly due to increase in collision frequency/effective
collisions.
2. Hydrolysis of ethyl acetate in an aqueous solution is of
eee order. =]. For an endothermic reaction, activation energy for the
3. The order of a reaction whose rate law is rate = forward reaction 1s more/less than activation energy for
RUA]®4 [BI is. ccc. the backward reaction.

4, The difference in energy between the energy of activated 8. For exothermic reaction, E, (forward) — E, (backward)
complex and the average energy of reactants is called is +ve/—-ve.
setrebewntee 9. For a second order reaction, when the concentration of
5. The factor e=“®" in Arrhenius equation is called ............. the reactant is tripled rate becomes nine/eight times.
factor. 10. The units of zero order reaction are molL“s7 / mol Ls.
la MODERN'S abe + OF CHEMISTRY
-AXIl

eles Memory Test WN

14, False. Plot of rate vs ¢ is a horizontal line but a plot of
Say True or False
[A] vs ¢ will be linear.
True. 2. True.
15. True.
False. The units are (atm)? s7}.
False. Slowest step is the rate determining step. By Complete the missing links
False. It becomes 9 times.
1. zero 2. first BA
False. It remains unchanged.
4, activation energy 5. Boltzmann 6. atm™s?
True.
7. rate constant 8. low 9. 0.693/k
False. Concentration becomes [A],/ a
coe
aes,
aia False. Molecularity may be equal also. 10. 56.4x10*molL ts? 11. order 12. mol “Ls
—_> False. Higher the activation energy, slower is the 13. 9 14. 128 min 15. 300s
reaction.
Choose the correct alternative
11. True.
12. True. 1. -k ae RA], o. more 4, low

12
5. two 6. effective collisions 7. more
8. —ve 9. nine 10. mol L-“!s!

—4 HOTS Higher Order Thinking Skills

a Advanced Level
QUESTIONS WITH ANSWERS
Q.1. Derive the rate law expression for the reaction: t 2a)"
2P + Q@—-> Products
if the first step is the reversible dimerization of P, followed
tC
by reaction of P, with Q in a bimolecular rate controlling 2 = get
step. Assume that the equilibrium concentration of P, is or nmn-l=1
very small as compared to [P]. i= 2
The reaction is second order.
Ans. op = FP. cht) Q.3. For a zero order reaction, starting with initial
concentration C,, how long will it take for the reaction
P,+Q Sw _, Products .-(it) to go to completion ?
From eqn. (2)
Ans. For a zero order reaction :
P, or Ee — KIP]?
1: |
[Py k= 7LCo—C] or t= Zoo]
Since step 2 is rate controlling,
where C = concentration of the reactant at time f.
Rate = k[P,] [Q] For the reaction to go to completion C=0.
= k(KIP]*) [Q]
ti = Co
= k' [P}? [Q] (k' =kK) k
Q.2. The ¢,,. of a reaction is halved as the initial Q.4. The probable mechanism for the reaction:
concentration of the reactant is doubled. What is the
Hg,** + Tl?* —— 2Hg* + TI
order of the reaction?
1 is Hg,** = Hg" + Hg
Ans. t
1/2 ms ql
Hg
+ Ti+ —*— > Hg? + Tr
Let initial cone. = a, (¢,.), =
Derive the rate law.
Initial cone. = 2a, (f45). = t/2
Ans. Hg,2* —“—= Hg? + Hg (i)
Hg + T+ —*-> Hp?* + TI (it)
CHEMICAL KINETICS

From eqn. (11)

rate = k’[Hg] [TI**] ...(111)
From eqn. (2)
2+ log [Aly
[RI]
[Hg5" ok
slope =5-393
Hg?*

or [He] = ml |
ie
Substituting the value of [Hg] in eqn. (ziz)
time (min)

Q.6. The rate of decomposition of ammonia is found

to depend upon the concentration of ammonia as:

rate = k’K [Hea |x |T1**| a d[NHs | = k, [ NH, |

[He*| dt - +k, | NH; |
what will be the order of reaction when :
Pl adhaul Pe
He
(1) concentration of NH, is very high?
(12) concentration of ammonia is very low ?
Ans. The rate law expression is
Q.5. For a certain chemical reaction, variation in the
concentration, In| R] vs time (min) plot is shown below: > d [ NH | _ ky [ NHs | _ k,
dt 1+k[NH;] 1/[NH,]+,
In[R] (z) when [NH.,] is very high, ! becomes negligible
(NH,|
_ d[NH, | kh _h
dt ~—ik
i.e., rate becomes independent of concentration and hence
it is of zero order.
- ; 1
(11) h when [NH.,] is3 very sma
small, NH will be very large so
t(min) 3
1
For this reaction that k, can be neglected in comparison to INH. J: Hence,
3
(4) What is the order of the reaction ?
d[ NH“4| =
—-—t_ hy
—_4__ —.|NH
(74) What are the units of rate constant, & for this dt 1/[NH, | INE
reaction ? Thus, the reaction is of lst order.
(711) Give the relationship between F& and f,,. of this Q.7. For a reaction A —*-s product, the reaction
reaction. occurs as:
(iv) If initial concentration for this reaction becomes A —2>at —2-, Bt —s_, product

+ le
half, how will ¢,,. vary?
The overall rate constant k& is given as:
(v) What does the slope of this line indicate ? 2/3

(vi) Draw the plot of log [R],/[R] vs time (s).

Ans. (1) Reaction is of first order because for the first order
If E,,, Ea,and E,,are the activation energies of these
reaction :
steps, then what is the relation between overall activation
In{R] =— kt + In[R], energy E, and the activation energies of these steps.
The plot of In[R] vs t is a straight line with slope = —& and Ans. Rate constant is related to activation energy as
intercept In[R]>.
k = Ae *4/RT 5 that
(it) Units of rate constant : min™!
0.693 k, -= Ae,= Ea,/RT ,k, _= Age —Eag/RT andk,=_ A,e~”
_~Eaa /RT
(zit) For a first order reaction, t,,, =
Rk
(tv) No change in ¢,,, because half life period is independent Now Rk
of initial concentration.
ke

2/3
(v) Slope of line is equal to — &. Ae7Ea/RT Ave —Eag /RT |
2A,ePa/RT |
A, oEag/RT
(vt) The plot of log [R],/R vs time (min) is
ane | Pressure due toO,
MODERN'S abe + OF CHEMISTRY-AXIl

= x/2
2/8 —Eag/RT \2/9
Ae EU/RT _ on Ag | ,-EayRT,.|& ___ Total pressure after 30 min = 284.5 mm Hg
Az e "3

o- 933.8—x + 2x4 : _ 284.5

—Ea/RT
2/3 ——
—Ea- {Eag+, Eas
Ae = 2A, (2) e RT or x = 33.8 mm Hg
As, Pressure of N,O, after 30 min = 233.8 — 33.8
oe 2 = 200 mm Hg
-E, = —E,, ~ 9 Bag +3 EL,
; : [A]
For first order reaction, k = 2.303 lo u
2 2 t LA]
or E, = E,, + 3 ae ~ 3 Fas
Using the partial pressure for concentrations :
Q.8. For a reversible reaction
p= 2308 16, 2998 < 5.0 x 103 mint.
30 200
Q.10. The half life for the reaction :
derive an expression for the formation of HI.
. 1
_ 1d{HI] N,O. ——> 2NO, + a2
Ans. Rate of reaction
2 di is 2.4 hours at 30°C
- k,(H,] (1,]—2, (HU? (a) Starting with 100 g of N,O,., how many grams will
remain after a period of 9.6 hours ?
“. Rate of formation of HI,
(6) What time would be required to reduce 5 x 101°
d|{HI]
- 2k,[H,] (1,] - 2k, (HI? molecules of N,O, to 10® molecules ?
dt
Q.9. The decomposition of N,O, according to the Ans. & _ 0-693 ork _ 0.693 _ 9 989 hr
t 2.4
equation, 1/9
2N,0, (g) 4NO,(g) + O,(@) (2) For the first order reaction :
is a first order reaction. After 30 min from the start of 2.303 [A],
—_ —_hby —
the decomposition in a closed vessel, the total pressure t [A]
developed is found to be 284.5 mm of Hg and on complete 100
decomposition, the total pressure is 584.5 mm of Hg. [A], = Wp” [A] =(x/M), t = 9.6 hr
Calculate the rate constant of the reaction. M = Molecular weight (x = amount of N,O, left in gram)
Ans. 2N,O, (g) == 4NO,(g) + 0,(g) 0.289 — 2.303 log 100/M
9.6 ac/M
2 mol of gaseous N,O, on complete decomposition gives
100 0.289 x 9.6
6 mol of gaseous product (4 mol NO, and 1 mol O,). Therefore,
= i 2.303 :
initial pressure of N,O.,p,) = 584.5 x 2 100 | _ 200 _ 04
or = 16.02 orx= 1602.” a
= 233.8 mm Hg.
(iz) [A], = 5 x 10*°/N,, [A] = 10°/N,
Let x be the amount of N,O, decomposed after 30 min.
where N, is Avogadro number,
Therefore,
2.303. 5x10'°/N |
Pressure due to N,O, = 283.8 — x ee log —_,——* = 21.51 hr.
Pressure due to NO, = 2x k 10°/N,

= Revision Exercises
6. For a first order reaction, k = 2.5 x 10* s“/, what is the rate
>» Very Short Answer Questions <4 of reaction, when the initial concentration of the reactant
is 0.1 mol L?
1. Define half life period. (Jammu S.B. 2016)
7. Define pseudounimolecular reaction with an example.
2. Can order of a reaction be fractional ? Explain.
(Hr. S.B. 2018)
3. The specific rate of a reaction is 6.2 x 10° mol L's 71. What 8. What are the units of rate constant for first order reaction?
is the order of the reaction ? (Pb. S.B. 2018, H.P.S.B. 2018)
4, Is it possible for a reaction to have identical values for 9. For a reaction rate law expression is:
molecularity and order ? Rate = k[A]”? [B]?
Can the reaction be an elementary? Explain.
5. A reaction is found to be zero order reaction, will its
(Pb. S.B. 2018)
molecularity be also zero ?
CHEMICAL KINETICS

10. The rate law for the reaction 29. If agraph is plotted between In & and 1/T for the first order
CHCL,(g) + CL, (¢) —> CCI, + HCl reaction, the slope of the straight line so obtained is given
is rate = k [CHC1,][C1,]™. by
What is the order of reaction ? (a) ws" (oy; = =
R 2.303 R
11. What is the order of reaction whose rate constant has same
unit as the rate of reaction? (H.P.S.B. 2010) 2.303 K
12. If the units of rate constant of a reaction is mol! Ls-}, then Oi a ‘) ~ 3303
mention its order. (Karnataka S.B. 2018) . (Jharkhand S.B. 2012)
15. Define order of the reaction. (H_.P.S.B. 2018) a0. The unit of rate constant for a zero order reaction is
14. Rate of reaction = k[H,]°[C1,]°, according to rate law (a) mol Ls (b) s+
equation. Predict the order of reaction. (H.P.S.B. 2018) (c) L mols? (d) L?mol?*s+
15. A first order reaction is found to have a rate constant (Mizoram S.B. 2014, Hr. S.B. 2017)
k=6.6 x 10-“ s"!. Find the half-life of the reaction. ol. A catalyst increases the speed of a chemical reaction by
(Karnataka S.B. 2018) (a) increasing activation energy
16. In a reaction, 2A ——-> products, the concentration of A (6) decreasing activation energy
decreases from 0.5 mol L7! to 0.4 mol L™ in 10 minutes. (c) increasing reactant energy
Calculate the rate during this interval. (d) decreasing threshold energy (Mizoram S.B. 2014)
(Meghalaya S.B. 2013) ode The units of the rate constant for the second order reaction
17. The rate constant of a reaction is 3 x 107 min“. What is the are:
order of reaction? (Assam S.B. 2012) (a) mol litre st (6b) mol litre? s+
18. What is instantaneous rate of reaction? (c) s2 (d) mol litre? s7?
(A.P.S.B. 2015, Mizoram S.B. 2017)
(H.P.S.B. 2016, Nagaland S.B. 2018)
oe The value of & for a reaction is 2.96 x 10-°° s-!. What is the
19. Give the definition of collision frequency
order of the reaction?
(4. P.5.5 2006, Assam S.B. 2016)
(a) Zero (b) 3
20. For a reaction R — P, half life (¢,,) 1s observed to be
(c) 2 (d) 1 (H.P.S.B. 2015)
independent of the initial concentration of reactants. What
is the order of reaction? (D.S.5. 2017) oA, A reaction is found to be of second order with respect to
concentration of carbon monoxide. If concentration of carbon
21. Identify the order of reaction if the unit of rate constant is monoxide is doubled, the rate of reaction will
mol L7ts. (Kerala S.B. 2018)
(a) triple (6) increase by a factor of 4

»> CBSE QUESTIONS <4 (c) double (d) remain unchanged

(H.P.S.B. 2015)
22. Is there any reaction for which the rate does not decrease
with time? (A.S.B. 2006) oe If the concentrations are expressed in mol litret and time
in s, then the units of rate constant for the first-order
23. Express the rate of the following reaction in terms of reactions are
disappearance of hydrogen in the reaction :
(a) mol litre? s-} (6) mol? litre s-}
3H + Nog) —> 2NHxy (A.LS.B. 2007) (c) st (d) mol? litre? s7?
24, The reaction: A + 2B —-+ C obeys rate equation. (H.P.S.B. 2017, Hr. S.B. 2018)
Rate = & [A]? [B]?2 ob. The half life of a first order reaction having rate constant
What is the order of this reaction? (A.LS.B. 2007) 200 sis
(a) 3.465 x 10-*s (6b) 3.465 x 10s
25. Define order of a reaction. (A.LS.B. 2011, D.S.B. 2011,
(c) 1.150 x 10s (d) 1.150x 10s
Nagaland S.B. 2015, H.P.S.B. 2014, 2018) (Mizoram S.B. 2015)
26. Define activation energy of a reaction ods The rate of a reaction is 1.209 x 10-*L? mol s"!. The order
(A.TS.B. 2011, H.P.S.B. 2016) of the reaction 1s:
(a) zero (6b) first
27. What is the effect of adding a catalyst on
(c) second (d) third (Mizoram S.B. 2016)
(a) Activation energy (E,,) and
oo. A catalyst increases the rate of a reaction by
(b) Gibbs energy (AG) of a reaction (ors 20r7)
(a) increasing threshold energy
(6) increasing activation energy
MCQs from State Boards’ Examinations
(c) activating the reactants
28. A first order reaction has a halflife period of 34.65 seconds. (d) lowering activation energy (Mizoram S.B. 2018)
Its rate constant is
oO”. Time required for 100% completion of a zero order reaction
(a) 2610" e+ (b) 4x10¢%s1 is:
(c) 2057+ (d) 292x107 51 (2) lipo = alk (b) trooqm = a-k
(Jharkhand S.B. 2012) (C) Lipo, = a/2k (d) None ofthese (Hr. S.B. 2017)
ae
40). Arrhenius equation is represented by : A, Consider the rate equation
MODERN'S abe + OF CHEMISTRY
-AXIl

(a) k = Ae=*/RT (b) k= Ae=4/RT

Rate = k[A]"
(c) t, = 0.693/k (d) None ofthese (Hr. S.B. 2017) What is the change of rate that occurs on doubling the
Al, The overall order of a reaction, which has the rate expression: concentration of A, when
Rate = k[A]??[B]?” is: Gja=0 (2)2=1 G@Hujn=27?
(a) First order (6) Second order
(c) Third order (dq) Zero order . Consider the reaction A“; P. The change in concentration
of A with time is shown in the following plot:
(Mizoram S.B. 2018)
42. If half life period of a first order reaction is 100 seconds.
Then rate constant will be:
(a) 6.93 x 10° second (6) 6.93 x 10-7 second
(c) 0.6938 second (dq) 6.98 second (Hr. S.B. 2018) [A]

. Ifrate constant for a reaction is mole litre! second-!, then Concentration

order of reaction is:
(a) Aero order (6) First order Time (t)
(c) Second order (d@) None of these (t) Predict the order of the reaction.
(Hr. S.B. 2018) (it) Derive the expression for the time required for the
. Identify the order of reaction from the given rate constant completion of the reaction.
(C_B.S.E. Sample Paper 2007)
k-=2.6x10*Lmol's?
(a) First (6) Zero . What is meant by the rate constant, 'k' of a reaction? If the
(c) Second (d@) None of these concentration be expressed in mol L“! units and time in
(Hr. S.B. 2018) seconds, what would be the units for k
(1) for a zero order reaction and
. For a reaction: N, + 3H, - 2NH,, the rate of reaction with
respect to NH, will be: (11) for a first order reaction? (D.S.B. 2008)
d{NH,] _ d{NH,? . Derive the following relation :
(a) ais (b) a
Re E T,-T |
log— = a 21 P.S.B. 2010
"8, ~ 2.303R |ig :
OS )—-3 gq. *(Ar. S.B. 2018) . Starting from the integrated law of a zeroth order reaction,
46. Half life period of a first order reaction depends upon: RP, show that half-life time of a reaction is directly
(a) Concentration of reactants proportional to the initial molar concentration of the
reactant. (Assam S.B. 2018)
(6) Concentration of products
(c) Rate constant of reaction . Discuss the effect of temperature on the rate of a reaction.
(ad) None of these (Hr. S_B. 2078) (Pb.S.B. 2011, Ar.S.B. 2015, Jammu S.B. 2015)
10. Distinguish between rate expression and rate constant of
47, Half life period of a first order reaction is: a reaction. (D.S.B. 2011)
(a) directly proportional to the initial concentration of the 11. (a) What is the order of reaction whose rate constant has the
reactant same unit as the rate of reaction?
(6) half of the rate constant
(6) Caleulate the overall order of a reaction which has the
(c) same for all reactions
rate expression
(d) independent of the initial concentration of the
Rate = k[A]¥?[B]?”
reactants (Mizoram S.B. 2018)
(c) What is the rate determining step of a reaction?

»> em mel tele mlcarrying 2 or 3 marks <4 (Meghalaya S.B. 2018)

12. Derive the integrated form of rate equation for the first order
. What is rate of a reaction ? Discuss briefly the various reaction. (Pb.S.B. 2012, H.P.S.B. 2012, 2015, 2016)
factors which influence the rate of a chemical reaction. 135. (a) Define pseudo unimolecular reactions.
(Jammu S.4. 2018)
(6) What are zero order reactions ? Derive integrated rate
. What is meant by order of a chemical reaction ? The equation for zero order reaction.
reaction : (H.P.S.B. 2012, H.P.S.B 2007 )
2NO, + F,, ——> 2NO,F
14, How you differentiate between reaction rate and reaction
has been found to be first order with respect to NO, and
rate constant ? (J.K.S.B 2011, 2015)
with respect to F,,.
15. (a) Define activation energy of a reaction.
(1) Write the rate law equation for the reaction.
(11) What is the overall order of the reaction ? (6) How does the nature of a reactant affect the rate of a
chemical reaction? (JK SB. 2013)
(111) Suggest a suitable mechanism for the reaction.
a. Explain with examples the meaning of the terms average 16. (a) Reaction between NO, and F, to give NO, F takes place
rate and instantaneous rate of the reaction. by the following mechanism:
(H.P.S.B. 2007) NO,(¢) + Fg) — > NO,F) + Fe)
CHEMICAL KINETICS

Fast 28. What is half life of a reaction? If the half life of a first order
NO,(g) + F@) —~——> NO,F)
reaction in A is 2 minutes, how long will it take to reach
Write the rate expression and order of the reaction
25% of initial concentration? (Nagaland S.B. 2016)
(6) Calculate two-third life of a first order reaction having
29. (t) Define order of reaction.
k=6.48x10's1. (Pb S.B. 2018)
(it) Identify the reaction order from each of the following
17. A reaction is first order in A and second order in B.
units of reaction rate constant.
(:) Write differential rate equation.
(a2) mol Lt s+
(it) How is rate affected on increasing concentration of B io): Lanol a+ (Tripura S.B. 2016)
three times? (Ar. S.B. 2013)
350. (a) Give an example of a pseudo first order reaction.
18. (a) Give four differences between molecularity and order
of a reaction. (HP. S.B. 2018) (6) Write Arrhenius equation which relates the rate
constant with temperature.
(6) Write units of rate constant for second order reaction.
(c) A first order reaction takes 40 minutes for 30 %
(c) Give an example of first order reaction. decomposition. Calculate ¢,,. for this reaction.
(HP. S.B. 2013) (Tripura S.B. 2016, Meghalaya S.B. 2017)
19. (a) What is activation energy? ol. Derive the integrated rate equation for the first order
(6) What are the units of rate constant for second order reaction. Hence prove that half-life period for it is
reaction? independent of initial concentration.
(c) Write Arrhenius equation. (HP. S.B. 2018) (Meghalaya S.B. 2016, Jammu S.Z. 2018)
20. (a) Define molecularity of a reaction. ode (1) For the reaction:
(6) Define activation energy. me.
12°729- % 11 +H,O —#1; C,H,,0,
6-126 + C,H,,0
6-712 6
(c) For a first order reaction, show that time required
Write (a) Rate of reaction expression
for 99% completion is twice the time required for the
(6) Molecularity
completion of 90% of reaction. (H.P. S.B. 2014)
(iz) Give the units of rate constant for a zero order reaction.
21. Write two differences between ‘order of reaction’ and
‘molecularity of a reaction’. (H.P.S.B 2016)
(D.S.B. 2014, Meghalaya S.B. 2017) oo. (1) The rate constant for a chemical reaction at a given
22. (a) What are pseudo order reaction? temperature is 2.3 x 10° Lmol's-. What is the order
of the reaction?
(6) What is half life period? Show that half life period
for a first order reaction is independent of the initial (it) Show that for a lst order reaction, time required for
concentration of the reactant. (AP. S.B. 2015) completion of 99.9% is 10 times of half time of the
reaction. (Assam S.B. 2018)
23. The reaction : 2A + B—+C + D has the rate equation as:
oA, (a) The molecularity of the reaction 2NO + O, — 2NO, is,
rate = k [A]* [B}
(1) 6 (it) 2
(tz) What is the molecularity of the reaction?
(zit) 3 (zv) O
(it) Order of the reaction when B is present in large excess.
(6) (2) What do you mean by rate of a reaction?
(H.P. S.B. 2015)
(11) What will be the effect of temperature on rate of a
24, (a) What is the effect of catalyst on the activation energy
reaction?
of a reaction? (AP. S.B. 2015)
(c) A first order reaction is found to have a rate constant,
(6) Derive integrated rate equation for a zero order
k=6.6=10-“5s-!. Find out the half-life of the reaction.
reaction. (Hr. S.B. 2015)
(Kerala S.B. 2016)
25. Define the following terms:
oOe (a) Derive integrated rate law equation for first order
(t) Half life period of a reaction. reaction.
(it) Collision frequency (6) What are the units of rate constant for 3rd order
(111) Activation energy (Hr. S.B. 2018) reaction? (A.P.S.B. 2018)
26. (a) Give one example of pseudo first order reaction. o6. Define the following terms:
(6) A reaction is second order with respect to a reactant.
(a) Activation Energy (6) Molecularity
How does the rate of the reaction be affected if the
(c) Rate constant (Ar.S.B 2017)
concentration of the reactant is reduced to half?
Or Od. (a) Derive an integrated rate equation for rate constant of
Show that the time required for completion of 3/4th of a first order reaction.
a first order reaction is twice the time required for the (b) Draw a graph of potential energy vs reaction
completion of 1/2 ofthe reaction. (Assam S.B. 2016) co-ordinates showing the effect of catalyst on activation
27. What is meant by zero order reaction? Give an example of energy (E._) of a reaction. (Karnataka S.B. 2018)
such a reaction. Establish the integrated rate equation for oo. (a) The thermal decomposition of a compound is of first
a zero order reaction involving a single reactant. How can order. If 50% of the compound is decomposed in 120
the rate constant be determined using this equation? minutes, how long will it take for 90% of the compound
(Kolkata S.B. 2016) to decompose?
aso
_ Or 49, For the reaction
MODERN'S abe + OF CHEMISTRY
-AXIl

(6) The three-fourths of a first order reaction is completed 2N,0,(g¢) —> 4NO, (g) + O, (g),
in 32 minutes. What is the half-life period of the the rate of formation of NO, (g) is 2.8 x 10° Ms. Calculate
reaction? (Mizoram S.B. 2017) the rate of disappearance of N,O,(g). (A.L.S.B. 2018)
50. A first order reaction is 50% completed in 40 minutes at
359. Show that slope of the plot of /n & against bs is _Ea Give
300 K and in 20 minutes at 320 K. Calculate the activation
the graphical representation of the plot. R
energy of the reaction.
(Assam S.B. 2017) (Given: log 2 = 0.3010, log 4 = 0.6021, R= 8.314 JK" mol")
>» CBSE QUESTIONS <4 (A.L.S.B. 2018)

40). For a reaction at 500 K,

NO,(g) + CO (g) —> CO,{g) + NO)
Long Answer Questions carrying
5marks |<
1. (a) Derive activation energy by Arrhenius equation. Write
the proposed mechanism is as given below :
differences between order and molecularity of a reaction.
(1) NO,(@) + NO,(¢) —> NO() + NO,(g) (slow)
(6) What is the effect of catalyst on rate of a reaction ? A
(it) NO,(@) + CO) —— CO,(@) + NO,(g) (fast)
first order reaction has rate constant 1.15 x 10° sect.
What is rate law for the reaction ? How long will 5g of this reactant take to reduce to 3g ?
(A.LS.B. 2008, Pb.S.B. 2007) (Ar. S.B. 2012, 2015)
Al, (a) Derive the general form of the expression for the half » (a) Write down the unit of rate constant for zero order
life of a first order reaction. reaction.
(6) List the factors on which the rate of a chemical reaction (6) Derive the rate equation :
depends. (A.LS.B. 2008, D.S.B. 2008) 2.303 a
k = —— log
42. Define the following : a-x
() Elementary step in a reaction for first order reaction and establish the relationship
(11) Rate of a reaction. (A.JLS.B. 2009) between half life period and its rate constant.
Or
. Define the following:
(1) Whatis the difference between molecularity and order
(z) Order of a reaction of reaction?
(ii) Activation energy (A.I.S.B. 2009) (iz) For a first order reaction, half life period (Z,,.) 1s 100
. Areaction is of second order with respect to a reactant. How seconds. How long will it take for the reaction to
is the rate of reaction affected if the concentration of the complete 75%? (Uttarakhand S.B. 2013)
reaction is reduced to half? What is the unit of rate constant .» (a) A reaction is second order in A and first order in B.
for such a reaction? (A.LS.B. 2077) (1) Write the differential rate equation.
. What do you understand by the rate law and rate constant (11) Howistherate affected on increasing the concentration
of a reaction ? Identify the order of reaction if the units of of A three times ?
(111) How is the rate affected when the concentrations of
its rate constant are:
both A and B are doubled ?
vr be oneal |ee (6) A first order reaction takes 40 minutes for 30% decom-
(iz) Lmol's? (A..S.B. 2011) position. Calculate t*4 for this reaction.
46. A reaction 1s of second order with respect to a reactant. How (Given log 1.428 = 0.1548)
is its rate affected if the concentration of the reactant is (1) Cr
doubled (zz) reduced to half ? (AJS.B. 2012) (a) For a first order reaction, show that time required
AZ. (a) For a reaction A + B — P, the rate law 1s given by, for 99% completion is twice the time required for the
r = k[A)” [BI? completion of 90% of reaction.
What is the order of this reaction ? (6) Rate constant 'k' of areaction varies with temperature
(6) A first order reaction is found to have a rate constant 'T’ according to the equation:
k =6.6 x 10° "1. Find the half life of the reaction. E, [1
(AL. S.B. 2013) log k = log A— o303R =
. For a chemical reaction R -— P, the variation in the Where E, is the activation energy. When a graph is
concentration (R.) vs. time (¢) plot is given as plotted for log & vs. =. a straight line with a slope
of — 4260 K is obtained. Calculate 'E,' for the reaction
(R = 8.314 JK“ mol") (D.S.B. 2013)
4, (a) Derive the integrated rate equation for first order
reaction.
(6) Differentiate between order and molecularity of a
chemical reaction. (Uttarakhand S.B. 2015)
5. For the hydrolysis of methyl acetate in aqueous solution,
the following results were observed:

(1) Predict the order of the reaction. [ts

| o|» |0
(11) What is the slope of the curve ? (A..S.B. 2014)
CHEMICAL KINETICS

(t) Show that it follows pseudo first order reaction, as the (1) How is the rate of reaction affected if the
concentration of water remains constant. concentration of B is doubled?
(it) Calculate the average rate of reaction between the (11) What is the overall order of reaction if A is present
time interval 30 to 60 seconds. (Given log 2 = 0.3010, in large excess?
log 4 = 0.6021)
(6) A first order reaction takes 23.1 minutes for 50%
Or
completion. Calculate the time required for 76%
(a) For a reaction A + B —-+> P, the rate is given by completion of this reaction.
Rate = R[A][B]* (log 2 = 0.301, log 3 = 0.4771, log 4 = 0.6021)
(t) How is rate of reaction affected if the concentration (A.L.S.B. 2015)
of B is doubled ?
(it) What is the overall order of reaction if A is present
in large excess ?
>> San UV =i (er-Vin)=10)=) m1) a <q
(6) A first order reaction takes 30 minutes for 50% 1. The decomposition of sulphuryl chloride to SO, and Cl, is
completion. Calculate the time required for 90% a first order reaction whose half life is 30 minutes. What
completion of this reaction (log 2 = 0.3010) percentage of the reactant will be decomposed in 2 hours ?
(D.S.B. 2015) [Ans. 93.75%]
. (a) What is activation energy of a reaction? . The activation energy of a first order reaction at 300 Kis 60
(6) The rate of a reaction increases in the presence of kJ mol. In the presence of a catalyst, the activation energy
catalyst. Explain the statement by plotting a curve gets lowered to 60 kJ mol at 300 K. How many times the
between reaction coordinate and energy. reaction rate changes in the presence of a catalyst at the
(c) Fora reaction, the initial concentration of a reactantis same temperature ? [Ans. 55.08 times]
0.4M and rate constant is 2.6 x 10+ s-!. Calculate the . The rate constant for a first order reaction is 5.70 x 107
half life period of the reaction. (Manipur S.B. 2017) and 1.64 x 10s at 25°C and 40°C respectively. Calculate
. (a) Plot a graph showing variation in the concentration of the activation energy and the Arrhenius frequency factor.
reactants against time for zero order reaction. [Ans. 54.6 kJ mol, 2.17 x 10°]
(6) What do you mean by zero order reaction? . A first order reaction has k = 1.65 x 10s at 200°C. Ifthe
(c) The initial concentration of lst order reaction, reaction is allowed to run for 10 hours, what percentage
| 1 of the initial concentration would have changed into the
N,O.(¢) —> 2NO,(g) + 3 O,(g)
product ? What is the half life period of the reaction ?
was 1.24 x 10 mol L“! at 300K. The concentration of [Ans. 5.2%, 4.62 x 10° s]
N,O, after 1 hour was 0.2 x 10 mol L-!. Calculate the
. A first order reaction 1s 20% complete in 10 minutes.
rate constant of the reaction at 300K.
Calculate
(Kerala S.B. 2017)
(1) the time taken for the reaction to go to 75% complete
CBSE QUESTIONS <4 (12) specific rate constant of the reaction. (-/. K. S. 5. 2014)
[Ans. (7) 62.12 min (it) 0.02232 min]
8. (a) Explain the following terms :
(1) Rate of a reaction . The rate constants for the decomposition of HI at 283°C and
(11) Activation energy of a reaction. 508°C are 3.617 x 10-7 s71 and 3.954 x 10-7 s respectively.
(6) The decomposition of phosphine, PH.,, proceeds Calculate the frequency factor at 283°C and energy of
according to the following equation : activation of the reaction. [Ans. 1.206 x 10", 186.68 kJ]
4 PH, (g¢) ——> P, (g) + 6H, &) . The catalytic decomposition of hydrogen peroxide was
It is found that the reaction follows the following rate studied by liberating it at different intervals with KMnO,
equation : solution. Calculate the rate constant from the following data
Rate = [PH.]. assuming the reaction to be of the first order :
The half-life of PH, is 37.9 s at 120°C.
t (seconds) 0 600 1200
(.) How much time is required for 3/4th of PH, to
KMn0O, (mL) 22.8 13.8 §.2
decompose ?
(it) What fraction of the original sample of PH, [Ans. 0.000845 s-4]
remains behind after 1 minute ? (A.[.S.B. 2010) . A first order reaction is 40% complete in 50 minutes.
9. (a) What is rate of reaction? Write two factors that affect How long will it take to 80% complete? (Given log
the rate of reaction. 1.6667 = 0.2220 and log 5 = 0.6990) (Pb.S.B. 2010)
(6) The rate constant of a first order reaction increases from [Ans. 157.5 min]
4x 107 to8 x 10° when the temperature changes from . In a hydrolysis reaction, 5g ethyl acetate is hydrolyzed in
27°C to 37°C. Calculate the energy of activation (E,). presence of dilute HCl in 300 minutes. If the reaction is of
(log 2 = 0.301, log 3 = 0.4771, log 4 = 0.6021) first order and the initial concentration of ethyl acetate is
Or 22 g/L, calculate the rate constant of the reaction.
(a) For areaction A + K—+P, the rate is given by (CBSE Sample Paper 2010)
Rate = k [A] [B]? [Ans. 8.60 x10-* min“)
Slane
10. The half life period of a first order reaction is 3 minutes.
MODERN'S abe + OF CHEMISTRY-AIl

15. For a reaction 2A -> 4B + C, the concentration of B is

Calculate the time taken to complete 75% of the initial increased by 5.0 x 10° mol Lin 10 seconds. Calculate the
concentration. (Mizoram S.B. 2014) rate of disappearance of A. (Assam S.B. 2017)
[Ans. 6 minutes] 16. Calculate the time required for the completion of 90% of a
11. The following data were obtained during the first order reaction of first order kinetics; ¢,, = 44.1 minutes.
thermal decomposition of SO,Cl, at a constant volume : (Pb. S.B. 2017)
17. Following data are obtained for the reaction:
SO,CI, (g) —> SO,(g) + Cl, (g)
N,0O, > 2NO, " 40,

1 0
Total Pressure/atm
0.4
[|
0 | 30 | 00
[N,O,]/mol L* 1.6x 107 |. 0.8x 107 | 0.4x 10?
2 100 0.7
(a) Show that it follows first order reaction.
Calculate the rate constant. (Given : log 4 = 0.6021,
(b) Calculate the half-life.
log 2 = 0.3010) (A.LS.B. 2014)
(Given log 2=0.3010, log 4=0.6021) (D.S.B. 2017)
[Ans. 1.38 x10 s“4]
12. A first order reaction is 75% complete in 60 minutes. Find 18. For hydrolysis of methyl acetate in aqueous solution, the
the half life period of the reaction. (Given log 4 = 0.6021) following results were observed:
(Nagaland S.B. 2015) |Ans. 30 min]
135. A first order reaction takes 40 minutes for 20% completion.
4) © ee eee
Calculate its half life period. (Assam S.B. 2015)
c/mol L+
[Ans. 1.24 x 10? min]
14, For a first-order reaction, it takes 5 minutes for the initial
Show that it follows pseudo first order reaction as the
concentration of 0.6 mol L~! to become 0.4 mol L7!. How
concentration of water remains constant.
long will it take for the initial concentration to become 0.3
mol L71? (Meghalaya S.B. 2016) (Kerala S.B. 2018)

36. (5) 37. (d) 38. (a) 39. (d)

AO. (6) Al. (6) A2. (a) 43. (a)
. Yes e.g., order of the reaction for decomposition of AA, (c) 45. (c) AG. (c) AT. (d)
acetaldehyde is 3/2.
. Itis zero order reaction. This can be decided on the basis
of units of rate constant (for zero order reactions, units
of rate constant are mol L7 sl). . (i) Rate = k [NO,][F,]
4, Yes, for reaction proceeding in a single step. (12) two
» No (ii) NO,+F,——>NO,F+F (slow)
6. Rate = [conc.] = (2.5 x 10s") x (0.1 mol L“)
NO, + F——> NO,F (fast)
-2?.6x 10° mol Ls.
4, (1) Nochange (ii) rate becomes double
. st
(111) Rate becomes nine times.
9. No, because order with respect to A cannot be fractional
for an elementary reaction. 5. (2) zero order reaction.

6. (2) mol Ls? (ii) s7

10. 41 11. zero order reaction
9
12. second order 14, zero order
15. 1.26105 16. 1 x 10°? mol L7? min“
0.6953
17. First order 20. First order =ee
30. ee, |
= 0.0231 min
21. Zero order reaction. 22. Zero order reaction

28, Rate
- 1 2lia! 24, Order
= 142 =2 g6231 = 2°) 9
3 dt 2 2 120 a-x

27. (a) decreases (0) no effect

Calculate eee = 156.98 and
28. (a) 29. (a) 30. (a) 31. (6) a-x
a2. (a) 33. (d) a4. (bd) 35. (ce) x= 0.9875 a or 93.75% decomposed.
CHEMICAL KINETICS

k= log Al, _ 2 a
k, > 2.303RT
+ 9. log Ry _ E,-E,
t [A] t 17
303
ky 60000 — 50000
log| = 2303x8314
x300 ~+744
= ——— x 0.112 = 8.60 x 10+ min"
300
¢ 10. k = we we = 0.231 min
log“2 = 56.08. bye
For 76% compl etion , if [A], =a, [A] =a — ax75 = 0.264
Rate increases by 55.08 times. 100
1.64 x 10* E, 313 -— 298 / 2803, AL
OB | a49- 000
5.70x10° 2.303 x 8.314 313 x 298 a [A]
EK, = 54.6 kJ mol
2.303 ‘2
0.2381 °° 0.25a
log; A == logk + 2508
E,
RT
— m= ad
0.231 mm 0.6020
U. == 6.0
0. min
Mi1fl

log (6.70 x 107°) +

54.6 x 10°
¢ 11. Similar to Solued Example 21 (Page 29)
2.303 x 8.314 x 298
2.303, [Ah
= 6.336 and A = 2.17 x 10° + 12. k= i logo2 —2
[A]

2.303 a
: = lo _a x75
: k = 36000 8 a-x [A], =a, [A] = a = 0.25 a, t = 60 min
2.303 a 100
Pb x 10" 6 =
_
36000 © a—x — log
k a log —* 0.0231
Solving x = 0.0624 = "60 = 025a ~”
% of initial conc. changed = 5.2% 0.693 ;
= = 30
0.693 “0.0231 _
tayo = 15x10° 4.62 x 10s
2.303 loglAb
¢ 13. k=
» 5 -; =
2.303
——jk
a .
= 0.02232
.
m
a | t [A]
: 10 s 0.8a mn ax? :
[A], =a, [A] = enn = 0.80 a, t = 40 min
2.303 Se a
t = 9.02932 °° 2.25 = 62-12 min. 2.303 a
k = = 56.68
x 10°
3.954 x 107 E 781-556
40.” 0.80a
¢ 6. ME eaaga oi |cece 0.693 :
$.517x10°' 2.303 x 8.314] 556 x 781
tao = 558x102 — 1,24 x 107 min
E, = 186.68 kJ
; E 2.303 | [Alp
log A = log k +——2—
. °8 ©" 9.303 RT t [A]

186.68 «10° 2.303 0.6

log 3.517 x 107! + k=
2.303 * 8.314 x 556 Q 0.4

11.0816 or A= 1.206 x 10"! Z — x 0.176 = 0.0811 min

¢ 7. Calculate & at different times,
Now f= 2.303 16 [Alo
mean k = 0.000845 st k ~ [A]
2.3903 1 0.6
— oOo ———

¢ 8. Let [A], = a, [Al=a-2a =0.6a 0.0811 . 0.3

100
_ 4.303 y 9 3010 = 8.55 min
p= 230864 — 1.022 x 102 min 0.0811
50 0.6a
+ 15. Rate = 1d{A]_1d{B]_
diC]
For 80% completion, [A] = a@ - = 0.2a
2 dt 4dt dt

2.303 o
da[B] _ 5.0x10™ _ 5.0 x 102 mol L's
dt 10
1.022x102 -” 0.2a _
t = ———— lo _._ = 157.5 1

Rate of disappearance of A

¢ 9. (Al,=— mol L-1 _GAI_ 2 d/BI

dt 4 dt
[A] = 22-5 = i mol L7!
88 88
5% 5.0 x 10-2 = 2.5 x 102 mol L2 5
a AIA MODERN'’S abc + OF CHEMISTRY-XII
—_ 0.693 0.693 ky = 2.303 i
2
(1.6x10™~)
¢ 16. —~ VOPO _ 157 x 102 min
is 44.1 600 ~~ (0.4107)
=231x 10°51
_ _, @ax90 _
[Alp = @, IA] =a 100. oe Since & is constant, it follows first order reaction.
5 0.693 0.693
(iz) t,. = = ————_.. = 3013 8
t — 2.303 14, Alo e k 2.3x10°
k [A]
ae 1 618. tmin) c(M) &= 2303),,%
= ————_lo = 146.7 min t
1.5710 O.la 0 0.60 —
. 2.303 [A] 2.303, 0.60
o17 (i k= =" log —2% 30 0.30 k = ——log——
as t [Al : 30.” 0.30
At 300 s, =2.31x107%s!
2.303 (1.61077) 2.303, 0.60
k, = —— le ———_— 60 0.15 k = — log—
1” “300” .8x10~) . | 30 "0.15
-~ 231x103 s1 = 231x107? s+
Similarly, at 600 s, Since k[H,O] is constant, it is pseudo first order
reaction.

o,@

mpetiuon Oo tle Additional Useful Information and Objective Questions

ee

ADDITIONAL USEFUL INFORMATION

> CARBON DATING TECHNIQUE TO FIND AGE OF ARCHAEOLOGICAL OBJECTS

The principle of carbon dating is based on the fact that all living matter contain a definite amount of radioactive isotope C-14
formed in the upper atmosphere by the bombardment of N-14 with cosmic rays.
14aN 2 1 — 14Ae pe 1iH

A plant or any other living being during its life time maintains a reasonable balance of C—14 in its tissues. The death of the plant
brings an end to its tendency to take up C-14. Apart from that, the C-14 contents of the plants slowly decrease because it decays as:
age —
= EN 4 Fe
The half life period of C—-14 is 6770 years. This means that after 5770 years, half of the C-14 content remains and after 11540
years (56770 x 2) only 25% of the initial concentration of C-14 remains and so on. A comparison of B-activity of the dead matter with
that of carbon still in circulation helps to measure the period of isolation of the material from the living cycle. Thus, by knowing the
equilibrium concentration of C—14 in the living plant and the concentration of C—14 in the piece of dead material at a particular
time, the age of the material can be determined. This method is illustrated by the following examples:
4) Example 1. A piece of wood from an archaeological source has a C activity which is 60% of the activity found in
fresh wood today. Calculate the age of the archaeological sample (the half life period of C—14 ts 5770 years).
Solution : Decay constant, A = cL 1.2 x 10+ year"!
tyjo 5770

Since the activity 1s proportional to the number of C—14 atoms in the sample,
N, = 100, N=60
2.303 | No 2.303 100
Now, t = 0 oe = ee = 4258 years
» -N 12x10* ~~ 60

LJ Example 2.A sample of carbon from a wooden article ts found to give 7.6 C-14 counts per minute per gram of carbon.
If the freshly cut wood gives a count of 15.8 counts per minute per gram, calculate how old is the wood piece? (£, ;5
of C-14 = 5770 years).
0.693 — 0.693
Solution : Decay constant, A = ——— = —— =1.2~x10~* year!
ty2 ‘5770
CHEMICAL KINETICS 4/95 —=

N, ec counts observed for fresh wood = 15.8

N « counts observed for wooden article = 7.6

2.303, N
t a foe
1 PN
a , _ 2303) 15.8
12x10" ° 76

2.303 x 0.3178
t = ———\ = 6094 years.
1.2x 1074
UW Example 3. The B-activity of a sample of CO, prepared from a contemporary wood gave a count rate of 25.5 counts
per minute (c.p.m). The same mass of CO, from an ancient wooden statue gave a count rate of 20.5 c.p.m. in the
same counter conditions. Calculate its age to the nearest 50 years taking t,,,. for 14C as 5770 years. What would be
the expected count rate of an identical mass of CO, from a sample which ts 4000 years old?

Solution : i. = ele ; €,,. = 5770 years

byi9

AK = oe 1.2 x 10“ year?

5770
Since rate of counts is proportional to the number of }*C atoms in the sample,
N, = 26.6, N = 20.6
+ - 2.303 lo No _ 2.803 ro 25.5
» PN 12x104 "205
= oe as 0.0948 = 1819 years
1.2x10
Now, ¢ for another sample = 4000 years
2.303,, N
t = —_log— ,N=?
VE K
4000 ” ais ee 25.5
1.2x10 N
low 25.5 d 4000 Je*1.2* 10 a _ 0.2084
N 2.303

= = Antilog 0.2084 = 1.616

25.5 :
ih 1616 7 15.78 counts per min.

> MECHANISM OF TYPICAL REACTIONS

1. Reaction involving two first order consecutive reactions. In such reactions, the
reactants form a stable intermediate compound before they are finally converted into
the products. For example, reactants (R.) are first converted to intermediate (I) which is
then converted to product (P) as: =
2
hy [J] —=+-
kh ——+— hy P i
fe
—
=
Therefore, the reaction takes place in two steps, both of which are first order 1.e., o
©

Step I RN I
la
o
O

Step II [ics p
This means that I is produced by step I and consumed by step II. In these reactions,
Fig. 19. Concentration profile of
each stage will have its own rate and rate constant.
reactants (RK), intermediate (I) and
When we start with pure R, its concentration will decrease with time. The products (P) as a function of time.
concentration of the intermediate I will first increase as it accumulates and reaches a
maximum value. After attaining maximum value, it decreases and decays to zero concentration and is converted to the final product.
The concentration of the product, P will always increase. These results are shown in Figure 19.
2. Reactions involving slow step. When a reaction occurs by a sequence of steps and one of the steps is slow, then the rate
determining step is the slow step. For example, in the reaction :
a AI96 MODERN'’S abe + OF CHEMISTRY-XII

ify ae |
ko
[—+-+ P
Ifk, <<k,, then I is converted into products as soon as it is formed. We can say that
d{[R] d[P]
a he
This has already been learnt in complex reactions.
3. Reversible reactions. For reversible reactions such as

H, 22k
+1
ky 2HI

Rate = ant
1 d[HI
- k,{H,] 0.) — 2, {HI
4, Parallel Reactions. In such reactions, the reactants are consumed by two or more reactions, which may have different orders
of the reactions taking place simultaneously. For example, in a system containing NO, and 5O,, NO, 1s consumed in the following
two reactions :
2NO, —!— N,0,
NO, +SO, _*2_, NO+SO0,
The rate of disappearance of NO, will be sum of the rates of the two reactions, i.e.,
d{NO,] = 2k,[NO, + k, [NO,1[SO,]
d

If the pressure of N,O, fall from 0.50 atm to 0.32 atm is

30 minutes, the rate of appearance of NO,(g) is:
(a) 0.006 atm min? (5) 0.003 atm min
Rate of Reaction, Order and Molecularity (c) 0.012 atm min’ (d) 0.024 atm min™
Al. Which of the following statement is not correct for the A3. If the concentrations are expressed in mol litre? and
reaction time in s, then the units of the rate constant for the first
order reaction are :
BS ae BaD . (a) mol litre? s? (6) mol litre s+
(a) the rate of disappearance of B is one—fourth the rate oy a (® moi? tee? st

ar disappearance srry A4. The rate of a first order reaction is 1.8 x 10 mol L min
(5) the rate of appearance of C is one—half the rate of when the initial concentration is 0.3 mol Lt. The rate
disappearance of B. constant in the units of second is:
(c) the rate of formation of D is one—half the rate of (a) 1x10%s1 (6) 1x10¢%¢s1
consumption of A. (c) 6x102s1 (d) 6x 10-25.
(d) the rate of formation of C and D are equal. A5. The rate constant of a reaction is
A2. Nitrogen tetraoxide (N,O,) decomposes as 1.2 x 10° mol litre? s-!. The order of the reaction is :
(a) zero (6) 1
N,O,(g)—> 2NO,(g) (c) 2 (d) 3.

Aaswets
Al. (5) A. (c) A3. (c) AA. (5) A5. (d)
CHEMICAL KINETICS

A6. For a reaction, 2NO(g) + O,(¢) —> 2NO,{g) The correct rate expression from these data is :
Rate = k{NO}*[O,]. If the volume of the reaction vessel (a) r=R[A}?[B? (b) r=k{[A] [BI
is doubled, the rate of the reaction : (c) r=k[A]? (dq) r=k[A] [B}*.
(a) will diminish to 1/4 of initial value . Therate for the first order reaction is 0.69 x 10 mol L7 min
(6) will diminish to 1/8 of initial value and the initial concentration is 0.2 mol L~!. The half life
(c) will grow 4 times period
is :
(d) will grow 8 times.
(a) 1205s (6b) 830s
AT. For the reaction :
(c) 6008 yn 5
2N,0, ——-+ 4NO, + O, rate and rate constant are
. For the first order reaction, the half life period is (if 2 is
1.22 x 104 571 and 3.4 x 10° s? respectively, then the
rate constant and a is initial concentration),
concentration of N,O, at that time will be :
(a) 1.782 (6b) 3.6 (a) in;2
In 2
fta
(b)
1

(c) 1.02 10* (7) 3.4% 10°.

A8. The reaction : (cy) mk (d) losk
1 _ 9 5
N,O, (in CC1,) ———> 2NO, + 2 O, (g) is first order in
Al5. The following rate data were obtained at 303 K for the
following reaction :
N,O, with rate constant 6.2 x 10~ s“*. What is the value
2A + B—+C+D
of rate of reaction when [N,O,] = 1.26 mol L+?
(a) 7.75 x 10 mol L's! Experiment [A] [B] Initial rate of
(6) 6.35 x 10° mol L's! formation of D
(c) 6.15 x 10° mol Ls
I 0.1 0.1 6.0 x 10
(7d) 3.85 x 10+ mol L's!
II 0.3 0.2 7.2 x 10?
Inte ated Rate of Equation and Half-life Period Ii 0.3 0.4 2.88 x 107!
The half life period for a first order reaction is 69.3 s. Its IV 0.4 0.1 94x 10
rate constant is :
The order of the reaction is :
(a) 107s (6) 10451
(a) 2 (b) 38
(c) 1057 (dq) 10? s71.
(c) 1 (d) A.
Al10. Half life period of any first order reaction is Al16. For reaction A — B, the rate of reaction increases by a
(a) directly proportional to the initial concentration of factor of 1.857 when the concentration of A is increased
the reactant by 1.5 times. The order of reaction with respect to A is
(6) half of the rate constant (a) 1 (b) 1.5
(c) same for all reactions (c) 2 (dq) 2.6.
(d) independent of initial concentration of reactants. Al7. For the first order reaction, time required for 99%
All. For the reaction; A ——> C, it is found that the rate of completion is :
(a) half the time required for completion of 90% of
the reaction quadruples when the concentration of A is
reaction
doubled. The rate for the reaction is.
(6) thrice the time required for 90% completion of reaction
Rate = [A]" where the value of 7 is : (c) twice the time required for 90% completion of reaction
(a) 1 (6) 2 (d) none of these.
(c) zero (d) 3. A118. For zero order reaction, the integrated rate equation is :
A112. For a chemical reaction A + 5 —-> C, the following data [A]
(a) kt =—— (b) kt = [A] —- [A]
were found : [Aly °
Initial conc. Initial Conc. Rate (c) [A] =— t+ [A], (d)_ [A] = Rt - [A].
of A of B (mol litre sec!) A119. For a first order reaction involving decomposition of N,O,,
(mol litre!) (mol litre) the following information is available :

2.0 o.0) 0.10

2N,0,(g) ——> 4NO,(g) + O, (g) Rate = k [N,0,]
6.0 3.0 0.90
N,0,(g) ——> 2NO,(g) + %0,(g) —-Rate = k’ [N,0,].
Which of the following expressions is true ?
6.0 6.0 0.90

EE
(a) k=R’ (6) k' =2k
(c) k’ = 12k (dq) kR>R.

AG. (bd) A7 (0) A8. (a) AY. (a) Al0. (d) All. (dD) A12. (c) Al3. (a) Al4. (a) ~~ AI5. (5)
Al16. (5) Al7. (c) Al19. (5)
ase MODERN'S abe + OF CHEMISTRY-AXIl

A20. Which of the following graphs correspond to first order

reaction ? (a) (6b) 2

(c) (d) 4
(a) Rate (b) Rate Rl
bole
.» A reaction is 560% complete in 2 hours and 75% complete
in 4 hours. The order of reaction is
C 1/C (a) O (hb) ab
(c) 2 (dq) 3
(c) Rate (d) Rate » The reaction : A —~> B follows first order kinetics. The
time taken for 0.8 mol of A to produce 0.6 mol of Bis 1
hour. What is the time taken for conversion of 0.9 mol
of A to produce 0.675 mol of B ?
C Cc
(a) 1 hour (ob) 0.5 hour
» Which of the following relation is correct for zero order (c) 0.25 hour (d@) 2 hour
reaction ?
. The time taken for 90% ofa first order reaction to complete
(Q) fy = Shs KO) tage = LE tgs
is approximately
, i) 1 (a) 1.1 times that of half life
ic i= 9 tue (dq) fay = 3 fu2"
(6b) 2.2 times that of half life
. The half life period for a zero order reaction is equal to : (c) 3.3 times that of half life
|
(a) 2k/(Al, 6) [Al= (d) 4.4 times that of half life
A3l. The rate law for a reaction between the substances A
and B is given by
(c) 0.693 (d) 0.693
k KAI, Rate = R[A]" [B]™
On doubling the concentration of A and halving the
. For a second order reaction rate at a particular time
is x. If the initial concentration is tripled, the rate will concentration of B, the ratio of the new rate to the earlier
become: rate of reaction will be
(a) 3x (b) Ox? (a) m+n (0) n— m
(c) Ox (d) 2 IX. 1
. For a zero order reaction, linear plot was obtained for
(c) p(n — m)
(d) gm+n

[A] vs t. The slope of the line is equal to: . Ina first order reaction, the concentration of the reactant
(a) Ry (o) —k, decreases from 800 mol/dm® to 50 mol/dm® in 2 x 10* sec.

ook,, (d) __*o

The rate constant of the reaction in sec?! is

2.303 (a) 2x 104 (6) 3.45 x 10°

. For a reaction having rate law expression : (c) 1.386 x 10+ (qd) 2x 10+.
Rate = k[A]*”? [B]-12 . The rate of a first order reaction is
If the concentration of both A and B become four times, 1.5 x 10 mol L* min“ at 0.5 M concentration of the
the rate of reaction reactant. The half life of the reaction is:
(a) becomes four times
(a) 23.1 min (6) 8.738 min
(6) becomes 16 times
(c) decreases four times (c) 7.53 min (d@) 0.383 min.
(dq) remains same. . The rate equation for the reaction :
» For a chemical reaction, A ———> 5, it is observed that 9A + B—-> Cis found to be rate = R[A] [B]. The correct
the rate of reaction doubles when the concentration of A statement in relation to this reaction is that the
is increased four times. The order of reaction in Ais: (a) units of k must be s?
(a) Two (6) One
(6) t,. 18 constant
(c) Half (d) Zero
(c) rate of formation of Cis twice the rate of disappearance
» The conversion of A———> B follows second order kinetics.
of A
Doubling the concentration of A will increase the rate of
formation of 5 by a factor of (d) value of & is independent of the initial concentration
of A and B.

pascwgers
A20. (a) A21. (bd) A22. (b) A23. (c) A24, (5) A25. (a) A26. (c) A277. (d) A28. (b) A229. (a)
A30. (c) A831. (ce) A382. (c) A33. (a) A34, (d)
CHEMICAL KINETICS A/I99 =

Effect of Temperature on Rate of Reaction (c) ky = Ake al (d) k, = 2k,e%%2/*"

A35. On increasing temperature of the reacting system by A40. A substance undergoes first order decomposition. The
10 degrees the rate of reaction almost doubles. The decomposition follows two parallel first order reactions as :
most appropriate reason for this is : k B
(a) Collision frequency increases a
(6) Activation energy decreases by increase
in temperature ae
(c) The fraction of molecules having energy equal to Ry Cc
threshold energy or more increases
on —
(dq) The value of threshold energy decreases. ky =126x10%s
k, = 3.8 x 10° st
A36. If k, and ‘i are rate oe at ae caus ie and The percentage distribution of B and C are
T, respectively, then according to Arrhenius equation, (a) 75% B and 26% C (b) 80% B and 20% C

ay ib ky 2303R[{[1 1 | (c) 60% B and 40% C (d) 76.83% B and 23.17% C

. ky E, T, Ts A41. Milk turns sour at 40°C three times faster than it
does at 0°C. This shows that the activation energy of
(6) wghy E
Ba (11
1 14) souring of milk in (kJ mol) is (R = 8.3 JK mol")
& 2303R\T, TT, (q) -2:308X8.3x 273x313),
40) .
1 i &E 1 1
8 2303R|T, 7, 2.303 x8.3x 273x313) 1
| (6) 40 e3
k E 1 1)
(d) log—+=—4 Gane 2.303 x 8.3 x 40 |
k, 2.303 |T, T, (c) ——————
273x313. log
°8 3

A37. In the reversible reaction, 2NO, == N,0,, the rate

2 2.0035 X*2 73 X313
of (d) ale Ree Se log 3
40
disappearance of NO, is equal to :
A42. The activation energy of a reaction is 56.2 kJ/mol. The
2k, 9 ratio of rate constants at 500 K and 306 K is (RK = 8
(a) Ry [NOg| (6) 2k, [NO,] — 2k[N,0,) J mol! K-!) about:
(a) 1.26 (6b) 1.A7
(c) 2k,[NO,]? — 2k,[N,O,] (d) (2k, —%,) [NO,].
(c) 1.10 (d) 1.60
A38. When /n & is plotted against 1/T, the slope was found to
A43. An exothermic reaction A > 5 has an activation energy
be —10.7 x 10° K, activation energy for the reaction would
of 17 kJ per mole of A. The heat of reaction is 40 kJ. The
be :
activation energy for the reverse reaction B — A is:
(a) —78.9 kJ mol (b) 2.26 kJ mol?
(a) 23 kJ (6) 97 kJ
(c) 88.9 kJ mol (dq) 10.7 kJ mol. () 87 kd (dd) 17kd

A39. A reactant (A) forms two products : A44, Which of the following statement is true?
A —"\_;B, Activation energy, E,, (a) The reaction is fast if the activation energy is low.

A 2c, Attn ney, Bo

If E,, =2 Re , then &, and &, are related as
een
(c) Acatalyst increases the rate of a reaction by decreasing
Eg, /RT Bay /RT the rate of backward reaction.
(a) k= he (6) k= ke™ (d) Reaction rates increase with temperature because
the activation energy decreases at high temperature.

sweets
A35. (c) A386. (6) A387. (c) A3s. (c) A389. (c) A40. (d) Adi. (a) A42z (5) A43. (c) A444, (a)
 MODERN'S abe + OF CHEMISTRY
-AXIl

(a) Rate = R[A] [B]? (6) Rate = k[Al? [BI?

(c) Rate = [A] [B] (d) Rate = [A]? [BI
(C.B.S.E. Med. 2009)
B5. Half life period of a first order reaction is 1386 seconds.
AIPMT & Other State Boards’ The specific rate constant of the reaction is
Medical Entrance (a) 0.6x 107 51 (6) 0.6 x 10% 5
fc) boxe (qd) 6.0 x 107% s1
Bl. If 60% of a first order reaction was completed in (C.B.S.E. Med. 2009)
60 minutes, 60% of the same reaction would be completed
in approximately : B6. For the reaction, N, + 3H, ——> 2NH,, 1f d| NH, |
at
(a) 456 minutes (b) 60 minutes
= 2 x 10+ mol/L/s, the value of —
d[H,| would be
(c) 40 minutes (d) 6560 minutes
(log 4 = 0.60, log 5 = 0.69) (C_.B.S.E. P.M.T. 2007) (a) 4x10*mol/L/s (5) 6 x 10+ mol/L’/s
B2. The bromination of acetone that occurs in acid solution (c) 1x 10% mol/L/s (d) 3 x 10%* mol/L/s
is represented by the equation (C.B.S.E. Med. 2009)
B7. In the reaction
CH,COCH,(aq) + Br,(aq) —~
BrO,” (aq) + 6Br + 6H* —-> 3Br, + 3H,O
CH,COCH,Br(ag) + H*(ag) + Br (aq)
the rate of appearance of bromine is related to the rate
These kinetic data were obtained for given reaction of disappearance of bromide ions as
concentrations.
Initial concentrations, M
(a) @[Bn]__
dt
5415]
3 dt
afBn]_54[Pr
dt 3. «dt
|
cf| d[Br 3 d| Br |
Bm) 387" @ d[Br, | _ 3 d[Br |
dt 5 dt t 5 dt
(C_.B.S.E. Med. 2009)
B8. During the kinetic study of the reaction.
2A + B—+C + D, following results were obtained :
Initial Rate, disappearance of Br,, Ms* Based on the above data which one of the following is
5.7x10° correct?
5.7 x 10°
Initial rate of
1.2 x 10+ fe!
formation of
3.1x 10“ D/mol L-! min!
Based on these data, the rate of reaction is :
Par =
(a) rate = k[CH,COCH,] [Br,] I 0.1 . 6.01 x 10-8
(6) rate = k[(CH,COCH,] [Br,] [H*]? 7.2 x 107
(c) rate = k[(CH, COCH,] [Br,] [H*] 9.88 x 1071
(d) rate = k[(CH, COCH,] [H*] (C.B.S.E. P.M.T. 2008)
9.40 x 10-2
Bs. The rate constants k, and &, for two different reactions are
1076, ¢-2000/T and 10)°.¢ 2 respectively. The temperature Based on the above data which one of the following 1s correct?
at which &, = &, 1s (a) rate = k[A]? [B]? (b) rate = R[A] [B]*
2000 : A (c) rate = k[A]? [B] (d) rate = k[A] [B).
(@) 9303 ae oyr (C_.B.S.E. P.M.T. 2010)
1
(c) 1000, (d) 1000K B9. For the reaction N,O,(¢) ——— 2NO,(g) + 9 V2) the
2.303 (C.B.S.E. P.M.T. 2008)
B4, For the reaction A + B — product, it is observed that value of rate of disappearance of N,O, is given as
6.25 x 10° mol Ls. The rate of formation of NO, and
(1) on doubling the concentration of A only, the rate of
O, is given respectively as :
reaction is also doubled.
(zt) on doubling the initial concentration of both A and (a) 6.25 x 10-9 mol L7! s“! and 3.125 x 10° mol L7! s1
B, there is change by a factor of 8 in the rate of (6) 6.25 x 10° mol Ls! and 6.25 x 10° mol L? s"
reaction. The rate of reaction is given by (c) 6.25 x 10° mol L's! and 6.25 x 10° mol L? s"
(d) 1.25 x 10-7 mol Ls and 3.125 x 10% mol Ls"
(C_.B.S_E. P.M.T. 2010)
nswets
Bl. (a) B2. (d) B38. (ce) B4,. (a) B5. (0) B6. (d) B7. (d) B8. (5) B9. (d)
CHEMICAL KINETICS

B10. In a reaction, A + B -> Product, rate is doubled when B18. The decomposition of phosphine (PH,) on tungsten at low
the concentration of B is doubled, and rate increases by pressure is a first order reaction. It is because the
a factor of 8 when the concentration of both the reactants (a) rate 1s proportional to the surface coverage
(A and B) are doubled. Rate law for the reaction can be (5) rate is inversely proportional to the surface coverage
written as (c) rate is independent of the surface coverage
(a) rate = k[A][B]? (b) rate = R[A]*[B]? (d) rate of decomposition is very slow
(c) rate = k[A][B] (d) rate = k[A]*[B] (NEET 2016)
B19. Mechanism of a hypothetical reaction
(Af: P.M_T. 2072)
X, + Y, — 2XY, 1s given below:
Bll. In a zero-order reaction for every 10° rise of temperature, (i) X,>X+X(fast) (11) X+Y, — XY + Y (slow)
the rate is doubled. If the temperature is increased from (ait) X+ Y — XY (fast)
10°C to 100°C, the rate of the reaction will become
The overall order of the reaction will be
(a) 2566 times (6) 612 times
(a) 2 (b) O
(c) 64 times 128 times (d)
(c) 1.5 (d) 1 (NEET 2017)
(A.L.P.M.T. 2012)
B20. A first order reation has a specific reaction rate of 10°
B12. What is the activation energy for a reaction if its rate sec’+. How much time will it take for 20 g of the reactant
doubles when the temperature is raised from 20°C to to reduce to 5 g?
36°C ?(R = 8.314 J mol? K?) (a) 138.6 sec (6) 346.5 sec
(a) 34.7 kJ mol (6) 16.1 kJ mol
(c) 693.0 sec (d) 238.6 sec (NEET 2017)
(c) 342 kJ mol (dq) 269 kJ mol
B21. The correct difference between first and second order
(NEET 2013)
reaction 1s that
B13. The rate constant of the reaction A —-> B is 0.6 x 10°
(a) the rate of a first-order reaction does not depend on
mole per second. If the concentration of A is 5 M, then
reactant concentrations; the rate of a second-order
concentration of B after 20 minutes is:
reaction does depend on reactant concentrations
(a) 0.36 M (6) 0.72 M
(c) 1.08 M (d) 3.60 M (AIPMT 2015)
(b) the half-life of a first-order reaction does not depend
on [A],; the half-life of a second-order reaction does
B14. The activation energy of a reaction can be determined
depend on [A],
from the slope of which of the following graphs?
(c) a first-order reaction can be catalysed; a second-order
1 T 1 reaction cannot be catalysed
(a) Ink V8.7 (b) inf Vs. 7
(d) the rate of a first-order reaction does depend on
reactant concentration; the rate of a second-order
i tak (gq) TT
ms vs.T (AIPMT 2015) reaction does not depend on reactant concentrations.
(NEET 2018)
B15. When initial concentration of a reactant is doubled in a
B22. When initial concentration of the reactant is doubled, the
reaction, its half-life period is not affected. The order of
half-life period of a zero order reaction
the reaction is
(a) 1s halved (6) 1s doubled
(a) second
(c) is tripled (dq) remains unchanged.
(6) more than zero but less than first
(NEET 2018)
(c) zero
(d) first (AIPMT 2015) B23. If the initial concentration of the reactant is doubled,
the time for half reaction is also doubled. Then order of
B16. The addition of a catalyst during a chemical reaction
the reaction is
alters which of the following quantities?
(a) zero (6) fraction
(a) Enthalpy (6) Activation energy
(c) three (d) one
(c) Entropy (d) Internal energy
(e) two (Kerala P.M.T. 2007)
(NEET 2016)
B24, For a reaction taking place in three steps, the rate
B17. The rate of first-order reaction is 0.04 mol L“! s at 10 constants are k,, k, and k,. The overall rate constant &
seconds and 0.03 mol L7! s“! at 20 seconds after initiation
of the reaction. The half-life period of the reaction is? = uti . If the energy of activation values for the first,
(a) 44.15 (6) 54.158 second and third stages are respectively 40, 50 and 60 kJ
(c) 2415 (d) 34.18 mol, then the overall energy of activation in kJ mol
(NEET 2016) is
(a) 30 (6) 40
(c) 60 (d) 60
rastyees (e) 160 (Kerala P.M.T. 2008)

B10. (d) Bll. (5) B12. (a) B13. (6) B14. (a) B15. (d) B16. (3) B17. (c) B18. (a) B19. (c)
B20. (a) B21. (bd) B22. (db) B23. (a) B24. (a)
_lusaa MODERN'S abe + OF CHEMISTRY
-AIl

B25. For a zero order reaction, the plot of concentration of (a) 3, 2; 0 (6) 3,2, 1
reactant vs time is (intercept refers to concentration axis) fe} 22 (ay 2S 1
(a) linear with +ve slope and zero intercept
(6) linear with —ve slope and zero intercept (ea) 2.1.0 (Kerala PMT 2011)
(c) linear with —ve slope and non-zero intercept B29. For a reaction A + B —-> C + 2D, experimental results
(d) linear with +ve slope and non-zero intercept were collected for three trials and the data obtained are
(e) a curve asymptotic to concentration axis given below :
(Kerala P.M.T. 2008)
Initial Rate, Met
Pa | 040 of 0g0 | 65x10*
B26. Consider the decomposition of N,O, as

N,O, ———>» 2NO,+4 50 | 2 | 08% Mee27 | 565x10*

a [odo [|040 [22109
2

The rate of reaction 1s given by

d|N,O;|_ 14[NO,] __ a[o,] The correct rate law of the reaction is

a "a @ ea (a) rate = k[A]® [BP (6) rate = Rk[A] [BI]?
(c) rate = k[A] [B] (d) rate = R[A] [B]®
Therefore, -4IN:5) = k,[N,0,] (e) rate = k[A]® [B] (Kerala P.M.T. 2012)
f
B30. In a first order reaction, the concentration of the reactant
+ ZNOs] - 2k,[N,0,]= # [N05] is reduced to 1/8 of the initial concentration in 75 minutes
at 298 K. What is the half-life period of the reaction in
dlO, 1 F minutes ?
(a) 6560 (b) 16
Choose the correct option : (c) 46 (d) 265
(a) k, =k =k, (0) k,=2k, =k ler /30 (Kerala P.M.T. 2012)
B31. Inthe Arrhenius plot of ln& vs T a linear plot is obtained
(c) 2k, =k, =4k, (b) 4k, =2kh =k
(A.M.U. Med 2010, 2011) with a slope of — 2 x 10* K. The energy of a activation of
B27. Consider the following statements : the reaction (in kJ mol") is
(.) increase in concentration of reactant increases the (R value is 8.3 JK“ mol?)
rate of a zero order reaction (a) 83 (b) 166
(11) rate constant & is equal to collision frequency A if (c) 249 (d) 332
E,, = 0. (e) 830 (Kerala P.M.T. 2012)
(iit) rate constant & is equal to collision frequency A if B32. The decomposition of ammonia on tungsten surface at
BE a = 0. 500 K follows zero order kinetics. The half-life period of
(iv) In k vs T is a straight line. this reaction is 45 minutes when the initial pressure is
(vy) Ink vs 1/T is a straight line. 4 bar. The half life period (minutes) of the reaction when
Correct statements are the initial pressure is 16 bar at the same temperature is
(a) (i) and (iv) (ob). (it) and (v) (a) 120 (6) 60
(c) (wt) and (iv) (d) (iw) and (iit) (c) 240 (d) 180
(e) (t) and (v) (Kerala PMT 2010) (e) 300 (Kerala P.M.T. 2012)
B28. The initial rates of reaction B33. The rate constant of a first order reaction is doubled
3A + 2B + C —-> Products, at different initial when the temperature is increased from 20°C to 26°C.
How many times the rate constant will increase if the
concentrations are given below
temperature is raised from 20°C to 40°C ?
(a) 4 (b) 8
5.0
x 107 (c) 16 (d) 32
5.0 x 10~ (e) 64 (Kerala P.M.T. 2012)
Ut ee 0d B34, The rate of a reaction is given by rate, r = k [H*]"
Leb ii If the rate becomes 100 times when the pH changes from
2 to 1, the order of the reaction is
The order with respect to the reactants, A, B and C are (a) O (6) 1
respectively (c) 2 (d) 3 (A.M.U.Med. 2013)

Aaswecs
B25. (c) B26. (c) B27. (5) B28. (e) B29. (a) B30. (d) B31. (5) B32. (d) B33. (c) B34. (c)
CHEMICAL KINETICS

B35. In a first order reaction, 80% of the reactant at an instant B42. The rate of a reaction doubles when its temperature
was reduced to 8% in 4606 seconds. The rate constant of changes from 300 K to 310 K. Activation energy of
the reaction is such a reaction will be
(a} 2308 x 10*s" (b) 4.606 x 10% s? (R = 8.314 JK mol’ and log 2 = 0.301)
(c) 6.000 x 10% 51 (d) 6.000 x 10% s? (a) 60.5 kJ mol-1 (6) 63.6 kJ mol-1
(e) 4606 x 10% 51 (Kerala PMT 2015) (c) 48.6 kJ mol—-1 (d) 68.5 kJ mol—-1
B36. The decomposition of N,O, in CCl, at 318 K is studied (JEE Main 2013)
by monitoring the concentration of N,O, in the solution. B43. For the non-stoichiometric reaction:
Initially the concentration of N,O, is 2.4 mol L™ and 2A +B—-+C+D, the following kinetic data were obtained
after 200 minutes, it is reduced to 2.00 mol L-!. What in three separate experiments, all at 298 K.
is the rate of production of NO, during this period in
mol L-! min? ? Initial Initial rate of
concentration concentration | formation of C
(a) 4x 10° (b) 2x 10°
[A] (mol L-'!s-!)
(jy ixa6~ (d) 2x 10+
(fe) Bx 10° (Kerala PMT 2015)
B37. In a first order reaction, the concentration of the reactant
decreases from 0.6 M to 0.3 M in 30 minutes. The time
taken for the concentration to change from 0.1 M to
0.025 M is The rate law for the formation of C is

(a) 60 min (6) 30 min ~ | JA dc

(a) EP k[A] (b) a [A][B]
(c) 16 min (dq) 50 min
(e) 90 min (Kerala PMT 2015) dC | dC _
(c) ao k{[AP[B] (d) a = k(A][BF :
JEE (Main) & Other State Boards’ (JEE Main 2014)
Engineering Entrance B44, Higher order (> 3) reactions are rare due to
B38. The half life period of a first order chemical reaction is (a) shifting of equilibrium towards reactants due to
6.93 minutes. The time required for the completion of 99% elastic collisions
of the chemical reaction will be (log 2 = 0.301)
(d) loss of active species on collision
(a) 2380.3 minutes (6) 23.03 minutes
(c) low probability of simultaneous collision of all the
(c) 46.06 mintues (d) 460.6 minutes
reacting species
(AJ_E.E.E. 2009)
B39. The time for half life period of a certain reaction (d) increase in entropy and activation energy as more
A—-> Products 1s 1 hour. When the initial concentration molecules are involved. (JEE Main 2015)
of the reactant ‘A’ is 2.0 mol L7!, how much time does it take B45. Decomposition of H,O, follows a first order reaction.
for its concentration to come from 0.60 to 0.25 mol L* if it In fifty minutes, the concentration of H,O, decreases
is a zero order reaction? from 0.5 to 0.1265 M in one such decomposition. When
(a) 0.25h (b) 1h (c) 4h (d) 0.6 h. the concentration of H,O, reaches 0.06 M, the rate of
(A.LE.E.E. 2010) formation of O, will be
B40. The rate of a chemical reaction doubles for every 10°C (a) 6.93 X 10° mol min“
rise of temperature. If the temperature is raised by 50°C,
(6b) 6.93 < 10-* mol L? min?
the rate of the reaction increases by about
(a) 10 times (6) 24 times (c) 2.66 L min” at STP
(c) 32 times (d) 64 times (dq) 1.34 X 10°? mol min? (JEE Main 2016)
(A.LLE.E.E. 2011 B46. Two reactions R, and R, have identical pre-exponential
B41. For a first order reaction, (A) — Products, the concentration factors. Activation energy of R, exceeds that of R, by 10
of A changes from 0.1 M to 0.025 M in 40 minutes kJ mol. Ifk, and k, are rate constants for reactions R,
The rate of reaction when the concentration of A is and Rh, respectively at 300 K, then In(#,/k,) is equal to :
0.01 M is (R = 8.314 J mol ?K“)
(a) 8.47 x 10+ M/min (b) 3.47 x 10° M/min (a) 8 (b) 12
(c) 1.73 x 10+ M/min (d@) 1.73 x 10° M/min
(c) 6 (d) A (JHE Main 2017)
(A.J ELELE. 2072)

sweets
B35. (d) B36. (a) B37. (a) B38. (c) B39. (a) B40. (¢) B41. (a) B42. (5) B48. (a) B44, (c)
B45. (5) B46. (d)
lan 04 MODERN'’S abc + OF CHEMISTRY-XII

B47. Which of the following lines correctly show the temperature (a) 107 (bh) 10°
dependence of equilibrium constant, K, for an exothermic (c) 2x103 (d) 2x 102
aie ep e |
ai = (Karnataka CET 2010)
B58. Half lives of a first order and a zero order reactions are
same. Then the ratio of the initial rates of first order
reaction to that of the zero order reaction is
| 1
(a) 0.693 (b) 2x 0.693

2
(ec) 0.693 (dq) 0
693

(e) 6.93 (Kerala PET 2010)

B54. If the activation energy for the forward reaction is 150
(a) AandB (b) BandC kJ mol and that of the reverse reaction is 260 kJ
(c) CandD (d) AandD (JEE Main 2018) mol, what is the enthalpy change for the reaction?
B48. At 518°C, the rate of decomposition of a sample of gaseous (a) 410kJ mol (6) —110 kJ mol
acetaldehyde, initially at a pressure of 363 torr, was 1.00 (c) 110 kJ mol (d) 410 kJ mol
torr s! when 6% had reacted and 0.5 torr s+ when 33% - —
had reacted. The order of the reaction is: (e) 90 kJ mol (Kerala PET 2010)
(a) 2 (b) 3 B55. A first order reaction is 560% complete in 69.3 minutes.
(c) 1 (d) 0 (JEE Main 2018) Time required for 90% completion for this reaction is
B49. At 500 K, the half life period of a gaseous reaction at an (a) 100 minutes (6) 230 minutes
initial pressure of 80 kPa is 360 sec. When the pressure (c) 2303 minutes (dq) 125 minutes
is 40 kPa, the half life period is 176 sec. The order of the (Odisha JEE 2010)
reaction 1s
(a) zero (b) one B56. The following data were obtained during the first order
(c) two (d) three decomposition of 2A(¢) ——> B(g) + C(s) at a constant
(e) half (Kerala C_E.T. 2007) volume and at a particular temperature.
B50. For the two gaseous reactions, following data are given:
A —->B; R, = 101° e20000/r S.No. | Time Total pressure
C —+D;k, = 10% e 4000T in Pascal
The temperature at which k, becomes equal to &, is 1 At the end of 10 min 300
(a) 400K (6) 1000 K a After completion 200
(c) 800K (qd) 1600 K
(c) 500K (Kerala P.E.T. 2008) The rate constant in min is
B51. The activation energies of two reactions are E, and (a) 0.0693 (b) 69.3
EK, (Ef,> E,). Ifthe temperature of the system is increased (c) 6.93 (d) 6.93 x 10~
from T, to T,, the rate constant of the reaction changes |
from &, to Rk," in the first reaction and k, to &,' in second (Karnataka CET 2011)
reaction, predict which of the following expression is correct? B57. The rate of the reaction A — Products, at the initial
(a) Ry _ ky (b) ky " ky concentration of 3.24 x 10~ M is nine times its rate at
k, Ro k, ko another initial concentration of 1.2 x 10° M. The order
; of the reaction is
(c) LW (d) 9 (a) : (b) E
ky hy ky ky 2 4
(Kerala C.E.T. 2009) (c) 3 (d) 2
B52. The activation energy for a reaction at the temperature 2 3
T K was found to be 2.303 RT J mol. The ratio of the 1
rate constant to Arrhenius factor is (e) 3 (Kerala PET 2011)

SWS
B47. (a) B48. (a) B49. (a) B50. (6) BS5l. (6) B52. (a) B53. (5) B54. (5) B55. (5) B56. (a)
B57. (d)
CHEMICAL KINETICS

B58. A given sample of milk turns sour at room temperature B65. Ammonium ion (NH,*) reacts with nitrite ion (NO,~) in
(27°C) in 6 hours. In a refrigerator at —3°C, 1t can be aqueous solution according to the equation:
stored 10 times longer.
NE
g*aq)+ NOx (aq) —? Nagy + 229,
The energy of activation for the souring of milk is
The following initial rates of reaction have been measured
(a) 2.803 x 10R kJ. mol?(6) 2.303 x 6 RkKJ. mol
for the given reactant concentrations.
(c) 2.303 x 3 R KJ. mol (d) 2.303 x 2.7 R kJ. mol?
(Karnataka C.E.T. 2012) [NH,*], (VD |[NO,-1, (MD |Rate (M/hr)
B59. At 300 K, a gaseous reaction : A — B + C was found to
follow first order kinetics. Starting with pressure A, the 0.016 0.020 0.030
total pressure at the end of 20 minutes was 100 mm of Hg.
The total pressure after the completion of the reaction is 0.010 0.010 0.006
180 mm of Hg. The partial pressure of A (in mm of Hg)is Which of the following is the rate law for this reaction?
(a) 100 (6) 90 (a) rate =k [NH;] [NO;]* (6) rate = k [NHj] [NO,]
(c) 180 (d) 80
(c) rate =k [NH}] [INO]? (d) rate = k [NH}1? [NO,]
(Karnataka C.E.T. 2012)
B60. The half-life for decay of 14C by B-emission 1s 5730 years. (e) rate=k [NHj]”" [NO,]“ (Kerala PET 2014)
The fraction of 14C decays, in a sample that is 22,920 B66. For the reaction A + 2B——>C, the reaction rate is doubled
years old, would be if the concentration of Ais doubled. The rate is increased
(a) 1/8 (b) 1/16 by four times when concentrations of both A and B are
(ce) 7/8 (d) 165/16 increased by four times. The order of the reaction is
(W.B.JEE Engg. 2013) (a) 3 (6) 0
B61. For a chemical reaction at 27°C, the activation energy is
(ce) A (d) 2 (W.B. JEE 2015)
600 RK. The ratio of the rate constants at 327°C to that
BG7. The relationship between rate constant and halflife period
of at 27°C will be
of zero order reaction is given by
(a) 2 (b) 40
(c) e (d) e (a) ‘1= Al, 2k ‘222
2 k
(WBJEE Engg. 2013)
B62. If 50% of the reactant is converted into a product in a , t, _ Ab 2[Ah
(dd) 4-0
first order reaction in 25 minutes, how much of it would
) 5 OR 3 k
react in 100 minutes ?
(MH-CET 2015)
(a) 93.75% (b) 87.5% B68. For the reaction Ox) + OW) — > 20 Ag)? if the rate law
(ce) 76% (d) 100% expression is, rate = k[O,] [O], the molecularity and order
(Karnataka CET 2013) of the reaction are respectively
B63. The reaction A + B > Products 1s first order with respect (a) 2and2 (6b) 2 and 1.33
to A and second order with respect to B. When 1.0 mol (c) 2and1 (d) land2 (MH-CET 2015)
each of A and B were taken in one litre flask, the initial B69. In the reversible reaction:
rate of the reaction is 1.0 x 10° mol L! s. The rate 2NO,
Ay
= N,O ae the rate of disappearance of NO, is
of the reaction when 50% of the reactants have been
equal to
converted into products is
2k
(a) 1.00 x 10° mol L4+s+ (6) 0.06 x 10°? mol Ls? (a) 7%, NOs (6) 2k,[NO,] — 2k,[N,O,]
(ce) 1.26 x 10% mol L-4+ s+ (d) 4.00 x 10°? mol Ls?
(e) 2.00 x 10°? mol L+ s+ (Kerala P.E.T. 2013) (c) 2k,[NO,]? — 2k,[N,O,]
B64. A piece of wood from an archaeological sample has 5.0 (d) (2k, —k,) [NO,] (A.M.U. Engg 2015)
counts min“ per gram of C-14, while a fresh sample of
B70. The reaction takes place in two steps as:
wood has a count of 15.0 min“ gran. If half-life of C-14
is 56770 years, the age of the archaeological sample is
(i) NO,Clg) > NO,(g) + Clg)
(a) 8,500 years (6) 9,200 years (ii) NO,CKg) + Clg) —2-+ NO,(g) + CL(g)
(c) 10,000 years (d) 11,000 years Identify the reaction intermediate
(W.B. JEE 2014) (a) NO,Clg) (6) NO,(g)
(c) CL(g) (d) Clg) (MH-CET 2016)

Answer
B58. (d) B59. (d) B60. (d) B61. (c) B62. (a) B63. (c) B64, (5) B65. (c) B66. (c) B67. (c)
B68. (a) B69. (c) B70. (d)
janes MODERN'S abe + OF CHEMISTRY-AXIl

B71 The rate constant of the reaction, 2N,O, —- 4NO, + O, B77. What will be the correct unit of rate constant & for a
at 300 Kis 3 X 10° sl. If the rate of the reaction at the reaction whose order is three?
same temperature is 2.4 * 10° mol dm s", then the (a2) mole“ litre sect (6) mole? litre sec*
(c) sec} (d) mole@ litre? sect
molar concentration of N,O, is
(J. K. CET 2018)
(a) 04M (b) 0.8M
B78. The following equation is the Arrhenius equation,
(c) 0.04 M (dq) 0.08 M
k = Ae *“ET where E_ is the minimum energy molecules
(ge) 0.6M (Kerala PET 2016)
must possess in order to react to form a product, & is
B72. In the reaction A — Products, when the concentration of
the rate constant, A is the frequency factor, R is the gas
A was reduced from 2.4 X 107M to 1.2 x 10°? M, the rate
constant and T is the Kelvin temperature. Under normal
decreased § times at the same temperature. The order of
circumstances, the Arrhenius plot is obtained by plotting
the reaction is (a) logarithm of the inverse of rate constant 1/k, versus
(a) 0 (6) 1 the inverse temperature 1/T
(c) 2 (d) 3 (d) logarithm of the rate constant k, versus the
(e) 0.6 (Kerala PET 2016) temperatureT
B73. The activation energy of a chemical reaction can be (c) logarithm of the rate constant &, versus the inverse
temperature 1/T
determined by
(a) evaluating rate constants at two different temperatures (d) logarithm of the inverse of rate constant 1/k, versus
the temperature T
(6) changing the concentration of reactants
(J. K. CET 2018)
(c) evaluating the concentration of reactants at two
different temperatures B79. The half-life of C!* is 6760 year. For a 200 mg sample of
(d) evaluating rate constant at standard temperature C14, the time taken to change to 26 mg is
(Karnataka C.E.T. 2016) (a) 11520 years (6b) 23040 years
B74. The half-life period of a first order reaction is 60 minutes. (c) 56760 years (d) 17280 years
What percentage will be left over after 240 minutes? (WB. JEE 2018)
(a) 6.25% (b) 4.25% B80. The temperature coefficient of a reaction is 2. When the
(c) 5% (d) 6%( Karnataka C.E.T. 2016) temperature is increased from 30°C to 90°C, the rate of
reaction is increased by
B75. Which of the following statement is incorrect? (a) 160 times (6) 410 times
(a2) Molecularity is only applicable for elementary
(c) 72 times (d) 64 times
reaction.
(Karnataka CET 2018)
(6) The rate law for any reaction cannot be determined
experimentally. B81. The value of rate constant of pseudo first order reaction
(c) Biomolecular reactions involve simultaneous collision (a) depends only on temperature
between two species. (6) depends on the concentration of reactants present in
(d) Complex reactions have fractional order. small amounts
(c) depends on the concentration of reactants present in
(Karnataka CET 2017)
excess
B76. Which of the following is not true about a catalyst?
(d) is independent of the concentration of reactants.
(a) Mechanism of the reaction in presence and absence
(Karnataka CET 2018)
of catalyst could be different.
(6) Enthalpy of the reaction does not change with B82. For the reaction, 250, + O, —— 280,, the rate of
catalysts. disappearance of O, is 2 x 10* mol L? s7. The rate of
(c) Catalyst enhances both forward and backward appearance of SO, is
reaction at equal rate. (a) 2x10*molL'‘s?
(d) Catalyst participates in the reaction, but not
(6) 4x10*molL?s?
consumed in the process.
(e) Use of catalyst cannot change the order of the (c) 1x10? molL's?
reaction. (Kerala PET 2017) (d) 6x10* mol L's? (Karnataka CET 2018)

Answets
B71. (5) B72. (d) B78. (a) B74. (a) B75. (6) B76. (e) B77. (d) B78. (c) B79. (d) ~~B80. (d)
B81. (a) B82. (5)
CHEMICAL KINETICS

B83. The data given below are for the reaction of A and D, to
form product at 295 K. Find the correct rate expression respectively. Ratio Fy of the rate constants for first
for this reaction.
order (k,) and zero order (R,) of the reaction is
D,/mol L*? Initial rate/mol L~ s
a
(a) 0.6 mol! dm® (6) 1.0 mol! dm=
(c) 1.6 mol dm™= (d) 2.0mol!dm? (1.1.T. 2008)

[oas [008 [sto B89. For a first order reaction, A ——>

dependent rate constant (£) was found to follow the
P, the temperature

equation :
log k = —(2000)/T + 6.0
(a) kID,} [AP (6) AID,J2 [AP
The pre-exponential factor A and the activation energy
(c) kID,]* [AP (d) kID,]? (Al? EK,» respectively are :
(e) RID,]* [Al° (Kerala PET 2018)
(a) 10x10®%st and 9.2kJ mol
B84. Find the unit of the rate constant of a reaction represented (6) 6.08 and 16.6 kJ mol
with a rate equation, rate = R[A]”” [B]°”
(c) 10x10%s* and 16.6 kJ mol
(a2) mol?Ls+ (b) s?
(dq) 1.0x10°st and 38.3 kJ mol} (LL.T. 2009)
(c) mol Lt s+ (dq) mol? L? s+
B90. Plots showing the variation of the rate constant (2) with
(e) mol? Les? (Kerala PET 2018)
temperature (T) are given below. The plot that follow
B85. Under what condition the order of reaction, Arrhenius equation is

2Hi(g) a
SS" > He) +L) is zero?
(a) At high temperature
(a) |
(6) At high partial pressure of HI
(c) At low partial pressure of HI ‘— T+
(d) At high partial pressure of [,
(e) At high partial pressure of H, (Kerala PET 2018)
(c) | (d) | >

JEE (Advance) for ITT Entrance T™— —-?

B86. The reaction : (.I.T. 2010)
X — > Product
B91. In the reaction, P + @—+R +5,
follows first order kinetics. In 40 minutes the concentration
the time taken for 76% reaction of [Q],
of X changes from 0.1 to 0.025 M. Then the rate of reaction
P is twice the time taken for 50%
when concentration of X is 0.01 M is
reaction of P. The concentration of @ [Q]
(a) 1.73 x10¢*M min! (6) 3.47 x 10° M min"! varies with reaction time as shown
(c) 3.47x104*M min! (d) 1.73 x 10° M mir!. in the figure. The overall order of
(.I.T. 2004) the reaction is ime
B87. Consider a reaction, aG + 6H ——+ Products. (a) 2 (b) 3
(c) O (dq) 1 (JEE Advance 2013)
When concentration of both the reactants G and H is
doubled, the rate increases by eight times. However, when B92. The initial rate of hydrolysis of methyl acetate (1M) by
the concentration of Gis doubled keeping the concentration a weak acid (HA, 1M) is 1/100* of that of a strong acid
of H fixed, the rate is doubled. The overall order of the (HX, 1M), at 26°C. The K, of HA is
reaction is : (a) 1x10>+ (6) 1x 10°
(c) 1x10° (dq) 1x 10°
(a) O (6) 1 (JEE Advance 2013)
(c) 2 (dq) 3 (1.7. 2007) B93. For the elementary reaction M ———+> N, the rate of
B88. Under the same conditions, initial concentration of 1.386 disappearance of M increases by a factor of 8 upon
mol dm~ of a substance becomes half in 40 seconds and doubling the concentration of M. The order of the reaction
20 seconds through first order and zero order kinetics with respect to M is
(a) 4 (b) 3
(c) 2 (d) 1 (JEE Advance 2014)
nswets
B83. (a) B84. (a) B85. (5) B86. (c) B87. (d) B88. (a) B89. (d) B90. (a) B91. (d) B92. (a)
B93. (5)
 MODERN'S abe + OF CHEMISTRY-AXIl

VMIULTIPLE CHOICE QUESTION C5. Which of the following plots are not correct ?

with more than one correct answers Second order

(a) (b)
Cl. Consider the rate law expression for a reaction : bao First order baio

rate = k[NO,] [I] [H*]?

Lo [A],
Which of the following is/are not correct ?
(a) When concentration of both NO, and I are doubled
First order Second order
rate becomes 4 times.
slope =—k
(6) When concentration of H* is tripled, rate becomes (c) [Al (d) LTA] slope = k
nine times.
(c) When concentration of each of Ht, NO, and I are
tripled, rate becomes nine times.
(dq) When concentration of NO, is doubled, of lis halved
C6. For the first order reaction
and of H* is doubled rate becomes 16 times.
2N,0.(¢) —> 4NO,(g) + O,(g)
C2. For a first order reaction :
(a) the concentration of the reactant decreases
(a) The degree of dissociation is equal to 1 — e* exponentially with time.
(6) <A plot of reciprocal of concentration of reactant vs (6) the half-life of the reaction decreases with increasing
time gives a straight line. temperature.

(c) The time taken the completion of 75% of reaction is (c) the half-life of the reaction depends on the initial
thrice the ¢,,. of the reaction. concentration of the reactant.
(d) the reaction proceeds to 99.6% completion in eight
(d) The pre-exponential factor in the Arrhenius equation
half-life duration. (LET. 2011)
has the dimensions of time™t.
C7. According to the Arrhenius equation,
C3. In acidic medium, the rate of reaction between BrO, and
Br’ is given by the expression : (a) a high activation energy usually implies a fast
reaction.
d{BrO
_ Er! =k [BrOy ][Br~ ][H*P (6) rate constant increases with increase in temperature.
This is due to a greater number of collisions whose
energy exceeds the activation energy.
which of the following statements are correct ?
(c) higher the magnitude of activation energy, stronger
(a) Rate of reaction is independent of the concentration
of acid added. is the temperature dependence of the rate constant.

(6) Rate of reaction is affected by change in pH of the (d) the pre-exponential factor is a measure of the rate
solution. at which collisions occur, irrespective of their energy.
(JEE Advance 2016)
(c) Doubling the concentration of H* ions increases the
reaction rate by 4 times. C8. Which of the following statements is in accordance with
(d) This is an example of pseudo second order reaction. the Arrhenius equation?
C4, The rate law for the reaction : (a2) Rate of a reaction increases with increase in
RCI] + NaOH m—> ROH + NaCl temperature.
is given as : rate = k[ RCI]. (6) Rate of reaction does not change with increase in
The rate of this reaction : activation energy.
(a) is doubled by doubling the concentration of NaOH. (c) Rate constant decreases exponentially with increase
(5) is halved by reducing the concentration of KCl by in temperature.
one half.
(d) Rate of areaction increases with decrease in activation
(c) 1s increased by increasing the temperature of the
energy. (Karnataka CET 2017)
reaction.
(d) is unaffected by change in temperature.

Cle ink CS ta) a. tbe) a ee) a ie Che ta, b,c) (ie lhe, a) Se. le, ae)
CHEMICAL KINETICS 4/109 —

C9. In a biomolecular reaction, the steric factor P was

experimentally determined to be 4.5. The correct option(s)
among the following is(are) ;
(a) experimentally determined value of frequency factor (a) (d)
is higher than that predicted by Arrhenius equation
In(3po—p,)
(6) the value of frequency factor predicted by
Arrhenius equation is higher than that determined
Time
experimentally
(c) the activation energy of the reaction is unaffected
by the value of steric factor
(d) since P = 4.5, the reaction will not proceed unless
an effective catalyst is used. (JHE Advance 2017) (c) (d)
C10. Fora first order reaction A(g)—> 2B(g) + C(g) at constant 7
volume and 300 K, the total pressure at the beginning In(po-P,)
(é = 0) and at time ¢ are P, and P,, respectively. Initially, Rate
constant
only A is present with concentration [A],, and ¢,,, is the Time
time required for the partial pressure of A to reach 1/83rd
of its initial value. The correct option(s) 1s (are) (assume (JEE Advance 2018)
that all these gases behave as ideal gases):

rastyaes
C9. (a,c) C10. (a, d)

D2. For a second order reaction, the correct plot of ¢,,. vs

1/[A], is
based on the given passage/comprehension

Passage I. (b) ty

i
The integrated rate equations can be fitted with
kinetic data to determine the order of a reaction. The
integrated rate equations for zero, first and second
order reactions are:
Zero order : [Al =— kf @abaAls (d) typ

First order : log [A] = X + log [A],

2.305 VIA
Second order : Ye
[A]
bt + “2
[Al D3. For a second order a
oe
rate at a particular time 1s x.
0 If the initial concentration is tripled, the rate will become
These equations can also be used to calculate the half (a) 9x2 (b) 27x
life periods of different reactions, which give the time during (c) 9x (d) 3x
wo col |
which the concentration of a reactant is reduced to half of its
initial concentration, 1.e., at time ¢,,.; [A] = [A],/2
D4. Theee
rate for the first order reaction 15
er reaction is 0.0069 mo
mol L7! minmin“
and the initial concentration is 0.2 mol L”!. The half life
Answer the following questions : period = |
D1. The decomposition of nitrogen pentoxide : (a) 636 s (6) 0.636 s

is a first order reaction. The plot of log [N,O,] vs time D5. The plot of [A] versus ¢ for zero order reaction gives slope
(min) has slope = — 0.01389. The rate constant & is hy = k (b) _ ke
(a) 1.389 x 10% min (6) 3.2x 10% min! | 2.303 2.303
(c) 6.03 x 10° min (d) 71.99 min“ (c) 2.3038 k (d) —k

mswecs
Passage I. D1. (0d) D2. (c) Ds. (c) D4. (d) D5. (d)
lusio MODERN'S abe + OF CHEMISTRY
-AXII

Passage II. D9. At 27°C in the presence of a catalyst, the activation

According to collision theory of chemical reactions, rate of energy of a reaction is lowered by 10 &J mol. The ratio of
a reaction depends upon collision frequency and fraction log & (catalyst)/k (uncatalysed) is
of effective collisions. The rate of a reaction generally (a) 1.741 (6) 191.47
increases with rise in temperature mainly because of
increase in number of effective collisions. Arrhenius (c) 0.084 (d) 0.01465
proposed a quantitative relation between rate constant D10. The rate of a chemical reaction becomes double for every
and temperature as 10°C rise in temperature. If this generalisation holds for
k = Ae *a/RT a reaction in the temperature range 290 K to 300 K, what
where E_ is activation energy. It is equal to the difference would be the approximate value of E, for the reaction ?
between threshold energy and average kinetic energy of
(a) 650kJ mol (b) 26 kJ mol
reacting molecules.
(c) 60 J mol (d) 403 mol
Answer the following questions : D11. If activation energy for a reaction is zero and & is
D6. Which of the following plot will be linear ? 1.72 x 10° s? at 300 K, the rate constant at 310 will be
(a) in k versus T with —ve slope
(6) In k versus 1/T with —ve slope 310 x 1.72 x 10° 1.72 x 10° x 300
| b
(c) in k versus 1/T with +ve slope (a) 300 o 310
(d) k& versus 1/T with —ve slope.
|5 1.72 x 10° x 10
D7. For a first order reaction, the plot of log K versus 1/T gives (c) .1.72 x10 (ad) aaa eS
300 x 310
straight line. The slope of the line has been found to be a
— 8.95 x 10° K. The activation energy for the reaction is D12. If x is the fraction of molecules having energy greater
(a) 74.4 kJ mol} (6b) —171.4 kJ mol} than activation energy. E, then
(c) 171.4 kJ mol (dq) 20.61 kJ mol)
D8. The pre-expotential factor in Arrhenius equation of a (a) x=-=— (b) x = e™a/RT
second order reaction has the units
(a2) mol Ls (6b) st (c) logx=—-—___ ft (qd) x =10-%/RT
(c) Lmol? s) (d@) dimensionless 2.303 RT

¢mswiens
Passage II. D6. (5) D7. (c) Ds. (e) D9. (a) D10. (a) D111. (ce) D112. (c)

o. Assertion : The half life period for a first order reaction

Assertion Reason Type Questions is independent of initial concentration of
reactants.
The questions given below consist of an Assertion and
Reason. Use the following key to choose the appropriate answer.
0.693
Reason : For first order reaction, f,,. =
k
(a) If both assertion and reason are CORRECT and reason
4, Assertion : For the first order reaction the units of rate
is the CORRECT explanation of the assertion.
constant are time.
(b) If both assertion and reason are CORRECT but, reason
is NOT THE CORRECT explanation of the assertion. Reason : The rate of first order reaction remains
(c) If assertion is CORRECT but, reason is INCORRECT. constant throughout.
(dq) If assertion is INCORRECT but, reason is CORRECT. 5. Assertion : For a second order reaction, graph of [A] vs.
(e) If both assertion and reason are INCORRECT. tis a straight line.

Reason : For second order reaction, [A] = kt + 1

1. Assertion : Rate of reaction
temperature.
increases with increase in
[All
Reason : Number of collisions increases with increase 6. Assertion : For complex reactions molecularity and order
in temperature. are not same.
2. Assertion : Reactions of higher order are rare. Reason : Order of a reaction may be zero.
Reason : The chances of simultaneous multimolecular
7. Assertion : A catalyst increases the rate of a reaction.
collisions are extremely small.
Reason : Acatalyst forms an activated complex of lower
mswiecs potential energy.

ta) ee 3. (a) 4. (c) 5. (e)

CHEMICAL KINETICS

8. Assertion : The molecularity of the reaction half when the concentration of RClis reduced
H, + Br, ——-+ 2HBr is 2. to half.
Reason :! The rate of reactions is represented by 2[RCI]
Reason : Order of the reaction is 3/2.
i.e., 1t 1s a first order reaction.
(A.LI.M.S. 2004)
10. Assertion : Photochemical reactions always occur in the
9, Assertion : For the reaction : RC] + NaOH (ag) ———> presence of light.
ROH + NaCl, the rate of reaction is reduced to
Reason : Photochemical reactions even with, AG = +ve
occur.
Aaswecs
6G. (d) % 8. (bd) 3 ES 10. (5)

Matrix Match Type Questions Column I Column IT

(A) sl (p) First order reaction

Each question contains statements given in two columns, (B) L? mol? s@ (gq) Second order reaction
which have to be matched. State- p q r S
(C) L msl gs? (r) Third order reaction

AB,CandDwhereas
statements A|(p) @)@ (S) (D) mol L-*! s+ (s) Zero order reaction
in Column II are labelled as p, gq, 2. Match th e type of reaction in Column I with the property
rand s. Match the entries of Col-
umn | with appropriate entries of
B
®@O0©® given in Column II.
Column IT. Each entryin Column
I may have one or more than one
©¢
©e)@OO® Column I Column IT

correct option from Column II.The

answers to these questions have
p
© @O0® (A) Zero order reaction
A —-> Products
(p) Plot of log [A} vs
linear plot.
fis a

to be appropriately bubbled as il- (B) First order reaction (q) Units of & are
lustrated in the following example. A —-> Products neler
If the correct matches are A-g, A-r, B-p, B-s, C-r, C-s and (C) Second order reaction (r) Doubling conc. of A,
D-q, then the correctly bubbled matrix will look like the following: A+B —-> Products rate becomes twice.
1. Match the units in Column I with the type of reaction in
Column IT (D) Second order reaction NN A
[Alo
Ok
2A —-> Products

Araswets
(1) : (A)—(s) (B) —(p), (s) (C) — (q), (s) (D) -(r)
(2) : (A)—(@), (s) (B) —(r) (C) —(q) (D) -—@)

Integer Type or Numerical Value Type Questions 2. For a reaction : 2A —- A, the rate of reaction becomes 27
times when the concentration of A changes from x to 3x.
The order of reaction is .......
Integer Type: The answer to each of the following
question is a single-digit-integer ranging from 0 to 9. 3. The rate of a reaction is expressed as : 3.66 x 10°
atm! s-!. The order of reaction
1. The concentration of RK in the reaction K ——> P was
measured as a function of time and the following data is . The rate of a reaction of Br- ions with BrO, ions in the
obtained : acidic medium is

RI moiey [XO [07 [ao [or0—

t@min) | 0.0 10.06 | 0.12 40.18
rate= [Br |[BroO, |[H" I

The order of reaction is .......

The order of the reaction is ....... 5. The order of the following reaction is
(LL.T. 2010) C,.H,.0,, + H,Q ————-+ C, H,,0, + C,H,.0,

fswe
1. O 2. 3 3. 2 4, 4 * 1
 MODERN'S abe + OF CHEMISTRY
-AXIl

6. An organic compound undergoes first-order decomposition. Numerical Value Type. Give the correct numerical
The time taken for decomposition to 1/8 and 1/10 of its value (in decimal notation truncated/rounded off to the
initial concentration are t,,. and t,,,, respectively. What second decimal place).
is the value of
8. Consider the following reversible reaction,
it ;

om,
vs] x 10 ? (take log,, 2 = 0.8) .......
1/10
‘1/ Ag + Be + AB.)
(LLT.J.E.E. 2012)
The activation energy of the backward reaction exceeds,
- In dilute aqueous H,SO,, the complex diaquodioxalato that of the forward reaction by 2RT (in J mol-). If the
ferrate (II) is oxidized by MnO, . For this reaction, the pre-exponential factor of the forward reaction is 4 times
that of the reverse reaction, the absolute value of AG*
ratio of the rate of change of [H*] to the rate of change
(in J mol’) for the reaction at 300 K is ...........
of [MnO,] is .......
(JEE Advance 2015)
(Given : In (2) = 0.7, RT = 2500 J mol” at 300 K and
G is the Gibbs energy) (JEE Advance 2018)

8. 8600

Exemplar Problems //
Objective Questions
(6) Activation energy of forward reaction is EK, + E, and
product is more stable than reactant.
1. The role of a catalyst is to change (c) Activation energy of both forward and backward
(a) gibbs energy of reaction. reaction is E, + E, and reactant is more stable than
(6) enthalpy of reaction. product.
(c) activation energy of reaction. (d) Activation energy of backward reaction is E, and
(d) equilibrium constant. product is more stable than reactant.
. Inthe presence of a catalyst, the heat evolved or absorbed 5. Consider a first order gas phase decomposition reaction
during the reaction given below :
(a) increases. (6) decreases. A(g) —> B@) + C@)
(c) remains unchanged. (d) may increase or decrease. The initial pressure of the system before decomposition
. Activation energy of a chemical reaction can be of A was p.. After lapse of time ‘7’, total pressure of the
determined by Cw system increased by x units and became ‘p,’. The rate
(a) determining the rate constant at standard temperature. constant & for the reaction 1s given as
(6) determining the rate constants at two temperatures.
(c) determining probability of collision. (a) 2.303 log Pi
(d) using catalyst. Activated complex t Py *
. Consider the following
2.303 F
figure and mark the } (0) ; log 9 P
correct option. ae
(a) Activation energy of Sf Products
| ve ae; 2.303 P;
forward reaction is “ E (c) log
E, + E, and product & y- t P; — P,
is less stable than Reactants 2.308 :
reactant. Reaction coordinate > (d) t log =

sweets
1. (c) ee) 3. (5) 4, (a) 5. (5)
CHEMICAL KINETICS 4/113 —

6. According to Arrhenius equation rate constant & is equal

to A e EYRT| Which of the following options represents V.
the graph of ln & vs =? Vv,
Vs
(a)
V2
t Vv.
Ink

02030 40 50
1/T-> V._V
(a) Average rate upto 40 seconds —3 2
(b) 40
V, — V,
- (6) Average rate upto 40 seconds is —*——2
Ink , 40-30

(c) Average rate upto 40 seconds is 40

_ Vs

al (d) A verage (oupie

rate upto d0-ceeonds
seconds 4g =
18 7) 5

tc) 9. Which of the following statements is not correct about

order of a reaction ?
tT (a) The order of a reaction can be a fractional number.
na (6) Order of a reaction is experimentally determined
quantity.
(c) The order of a reaction is always equal to the sum
1/T-> of the stoichiometric coefficients of reactants in the
balanced chemical equation for a reaction.
(d) (dq) The order of a reaction is the sum of the powers of
molar concentration of the reactants in the rate law
tT expression.
Ink 10. Consider the graph given in previous question. Which
of the following options does not show instantaneous
rate of reaction at 40 second ?
1/T-> (a) V;— Vo (b) V,-V,
7. Consider the Arrhenius equation given below and mark 50-30 50-30
the correct option. k = A e®v/*T
(a) Rate constant increases exponentially with increasing (c) V3 ~Vo (d) V3~ Vi
activation energy and decreasing temperature. 40 —30 40 — 20

(6) Rate constant decreases exponentially with increasing 11. Which of the following statements is correct?
activation energy and decreasing temperature. (a) The rate of a reaction decreases with passage of time
(c) Rate constant increases exponentially with decreasing as the concentration of reactants decreases.
activation energy and decreasing temperature. (6) The rate of a reaction is same at any time during
(d) Rate constant increases exponentially with decreasing the reaction.
activation energy and increasing temperature. (c) The rate of a reaction is independent of temperature
8. A graph of volume of hydrogen released vs time for the change.
reaction between zinc and dil.HCl is given in figure. On (d) The rate of a reaction decreases with increase in
the basis of this mark the correct option. concentration of reactant(s).

arses
6. (a) a 1) 8. (c) ic! 10. (5) 11. (a)
olan MODERN'S abe + OF CHEMISTRY-AXIl

12. Which of the following expressions is correct for the rate 15. Which of the following statements is incorrect about the
of reaction given below? collision theory of chemical reaction?
6Br(aqg) + BrO, (ag) + 6H*(aq) —> 3Br,(aq) (a) It considers reacting molecules or atoms to be hard
+ 3H,O(W) spheres and ignores their structural features.
(6) Number of effective collisions determines the rate of
_ A{Br7] ALH* | A[ Br’ | 6 A[H*| reaction.
() At aa 5 ot (c) Collision of atoms or molecules possessing sufficient
threshold energy results into the product formation.
AL Br7 | 5 ALH*] A( Br’ | A{H*]
(d@) Molecules should collide with sufficient threshold
oe -o & ar rT energy and proper orientation for the collision to be
13. Which of the following graphs represents exothermic effective.
reaction? 16. A first order reaction is 50% completed in 1.26 x 10** s.
Activated complex How much time would it take for 100% completion?
(a) 1.26 x 10 s (6) 2.62 x 10% 5
(c) 2.62 x 107° s (d) infinite
17. Compounds ‘A’ and ‘B’ react according to the following
chemical equation.

J\
Energy
— A(g) + 2B (g) —> 2C (g)

Products Concentration of either ‘A’ or ‘B’ were changed keeping

the concentrations of one of the reactants constant and
Reaction coordinate —> rates were measured as a function of initial concentration.
Following results were obtained. Choose the correct option
Activated complex
for the rate equations for this reaction.

Experiment Initial Initial rate of

econcentration| concentratic formation of
of [A]/mol L*| of [B]/mol L| [C]/mol Ls!
(iz)
Energy
>
Tk.
Reactants

Reaction coordinate —- (a) Rate = k[A]? [B] (b) Rate = [A] [B]?
(c) Rate = R[A] [B] (d) Rate = R[A]* [B]°
Activated complex
18. Which of the following statement is not correct for the
catalyst?
(a) It catalyses the forward and backward reaction to
the same extent.
(121) Energy
> (6) It alters G of the reaction.
Reactants Products
(c) Itis a substance that does not change the equilibrium
Reaction coordinate
constant of a reaction.
(d) It provides an alternate mechanism by reducing
(a) (1) only (6) (11) only activation energy between reactants and products.
(c) (tit) only (d) (a) and (iz) 19. The value of rate constant of a pseudo first order reaction
14. Rate law for the reaction A + 2B ——> C is found to be
Rate = k [A][B] (a) depends on the concentration of reactants present in
Concentration of reactant ‘B’ is doubled, keeping the small amount.
concentration of ‘A’ constant, the value of rate constant (6) depends on the concentration of reactants present in
will be EXCESS.
(a) the same (6) doubled (c)is independent of the concentration of reactants.
(c) quadrupled (d) halved (d) depends only on temperature.

nswets
12. (ec) 13. (a) 14, (bd) 15. (c) 16. (d) 17. (0) 18. (5) 19. (5)
CHEMICAL KINETICS 4/115 —

20. Consider the reaction A — B. The concentration of both (a) Order is same as molecularity.
the reactants and the products varies exponentially with (6) Order is less than the molecularity.
time. Which of the following figures correctly describes (c) Order is sreater than the molecularity.
the change in concentration of reactants and products (d) Molecularity can never be zero.
with: wine? 23. In any unimolecular reaction
(a) only one reacting species is involved in the rate
[B] determining step.
(6) the order and the molecularity of slowest step are
equal to one.
(c) the molecularity of the reaction is one and order is
me zero.
(d) both molecularity and order of the reaction are one.
Concentration—3 24, For a complex reaction
(a) order of overall reaction is same as molecularity of
Time —>
the slowest step.
(6) order of overall reaction is less than the molecularity
of the slowest step.
(c) order of overall reaction is greater than molecularity
of the slowest step.
(d) molecularity of the slowest step 1s never zero or non
o integer.
Concentration—> 25. At high pressure the following reaction is zero order.

Time > 2NH5(8)

1130Krere
—piagnum N.(g) + 3H,(g)
;
Which of the following options are correct for this reaction?
(a) Rate of reaction = Rate constant
(6) Rate of the reaction depends on concentration of
ammonia.
(c) Rate of decomposition of ammonia will remain
a
as,
constant until ammonia disappears completely.
(d) Further increase in pressure will change the rate of
Concentration—->
reaction.
Time —- 26. During decomposition of an activated complex
(a) energy is always released
(6) energy is always absorbed
(c) energy does not change
(d) reactants may be formed
27. According to Maxwell Boltzmann distribution of energy,
2
(a) the fraction of molecules with most probable kinetic
Concentration- energy decreases at higher temperatures.
Time —> (6) the fraction of molecules with most probable kinetic
energy increases at higher temperatures.
»» Multiple Choice Questions (Type-ll) <a (c) most probable kinetic energy increases at higher
ae ~*~ temperatures.
Note : in the following questions two or more options may (dq) most probable kinetic energy decreases at higher
be correct. temperatures.
21. Rate law cannot be determined from balanced chemical 28. In the graph mala: Maxwell Boltzmann distribution
equation if of energy,
(a) reverse reaction is involved. (a) area under the curve must not change with increase
(6) it is an elementary reaction. in temperature.
(6) area under the curve increases with increase in
(c) it 1s a sequence of elementary reactions.
temperature.
(d) any of the reactants is in excess.
(c) area under the curve decreases with increase in
22. Which of the following statements are applicable to a temperature.
balanced chemical equation of an elementary reaction? (d) with increase in temperature curve broadens and

Answer
shifts to the right hand side.

20. (5) Z1. (a, c, d) 22. (a, d) 23. (a, 5) 24, (a, d) mete a) 26. (a, d) ie et 28. (a, d)
lan 16 MODERN'’S abe + OF CHEMISTRY-XII

29. Which of the following statements are in accordance with

the Arrhenius equation?
(a) Rate of a reaction increases with increase in
slope
= —k
temperature.
(e
(6) Rate of a reaction increases with decrease in activation
energy. of
reactant
>
Concentration
(c) Rate constant decreases exponentially with increase Time?
in temperature. 32. Which of the following graphs is correct for a first order
(d) Rate of reaction decreases with decrease in activation reaction?
energy.
30. Mark the incorrect statements.
(a) Catalyst provides an alternative pathway to reaction
mechanism. (a) ty,
(6) Catalyst raises the activation energy.
(c) Catalyst lowers the activation energy.
(d) Catalyst alters enthalpy change of the reaction. [R],
31. Which of the following graphs is correct for a zero order
reaction?

ty,

(d)

(a)
° IRI,
rate—>
Reaction
Time —->

& Molar
(b)
of
reactant
> concentration[P]-_,
Concentration
Time —>

(c)
rate>
Reaction
Time >
Time—>

(SWIG
29. (a, 5) 30. (6,d) 31. (a,d) 32. (a, d)
CHEMICAL KINETICS ani,

>> ee <
Note : In the following questions match the items of Column I with appropriate item given in Column IT.
3o. Match the graph given in Column I with the order of reaction given in Column II.
More than one item in Column I may link to the same item of Column II.

Column I Column Il

T i
be s
(a) a (b) 2 (z) Ist order

Concentration—- Concentration—

g t
E 3
(c) “© hat es5 :
(ii) Zero order
= oh
O A a)
me—->
: time —>

34. Match the statements given in Column I and Column II.

(a) Catalyst alters the rate of reaction

Cota T
(z) cannot be fraction or zero
(6) Molecularity (it) proper orientation is not there always
(c) Second half life of first order reaction (iit) by lowering the activation energy
fdjce =e (iv) is same as the first
(e) Energetically favourable reactions are sometimes slow (v) total probability is one
(f) Area under the Maxwell (vi) refers to the fraction of molecules with energy equal
Boltzman curve is constant to or greater than activation energy

3D. Match the items of Column I and Column II.

(a) Diamond (1) short interval of time

(6) Instantaneous rate (zz) ordinarily rate of conversion is imperceptible
(c) Average rate (tiz) long duration of time

36. Match the items of Column J and Column II.

Mathematical expression for rate of reaction rate constant

Rate of reaction for zero order is equal to rate law reaction
Units of rate constant for zero order order of slowest step
reaction is same as that of
Order of a complex reaction is determined by rate of a reaction

Aaswets
83. (a) — (i); (6) (i) ;() —) ; O—W
84. (a) — (iii) ; (6) —@ ; (©) —Wv) ; @ — vi) ; ©) —@); (Q—)
35. (a) — (ii); (6) —@; (© — Gid)
36. (a) — (ii) ;(6) —@); © — iv) ; d) — Wii)
lune MODERN'S abe + OF CHEMISTRY
-AXIl

Assertion and Reason Type Questions <a molecularity is the sum of the stoichiometric coefficient
of rate determining elementary step.
Note: In the following questions a statement of assertion 39. Assertion : The enthalpy of reaction remains constant
followed by a statement of reason ts given. Choose the correct in the presence of a catalyst.
answer out of the following choices. Reason : A catalyst participating in the reaction, forms
(a) Both assertion and reason are correct and the reason different activated complex and lowers down the activation
is correct explanation of assertion. energy but the difference in energy of reactant and product
(6) Both assertion and reason are correct but reason remains the same.
does not explain assertion. 40. Assertion : All collision of reactant molecules lead to
product formation.
(c) Assertion is correct but reason is incorrect.
Reason : Only those collisions in which molecules have
(d) Both assertion and reason are incorrect.
correct orientation and sufficient kinetic energy lead to
(e) Assertion is incorrect but reason is correct.
compound formation.
37. Assertion : Order of the reaction can be zero or fractional. 41. Assertion : Rate constants determined from Arrhenius
Reason : We cannot determine order from balanced equation are fairly accurate for simple as well as complex
chemical equation. molecules.
38. Assertion : Order and molecularity are same. Reason : Reactant molecules undergo chemical change
Reason : Order is determined experimentally and irrespective of their orientation during collision.

Aaswecs
37. (bd) 38. (e) 39. (a) AO. (e) Al. (c)

p l a nations for
Hi n t s & E x Difficult Objective Type Questions
A. mcq with only one correct answer
A7. (6) : Rate = k[N,O,]
1.22 x 10 = 3.4 x 10°[N,0,]
Al. (5): The rate of appearance of C is double the rate of
| 4 1.22 x 107 ne
disapperance of B; is correct.
A2. (c): Rate of disappearance of N,O, ages paeage oo
AIN,O,] 0.50-0.32 A8. (a): Rate =k[N,O,] = 6.2 x 10% x 1.26
At —-30 = 7.76 x 10+ mol L? =
= 0.006 atm min? a 0.6935
_=0.01 s! 1 or 21
AS. (a): k= 693s 10"s
Rate of appearance of NO,
= Twice rate of disappearance of N,O, A10. (d) : Halflife period of a first order reaction 1s independent
2 x 0.006 = 0.012 atm min of the initial concentration of reactants.
A3. (c): mol L s!=k mol L" A12. (c): Inspection of table shows that by making the conc.
- units ofkis st. of A three times (keeping B constant) rate becomes
Ad. (b): Rate = R[A] nine times 1.e., Rate « [A]?
1.8 x 10° mol L? min = & (0.3 mol L-) By doubling conc. of B (keeping A constant) rate
remains same i.e., Rate « [B]®
p — 1.8x105 Oey hs ft 8x10"
.. Rate = R[AFP.
i) 60
=1x10*51, Al13. (a) : Rate = & [A] ;
A5. (d): The units of k correspond to third order reaction. 0.69 x 102 =k (0.2) -. k = ——
A6. (6): On increasing the volume to a twice value, the
concentration of each species is reduced by a factor of 2. 3.45 x 10-° min}
Therefore,
3.45107
Rate, = k[NO]?[0,] ~ 60
cy 2 QO
Rate, = A a
RON [! —- §.76x10%¢s 1
0.693 0.693
Rate, 1 = Vs 1205 5.
ue k 5.75x107
Rate, 3°
CHEMICAL KINETICS

A115. (0): Inspection of table shows that A31. (c) : Earlier rate, rate= & a"b™

Rate = k[A] [B]? .~. Order = 3. New rate, rate’ = k(2a)" (+) |
Al6, (5): (1.5) = 1.837
rate’ 7 le an oye

= log 1.837 _
1.5.

log 1.5 rate eo”

ot On O om. = on—m

A19. (6): 2N,0,(¢) ———> 4NO, + O,(g)

k = 2.3503 l [A] 0
A32. (c) : ; og TA
Zs [N,0,]
Rate = = k[N,O.]
2 dt
2.303 800
d[N.O. |] = 2x10° ” 50
or Rate = — a = 2k[N,0,]
or k = 1.88 x 10% sec.
1
For N,O, ——> 2NO, + 9 0, A838. (a): Rate = k[C]or p=
dIN,O.) = # IN,O,]
-—2© k _-
115x107.
———_
05 =33.0 x 1 10
4%

or Rate = —
dIN,O,] =k’ IN,O,]
—
2-5 te =
0.693
3x102
:
= 20.1 min.

Since rate must be same, k” = 2k. 1 d{NO,]

AS7. (c) : Rate of reaction = Oo at
A238. (c): Rate = k[A]? =x
If cone. is tripled 1.e., A° = [8A] = k,[NO,]? — &,[N,0,]
Rate’ = &[3A]}? = k.9[A] = x’ Rate of disappearance of NO,
x . , ;
,

. — =91.e., becomes nine times (9x). d{NO,]

a = 2k, [NO,]? - 2k,[N,O,].
x
A24, (6): For a zero order reaction :
A38s. (c): Slope = — HE, =— 10.7 x 10° R
[A] = —,¢ + [A], i = TOT s 10° x 8.314 = 88.9 x 10°
.. Plot of [A] vs. ¢ gives slope = — Rp. — 88.9 ke) mol '!,

A25. (a): rf, = hfey (by

r,2 = k (4a)? (4b) 1" A39.(c) : big
-E, /RT

Sa
los?
m
= (4) (412 = 4, Re = Ase 2/

1 Ea, + Fa,
A26, (c): Rate = k[A]
1
2=k[4A)" te, 4" =2orn= 5 Ry Ay
A
A28. (5) : For a first order reaction, time required to 75% Now, —1
A, = constant and HK, =H
complete is twice the time required to 50% complete.

A29. (a): The fraction of A reacted in each case is same -E, +2E,
= - e 1 1

1.€.,
06 3. .0675 3 RT
0.84 0.90 4
™/RT ork,= Ak,e Ea, /RT
Eq
or = Ae
-. Time taken is same.
|
i
A380. (c):
_2.803;,, 4 _ 2.308 4, 49 _ 2.303 A40. (qd): % of formation of B =
k
1 +100
90% k a—-0.9a R k, +k,

2.303, 4 _ 2.303 |, 1.26 x 107%

w= —B a-O05a k ® Oe eee «100
~ 126x10*+3.8x10°
, _ 2.808 x 0.3010 —
ac: aa _ 1.26 x 10 ~100

loon 1 (1.26 + 0.38) x 1074

=3.3 -. tye = 3.3t,
- 0.3010 90% ue 76.83%
luizo MODERN'S abe + OF CHEMISTRY
-AIl

Re E or 5
1000
A4l, (a): log—= a

k, 2.303R T, T,
2.003

Ba, (a): Rate = k[A]™ [B]" ite)

oe 1 1 2 Rate — k[2A]™ [B]* (it)
log 3
2.303x8.3 [273 313
— CO eS
es a Pe

8 Rate — k[2A]™ [2B]" .{tit)

From (z), (iz) and (zzi)
E - 2.303 *8.3 x 273x313
log 3
a
40 6 m=—las=2
Rate = Rk[A] [Bl]?
A42. (6): log K

~ 2.303R
aa
BS. (6): tp k
1
a qT q,

_56.2x10°f 1 1 _ py 0693 _ 0.698 _ 9 1 9-3.-1

log
|
=
2.308 X 8 300 305 | Ex: 1386
_ 56.2 10° 5 1d|H 1 d| NH
= __* = 0,167 B6. (d): ap Jira! - 14[NH,]
9
eam
aw
2.303 x8 300
x 305 t 2 dt
k = *(2x10~) mol L's“
2-147 a
k1
A438. (c) : For exothermic reaction, -d|[H, | _ 3 9x104
KE, (backward) = E, (forward) + AH (magnitude) dt 2
= 3x 10* mol L's
-~17+40=57kJ
| d|B
B7. (d): _1d[Br] _ 14[Br]
B. mcq from Competitive Examinations 5 dt a dt

d[Br] 3 d[Br |
2,303 [A],
Bl. (a): k
t
log ——
[A]
™" dt ~ 5 dt
B8. (6): Let order w.r.t. A be a and order w.r.t. B be 6b
60 Rate law is Rate — kLA]2 [B]?
Here [A] [Alp — +90 [Aly = 0.4 [Aly
Dividing (III) by (II)
2.303
ee doe [Alp (0.3)°(0.4)” _ 2.88x10"
Rk
60 0.4[A], (0.3)"(0.2)” ——-7.2x10-
chi log 1°
60 4 g= 4
or oo
2.303
60
x 0.4 : b=2
0.01563 Dividing (IV) by (D
Now typ 0.693 (0.4)°(0.1)’ _ 2.40x10—
k
(0.1) (0.1) 6.01x10~
0.693
= 45.29 = 465 min. At 4
0.0153 or A? — At
B2. (d): In expt (1) and (2) rate does not depend on [Br,]. ; ‘aE
.. Rate expression does not include [Br,] Rate law = &[A] [Bl]?
10 16 ge a000/T
Ba. (ce): k1
k 2 ste 1015 ge L000/T B9. (d): N,0,(g) ———> 2NO,(g) + =0218)
k 1 =k,
When
d{N,O,] _ 1 d{NO,] | 2d|0, |
1016 e—2000/T = 1015 e— Lo00/T

10 16-15 = e(—1000 + 2000VT

wm 2 a dt
10 _ p1000/T d|NO, | = _2d[N,0, |= 2x 6.25 x 10°
or
1000
— 2.303 log 10 dt dt
T = 1.25 x 107 mol L's}
CHEMICAL KINETICS

B18. (a): At low pressure, the decomposition of NH, 1s a first

d|0, | 6 1[N,0,] _ 1g 925x107 order reaction and the rate is directly proportional to
dt 2 dt 2 the coverage of surface. However, at high pressure,
the decomposition of NH, on tungsten surface is a
= §.195 * 10“ mol Ls"
zero order reaction and the rate is independent of the
B10. (d) : Let rate —[A]’ [B]’ =r i) coverage of the surface.
rate — [A] [2B]? = 2r ii) B19. (c): Overall order of reaction
Dividing eq. (ii) by (2) = Rate of slowest step (11)
2 = Dor 2 =2lie.g=1 Rate = & [X] [Y,] (Lt)
Now, rate = [2A] [2B]? = 8r (itt) Assuming step (z) to be reversible,
Dividing eq. (212) by eq. (2) xX, = K ex
Yo" 22 R 2
Ko = [X]
or x2
rate
=8or2
= k[A]* [B]
=4ie, 2 =2 orp=2
IS
B11. (6): By 10°C rise in temperature rate becomes double For or [XJ ¥ (K,, [X,])” (it)
100°C rise in temperature rate will become (2)° times Rate = k K,,” [X,]* [Y,]
1.e., 612 times.

B12. (a):
kp Be {1 1 or = k'[X,PLYs]
1
— eat qT T,

T, = 278 + 20 = 298 K, T, = 273 + 36 = 308 K Order = i As

2 2
| E, 1 1
log 2 = ——S&_——__|_____ ___ 0.6958 0.693
2.000% 8.d14 (293 308
B20. . = t= = 69.3
- an: 107 °
0.36010 = fm
Ea ~ ees
=
2.3508 x 8.3514 2938 308 For the reaction of 20 g of reactant to 5 g, two half-life
0.35010 x 2.508 =x 8.514 x 295 =x S08 times are required.
ee Se
S 15 - t¢=2 x 69.3 = 138.6 s
— 34673 J mol! =34.7 kJ mol’. B21.(6): For a first order reaction,
B13. (6): The units of rate constant indicate that the reaction is _ 0.698
a zero order reaction. eR
k =(RL -IRD t,, is independent of initial concentration of reactant

or [R], —[R] = kt = 0.6 x 10% x 20 x 60 For a second order reaction,

= 0.72 mol L*? 1
Moles of A reacted 1.e., [R], — [R] = Moles of B produced
by = RAI,
.. Moles of B produced = 0.72 M
B14. (a): Arrhenius equation is t., depends upon the initial concentration of the
b = Aea/ET reactants.
E
Ink = nA-—
= RT B22. (5) : t,, (zero order reaction) = Io
so, by plotting In & vs 1/T, slope is — E,/R and hence 2k
activation energy can be obtained. When the concentration of the reactant is doubled,
B15. (d): For a first order reaction, half life is independent of the half life period of the reaction is also doubled.
concentration.
tio = 0.693/k B23. (a): For a zero order reaction, if the initial conc. is
B16. (6): On adding the catalyst, the activation energy of a doubled the half life period is also doubled.
reaction decreases. #4 = [A],‘*.
2.303 0.04 B24, (a): According to Arrhenius equation,
B17. (c): k=
20-10
Pr re
~ 0.03 k = Ae®rT
where E is activation energy
_ 2.303 , 9 1949
10 Now k= Myke
Rg
= 0.0287 s?
Ap E/BT | o-Ep/RT
— 0.693 0.693
. - 24.1 Aeow = Ae Es/RT
v2 0.0287 .
lusza MODERN'S abe + OF CHEMISTRY
-AXIl

2.303.
ioe1
-Ey/RT | ,-E,/RT
-E/RT BGO = he gs
. a o-Bs/RT it a—x 75 yy,

= . ~~, +8, aos log8 = 2,303 . 9.903 min-*

RT — RT 75 75
or EK = E, + E, — E, = 40 + 50 — 60 0.693 0.69375 — 25min
= 30 kJ mot".
M% k 2.303x0.903
B25. (c): For a zero order reaction, the plot of conc. of B31. (5): Slope = - or EK, =—SlopexR
reactant vs time is linear with —ve slope and non-
zero intercept. ae Fk 10*)x 8.3
tt = 16.6 x 10*J mol
B26. (c) k,(N,0,] = 5/1 [N20s] or = 166 kJ mol"
B32. (d) : For a zero order reaction :
k,[N,O,] = 2k"[N,O,] t,, « [A], z.e., initial conc. or initial pressure
. ba :
bat. _ Pe .
({t
(44), _ 16 bar
Equating &,[N,O,] = eM [N.O, | = 2k”[N,O,]

or 2k, = k' = 4k" iy)

(t | 45 4 bar

B27.(6): The effect of temperature on rate constant is given

by Arrhenius equation
(44), = = 45 = 180 min.
k = Ae ™®/RT B33. (c) : For 56°C rise in temperature, rate constant becomes
Here, if = hea double.
E “. For 20°C rise in temperature, rate constant becomes
Ink
InA-— = (2)* times 2.e., 16 times.
RT
The plot of In & vs 1/T is a straight line with slope B34. (c): pH = 2, [H*] = 10°
pH = 1, [H*] =107+
E

~ OR Initial rate, (rate), = k[H*]”

Hence statements (ii) and (v) are correct. (rate), = k(10°)"
B28. (e) : Expt. 1 and 2 show that there is no change in rate (rate), = k(10-+)”
with the change in concentration of C. So, the order
w.r.t. C is zero.
rates
rate,
_ 199 - te
10—
|
Expt. 4 and 1 show that by only doubling the conc.
100 = (10)" orn =2.
of A rate becomes four times, so that the order w.r.t.
A is 2. 2.303, [Rh
B35. (d) : k = ; los TR]
Expt. 1 and 3 show that by only doubling the conc.
of B rate becomes double so that the order w.r.t. B 2.303, 80
oS log — = 5.00 x 10-4 s-
is 1. 4606” 8 on
.. The order w.r.t A, B and C is 2, 1 and 0 respectively.
B36. (a) : 2N,0, ——-> 4NO, + O,
B29. (a): Let rate = k [A}* [BP
_1AIN20O5] 7 1 AINOg]
From trial 1 and 2 mu At A AE
k(0.4)° (0.2)” = 6.5 x 10-* AIN,O;]
Ad =
2.0-2.4
300 —~—2x 10
ee
mol L? min
k(0.8)x (0.2)y = 6.5 x 10+
AINOg] 4 NoO
_ 5(-“Se'} -29x%2x%103
] —~lor 2? =20 -x=0 At 2 Ag
0.4
From trial 1 and 3 —~ 4x 107° mol L? min
2.503 R
k (0.4) (0.207 =55-x 10% B37. (a): z= ; log
k (0.4) (0.40P” =2.2x10°%
= cclicaulad ea = 0.0231 min?
0.40)" : os 30 0.5
i -Aor 2=-2 ~ y=2 2.303,
_ Ss [Rh
.. The correct rate law is _=—— THI
rate = k[A]° [B]? 2.303 0.1 .
- ———— log —_—_ = 60 min
0.0231 ~ 0.025
CHEMICAL KINETICS 4/123 —

—3
B38. (c): i 0888 _ 28§ onan Sew 2 oe
thio 6.93 12x10
| , 2 =
, — 23038), [A], _ 2.303, 100 . a os
kA] (OL 1 Rate = k [Al
_ 2.503 aox 2 _ uno yes Hence, d|C]
ae” sea Rk (Aj+ 1 [B]° (RO =_ & [A]
0.1 , |
B39. (a) : For zero order reaction B45. (6): k= 2.303 15 LRlo= 2.303 9.5 2.303 og 4
[A] t [R] 50 0.125 50
na = ae = 0.0277 min-
When = _[H,0,] = 0.06 M,
— [A], 2
= m, = Diet Rate = k [H,O,] = 0.0277 x 0.05
= Se ee = 1.385 x 10°? mol L min“
= eee According to the reaction,
—_ == H,0, 2H,0
++0,
i - [Alo - [A] Rate = ~MH201 _ 9 192!
7 kh dt dt
: = Gene vi =5 x Rate of reaction = 5 x 1.385 x 10°
B40. (c): Increase in reaction rate = 2” = 32 times. = 6.93 x 10“ mol L™ min™
B41. (a): For a first order reaction : B46. (d) : ky = Ae ~®a,"

t [A] hy — e-Bay + Ea,VRT

At t = 40 min, [A], = 0.1M, [A] = 0.025 M Ry
k = —— log ——
2.303 0.1 Re
—= = eBay
Fa RT
40.” 0.025 ky - =
EK, —E 3
= 2.508 log 4= 0.0347 min? ee _- —__* _ _
KI =
A() k, RT 8.314 x 300
Rate = k[A] = 0.0347 x 0.01 = 3.47 x 10+ M/min. B47.(a): AG=AH-—TAS
B42. log i; ee
(5):ee. ee
2303R(T, T, a
k = | AH-
_RT InAH AS
TAS
— E,
or 9 — —__2
| 1
|/& “
1 | - RT R
S* * 2.303 x 8.314 (300 310 The plot ofIn& vs. + is a straight line with slope
E x
10
—____
AH
Sia T
0.3010 = —4—___
2.303 x 8.314 300 x 310 R
0.3010 x 2.303 x 8.314 x 300 x 310 since AH is negative (exothermic reaction), slope
= Janay is positive. Therefore, lines should be A and B.
= 63.6 kJ molt. B48. (a): Rate =k (py)

B43. (qa): Initial rate, = = Rk[A} [BP r, =k

= k(p,Y
dt ~ 363 — 363 XO = $44.85
12x 10% = k(0.1)*(0.1 i) i oa 100
12x107% = &(0.1F (0.2 ohBt) r, = k(344.86)" (t)
Divid; “(ay been. G
ividing pyaar eq. (2) ms r, = R(p,)
ee ee 363 X33
12x102 (=) PD, = 863 — ——— = 243.21
0
1 = 2 or2=2 r, = k(243.21)" (ii)
- y = iD s
Now 24x10% = k(0.2F (0.1Y ...(1it) A = a |= (1.41)"
Dividing eq. (iii) by eq. (i) rm \243.21
Sanz MODERN'S abe + OF CHEMISTRY-AXIl

1 eT [A]
oR TA = (/2) = aE
B53. (5) : ¢,,. for zero order reaction

2= (2)"or (vB)=(v2)" 0 =2 t,. for first order reaction

= ee9
ke

If initial rate, [A], = 1

B49. (a): Pp, = 80 kPa, Po = 40 kPa,
(f4.9), = 350 see (¢,.), = 176 sec 1 0.693 R'
on f or 2 2x 0.693

Now
350 om
80 _ 6 B54, (6): For a reversible reaction
175 40
AH = E, (forward) — E, (backward)
Pr _ bya) AH..= 160 — 260 =— 110 kJ mol}
P2 (tyj2)e
ak ny. x. fe ad
or aq = Cyady or
55.(b): k= Gog = 0.01
ty19 o

Ay (ty/2)e
2.303 100 =. 2.303 .
t= —— log
This is true for zero order reaction.
0.01 ~ ——
10 = ——
0.01 = 230.3 min
B50. (5) : When R, — k,
B56. (a): 2A(2) —+> B(g) + C(s)
101%)_-20000/T — 10912 » 24606
2(1—-x)x
et606/T — 100
At end of the reaction, only 1 mol of gas is present whose
pressure is 200 Pa.
a = 2.303 log 100
. Inthe beginning of the reaction, when 2 mol of gas were
present, pressure would have been 2 x 200 = 400 Pa
4606 = 2.308 x 2 At the end of 10 min, moles of gas present,
Ab
2—-2X 4x4 =2-X
qi. S606 . _j000K But pressure of 2 mol of gas = 400 Pa
2.303
x2
400—x = 300 or x=100
Pressure due to 2 — 2x mol of A = 400 — 2 x 100
B51. (5) : get = Ey h-hh
= 200 Pa
k, 2.303R| TT,
Now, k= clad Fad
f a-x
i = EK, aS |
ky 2.303R | T, Ts _ 2.303 lo 400 _ 2.303 log2
10 ? 200 10
Since E, > E,

1g ot _ = 0.3010 — 0.0603 min?

hy FF
B57. (d): If rate at cone. 1.2 x 10-? M is r, then
log“.
Ro r = R(1.2~x 103)" .. Gi)
Or = k(3.24 x 10) (ii)
or ky > ky
ky ko Dividing eq. (iz) by eq. (z)
—?.a
E 9 _ (3.24x10™) _ 97%
B52. (a): 2.303 log k = 2.303 log A-— —*
RT (1.2x107°)"
EK a = 2.303 RT or a3"
2.303 RT oa =2 or a=2/3
2.303 log k = 2.303 log
A— RT
B58. (d): T, = 27°C = 300K

(i
logk = log A-1
i. = —3°C = 270K

—] fe dt
k, 10
or = 10°71 log - —Ba_[1_1
E
ax
|> ky 2.303R |T, T,
CHEMICAL KINETICS

E 1 1 0.693 =0.693 219 %10"

|
log1071 = a sa B64, (5): k= your
°8 2.303R/300 270 tie 5770 ee
1. eed Ageofsample, ¢ = 2.303
k
1, (Rh
[R]
2.303R |270x300
2.303 15

E, =
2.303R x 270 x 300
30
12xi0t °° 5
= 91564 years = 9200 years
= 2.303R x 2700 J mol
= 2.303 x 2.7 RkJ mol! a,
B69. (c): 2NO,
1 d{NO,]
hy aa
B59. (d): Let P is the initial pressure of A and p is the decrease
Rate =
in pressure after 20 minutes. Y a a k,[NO,}° i Ry [N,O,]
A — > B + C
.. Rate of disappearance of NO,;
Initial P 0 0
at t = 20 P—p p p _dlNO,| = 2k,[NO,]°
2
— 2k,[N,0O,]
At completion 0 P P dt
At completion of reaction (t = <) B71. (0): = 3 x 10° s7; Rate = 2.4 x 10-° mol dm s7
2P = 180 Mae) 7 ?
or P = 90
Rate = k[N,O,]
At time = 20 min
Total pressure :P—p+p+p=100 24x 10°=3 x 10° x [N,O,]
or P+p = 100 2.4x10°
[N,O,] = — 0.8 mol dm™ or = 0.8 M
or 90+p = 100 8x10"
p =10 _9 ]|*
.. Partial pressure of A at ¢ = 20 min
B72. (d): Sa SA
= P—p=90—-10=80 mm. Pg
8 - 2°
Rev.) Number of inline = or 2-2 .x=8s
5730
N N B74, (a): & =
0.693 _ 0.693 _ 4 gi in mint
Amount left after 4 half lives = s = ae ft
y,
az
60
j

N , _ £:000)
2 303 [AR] 0
The fraction of “C that decayed = N, — ae - a f
ee TRI
B61. (c): In @ = Eaft_+ 2.303 1 [Ro
kh R(T 1, 240 =
0.0115 [R]

itt 2 OR S - as [Rl _ 240x0.0115 _, 199

er:
log
ky R_ (300. 600 [R] 2.303
600 R (2-1
log IRI __1198 or [R] = Antilog(—1.198) = 0.063
+!
k, in 600 [R]y [Rp

Percentage left = LR] x 100 = 0.0638 * 100 = 6.3%

or in Ly = Ine [Rly
hy B75. (6): The rate law for any reaction cannot be determined
theoretically but it is determined experimentally.
or ky — om B76. (e): A catalyst may change the order of the reaction as the
Ry
mechanism in presence of catalyst could be different
B62. (a): Half life = 26 min.
than that in the absence of it.
No. of half lives, n = ee =A4 B77. (d): Rate = k[A]*
mol L71s = &(mol L71)?
Amount left =
[Aly
—
[Aly
i
_[Alp
2" 2 16 - k = mol? Ls
‘
Fraction reacted = [Alp
[A], [A], 15
_—8——J/A
16-16 [Alo B78. (c): k& = Ae ERT

= 93.75 %. log k = log A E, i

B63. (c): Rate — & [A] [B]? Be = 08 9 303R( T
= 1x 10~ x (0.60)(0.50)2 log & vs 1/T is a Arrhenius plot.
= 1.26x 10% mol L's.
laze MODERN'S abe + OF CHEMISTRY
-AXII

B79. (d): [R], = 200 mg [R] = 25 mg B87.(d): If order of reaction w.r.t. G is x and w.r.t. H 1s y,
then on doubling [G] and [H], the rate becomes 8

mc)
[Rl | @ Gama)
200) \2
times i1.e.,
2°2” — 8 or 2*+) — 23
xXx+yVY=d

* o(3) -(3)
or ||
2
=|=
2
B88. (a):
*. Order of reaction = 3
bf ain
.nm=s 40
Time taken = 6760 x 3 = 17280 years Ran. 1.386 _ 1.386 eee ee
B80. (d): Temperature coefficient 2 means that the rate 2x20 40
of reaction becomes double for every 10° rise in
a 60. — 1 mol-tdm?
temperature.
ko 2.
re = 2° = 64 times B89. (d): Arrhenius equation is
E
logk = log A— —#__
1 d[SO, | _ dO | 1dl{so,| ne 8 2.303 RT
kia iar
er ha ara logk = 6.0 —2000/T
log A = 6.0
9 9I| 9 104 A = 10®s1?

a[SoO, | E, = 2000
3° —-9x9x107* =4x107%* mol Ls! 2.303 R
E_ = 2000 x 2.303 x 8.314
B83. (a): Rate = k[D,][AP = 38.28 kJ mol?
1 x 10° = k (0.06)" (0.05P w.. (z) B90. (a): k = Ae ##8T
3 x 10% = k (0.15) (0.06Y ... (it) '. As T increases, & increases exponentially.
Dividing eq. (zi) by eq. (z) B91. (d): For P, if tig =% then t,.,, = 2x. This means the order
4 | with respect to P is one.
oe -(o2] or gaa" 4221
From the graph, concentration of Q decreases linearly
with time. So rate with respect to Q remains constant.
9 x 10-3 = k (0.06) (0.16) .. (iti) Therefore, order of reaction with respect to @ is zero
Dividing eq. (zit) by eq. (2) Rate = R[P]} (Q]° Order=1+0=1
9x10° (0.15) | B92. (a): Rate with respect to weak acid,
1x10° (5a) ae
rate, = RAT) Leak acid

Rate law = k[D,][A]’ Rate with respect to strong acid

B84. (a): Rate = k[A]?” [B]*”
mol L-1s-1 = k(mol L74)”* (mol L4)*? rate, _ RL") ong acid

mol L's = k(mol L7?)? rate; _ LEI" eosk acid = 1

k=moltLs! rate. MH *liompacia 100
B86. (c): For a first order reaction, 1
p= 2303, |A ly - [H+] oak arid = 100 = 0.01 M

t [AL HA = Ht + A-
7 £908
2.303 1o5 AT... 1—0.01 0.01 0.01
AO © 0.025
025 =]
[H*y[A7] 0.01 0.01
or = aT log 4= = x 0.6020 K=ee
Tay x_ dO.
—4

= 0.0347 min“!
Now, at 0.01 M concentration C. mcq more than one correct answer
Rate = R[A]
= 0.0347 x 0.01 Cl. (a, 6): (c) rate becomes 81 times.
— 3.47 x 10¢ mol L" min. (d) rate becomes 4 times.
CHEMICAL KINETICS

C10. dad) > A(z) — > 2B(g) + Clg)

C2. (a, d): For a first order reaction, degree of dissociation = ci
t=—0 [A],
1 a a
k=—Il1n
it a-x
a a _ kkt
In = bt OF a ie [A] © Do
a-Xx [A], —x + 2x +x or [A],
+ 2x x p,
a-X ne or 2x oC Pp, — Do
a a
x
Le 3
eget
a ly
or degree of dissociation = 1 — e* A
pa Ay, lA
As E,/RT is dimensionless therefore, A has the
k [A]
dimensions of k, 1.e. time.
C3. (6, c): Since rate depends upon [H*]?, it is affected by _i,,
A
change in pH of solution. Doubling the conc. of Ht
Po lnm,
k P,~ Po
increases the rate four times.
C4. (5, c): (a) is wrong because it is independent of [NaOH].
Dy
(d) is wrong because all reactions are affected by ii,
“0
temperature.
k 2p >P,
+Po
C6. (a, 6, d): (a) For a reaction, concentration of reactant
decreases exponentially with time. It is true.
(6) Half life period decreases with increase in Or kt = =1in _*Po
3p, — PB, or = In
IN 2p, — 1n(3 PoP )
2p,—
concentration because it is inversely proportional
to R. or In(3p,.—p,) = —Rkt + 2 py
0.693 . Graph between In (8p,—p,) vs ¢ 1s a straight line
(d) k = ...(1)
Lie with —ve slope. Hence, option (a) is correct.
For 99.6% completion, a = 100, a —-x = 100 — 99.6
= 0.4.
k= — x log — k Po / 3 k

Rate constant is independent of [A],, hence option

(d) is correct.

From eq. (z) and (iz) D. mcq based on comprehension

0.693 . _ 2.303 x24
k
D1. (5): Slope
tie 99.6 2.308
t =
2?303
x Dod XK #
k — 2.303 x slope
09.6 0.693 1/2
= — 2.303 x 0.01389 = 3.2 x 107 min“
= Pees Spor - 8 7, - D4, (d): Rate = k [c]
C8. (a, d) : According to Arrhenius equation, 0.0069 = (0.2) k
b = Ae-Ea/RT
k= 0.0069 _ 3.45 * 107 —~§.75x10“2¢1
On increasing temperature (T) and decreasing activation
0.2 60
energy (E_), rate of reaction increases.
Co. (a, c): (a) A= PZa&
P = frequency factor, Z,, = collision frequency
tn ~ xigt
Sag "14
D6. (5): Ink 7
A = Arrhenius factor RT
Assuming Z,, to be same, Therefore, plot of In & versus 1/T is linear with
E
(A) slope = - R
p= ——?
(A) neo
E,
Since P=4.51eP>1 |e Be Slope = — 2.303R
A. > (A) theo
E a =—(— 8.96 x 10°) x 2.303 x 8.314
(c) The activation energy of the reaction is unaffected
— 171.4 kJ mol.
by the value of stearic factor.
laze D8. (c) : The factor A has the same units as those of k.
MODERN'S abe + OF CHEMISTRY
-AXIl

= a log8 (i)
For a second order reaction, & has the units
L mol? 1. Att = ty , [A] =[A],/10
D9. (a): For uncatalysed reaction :
2.303, [Al _ 2.303
4 . lore A-—_* — 1G = og log10 ...(zz)
log k = 8" 2.303 RT
For catalysed reaction (2’ is constant) From eq. (1) and (iz)
BA _ log 8
+ log A- 0
log R= 108 “~ 9.303 RT 3 Ee log10
t
Rega 10 x28 2 3 _ 10x3log2
or logk’ = ae 4
2.303 RT 2.303 RT ty, log 10 log 10
: 10 40
Subtracting, log k’ — log k = 2.303 RT .- 10x3x0.87 =
ep 9°

log =k 2.303 x 8.314

a x 300 =1.741 7. (8): In the complex [Fe(C,O,), (H,O),]?”
The oxidation state of iron is +2
D10. (a): On solving E, comes out to be 50 kJ mol. In acidic medium Fe** is oxidised to Fe** as
D11. (c): E, = 0 2MnO,- + 10Fe** + 16 H* ——> 2Mn** + 8H,O + 10Fe**
or MnO, + 6Fe** + 8 H* —-> Mn* + 4H,0O + 5Fe**
k
log4 =0 Rate of change of [H*] 8
k,
k Rate of change of[MnOj;] 1
or oo ea k, =k,
NCERT Exemplar Problems : MCQs Type-I
D12. (c): Fraction of molecules having energy greater than
EK, at any temperature T is given as 1. (ec): A catalyst lowers the activation energy of a reaction.
=o os I x= ‘a bo .
(c): In the presence of a catalyst, AH does not change.
N r RT 4, (a): The activation energy for the forward reaction is
log x = -——2— EK, + E, and product is stable than reactants.
or 2.303 RT
7. (d): Rate constant increases exponentially with decreasing
E+ and increasing temperature.
Integer Type Questions
9. (c): The order of a reaction is not always equal to the sum
of the stoichiometric coefficients of the reactants in
1. (0): For a zero order reaction,
the balanced chemical equation.
dk _k 1AlBr] 1 AH" |
dt 12. (c):
From 1 to 0.75 5 At 6 Af
0.25 _
or
A([Br°]_ 5 A[H™]
0.05
At 6 At
From 0.75 to 0.40
13. (a): Graph represents (a) is exothermic reaction in which
0.35 _ 5
I eaauehe < |: eee
0.07
From 0.40 to 0.10 14, (5): Rate will become double.
0.30 _5 16. (d): It will take infinite time for completion.
0.06 17. (6): On doubling conc. of B, rate becomes four times (exp.
Thus, order of reaction is zero. 1 and 2)
6. (9): For a first order reaction : “. rate oc [B]?

_ 2.303, [Ale On doubling conc. of A, rate becomes double (exp. 1 and 3)

Rate oc [A]
k [A]
At ty, [Al = [Al/8 Rate = [A] [B]*
18. (6): A catalyst does not change AG or AH of the reaction.
ft, 2.303,
— 1. [A] 0 19. (5): In pseudo first order reaction, rate constant depends
%~ hk FTA /g on the concentration of reactant present in excess.
Ho
CHEMICAL KINETICS 4/129 —

Y Unit Practice Test ¢

Hxamination

Time Allowed : 2 Hrs. Maximum Marks : 35

1. Define activation energy of a reaction. (1)

2. 75% of a radioactive substance disintegrates in 50 s. What is its half-life period? (1)
3. For a chemical reaction A—~= B, the rate increases by a factor of 2.25 when the concentration of A is increased
by 1.5. What is the order of the reaction? (1)
4. Can order of a reaction be fractional? Explain. (1)
5. What is the order of a reaction whose rate constant has same units as the rate of the reaction? (1)
6. The decomposition of ammonia on platinum surface is zero order reaction. What are the rates of production of N,
and H, if k= 2.5 x 10* mol L's”? (2)
7. Show that half life period of a first order reaction does not depend upon the initial concentration of reactants.(2)
8. A first order reaction is 15% complete in 20 minutes. How long will it take to complete 60%? (2)
9. Give differences between rate constant and rate of a reaction. (2)
10. A reaction is of second order with respect to a reactant. How is the rate of reaction affected if the concentration
of the reactant is reduced to half? What is the unit of rate constant for such a reaction? (2)
11. The rate of a particular reaction quadruples when the temperature changes from 293 K to 313 K. Calculate the
energy of activation for such a reaction. (8)
12. A first order reaction has a rate constant of 0.0051 min—. If we begin with 0.10 M concentration of the reactant,
what concentration of the reactant will be left after 3 hours ? (3)
13. Explain the following: (8)
(4) pseudo first order reactions
(ii) graphical method for measuring rate of a reaction.
14. Discuss the effect of temperature on the rate of a reaction. How can this temperature effect on rate constant be
represented quantitatively ? (3)
15. During nuclear explosion one of the products is °°Sr with half-life of 28.1 years. If 1 pg of °°Sr was absorbed in
the bones of a newly born baby instead of calcium, how much of it will remain after 10 years and 60 years if it is
not lost metabolically? (8)
16. (a) What is meant by order and molecularity of a reaction? How do these differ?
(6) Derive an expression for the rate constant of a zero order reaction.
(c) Areaction rate is first order in A and second order in B. How is its rate affected on increasing concentrations
of A and B two and three times respectively? (5)

To check your performance, see HINTS AND SOLUTIONS TO SOME QUESTIONS at the end of
Part I of the book.
 SURFACE
CHEMISTRY
Building on.... Assessing.... Preparing for Competition....
Understanding Text 1 @ Quick Memory Test with @ Additional Useful Information 65
@ Conceptual Questions Hee We) Answers iy eo. Vallee ae ‘aataa 6s 65
® Competitive Examination
CHAPTER SUMMARY & QUICK ¢ HOTS & Advanced Level SS AIPMT & Other State Boards’
CHAPTER ROUND UP 50 Questions with Answer 58 Medical Entrance 67
NCERT FILE REVISION EXERCISES > JEE (Main) & Other State
: : als Boards’ Engineering Entrance 68
+ In-text Qs & Exercises with ee Sear > JEE (Advance) for IIT Entrance
St 53 & Other State Boards Qs) 60 70

¢ ae
NCERT Exemplar
peeoee
Problems
ee
withne ¢ Hints
eee
& Answers for Revision G4
a a ede
(Objective Questions) 74
swers & Solutions (Subjective) 50 @ Hints & Explanations for
UNIT PRACTICE TEST 6/61 Tikes Peston 79

Saries chemistry ts the branch of chemistry which deals with the nature
of surfaces and the phenomena that occur at the surfaces or interfaces.
There are many properties of substances particularly of solids and liquids,
which depend upon the nature of the surface. Surface represents
the boundary which separates two bulk phases. This is also called
interface and is generally represented by separating the bulk phases
by a hyphen or a slash. For example, the interface or surface
between a solid and a liquid may be represented by solid-liquid
or solid/liquid interface. There is no interface between gases
because they are completely miscible.
Adsorption on solid or on solution surfaces, colloidal properties,
electrode processes, heterogeneous catalysis, dissolution and
crystallisation, corrosion etc. are important surface effects which
‘ are useful to understand many physical and chemical properties
/ of the substances.

ADSORPTION
There are many examples which show that the surface of a solid has a tendency to attract and retain the
molecules of the phase with which it comes into contact. These molecules, however, remain only at the surface
of the solid and do not penetrate into the bulk. For example, when a small amount of finely divided charcoal is
put into vessel containing a gas, it is observed that the pressure of the gas decreases rapidly at first and then
gradually. The decrease in pressure of the gas is due to the accumulation of the gas on the surface of charcoal.
It has been observed that the gas molecules remain only on the surface and do not penetrate into the bulk of the
solid. Since these molecules remain only at the surface and donot go deeper into the bulk, their concentration
is more at the surface than in the bulk of the solid. Thus,

i
 MODERN'S abc + OF CHEMISTRY-All

the phenomenon of attracting and retaining the molecules of a

substance at the surface of a solid or a liquid resulting into higher
concentration of the molecules on the surface than in the bulk is
‘2 pee
called adsorption.
(gas or solute)
Fi a As a result of adsorption, there is decrease of surface energy.
*} Adsorbent Adsorbent and Adsorbate
:\(solid or liquid): The solid substance on the surface of which adsorption occurs 1s
: ‘ known as adsorbent.
The substances that get adsorbed on the solid surface due to
intermolecular attractions are called adsorbate.The process of removal
of an adsorbed substance from the surface on which it is adsorbed is called
desorption. It is reverse of adsorption and can be brought about by heating
Fig. 1. Adsorbent and adsorbate. _, or by reducing the pressure.
The phenomenon of adsorption of gases on the surface of metals
is called occlusion.
The adsorbent may be a solid or a liquid and the adsorbate may be a gas
or a solute in some solution.
Examples of adsorption
1. Adsorption of a gas by charcoal. If a gas like ammonia, sulphur
dioxide, chlorine, oxygen, hydrogen, carbon monoxide or phosgene is taken in
a closed vessel containing powdered charcoal, it is observed that the pressure
of the gas decreases. The gas molecules concentrate at the surface of the
charcoal i.e., gases are adsorbed at the surface. In this case, charcoal acts as
an adsorbent while gas molecules act as adsorbate.
Solids particularly, finely divided have a large surface area and therefore,
they show the property of adsorption to a much larger extent. For example,
charcoal, silica gel, alumina gel, clay, colloids, metals in finely divided state,
etc. are highly good adsorbents because they have highly porous structures
and hence large surface area.
2. Adsorption of a dye by charcoal. When animal! charcoal is shaken
with a solution of an organic dye such as methylene blue it is observed that
the solution turns colourless. The discharge of the colour is due to the fact
that the coloured component (generally an organic dye) gets adsorbed on the
surface of animal charcoal. Therefore, animal charcoal is used for decolourising
a number of organic substances in the form of their solutions.
3. When aqueous solution of raw sugar (which has yellowish brown colour)
1s passed over beds of animal charcoal, it becomes colourless because the
colouring substances are adsorbed by the charcoal.
4. The air becomes dry in the presence of silica gel because the water
molecules get adsorbed on the silica gel.
Difference between Adsorption and Absorption
The terms adsorption and absorption are different. Adsorption
Water vapours is a phenomenon in which there is higher concentration of another
| i substance on the surface than in the bulk. On the other hand
Piece of absorption ts a phenomenon in which the molecules of a substance
anhydrous CaCl, are uniformly distributed throughout the body of other substance.
Thus, adsorption of substance A by B means that A is
present on the surface of B and the concentration of A in parts
Piece of silica gel
of B away from the surface is negligible. On the other hand,
absorption of A by B means that A is uniformly distributed over
(a) Adsorption (6) Absorption B. For example, when a stick of chalk is dipped in ink, the surface
retains the colour of ink due to adsorption of coloured molecules.
Fig. 2. Phenomena of adsorption and absorption. On the other hand, the solvent of the ink goes deeper into the
stick due to absorption. When chalk stick is broken, it 1s found
to be white from inside.
REMEMBER The distinction between adsorption and absorption can be made
by taking the example of water vapour. When silica gel is placed in
Silica gel adsorbs water| the environment of water, it adsorbs the water vapour. As shown in
vapour while Fig. 2 (a), the water vapours are present in high concentration at the surface
anhydrous calcium chloride of silica gel. On the other hand, when anhydrous calcium chloride is placed
in the environment of water, it absorbs water. The water vapours uniformly
absorbs water.
get distributed throughout the body of calcium chloride as shown in Fig. 2(d).
SURFACE CHEMISTRY

Thus, silica gel adsorbs water vapour while anhydrous calcium chloride absorbs Illustration of adsorption,
water. Similarly, when ammonia gas is placed in contact with charcoal, it gets absorption and sorption
adsorbed on the charcoal.
Thus, adsorption is a surface phenomenon while absorption is a bulk
property.
The important points of distinction between adsorption and
absorption are:

Aasonption
It is the phenomenon in which the | It is the phenomenon of higher concen-
particles ofgasorliquidgetuniformly | tration of particles of gas or liquid on the
distributed throughout the body of | surface than in the bulk of the solid.
the solid.
The concentration is the same The concentration on the surface of
throughout the material. Therefore, the adsorbent is different from that in
it is a bulk phenomenon. the bulk. Therefore it is a surface phe-
nomenon.
Absorption occurs at uniform rate. Adsorption is rapid in the beginning and
its rate slowly decreases.
Sorption. In some cases, both absorption and adsorption occur together and are
not distinguishable. In such cases, the substance gets uniformly distributed into the
bulk of the solid but at the same time, its concentration is higher at the surface than
in the bulk. Such a phenomenon 1s called sorption.
Positive and Negative Adsorption
Positive adsorption. When the concentration of adsorbate is more on
the surface of adsorbent relative to its concentration in the bulk, it is called
positive adsorption.
Negative adsorption. When the concentration of the adsorbate is less
on the surface relative to its concentration in the bulk, it is called negative
adsorption. For example, in case of some liquid solutions, it is observed that
the concentration of the solute is less on the surface than in the bulk of the
solution. This type of adsorption is called negative adsorption.
For example, when a concentrated solution of potassium chloride (KCl)
is shaken with blood charcoal; it shows positive adsorption but with a dilute
solution of KCl, it shows negative adsorption.

LA TMA of Adsorption
Adsorption is a surface phenomenon, it arises because of the
unbalanced forces on the surface of solids and liquids. This is Net inward
because of the fact that the surface particles of the adsorbent (solid force
or liquid) are not in the same environment as the particles inside
the bulk. If we consider a solid, it is observed that a molecule
present in the bulk of the solid is being uniformly attracted from No resultant |
all sides by the neighbouring molecules [Fig. 3 (a)]. As a result, force
there is no net pull on this molecule. However, a molecule which
les near the surface (known as a surface molecule) is being (a) A liquid or a
attracted only by molecules below it. This is because there are solid substance
no molecules above it. Therefore, surface molecules experience | A¢Sorption of gas
a resultant downward attractive force within the solid. In other
words, the surface is under strain or tension due to unbalanced
forces. Similar inward forces of attraction exist on the surface
of a liquid. As a result, the surface of the solid or liquid tends
to satisfy their residual forces by attracting and retaining the
molecules of other species (a gas or dissolved substance) when
brought in contact with them [Fig. 3 (5)].
Thus, the unbalanced forces of the adsorbent are responsible
for attracting the adsorbate particles on its surface resulting
adsorption. The extent of adsorption increases with the increase of
Fig. 3. (a) Inward forces at the surface of a solid or a
surface area per unit mass of the adsorbent at given temperature
and pressure. liquid. (6) Adsorption of a gas at the solid surface.
 MODERN'S abc + OF CHEMISTRY-All

TYPES OF ADSORPTION
Depending upon the nature of forces which hold the molecules of the
adsorbate on the surface of the adsorbent, the adsorption is classified into
two types :
1. Physical adsorption and
2. Chemical adsorption.
1. Physical adsorption
When the particles of the adsorbate are held to the surface of the adsorbent
by the physical forces such as van der Waals forces, the adsorption is called
physical adsorption or physisorption (short name for physical adsorption).
The attractive forces are weak and, therefore, these can be easily overcome
either by increasing the temperature or by decreasing the pressure. In other
words, physical adsorption can be easily reversed or decreased.
Characteristics of physical adsorption
(i) Low enthalpy of adsorption. The attractive forces between adsorbent
and the adsorbate molecules are weak (van der Waals forces) and therefore,
molar enthalpy of adsorption is low and is of the order of 20-40 kJ mol.
(ii) Reversible nature. The physical adsorption process is generally
reversible and therefore, equilibrium is reached rapidly. Thus,
Solid + Gas = — Gas/Solid + Heat
Adsorbent Adsorbate
Applying Le Chatelier's principle, when we increase the pressure (or decrease
the volume), the equilibrium shifts in the forward direction i.e. adsorption
increases. Therefore, more of gas is adsorbed when pressure is increased as the
volume of the gas decreases. Alternatively, gas can be removed by decreasing
the pressure.
(iii) Effect of temperature. Since adsorption process is exothermic,
therefore, physical adsorption occurs readily at low temperature and decreases
with increase in temperature according to Le-Chatelier's principle. If the
temperature is increased, the kinetic energy of the gas molecules increases
and they leave the surface of the adsorbent. Therefore, rise in temperature
decreases the extent of adsorption.
(iv) Lack of specificity. It is not specific in nature and therefore, all
gases are adsorbed on all solids to the same extent. This is because a given
surface of an adsorbent does not show any preference for a particular gas as
the van der Waals forces are universal.
(v) Nature of adsorbate. The extent of physical adsorption depends
upon the ease of liquefaction of the gas. The gases which are easily liquefied
(i.e., having higher critical temperatures) are adsorbed readily because van der
Waals forces are stronger near the critical temperatures. For example, 1g of
activated charcoal adsorbs more SO, (critical temperature 630 K) than methane
(critical temperature 190 K) which is still more than 4.5 mL of dihydrogen
(critical temperature 33 K).
(vi) State of adsorbate. In physical adsorption, the state of adsorbate
is same as 1n the bulk.
2. Chemical adsorption.
When the molecules of the adsorbate are held to the surface of the adsorbent
by the chemical forces or chemical bonds, the adsorption is called chemical
adsorption or chemisorption (short name for chemical adsorption).
In this case, a chemical reaction occurs between the adsorbed molecules
and the adsorbent on the surface. This type of adsorption is irreversible. Like
chemical reactions, there are activation energies for chemisorption.
Characteristics of chemical adsorption
(i) Enthalpy of adsorption. Attractive forces between adsorbent and
adsorbate molecules are strong chemical bonds and therefore, molar heat of
adsorption is high and is of the order of 80-240 kJ mol.
(ii) Irreversible nature. Unlike physical adsorption, it is irreversible
because chemisorption involves compound formation.
SURFACE CHEMISTRY

(iii) Effect of temperature. Chemical adsorption first increases with,

increase in temperature upto a certain extent and then decreases regularly.
A gas adsorbed at low temperature by physical adsorption may change into
chemisorption at a high temperature. For example, hydrogen is first adsorbed
on nickel by van der Waals forces. Molecules of hydrogen then dissociate to
form hydrogen atoms which are held on the surface by chemisorption. Usually
high pressure is also favourable for chemisorption.
(iv) High selectivity. Unlike physical adsorption, chemical adsorption
involves the formation of chemical bonds between the adsorbed molecules and
the surface of adsorbent. Therefore, it is highly selective. In other words, chemical
adsorption depends upon the nature of the chemical properties of the gas and the
adsorbent. For example, oxygen is adsorbed on metals by virtue of oxide formation
and hydrogen is adsorbed by transition metals due to hydride formation.
(v) State of adsorbed species. Since chemical reaction takes place
in this type of adsorption, therefore, the state of adsorbed molecules may be
different from that in the bulk. For example, oxygen exists as O, in the bulk
but on the surface it may exist as O5, OF, O, O-, O7, etc.
Explanation of chemisorption. Let us consider the example of adsorption
of H, gas on the surface of nickel or platinum. Due to unbalanced forces on the
surface of the solid, the hydrogen molecules are attracted towards it by weak
van der Waals force and hence get adsorbed on it. The adsorbed molecules
then dissociate into atoms and are chemisorbed and hence are held strongly.

Physical
ee ee ' Chemical
adsorption adsorption

Since chemical adsorption needs some activation energy, the process is

also called activated adsorption.
Enthalpy of adsorption
The amount of heat evolved when one mole of an adsorbate (gas
or liquid) is adsorbed on the surface of an adsorbent is called enthalpy
of adsorption.
REMEMBER
The enthalpy of adsorption for chemisorption is larger than that for
physical adsorption. For example, the enthalpy of adsorption for chemisorption AH aasorption 1S always —ve
is almost of the same magnitude as of chemical reactions of the order of ADS Fegan 1s —ve
80-240 kJ mol. On the other hand, the enthalpy of adsorption for physical For process of adsorption to
adsorption is of the order of heat of condensation of vapours into liquids i.e., occur t.e., AG to be —ve, AH must
about 20—40 kJ mol?. be > TAS.
i.e., AH should have sufficiently
Gibbs energy change during adsorption
high value (>TAS) so that AG
During adsorption, there is always decrease in residual forces of the surface 1.e.,
becomes negative.
there is decrease in surface energy, which appears as heat. Therefore, adsorption
1s an exothermic process and therefore, AH is negative for adsorption and favours
the process. On the other hand, the molecules of the adsorbate (gas) are held on the
surface of the adsorbent and, therefore, they have lesser tendency to move about
freely. In other words, entropy decreases i.e., AS 1s negative and the entropy factor
opposes the process. According to Gibbs Helmholtz equation,
AG = AH — TAS, or AG = (-) — T (-)
Thus for the process of adsorption to occur, AG must be negative, which is
possible only when AH > TAS in magnitude. Thus, for adsorption to be spontaneous,
AH should have sufficiently high negative value so that AG becomes negative. This
1s true in the beginning. However, as the adsorption continues, AH becomes less and
less negative and TAS keeps on increasing and ultimately AH becomes equal to TAS
so that AG becomes zero. This state is called adsorption equilibrium.
 MODERN'S abc + OF CHEMISTRY-All

It maybe noted that in exceptional cases, chemisorption may be endothermic

(i.e., AH = +ve). For example, H, adsorbs on glass endothermally. In this case H,(g)
splits into H atoms on glass as
H, (g) ——— 2H (glass)
so that AS is sufficiently positive to overcome the small positive enthalpy change (i.e.,
TAS > AH so that AG = —ve). Similarly, highly hydrated solutes, when adsorbed on
solids also have positive AH. But these are accompanied by large positive AS due to
release of water molecules on adsorption. Therefore, AG is also negative in these cases.

Differences between physical adsorption and chemical adsorption

The main points of differences between physical adsorption and chemical adsorption are summed up below :
Physical adsorption Chemical adsorption

The forces between the adsorbate molecules and the adsorbent The forces between the adsorbate molecules and the adsorbent
are weak van der Waals forces. are strong chemical forces similar to chemical bonds.
Low enthalpy of adsorption of the order of 20 to 40 ke mol! High enthalpy of adsorption of the order of 80 to 240 kJ mol.
Usually occurs at low temperature and decreases with It occurs at high temperature and increases with the increase
increase of temperature. of temperature.
It is reversible in nature. It is irreversible.
The extent of adsorption depends upon the ease of liquefication There is no correlation between extent of adsorption and the
of the gas. More easily liquefiable gases are adsorbed readily. ease of liquefication of gas. It also depends on the nature of gas.
Gases which can react with the adsorbent show chemisorption.
It is not specific in nature 1.e., all gases are adsorbed on It is highly specific in nature and occurs only when there is
the surface of a solid to some extent. bond formation between adsorbent and adsorbate molecules.
No apprecible activation energy is needed. High activation energy is sometimes needed.
The state of adsorbate is same as in the bulk. State of adsorbate molecules may be different from that in
the bulk.
It forms multimolecular layers. It forms mono-molecular layer.
). Rate of adsorption increases with increase in pressure Rate of adsorption usually decreases as the pressure
of adsorbate. increases.
. It depends on the surface area. It increases with an increase It also depends on surface area and also increases with an
of surface area. increase of surface area.

©OD OOlO © OO Kreis: Adsorption of N, on Iron

The behaviour of adsorption of N, on iron clearly distinguishes
OO CoO OO © ayers
Sees sobSoobs | between physisorption and chemisorption. At 83 K, nitrogen is
| Adsorbent | physisorbed on iron surface as N, molecules. The amount of N,
(Physical adsorption) M adsorbed decreases rapidly as the temperature increases. At room
0TLO-
temperature, practically, there is no adsorption of N, on iron.
However at 773 K and above, nitrogen is chemisorbed on the iron
Adsorbent surface as nitrogen atoms.
(Chemical adsorption)

Types of Forces : As already discussed, the atoms or molecules of a solid

surface have unbalanced or residual attractive forces. As a result, the surface
of the solid has the tendency to attract the molecules of a gas or a liquid when
they come in its contact. Since energy is released because of attraction, the
solid gets a more stable state. The adsorbed atoms or molecules are held on
the surface of a solid by physical van der Waals forces or chemical forces due
to residual valence bonds.
The forces of attraction increase when a solid is broken into pieces or
crushed to powder. This is because of formation of more surfaces. For example,
when a solid substance is broken into two pieces, two new surfaces are formed
SURFACE CHEMISTRY

and therefore, the number of unbalanced forces

become more (Fig. 4). As a result, the tendency for New mate
Orces
adsorption becomes large.
ADSORPTION OF GASES ON SOLIDS
Almost all solids adsorb gases to some extent. Breaking
The extent of adsorption of a gas on a solid surface —-
is affected by the following factors : | |
|
1. Nature of the gas | |
No. of unbalanced forces = 8 No. of unbalanced forces = 12
Nature of adsorbent
Specific area of the adsorbent Fig. 4. Unbalanced forces on the metal surface increase on
Effect of temperature breaking into pieces.
Effect of pressure
Fe
on
wh. Activation of adsorbent.
These factors are discussed below :
1. Nature of the gas (or adsorbate). The amount of gas adsorbed by a REMEMBER
solid depends on the nature of the gas. In general, under given conditions of Higher the critical temperature
of a gas, greater is the amount of
temperature and pressure, the easily liquifiable gases such as CO,, HCl, NH,,
that gas adsorbed.
Cl,, etc. are adsorbed more than the permanent gases such as H,, N, and O,.
The ease of liquefication of a gas depends upon its critical temperature
(T,). The critical temperature of a gas is the minimum temperature above
which a gas cannot be liquefied, however high the pressure may be applied.
The higher the critical temperature, the more easily a gas ts liquefied
and hence more readily it will be adsorbed because the van der Waals
forces are stronger near the critical temperatures. For example, 1 g of activated
charcoal can adsorb the following amounts of gases :

Critical temp. (K) 30 26 134 190 304 406 430

Amt. adsorbed (in mL) 4.5 8.0 9.3 16.2 48 180 380

Ease of liquefication increases |

Adsorption increases

However, the chemical adsorption is highly specific in nature and

a gas gets adsorbed on the solid only if it forms chemical bonds.
2. Nature of adsorbent. The extent of adsorption of a gas depends upon
the nature of adsorbent. Activated charcoal can adsorb gases which are easily
liquefied. Many poisonous gases are adsorbed by charcoal. Therefore, it is used
in gas masks for adsorbing these poisonous gases. Gases such as H,, N, and
O, are generally adsorbed on finely divided transition metals e.g., Ni and Co.
Most common adsorbents used are activated charcoal, finely divided metals,
metal oxides (silica gel, aluminium oxide, etc.), and clay. Each of these have
their characteristic adsorption properties.
3. Surface area of the adsorbent. The extent of adsorption increases with
the increase 1n the surface area of the adsorbent. The larger the surface area
of the solid, the greater would be its adsorbing capacity. Therefore, the porous
 MODERN'S abc + OF CHEMISTRY-All

and finely divided forms of adsorbents adsorb large quantities of adsorbate.

However, the pores of the adsorbent should be large enough to allow the gas
molecules to enter them.
4. Effect of temperature. The process of adsorption is an exothermic
process and is invariably accompanied by evolution of heat. Like any other
equilibrium, adsorption is a process involving a true equilibrium. The two
opposing processes involved are condensation (i.e., adsorption) of the gas
molecules on the surface of the adsorbent solid and evaporation (i.e. ,desorption)
of adsorbed gas molecules from the solid surface into gaseous phase. Since
the process of condensation is exothermic, the reverse process of evaporation
is endothermic. The equilibrium may be expressed as :
Condensation Gas adsorbed
Gas (adsorbate)+ Solid (adsorbent) Son on solid + Heat

195 K (-78°C) According to Le-Chatelier's principle, the increase in temperature

will favour the reverse process of desorption. Therefore, adsorption will
decrease with increase in temperature and adsorption will be favoured
244 K (-29°C)
oo by decrease in temperature. Thus, increase of temperature decreases
=
5 273 K (0°C) adsorption and vice versa. For sm gr it has been observed that one
= gram of charcoal adsorbs about 10 cm? 7 N, at 273 K (0°C), but the
o
caJ
same amount of charcoal adsorbs 20 cm? of N, at 244 K (—29°C) and
about 45 cm® at 195 K (— 78°C). This is shows in Fig. 5.
3oo
This is clear from the above figure that at a particular pressure,
=—
a| adsorption increases with decrease in temperature.
5. Effect of pressure. At a constant temperature, the adsorption
Pressure ———————*
of a gas Increases with increase in pressure. This can also be explained
on the basis of Le-Chatelier's principle. Adsorption of a gas leads to
decrease in pressure and therefore, according to Le-Chatelier's principle,
Fig. 5. Variation of adsorption of N, on charcoal] the magnitude of adsorption increases with increase in pressure. The
with pressure at different temperatures. variation of adsorption with pressure at different constant temperatures
is shown in Fig 5.
Thus, decrease of temperature and increase of pressure both
tend to increase the extent of adsorption of a gas on a solid.
6. Activation of adsorbent. Activation of adsorbent means increasing
of the adsorbing power of the adsorbent. It is very necessary to increase the
rate of adsorption. This can be done by the following methods :
(4) Metallic adsorbents are activated by making the surface of the adsorbent
rough. This is done by mechanical rubbing or by subjecting them to some
chemical reactions or by depositing finely dispersed metals on the surface of
adsorbent by electroplating.
(it) To increase the adsorbing power of adsorbents, they are sub-divided
into smaller pieces. As a result, the surface area increases and therefore, the
adsorbing power increases.
(4it) Some adsorbents are activated by strong heating in contact with
superheated steam or in vacuum at a temperature of 623-1273K so that gases
already adsorbed are removed. For example, charcoal is activated by subjecting
it to the action of superheated steam.
ADSORPTION ISOTHERMS
As already learnt, the adsorption on a given surface generally increases
with increase in pressure (for gases) and concentration (for solutions) at a
constant temperature.
The extent of adsorption of a gas per unit mass of adsorbent depends
5 upon the pressure of the gas. The relation between the amount of
substance adsorbed by the adsorbent and the equilibrium gas pressure
——> (or concentration for solutions) at constant temperature is called an
Saturation adsorption isotherm. This may be expressed in the form of an equation or
pressure
gas O
adsorbed
of
Amount graphical curve (or plot). The extent of adsorption is usually expressed as =
Pressure, P ——* ie m
Fig. 6. Adsorption isotherm. where x is the mass of adsorbate and m is the mass of the adsorbent. The
simplest type of adsorption is shown in Fig. 6.
SURFACE CHEMISTRY

It is clear from the figure that extent of adsorption (x/m) increases with
pressure and becomes maximum corresponding to pressure P_, called equilibrium
pressure. Since adsorption is a reversible process, the desorption also takes
place simultaneously. At this pressure (P_), the amount of gas adsorbed
becomes equal to the amount of gas desorbed so that the extent of adsorption
becomes constant even though the pressure is increased. This state is also
called saturation state and P. is called saturation pressure.
The scientists have tried to explain the adsorption in terms of some empirical
mathematical relations called adsorption isotherms. The most common types
are discussed below :
A. Freundlich Adsorption Isotherm
The variation of extent of adsorption (x/m) with pressure (P) at a particular
temperature was given mathematically by Freundlich in 1909. From the
adsorption isotherm (Fig. 6), the following observations can be easily made :
(i) At low pressure, the graph is almost straight line which indicates that
x/m is directly proportional to pressure (Fig. 7). This may be expressed as :

we Poe ae ...(Z)
m m
where 2 is a constant.
(ii) At high pressure, the graph becomes almost constant which means
that x/m becomes independent of pressure (Fig. 7). This may be expressed as :
0 |
constant or J P (3 P- = 1)
m

or RP” (ii)
3/%
S[k
(iii) Thus, in the intermediate range of pressure,
x/m will depend upon the power of pressure which lies
between 0 to 1 z.e., fractional power of pressure (probable Temperature
range 0.1 to 0.5). This may be expressed as constant

x oc Pin
m

x
“~ =p pla er

er my)

of
Amt.
(x/m)
adsorbed
gas P., saturation
where n can take any whole number valuewhich pressure
depends upon the nature of adsorbate and adsorbent. The
above relationship is also called Freundlich's adsorption Pressure —————-*

isotherm and is shown in Fig. 7.

Fig. 7. Adsorption isotherm in term of Freundlich.
Calculation of k and n of adsorption isotherm
The constants k and n can be determined as explained
below :
Taking logarithms on both sides of Eq. (tii), we get

log = =logk + z log P

m it

Thus, if we plot a graph between log (x/m) on y-axis

} Intercept = log k
(ordinate) and log P, on x-axis (abscissa), straight line will
log P
be obtained. This also shows the validity of Freundlich
isotherm. The slope of the line (Fig. 8) is equal to 1/n and
Fig. 8. Linear graph between log x/m and log P.
the intercept is equal to log &.
 MODERN'S abc + OF CHEMISTRY-All

Limitations of Freundlich adsorption isotherm

Freundlich adsorption isotherm fails at high pressure of the gas. Therefore,
this relation is considered as approximate and is applicable only at low
pressures. Irving Langmuir in 1916 derived a simple adsorption isotherm on
the theoretical considerations based on kinetic theory of gases. This is named
as Langmuir adsorption isotherm.
ADSORPTION ISOBARS
T ——
As we have learnt, with the increase in temperature at constant pressure,
(a) the extent of adsorption (x/m) will decrease. The graph between extent of
adsorption and temperature at constant pressure is called adsorption
isobar. However, this is true for physical adsorption as shown in Fig. 9 (a). In
case of chemisorption, the adsorption initially increases with rise in temperature
and then decreases as shown in Fig. 9 (b). This behaviour is expected because
like all chemical reactions, some activation energy is required for chemisorption.
At low temperature, x/m is small. As temperature is increased, the molecules
of the adsorbate gain energy and become equal to activation energy so that
|e
proper bonds are formed with the adsorbent molecules. Therefore, initially
(b) amount of gas adsorbed increases with rise in temperature. Further increase
Fig. 9. Adsorption isobars for of temperature will increase the energy of molecules which have already been
(a) physical adsorption and adsorbed. This would increase the rate of desorption and, therefore, decrease
(6) chemical adsorption. the extent of adsorption.
The adsorption isobar graphs can be used to distinguish between physical
and chemical adsorptions. In physical adsorption, there is a regular decrease
as temperature increases. However, in chemisorption, there is initial increase
and then it decreases [Fig. 9 (5)].
ADSORPTION FROM SOLUTIONS
The process of adsorption can take place from solutions also. For example,
when solution of acetic acid in water is shaken with charcoal, a part of the acid
is adsorbed by charcoal and therefore, the concentration of acetic acid decreases
in the solution. Similarly, when magnesium is precipitated as magnesium
hydroxide, in the presence of magneson reagent, it attains blue colour. The
colour is due to adsorption of magneson. The litmus solution when shaken with
We have learnt that increase charcoal becomes colourless because of adsorption from solution phase. It is also
in temperature tends to lower the observed that solid adsorbents adsorb certain solutes from solution in preference
extent of adsorption. Therefore, to other solutes and solvents. For example, animal charcoal decolourises impure
sugar solution by adsorbing colouring dye in preference to sugar molecules. The
in order to get the same amount
following observations are made in case of adsorption from solution phase :
of adsorption at a higher (1) The extent of adsorption depends upon the concentration of the solute
temperature, the pressure of in the solution. It increases with increase in concentration of solute in thesolution.
the system has to be increased. (it) The extent of adsorption decreases with increase of temperature.
Hence, a straight line relationship (it) The extent of adsorption also depends upon the nature of adsorbent
between temperature and and adsorbate.
pressure is generally observed. (tv) The extent of adsorption increases with an increase in the surface
The graph showing the variation area of the adsorbent.
The Freundlich's adsorption isotherms obtained for the adsorption of gases on
of pressure with temperature for
the surface of solid adsorbents have been found to be approximately applicable
a given amount of adsorption is to the adsorption of solutes from the solutions. Here, the equilibrium pressure
called isostere. in the adsorption of gases 1s replaced by the equilibrium concentrations (C) of
the adsorbates in solution. The adsorption isotherm may be represented as :
~*~ =rcow (i)
m
Fixed amount of
Taking logarithms, Eq. (i) becomes
adsorption
Temperature
——>
log ~ = log k + hog C
m fi

A graph between x/m and C has been found to be similar to one shown for
Pressure ——> x/m and P for gases on solid (Fig. 7). From the graph, the values of 1/n and log k
Fig. 10. Adsorption isostere. can be calculated as slope and intercept respectively. The equation can be tested
SURFACE CHEMISTRY

experimentally by taking solutions of different concentrations flask. The difference in the initial and final concentrations
of acetic acid. Equal volumes of solutions are added to equal gives the value of x. Using the above equation, Freundlich
volumes of charcoal in different flasks. After adsorption for adsorption isotherm can be verified.
a fixed time, the final concentration is determined in each

SOLVED EXAMPLES |
_} Example 1. 0.5
x 100 = 0.05 mol.
Three grams of oxygen are adsorbed on 1.2g of charcoal 1000
powder at 300 Kand 0.7 atm. Express the mass, number No. of moles of acetic acid left after adsorption
of moles and volume of oxygen at 300 K, 0.7 atm and at
0.49 x 100 = 0.049.
STP adsorbed per gram of the adsorbent. 1000
Solution: Mass of adsorbate, x =3 g Moles of acetic acid adsorbed = 0.05 — 0.049 = 0.001 mol.
Mass of adsorbent, m = 1.2 g or = 1x10? mol.
Mass of adsorbate per gram of adsorbent No. of molecules of acetic acid adsorbed
: ae 1 x 10° x 6.022 x 1074
m 12 8 6.022 x 102° molecules
No. of moles of adsorbate per gram of adsorbent Now, 1 g of charcoal has area = 3.01 x 10? m?
= 25 = 0.078 “. 6.022 x 1079 molecules of acetic acid gets adsorbed on
32 surface area = 3.01 x 10? m?
Volume of2.5 g of O, at 300 K and 0.7 atm “. 1 molecule of acetic acid gets adsorbed on surface area
_ nRT _ 3.01x10?
ig 6.02 10°
0.078 x 82.0 x 300 = 5.0 x 10-9 m?
0.7 _} Example 4.
(R = 82.0 cm? atm K+) 20% surface sites have adsorbed N,. On heating N,gas
= 2741.1 cm?® ts evolved from sites and were collected at 0.001 atm
Volume of2.5 g of O, at 273 K and 1 atm
and 298 K in a container of volume 2.46 cm?. Density
0.078 x 82.0 x273 of surface sites is 6.023 x 1014 cm~ and surface area is
= a ne = 1746.1 cm*
1000cm?. Calculate the number of surface sites occupied
_}) Example 2.
per molecule of Ng. (LI.T' 2005)
50 mL of 1 M oxalic acid (molar mass = 126) ts shaken with
0.6 g of charcoal. The final concentration of the solution Solution : For adsorbed N, on surface sites, p(N,) = 0.001
atm, V = 2.46 cm?®, T = 298 K, R = 82.0 atm cm? K+ molt
after adsorption has been found to be 0.4 M. Calculate
the amount of oxalic acid adsorbed per gram of charcoal. n(N,) = pV = 0.001 x 2.46 = 1.006 x 10-7
Solution: 1 M oxalic acid solution means 1 mole of oxalic RT 82.0 x 298
acid or 126 g present in 1000 mL solution. Molecules of N, adsorbed = 1.006 x 1077 x 6.022 x 1074
*. 50 mL of 1M solution will contain oxalic acid 6.022 x 1016
Total surface sites available No. of sites per cm? x Area
= = x50 =6.3¢
1000 6.023 x 10 x 1000
Concentration of solution after adsorption = 0.4 M 6.023 x 101"
1000 mL of solution contain oxalic acid = 0.4 x 126 = 50.4 g Surface sites on which N, is adsorbed
50 mL of solution will contain oxalic acid 6.023 x10*" x 20
=
50.4
7000 x50 =2.52 ¢
7 100
= 12.046 x 1016
Amount of oxalic acid adsorbed by 0.6 g of charcoal No. of sites adsorbed per molecule of N,
= 6.35 —2.52
12.046 x10'6
>3.78g
Amount of oxalic acid adsorbed per gram of charcoal ~ 6023x108 ~
3.78 L) Example 5.
= — =6.30
0.6 5 The following data were obtained for the adsorption of
_}) Example 3. carbon monoxide gas on 3.0 g of charcoal at O°C and
l atm pressure.
1 g of charcoal adsorbs 100mL of 0.5 M CH,COQG to
Pressure (mm Hg) 200 400
form a monolayer and thereby molarity of acetic acid
is reduced to 0.49 M. Calculate the surface area of Volume of gas adsorbed, x 18.6 aia
the charcoal adsorbed by each molecule of acetic acid. (reduced to STP)
Surface area of charcoal =8.01 x 107m?/g_ (1.1.T.2003) Calculate the values of the constants k and n using
Solution: No. of moles of acetic acid initially present Freundlich adsorption equation.
 MODERN'S abc + OF CHEMISTRY-All

Solution: According to Freundlich adsorption isotherm,

1 or log 1.688 hse 2
n
*. i Epa
iL
or 0.2274 + .0.3010
or log ba log k + = logP nt
m n
Substituting the values of the two given sets, we get n sa = 1.32
0.2274
Substituting the value of n in eqn. (2)
ie3 = ne be n oe 0 .@
1
log 6.2 = logk + log 400
1.32
log aa = loa tow 400 Gp
FL 0.7924 log k + ~ 2.602
Subtracting eqn. (1) from (iz) we get
1.32
0.7924 log & + 1.9712
31.4 1 400
log ——_ = —log — log k — 1.1788 = 2.8212
18.6 n 200
k = antilog (2.8212 ) = 0.0662 cm? g"!

APPLICATIONS OF ADSORPTION
Some of the important applications of adsorption are given below :
1. In gas masks. Activated charcoal or a mixture of adsorbents is generally
used in gas masks to adsorb poisonous and toxic gases from air. These masks
are commonly used by the miners because there are poisonous gases like CO,
CH,, etc. in the atmosphere in the coal mines. Therefore, these masks help to
purify the air for breathing.
2. In dyeing of cloth. Mordants such as alums are used in dyeing of cloth.
They adsorb the dye particles which, otherwise, do not stick to the cloth.
3. In dehumidizers for control of humidity. Silica and aluminium gels
are commonly used to adsorb humidity or moisture from air. This is necessary for
storage of delicate instruments which might otherwise be damaged by moisture.
4. Removal of colouring matter from solutions. Many substances such
as sugar, Juice and vegetable oils are coloured due to the presence of impurities.
They can be decolourised by placing in contact with adsorbents like activated
charcoal or fuller's earth. This method is commonly used in the manufacture
of cane sugar. The coloured sugar solution is treated with animal charcoal or
activated charcoal.
5. Heterogeneous catalysis. The phenomenon of adsorption is useful in the
heterogeneous catalysis. Adsorption of reactants on the solid surface of catalysts
increases the rate of reaction. The metals such as Fe, Ni, Pt, Pd, etc. are used
in the manufacturing process. Manufacture of ammonia using iron as catalyst
(Haber process), manufacture of sulphuric acid by Contact process and use
of finely divided nickel in the hydrogenation of oils are excellent examples of
heterogeneous catalysis. Its use is based upon the phenomenon of adsorption.
6. In ion-exchange resins. The organic polymers containing groups like
— COOH, - SO,H and — NH,, etc. possess the property of selective adsorption of
ions from solutions. These are quite useful in the softening of water.
7. In adsorption indicators. Many adsorption indicators are being used
in volumetric analysis e.g., dyes such as eosin and fluorescein are used as
adsorption indicators. In these methods, the dyes are adsorbed on the surfaces
of certain precipitates (such as silver halides) which give characteristic colour
at the end point.
8. In qualitative analysis. Certain qualitative tests such as the lake test
for the confirmation of Al** ions are based upon adsorption i.e., Al (OH), has the
capacity to adsorb the colour of blue litmus from the solution.
9. Production of high vacuum. The adsorption of air in liquid air helps to
create a high vacuum in a vessel. This process is used in high vacuum instruments
SURFACE CHEMISTRY

as Dewar flask for storage of liquid air or liquid hydrogen. The remaining traces
of air can be adsorbed by charcoal from the vessel evacuated by a vacuum pump
to give a very high vacuum.
10. Separation of inert gases. Due to the difference in degree of adsorption
of gases by charcoal, a mixture of noble gases can be separated by adsorption
on coconut charcoal at different temperatures.
11. In froth floatation process. A low grade sulphide ore is concentrated
by separating it from silica and other earthly matter by adsorption using pine
oil and frothing agent. This has been discussed in Unit 6.
12. In curing diseases. A number of drugs are used to kill the germs by
getting adsorbed on them.
18. Chromatographic analysis. The chromatographic technique for
purification used in analytical and industrial fields is based on the phenomenon
of adsorption.
CATALYSIS
There are many substances which increase the speed of reactions without
being used up in the reaction. For example, you must have learnt that when
potassium chlorate, (KCI]O,) is heated strongly at 653-873 K, it decomposes
very slowly as

2KC1O, ———> 2KCl + 30,

Potassium
chlorate

However, when a little of manganese dioxide (MnO,) is added, the

decomposition occurs considerably at lower temperature range of 473-633 K
and also at much faster rate. It is interesting to note that the added manganese
dioxide remains unchanged with respect to its mass and composition. In a
similar way, the rates of a number of chemical reactions can be increased by the
presence of a foreign substance. Berzelius (in 1835) was the first scientist who
made systematic study of the effect of various foreign substances on the rates of
chemical reactions. He suggested the term catalyst for such substances. Thus,
a substance which alters the rate of a chemical reaction without
itself undergoing any change in mass and chemical composition at
the end of the reaction is called a catalyst.
The phenomenon of increasing the rate of reaction by the use of catalyst is
called catalysis. The catalysts themselves remain chemically and quantitatively
unchanged after the reaction. Since catalysts are not consumed in the reaction,
very small non-stoichiometric quantities are generally required. The catalysts
play very important role in a number of industrial processes. Catalysts are very
essential for our existence. We cannot deny the fact that nature is the master
designer and user of catalysts. Living cells contain thousands of different kinds
of proteins called enzymes which act as catalysts. Every organism depends upon
enzymes (catalysts) to sustain life.
POSITIVE AND NEGATIVE CATALYSIS
It may be noted that a catalyst may increase or decrease the speed of a
reaction.
If a catalyst increases the rate of a chemical reaction, it is called a positive
catalyst and the phenomenon is called positive catalysis.
On the other hand, ifa catalyst decreases (retards) the speed of a reaction, it
is called a negative catalyst and the phenomenon is called negative catalysis.
For example, oxidation of SO, to SO, in the presence of V,O, (Contact
process) is an example of positive catalysis. However, the decomposition of
HO, in the presence of acetanilide or phosphoric acid gets retarded and is an
example of negative catalysis. However, the term catalyst used as such implies
positive catalyst.
 MODERN'S abc + OF CHEMISTRY-All

Function of a Catalyst.
Although there is no universal principle behind the action of
E, of uncatalysed | Catalysts, but in general, a catalyst provides an entirely new path
Es for for the reaction in which the reactants are convertedto the products
catalysed quickly. We have learnt that a chemical reaction takes place by a
reaction reaction path, first converted to activated state and then finally to the
products. It is believed that a catalyst forms a new activated complex
of lower potential energy. This means that thecatalyst provides a
new pathway of lower activation energy. Consequently, the fraction
Reactants of the total number of collisions possessing lower activation energy is
increased and hence, the rate of reaction also increases. Fig. 11 gives an
energy diagram which depicts the effect of a catalyst on the activation
energy. The solid lines show the path for uncatalysed reaction and the
Products dotted line shows the path adopted by catalysed reaction.

Reaction path ——> The following points should be kept in mind regarding the function
of a catalyst :
Fig. 11. Comparison of activation energies of a (1) A catalyst may undergo intermediate physical changes and it
catalysed and an uncatalysed reaction.
may even form temporary chemical bonds with the reactants but it is
recovered unchanged in original form at the end of the reaction.
(it) Although a catalyst speeds up the reaction, but it does not shift the position
REMEMBER of equilibrium. This is due to the fact that the presence of a catalyst reduces the
It may be noted that: height of barrier by providing an alternative path for the reaction and lowers
e positive catalyst lowers the activation energy. However, the lowering in activation energy is to the same
the activation energy of the extent for the forward as well as for the backward reaction.
reaction and
As a result, the increase in the rate of the forward and backward reactions
e negative catalyst raises
is same and hence, the position of equilibrium remains unaltered. However, the
the activation energy of the
equilibrium is attained earlier.
reaction.
(iit) Catalysts are highly specific in nature. A catalyst which can catalyse one
reaction may have no effect on another reaction even if that reaction is very similar.
(iv) The catalyst does not change A E of the reaction. This is clear that the
addition of a catalyst does not change the energies of reactants (E_.) and products
(E,,) so that AE (E, - E,) remains same.
(v) The catalyst does not change thermodynamic parameters such as change
in internal energy (AU), enthalpy (AH), entropy (AS) or Gibbs free energy (AG)
for a reaction.
Promoters and Poisons
Promoters are substances that enhance the activity of the catalyst. For
example, in Haber's process for the manufacture of ammonia, molybdenum is
used as promoter for iron, which acts as a catalyst.
Fe (catalyst)
N, (g) = 3H, (g) Mo (promoter) 2NH, (g)

The substances which decrease the activity of the catalyst are called catalytic
poisons. For example, certain substances like CO, arsenic, etc. if present act
as poisons because they lower the activity of the catalyst.
Classification of Catalysts
The catalysts may be of two main types :
1. Homogeneous catalysts
2. Heterogeneous catalysts
1. Homogeneous catalysts
When the catalyst is present in the same phase as the reactants, it is called
homogeneous catalyst and the process is called homogeneous catalysis.
Such type of reactions are called homogeneous catalytic reactions.
SURFACE CHEMISTRY

For example,
(1) In lead chamber process, SO, is oxidised to SO, in the presence of nitric
oxide as catalyst :

280,
(g) + 0,(g) ———“5
NO
280, @)
The reactants (sulphur dioxide and oxygen) and the catalyst (nitric oxide) all
are in the same phase.
(iz) Catalytic decomposition of ozone in the presence of NO or Cl atoms as
catalyst in the gas phase :
CligVNO(g)
O.(g) + O&) 20, (g)
(iit) Decomposition of hydrogen peroxide in the presence of iodide ion as
catalyst :
r
2H,0, — > 2H,O+0,
Hydrogen peroxide

(1v) Carbon monoxide is oxidised by O, in the presence of nitric oxide (NO)

as catalyst :

2CO (g) + O, (g) 2CO, (g)

NO (gz)

(v) Hydrolysis of an ester is catalysed by the presence of an acid :

O O
| | H* (aq) |
R—C—OR() +H,O@) ——“> R—C— OH) +R'OHW
Ester Carboxylic acid Alcohol

where R and R' are alkyl groups.

H'(a
e.g., CH,COOC,H, (1) + H,O (2) —— CH,COOH (/) + C,H.OH (/)
Ethyl acetate

(vi) Hydrolysis of sucrose is catalysed by the presence of dil. HCl or H,SO,.

H* (ag)
or H,,0 11 (Z) + H, O (Z) Fe CA, Ue (aq) + C,H je (aq)

“Bence (zlucose Fructose

(vit) Preparation of diethyl ether from ethyl alcohol using conc. H,SO, at
413 K. "

2CH,CH,OH () —“e=2—*>CH,CH,OCH,CH, (J) + H,0 ()

Ethyl alcohol Diethyl ether
In all these reactions, the reactants and the catalysts are in the same phase.
Mechanism of homogeneous catalytic reactions
These reactions can be explained on the basis of intermediate compound
formation. According to this theory, the catalyst combines with one of the
reactants to form an intermediate. Intermediate compound being unstable either
decomposes or combines with the other reactant to form the product and the
catalyst is regenerated. For example, the combination of SO, and O, to form SO, is
a slow process. However, in the presence of NO (catalyst) the reaction becomes fast.
NO(g)
2SO,
(g) + O,(g¢) ——_ _2S0, (g)
It is believed that in this reaction nitric oxide combines with one of the
reactants to form intermediate compound (NO,). This intermediate (NO,)
combines readily with SO, to form SO, and the catalyst NO is regenerated
in the last step :
(i) 2NO (g) +0,(¢) ——> 2NO,(g) (fast)
Catalyst Intermediate
 MODERN'S abc + OF CHEMISTRY-All

(ii) NO, (g) + SO, (g) ——} 50, () - NO (g) (fast)

Regenerated catalyst

and 250, (g) + O,(g) a,

———9 280, (g) (fast)
(a) Similarly, decomposition of ozone in the presence of NO takes place as :
NO (g) + O, (g) —— NO, (g) + O, (g)
NO, (g) + O (g) — > NOg)+0,@)
(6) The decomposition of H,O, takes place through the formation of
intermediate IO- (hypoiodite ion) as :
(i) HO, +1 — > (=e,
Intermediate

(ii) 10°-+H,O, — A H,O+¥0,+5

2. Heterogeneous catalysts
When the catalyst is in different phase than the reactants, it is called
heterogeneous catalyst and the process is called heterogeneous catalysis.
Such reactions are called heterogeneous catalytic reactions.
In heterogeneous catalysis, catalyst is generally a solid and the reactants
are generally gases. Sometimes, liquid reactants are also used. This is also
REMEMBER known as surface catalysis because the reaction starts at the surface of the
e Homogeneous catalysis: solid catalyst. These catalysts have very large surface area of the order of 1 to
500 m2 per gram for contact. It may be noted that many reactions which occur
Reactants and catalyst are in
on a metal surface such as decomposition of HI on gold or the decomposition of
the same phase.
N,O on platinum are zero order reactions. This is because, the rate determining
e Heterogeneous catalysis:
step occurs on the surface itself. Thus, despite an enormous surface area, once
Reactants and catalyst are in the reactant gas molecules cover the surface, the rate does not increase on
different phases. increasing the reactant concentrations.
These are very important reactions in industries. Some other examples are:
(1) Manufacture of NH, from H, and N, by Haber's process using finely
divided iron catalyst.

2NH, (g)
Fe (s)
3H, (g) + N, @)
Here reactants are in the gaseous state while the catalyst is in the solid state.
(ii) Methanol is prepared from CO and H, by using a mixture of copper,
zine oxide as catalyst and Cr,O, as promoter :
Cu, Z0Cr,0, (s)
CO (g) + 2H, (g) CH,OH (i)
(vit) Manufacture of SO, from SO, in the Contact process using platinised
asbestos or V,O.- as catalyst :
PtorV,0s(9) og O, (g)
> Ziegler-Natta catalyst 250, (g) + O, (g)
[Ti-R, Al, where RA)=>CH, or (iv) Dehydrogenation of ethanol by using nickel catalyst :
C,H,] is a heterogeneous catalyst Ni («
used in polymerisation of olefins. CH,CH,OH (i) x, CH,CHO (/) + H, (g)
> Wilkinson's catalyst (v) Oxidation of ammonia into nitric oxide in the presence of platinum
[RhCl (PPh,)] is a heterogeneous gauze in Ostwald’s process :
Pt (3) = e
catalyst used in the hydrogenation 4NH, (g) + 50, (g) : 4NO(g) + 6H,O (2)
of alkenes.
> Lindlar's catalyst (vi) Hydrogenation of vegetable oils in the presence of finely divided nickel
(Pd-BaSO,) is a heterogeneous as catalyst is also an example of heterogeneous catalytic reaction because one
catalyst. It is usually poisoned of the reactants is in liquid state and the other in gaseous state, while the
by traces of quinoline. catalyst is in the solid state.
Vegetable oils (J) +H, (g) ——~ Vegetable ghee (s)
SURFACE CHEMISTRY 5/17 —

Mechanism of heterogeneous catalytic reactions

Adsorption Theory
The mehanism of heterogeneous catalysis was explained on the basis of
a theory known as adsorption theory. According to this theory, the surface
of the catalyst unlike the inner part of the bulk has free valencies which
provide sites for chemical forces of attraction. The reactants in the gaseous
state or in solution are adsorbed on the surface of the solid catalyst. As the
reactant molecules are adsorbed, its bonds are weakened and the reaction
can proceed quickly because the bonds are more quickly broken. For example,
the most important step in the Haber process for the synthesis of ammonia
is the adsorption of N, molecules on iron and the weakening of the strong
N=N triple bond. Since the adsorption is an exothermic process, the heat
of adsorption is utilised in weakening the bonds in the reactants and hence
enhancing the rate of reaction. The increase in concentration of reactants on
the surface increases the rate of reaction.
The catalytic action can also be explained in terms of intermediate compound
formation, which has already been discussed.
Modern adsorption theory
The modern adsorption theory is a combination of old adsorption theory
and intermediate compound formation. The heterogeneous catalysis is regarded
as surface phenomenon in which the catalytic activity is localised on the
surface of the catalyst. The heterogeneous catalysis is a surface phenomenon.
It involves the following steps :
(4) Diffusion of the reactants to the surface of the catalyst.
(it) Adsorption of the molecules of the reactant at the active sites.
(zt) Occurrence of the chemical reactions on the surface of the catalyst
through the formation of an intermediate.
(iv) Desorption of product molecules from the surface and thereby making
the surface available again for more reactions to occur.
(v) Diffusion of products away from the surface of the catalyst. This is
shown below :

Adsorption of molecules
of the reactant at the A
A+B active site

. i <_
Reactants / B
Catalyst surface having |Occurrence of chemical
free vacancies reaction on the surface
of catalyst

A—B Desorption of ‘
=e ee
roduct molecules
Product . 5
molecules
diffuse away Catalyst recovered Intermediate

Fig. 12. Adsorption theory for mechanism of heterogeneous catalysis.

The role of heterogeneous catalysts can be explained in terms of adsorption

of reactants on the surface of the catalyst. The adsorption helps the reaction
in the following ways :
1. Adsorption increases the concentration of reactants on the surface of
the catalyst. Due to increased concentration of the reactants, the reactions
proceed rapidly.
a 5/18 MODERN'S abc + OF CHEMISTRY-All

2. Adsorbed molecules get dissociated to form active species like free radicals
which react faster than molecules.
3. The adsorbed molecules are not free to move about and, therefore, they
collide with other molecules on the surface.
4. The heat of adsorption evolved acts as energy of activation for the reaction
(chemisorption).
One of the most important examples of heterogeneous catalysis is the addition of H, to carbon-carbon double bonds
(C = C) of organic compounds to form C—C bonds. This is known as catalytic hydrogenation reaction and is
frequently used in petroleum, plastics and food industries. For example, conversion of vegetable oil into margarine.
The simplest hydrogenation reaction is conversion of ethylene into ethane as :
CH, = CH, (g) + H,@) —— CH, — CH, @)
Ethene Ethane
In the absence of catalyst, the reaction occurs very slowly. However, at high pressure of hydrogen and in the
presence of finely divided nickel, palladium or platinum (as catalyst), the reaction becomes rapid even at ordinary
temperature. The catalysed reaction is believed to proceed through the following consecutive steps as shown in
Fig. 13.

(H)
rs nee @
MHEESEtEtSS
(a) H, and C,H, adsord on Pt surface
petrtns
iiss
(b) H, splite up into 2H forming Pt-H bonds

H a“ = |

Ha
[Qe
W
o
i
S
e
ys NOS
(c) One H bonds with C5H, to form C5H, (d) Another C-H bond forms and
C,H, leaves the surface

Fig. 13.
(a) H, and ethene molecules approach the metal surface and get adsorbed to the metal surface.
(6) H, molecules get split up into H atoms which get chemically bound to the platinum catalyst 7.e., metal
atoms forming M—H bonds as :
H—H (g) + 2M (s) —— 2M—H
Catalyst
This step is the rate determining step in the overall process.
(c) The H atoms move over the surface of platinum metal and one of them combine with ethene molecule to
form C,H. which remain attached to the platinum surface.
(dq) Finally another H atom moves over the surface and combines with C,H, forming C,H, molecule, which
leaves the surface.
The reaction occurs as :
C,H,(g) + 2M—H — C,H, (g) + 2M (s)

The above theories explain why the catalysts remain unchanged in mass and chemical composition after the reaction
and is effective even in small quantities. However, the theories donot explain the action of catalytic promoters and
catalytic poisons.
SURFACE CHEMISTRY 5/19 —

Important Features of solid catalysts

The solid catalysts may be metals, alloys, metal oxides or metal sulphides.
The effectiveness of a catalyst depends upon the two important aspects —
activity and selectivity.
(1) Activity of a catalyst
The ability of a catalyst to increase the rate of a chemical reaction is called
activity. The activity of a catalyst depends upon the strength of chemisorption
to a large extent. The reactant must adsorb reasonably strongly for the catalyst
to be active but must not adsorb so strongly that they become immobilise and
the other reactants do not get space on the catalyst surface for adsorption. It
has been observed that for hydrogenation, the catalytic activity increases as
we go from group 5 metals to group 11 metals with maximum activity shown
by elements of group 7—9 the periodic table.
A catalyst may accelerate a reaction to as high as 101 times. For example,
the mixture of H, and O, can be stored for any period but in the presence of
platinum, the reaction occurs with explosive violence.
Pt
2H, (g) + 0, @) —— 2H,0 (g)
(11) Selectivity of a catalyst
The ability of the catalyst to direct a reaction to give a particular product
is called selectivity. For example, different catalysts give different products
for the reaction between CO and H, as shown below :
Wi

G) CO@) + H, @ ~~ CH, (g) + H,O @)

u, ZnO
(iz) CO (g) + 2H, (g) oO CH,OH (g) Catalytic converter for an Automobile
fa The catalytic converter in the exhaust systems
(ii) CO (g)+H,(g) ——— HCHO @) of cars, which converts polluting exhaust gases
Similarly, n-heptane in the presence of Pt catalyst gives | Ito non-toxic gases contains a heterogeneous
selectively toluene. catalyst. Mixtures of transition metals and their
nC_.H > CHCH oxides embedded in inert supports act as catalyst.
He oe Tolaene 3 When the gases are passed through the catalyst
| . 4 bed, carbon monoxide (CO) and unburnt petrol are
Propylene (CH,CH = CH,) reacts with O, in the Depence oxidised to carbon dioxide and water while nitric
of bismuth molybdate catalyst to selectively give acrolein oxide (NO) is reduced to N, as ;
(CH, = CHCHO). | ,
Similarly, acetylene on reaction with H, in the presence 2CO + O, Catalyst. 909
of Pt catalyst gives ethane while in the presence of Lindlar's :
catalyst (palladium and BaSO, poisoned with quinoline or Catalyst
sulphur) gives ethylene. Hydrocarbons = ze Coo Ho
P (Unburnt petrol) =

H_C=C_H+H, cre Ethane oe Catalyst. ea

Acetylene Lindlar’s Air ee Slt bed

catalyst
CH,=CH,
Ethylene
\ LF
4
Thus, the action of catalyst is highly selective. A given Seus— —e P PDD. iy ee
catalyst can act as catalyst only in a particular reaction and |
not in all reactions. In other words, a substance which acts as |
a catalyst in one reaction may fail to catalyse other reaction. Catalytic converter
Thus, catalyst is highly selective in nature.
ENZYME CATALYSTS
Large number of organic reactions are taking place in the body of animals
and plants to maintain the life processes. These reactions are generally very
slow and are remarkably catalysed by complex nitrogenous organic compounds
known as enzymes. These are also called biological catalysts or biochemical
eatalysts and are produced by the living cells in plants and animals.
Thus, enzymes are biological catalysts produced by living cells which
catalyze the biochemical reactions in living organisms.
Chemically all enzymes are proteins with molar mass ranging from 15,000
to 1,000,000 g/mol. Without enzymes, the living processes would be very slow
a 5/20 MODERN'S abc + OF CHEMISTRY-All

to sustain life. For example, without the presence of enzymes in our digestive
tract, it would take about 50 years to digest a single meal . About 3000 enzymes
have been identified. The enzymes differ from other types of catalysts in being
highly selective and specific.
Some common examples of enzyme catalysis reactions are :
(4) Normal conversion of glucose into ethanol by zymase (enzyme) present
in yeast.
C,H,,0, (aq) —_———>._ 2C, HOH (aq) + 2CO,
Aymase

Glucose Ethanol
(it) Hydrolysis of urea (NH,CONH,) by urease (enzyme) present in soyabean.
O
|
H,N—C—NH, + H,0 —““-. 2NnH, + CO,
Urea
(iit) Hydrolysis of starch into maltose by diastase (enzyme) present In malt.
2(C,H,,0,), +nH,O () —“"*_, n€,,H,,0,,
Starch Maltose
(iv) Conversion of maltose into glucose by maltase (enzyme) present in yeast.
Maltase
C,,H5,0;; t H,O , 2C,H,,0,
Maltose Glucose
(v) Hydrolysis of sugar into glucose and fructose by invertase (enzyme)
resent in yeast.
P y Invertase
C,5H,.0;, + HO C,H,.0, + C,H,,0,
Sucrose Glucose Fructose
(sugar)

(vi) Oxidation of alcohol to acetic acid by myecoderma aceti present in

old vinegar.

C,H,OH + 0,—““""_, CH,COOH + H,0

(vit) Decomposition of urea into ammonia and carbon dioxide by urease
enzyme.
NH,CONH, () + H,O () ————> 2NH, (g) + CO, (@
Ur é

(viit) In stomach, the pepsin enzyme converts proteins into peptides

whereas in intestine, the pancreatic trypsin converts proteins into amino
acids by hydrolysis.
(ix) Milk is converted into curd by the enzymatic reaction brought about
: - by lacto bacilli enzyme present in curd. Some common examples of enzymes
'R U Curious... % and enzymatic reactions are given in Table 1.
}0 Food in our body is digested Table 1. Some common enzymatic reactions.

Thedige
The digestion of food in our body
takes place through reactions
Enzyme
gee
Invertase Yeast
Enzymatic reation
sucrose
ym .
— Glucose + Fructose
catalysed by enzymes present Diastase Malt Starch —> Maltose
in our body. These biochemical Maltase Yeast Maltose — Glucose + Glucose
reactions are highly efficient and Zymase Yeast Glucose —> Ethyl alcohol + CO,
specific. These enzymes speed Urease Soyabean Urea — > CO, + NH,
up the rate of reaction by fac- Mycoderma Old vinegar Ethyl alcohol — Acetic acid
tors as high as 107°. Moreover, aceti .
extremely small quantities of Pepsin Stomach Proteins —> Amino acid
enzyme catalysts are required. Lactase Dairy product | Lactose — > Glucose + Galactose
Thus neti of food ‘2 very Amylase Starch Starch — > n Glucose
fast. Without the presence of Lacto bacilli | Curd Milk eee ear
enzyme in our digestive system,| Characteristics of Enzyme Catalysts
it would take about 50 years to The important characteristics of enzyme catalysts are :
digest a single meal. 1. High efficiency. Enzyme catalysts increase the speed of reactions
by 10° to 107" times as compared to the uncatalysed reactions. The enzymes
SURFACE CHEMISTRY

are highly efficient and one molecule of enzyme may transform one million
molecules of the reactant per minute.
2. Extremely small quantities. Extremely small quantities of enzyme
catalysts—as small as millionth of a mole—can increase the rate of reaction
byfactors of 10? to 10°. For example, the enzyme renin which is used for
coagulation of milk to make cheese coagulates over a million times its own
weight of milk protein.
3. Specificity. The enzyme catalysts are highly specific in nature. Almost
every biochemical reaction 1s controlled by its own specific enzymes. For example
the enzyme, urease catalyses the hydrolysis of urea and none of the several
thousand other enzymes present in the cell catalyse that reaction :
U
NH,CONH, + H,O —————> 2NH, + 2CO,
Urea

On the other hand, the same enzyme urease does not catalyse the hydrolysis
of N-methylurea, which is similar in constitution to urea.
CH,NHCONH, + H,O ————> No action
N-Methylurea
The enzyme invertase hydrolyses sucrose to glucose and fructose but does not
hydrolyse maltose to glucose though both are hydrolytic reactions. But maltase
catalyses the hydrolysis of maltose. No other enzyme can catalyse its hydrolysis.
Invertase
C,,H,,0,, + H,O ————— C,H,,,0,
‘G13 ~6
+ C,H,,0,
Sucrose (slucose Fructose

C,,H,,0,,
13°92" 11 + HO —~*"5 20,H,,0
6ti2™6
Maltose Glucose
4, Optimum temperature. The rate of an enzyme reaction becomes
maximum at a definite temperature known as the optimum temperature.
On either side of this temperature, the enzyme activity decreases. For example,
the enzyme catalysts are active at moderate temperature 298-310 K and the
human body temperature (310 K) is suited for enzyme catalysed reactions.
5. Optimum pH. The rate of an enzyme catalysed reaction is maximum
at a particular pH called optimum pH. This is between pH values of 5-7.
6. Control of activity of enzymes. The action of enzyme catalytic
reactions are controlled by various mechanisms and are inhibited by various
organic and inorganic molecules.
7. Regulated activity. The activity of most enzyme catalysts is closely regulated.
8. Increasing activity in the presence of activators or coenzymes.
Catalytic activity of enzymes is greatly enhanced by the presence of activators
or coenzymes. Activators are metal ions (Na*, Mn**, Co**, Cu* etc.) which
get weakly bonded to enzyme molecules and therefore, promote their catalytic
action. In some cases, most active enzymes are associated with some non-
protein components (vitamins) required for their activity. These are generally
metal ions or small organic molecules and are collectively called coenzymes.
The common metal ions are Zn, Mg, Mn, Fe, Cu, Co, Mo, K and Na.
9. Influence of inhibitors and poisons. Like ordinary catalysts, in some
cases the enzyme activity can be reduced or inhibited by the presence of certain
compounds known as enzyme inhibitors or poisons. These inhibitors or
poisons interact with the active functional groups on the enzyme surface and
often reduce or completely destroy the catalytic activity of the enzymes. The
use of many drugs is related to their action as enzyme inhibitors in the body.
Mechanism of Enzyme Catalysed Reactions
Biochemiusts are trying to explain the exact molecular basis of enzyme catalysis.
The various steps involved in the enzyme catalysed reaction are given below:
Step. 1. Binding ofthe enzyme (EL) to substrate (S)to form enzyme-substrate complex.
E+S = = ES (fast, reversible)
ES is called the enzyme-substrate complex.
Step. 2. Dissociation of enzyme-substrate complex to form the products.
ES —> EP —> E + P
Enzyme- Enzyme- Enzyme — Product
substrate product (slow and
complex association rate determining)
 MODERN'S abc + OF CHEMISTRY-All

The second step is slow and rate determining. The rate of enzyme catalysed
reaction depends upon the concentration of ES. It changes from first order to
zero order as the concentration of substrate is increased. The catalytic property
of enzymes is present at certain specific regions on their surfaces. These are
called active sites or catalytic sites. The active sites have characteristic shape
and possess active groups such as — NH,, — COOH, — OH, — SH, etc. These
molecules of the reactants (substrate) whith have complementary shapes fit
suitably into these active sites. Specific binding accounts for the high specificity
of these enzyme reactions. The specificity of fitting together of the substrate
structure and the enzyme structure is explained on the basis of two models :
1. Lock-and-key model.
2. Induced fit model.
According to lock and key model, the substrate, the molecule on which the
enzyme acts, fits into the slot as key fits into a lock. The shape of the active
site of any given enzyme is such that only a specific substrate can fit into it,
in the same way as one key can open a particular lock.
This is shown in Fig. 14.

_[E—S]
ee
site

/ snsaaelaa
—————_>

Enzyme Substrate Sawn Subse Enzyme-Product Enzyme Product

Catalyst (Reactants) Complex Association catalyst
(Like a lock) (Like a key)
Fig. 14, Enzyme-substrate binding.

Modern X-ray crystallographic and spectroscopic methods have shown that

in many cases unlike an ordinary lock, the protein molecule (enzyme) slightly
changes the shape when the substrate lands at the active site. The ability of
the enzyme to undergo the correct distortion also determines whether the 'key'
will fit or not. This refinement of the original lock-and-key model is known as
induced fit model. According to this model, the substrate induces the active
The binding site of the enzyme site to adopt a perfect fit rather than a rigidly shaped lock and key. Therefore,
is such that it can bind only one we can picture this model as hand in a glove, in which the glove (active site)
substrate. The particular shape does not attain its functional shape until the hand (substrate) moves into place.
and the nature and location of the Applications of Enzymes
atoms at the binding site account 1. Industrial applications. The enzymes are widely used in industrial
forthe extraordinary specificity processes. For example, enzymes are used
of the enzyme. (4) in breweries for the manufacture of beer, wine, etc. by the fermentation
of carbohydrates.
(ii) in food processing industries for preparing sweet syrup, etc.
(iii) in the production of cheese by coagulation of milk.
2. Enzyme deficiencies and prevention of diseases. The deficiencies of
enzyme in living system cause many diseases. Some of these are given below :
(1) Thedeficiency of phenylalanine hydroxylase enzyme causes a congenital
disease called phenylketone urea. This disease causes accumulation of
compounds in the body which results into severe brain damage and retardation
in children. This can be prevented by a diet with low phenylalanine content.
(it) Deficiency of enzyme tyrosinase causes albinism.
These diseases can be prevented by the supply of enzymes through diet.
3. Curing diseases. Certain enzymes are also useful for treating heart
diseases. An enzyme streptokinase is used to dissolve blood clot.
SURFACE CHEMISTRY

SHAPE SELECTIVE CATALYSIS BY ZEOLITES

The catalytic reaction which depends upon the pore structure of the catalyst
and the size of the reactant and product molecules is called shape selective
eatalysis. Zeolites are good shape selective catalysts because of their honey
comb like structures.
In recent years, one of the main advances in industrial chemistry have
been the development of catalysts based on zeolites. These are microporous > Catalytic poisons. Certain
aluminosilicates of the general formula M,,, |(AlO,), (5i0,)y]m H,O. These are substances like arsenic, CO, etc.
three dimensional networks of silicates in which some silicon atoms are replaced if present lower the activity of
by aluminium atoms. These are porous and have cavities of molecular dimensions. the catalyst. These are called
The internal structure of a zeolite is a network of tunnels and cavities. Therefore, eatalytic poisons.
zeolites have an enormous surface area which is largely on the inside of the solid. > Catalytic promoters. Certain
The zeolites can permit the entry and exit of molecules of a certain size into the substances if present along
active regions within the holes. These are used in petrochemical industries for with the catalyst increase the
cracking of hydrocarbons and isomerization. The reactions in zeolites depend activity of the catalyst. These
upon the size of the cavities (cages) and pores (tunnels) present in them. The are called catalytic promoters.
most remarkable feature of zeolite catalysis is the shape selectivity. Therefore, For example, molybdenum acts
the selectivity of catalyst depends on the pores structure. It has been observed as a promoter for iron catalyst
that the pore size in zeolites generally varies between 260 pm and 740 pm. in the manufacture of ammonia
Depending upon the size of the molecules of reactants and products and the by Haber's process.
sizes of the pores of zeolites, reactions proceed in specific manner.
> Autocatalysis. During a
For example, zeolite catalyst known as ZSM-5 converts alcohols to gasoline.
chemical reaction, if one of
The alcohol is dehydrated in the cavities and the hydrocarbons are formed.
the products formed acts as
The shape-selectivity in the reactions can be judged from the conversion of
a catalyst, the phenomenon
methanol and 1-heptanol to hydrocarbon mixtures.
is called autocatalysis. For
Product Starting with Starting with example, during the titration
CH,OH (%) n—-C,H, -OH(%) of oxalic acid with KMnO,
Methane solution in the presence of dil.
Ethane H,SO,, the colour of KMnO,
1so-butane solution in the presence of dil.
n-butane H,SO,, the colour of KMnO,
iso-pentane fades first slowly and then
Benzene faster due to the formation of
Toluene Mn?* ions which act as auto
Xylene catalyst.
The composition of the product mixture depends on the ability of the pores 2KMnO, + 3H,SO, + 5H,C,0O,
to accommodate linear and iso-alkanes as well as benzene derivatives. Oxalic acid
Catalysts in industry =e 2
To increase the rates of reactions and to get maximum yields of products 8H,O + 10CO,
In Minimum time, catalysts are used in the chemical industries. Some of the
important technical catalytic processes are given below in Table 2.
Table 2. Some important industrial catalytic processes.
Process Catalyst Conditions Reaction

Haber's process for Finely divided iron 200 bar N, (g) + 3H, (g) Fe (catalyst)
Mo (promoter)
2NH, (g)
the manufacture of (catalyst), molybdenum 723-773 K 200 bar, 723-773 EK
ammonia as promoter temperature

Ostwald's process for Platinised 4NH, (g) + 50, (g) Ptasbestos, 4NO (g) + 6H,O ©)
the manufacture of asbestos 573K
2NO (g) + O, (g) ———> 2N0, (g)
nitric acid ANO,(g) + 2H,O (2) + O, (g) —~ 4HNO, (aq)

Contact process for Platinised 673-723 K 280, (g) + O, (g) =~

—
Pt asbestos
280, (g)
the manufacture of asbestos or V0,
sulphuric acid vanadium pentoxide
(V,0,) reiOi fre a1gbs |4g etal speliatyh
Oleum
H,S,07
ce a @
+ H,O (1) —> 2H,SO, (aq)
 MODERN'S abc + OF CHEMISTRY-All

. How is the adsorption of a gas related to its critical temperature ?

. Higher is the critical temperature of a gas, greater is the ease of liquefaction of gas i.e., larger are the van der Waals
forces of attraction. Therefore, greater is the adsorption.
. Compare the heat of adsorption for physical and chemical adsorption.
. The heat of adsorption for chemical adsorption is high (of the order of 200—400 kJ/mol) while the heat of adsorption
for physical adsorption is low (of the order of 20—40 kJ/mol).
. Incase of chemisorption, why adsorption first increases and then decreases with temperature?
. Chemisorption involves activation energy. The initial increase in chemisorption is due to the fact the heat supplied
acts as activation energy and more and more molecules of adsorbate gain energy and possess energy greater than
activation energy. Therefore, adsorption increases with increase in temperature. Further increase will increase the
energy of the molecules absorbed and will increase the rate of desorption. Therefore, extent of adsorption decreases.
. Give reason why a finely divided substance is more effective as an adsorbent ?
. This is because a finely divided substance has larger surface area and, hence, more adsorption occurs.
. A small amount of silica gel and a small amount of anhydrous calcium chloride are placed
separately in two corners of a vessel containing water vapour. What phenomena will occur ?
. Adsorption of water will occur on silica gel and absorption of water will occur on calcium chloride.
- Which will be adsorbed more readily on the surface of charcoal and why : NH, or CO, ?
(A.L.S.B. 2004)
. NH, has higher critical temperature than CO, and therefore, it is more easily liquefiable. Hence, NH, has greater
intermolecular forces of attraction and will be adsorbed more readily.
. What form Freundlich adsorption isotherm equation take at high pressure ?
x
= K, i.e., it becomes independent of pressure at constant temperature.

. Howdothe size of particles of adsorbent, pressure of gas and prevailing temperature influence
the extent of adsorption ? (A.LS.B. 2004)
. (t) Smaller the size of the particles of adsorbent, greater is the surface area and hence greater is the adsorption.
(i) At constant temperature, adsorption first increases with increase of pressure and then attains equilibrium at
high pressure and becomes constant.
(zit) In physical adsorption, it decreases with increase of temperature but in chemisorption, it first increases
becomes maximum and then decreases.
. Consider the adsorption isotherms and interpret the variation in the extent of adsorption (x/m) when
(a)(i) Temperature increases at constant pressure.
(ii) Pressure increases at constant temperature.
(b) Name the catalyst and the promoter used in Haber's process for manufacture of
ammonia. (C.B.S.E. Sample Paper 2007)
. (a) (i) extent ofadsorption (x«/m) increases with decrease in temperature at constant pressure.
(it) extent of adsorption (x/nz) increases with increase in pressure at constant temperature.
(6) In Haber's process : , 195 K
Catalyst : finely divided iron m 244 K
Promoter : molybdenum f 273 K
Q. 10. Heat of adsorption is greater for chemisorption than physisorption. Why ?
(CL.B.S.E. Sample Paper 2011) - , x

Ans. Chemisorption has larger heat of adsorption than physisorption because chemical bonds are formed between
adsorbent and adsorbate.
Q. 11. Why is silica gel used as a dehumidizer ?
Ans. Silica gel has stronger adsorption tendency for humidity (moisture of the air). Hence, it is used as a dehumidizer.
Q.12. Name the enzyme which converts :
(1) Starch into maltose (i1)Glucose into alcohol (1i11)Sucrose into glucose and fructose. (Pb. S.B. 2014)
Ans. (1) Diastase (it) Zymase (iit) Invertase.
Q.13. Write one similarity between physisorption and chemisorption. (D.S.B. 2017, ALLSB. 2017)
Ans. Both are surface phenomena and increase with increase in surface area.
Q.14. Which enzyme is used to convert glucose into ethyl alcohol? (H.P.S.B. 2017)
Ans. Aymase
SURFACE CHEMISTRY

COLLOIDAL STATE
Thomas Graham in 1861 observed that certain solutes such as starch, glue,
gelatin etc. could not pass through the parchment membrane while the ordinary
solutes such as sodium chloride, urea, sugar etc. can easily do so. Graham
called the former solutes as colloids (Greek, Rolla meaning glue) while the
latter were called crystalloids. However, the above classification of solutes into
crystalloids and colloids proved unsatisfactory because a particular substance
would be crystalloid in one solvent and a colloidal in the other. For example
in aqueous solution, NaCl is a crystalloid, while in benzene, it behaves as
colloid. Similarly, soap is a typical colloid in water but it acts as a crystalloid
in alcohol. Further studies of the behaviour of these solutes have shown that
the nature of the substance whether colloid or crystalloid depends upon the
particle size. When the size of the particles is between 10-° m (1 nm) to 10*m
(1000 nm), it behaves like a colloid and in case, it is less than this range, it
gives the characteristics of crystalloid. Thus, colloid is not a substance but
it is a state of a substance which depends upon the molecular size.
Three Types of Solutions
On the basis of the particle size of the substance, solutions may be divided REMEMBER
into three types. These are :
Colloidal state of matter is a state
1. True solutions
in which the size of particles is
2. Suspensions
between 1 to 1000 nm and the
3. Colloidal solutions.
particles can pass through filter
1. True solution is a homogeneous solution which contains small solute
paper but not through vegetable
particles (molecules or ions) dispersed throughout a solvent. For example, the
or animal membrane.
solution of sodium chloride in water. The particle size is less than 1 nm.
The particles of a solute in a true solution are invisible even under microscope
and its particles can pass through ordinary filter paper as well as through
animal membrane.
2. Suspension is a heterogeneous mixture which contains small insoluble
particles. The particle size is more that 1000 nm. For example, dirt particles
in water. The particles of a suspension may not be visible to the naked eye
but are visible under a microscope. The particles of a suspension can neither
pass through an ordinary filter paper nor through animal membrane.
3. Colloidal solution is a heterogeneous solution which contains particles
of intermediate size. For example, milk. The particles of a colloidal solution
have diameters between 1 to 1000 nm. Such particles cannot be normally
seen with a naked eye. However, light reflected by them can be seen under an
ultramicroscope. The particles of a colloidal solution can pass through ordinary
filter paper but not through animal membrane. In a colloid, the dispersed phase
may consist of particles of a single macro molecule (such as synthetic polymer
or protein) or an aggregate of many atoms, molecules or ions.
Colloidal particles have an enormous surface —
area per unit mass. For example, consider a cube
having each side as 1 cm. It has total surface area
of 6 cm? because it has six faces and each face
has area of 1 cm?. Now, if it were divided equally
into 10 cubes, the cubes would be the size of
large colloidal particles and have a total surface
area of 60,000 cm? or 6 m?. This enormous area is
responsible for some special properties of colloids
which will be learnt in this unit.
Thus, colloidal solutions are intermediate
between true solutions and suspensions. In True solution Colloidal solution Suspension

: ea
other words. the size of dispersed particles in
colloidal solutions is more than that of solute
; :

1—1000 nm
particles in a true solution and smaller than that
of a suspension (Fig. 15). | Fig. 15. Three types of solutions.
a 5/26 MODERN'S abc + OF CHEMISTRY-All

The size of different solutions are sometimes expressed in other units also as given below :
Size (diameter) of particles in different units

True solutions Suspensions Relation

10-° m to 10®°m >10%m

1 nm — 1000 nm > 1000 nm 1nm=10°m
10 A— 10000 A > 10000 A 1A=10%m
1000 pm — 10° pm > 10° pm pm = im
The important distinguishing features of the three types of solutions are as follows:

Property Suspension Colloid True

Solution Solution
Nature Heterogeneous Heterogeneous Homogeneous
Particle size > 1000 nm 1 nm —1000 nm <1lnm
(or > 10° m) (or 10°-— 10° m) (or < 10°° m)
Separation by
(1) Ordinary filtration Possible Not possible Not possible
(it) Ultra-filtration Possible Possible Not possible
Setting of particles Settle under gravity Settle only on Do not settle
centrifugation
Visibility Particles visible to Scattering of light by the Particles are
naked eye or under particles is observed under invisible
a microscope. ultra-microscope
Appearance Opaque Generally transparent Transparent
Tyndall effect Shows Shows Does not show
Diffusion of particles Do not diffuse Diffuses slowly Diffuses rapidly
Brownian movement May show Shows Negligible
Note: The terms Ultra-filtration, Tyndall effect and Brownian movement mentioned above will be discussed in the characteristics
of colloids.

PHASES OF COLLOIDS AND THEIR CLASSIFICATION

We have learnt that a colloidal solution is of heterogeneous nature. It
Dispersed : : :
phase (Ag) consists of two phases i.e., a dispersed phase and a dispersion medium. |
(1) Dispersed phase. /f is the component present in small proportion
and is just like a solute in a solution. For example, in the colloidal solution of
silver in water, the former acts as a dispersed phases (Fig. 16).
Dispersion (ii) Dispersion medium. It is generally component present in excess
and is just like a solvent in a solution. In the above example, water acts as a
dispersion medium.
Thus, the particles of the dispersed phase are distributed in the dispersion
Fig. 16. A colloidal solution of silver | medium. Out of solid, liquid and gas, each one can act as a dispersed phase
in water. and dispersion medium leading to eight types of colloidal systems (Table 3).

CLASSIFICATION OF COLLOIDS
The colloids are classified on the basis of the following criteria :
A. Physical state of dispersed phase and dispersion medium.
B. Nature of interactions between dispersed phase and dispersion medium.
C. Type of particles of the dispersed phase.
A. Classification based on the Physical state of the Dispersed phase
and Dispersion medium
Depending upon the physical state of dispersed phase and dispersion medium
whether these are solids, liquids or gases, eight types of colloidal systems are
possible. The examples of the various types of colloids and their typical names
are given in Table 3 ahead. It may be noted that a gas mixed with another
gas forms a homogeneous mixture and therefore, it is not a colloidal system.
SURFACE CHEMISTRY 5/27 =

Table 3. Types of colloidal systems.

Dispersion Dispersion Type of

phase medium colloid

Solid sol Alloys, coloured glasses, gem stones, ruby glass

Sol Paints, cell fluids, starch dispersed in water, gold sol
Aerosol Smoke, dust storm, haze
Gel Jelly, butter, cheese, boot polish, curd
Emulsion Milk, hair cream, emulsified oils, medicines
Aerosol Mist, fog, cloud, insecticide spray
Solid sol Pumice stone, foam rubber
ae
ae
eee Foam Soap leather, froth, whipped cream, soda water

It is clear from Table 3 that many common commercial products and natural
objects are colloids. For example, whipped cream is a colloidal system (foam),
a gas dispersed in a liquid. Out of the different types of colloids, the most
common are sols (solids in liquids), gels (liquids in solids) and emulsions
(liquids in liquids).
Depending upon the nature of the dispersion medium, colloidal solutions
are sometimes given specific names. For example,

Dispersion medium Name of colloidal solution

Water Hydrosols or aquasol

Alcohol Alcosols
Benzene Benzosols
Aur Aerosols @ Competitiou Plus

B. Classification based on Nature of Interaction between Dispersed Nanomaterials are the materials
Phase and Dispersion Medium having at least one dimension
Depending upon the nature of interactions between dispersed phase andthe less than 100 nm. For detail, refer
dispersion medium, the colloidal solutions can be classified into two types as: Competition File, (Page 65).
(4) lyophilic and
(tz) lyophobic sols.
(i) Lyophilie colloids
The colloidal solutions in which the particles of the dispersed phase The word ‘lyophilic’ means liquid
loving.
have a great affinity (or love) for the dispersion medium, are called
lyophilic colloids. The word ‘yophilic’ means liquid loving. These solutions
are easily formed and the lyophilic colloids are reversible in nature. The
reversible nature of the sols is an important characteristic of lyophilic sols.
This means that if the dispersion medium is separated from the dispersed
phase (say by evaporation), the sol can be again formed by simply remixing it
with the dispersion medium. These sols are quite stable and cannot be easily
coagulated. In case water acts as the dispersion medium, the lyophilic colloid.
The common examples of lyophilic colloids are gum, gelatin, starch,
proteins, rubber, etc.
(ii) Lyophobiec colloids
The colloidal solutions in which there is no affinity (or love rather | The word 7yophobic’ means liquid
they have hatred) between particles of the dispersed phase and the _| ating.
dispersion medium are called lyophobic colloids. Such solutions are formed
with difficulty. These sols are readily precipitated (or coagulated) on the addition
of small amounts of electrolytes, by heating or by shaking. Therefore, these
are not stable. Further, once precipitated, they do not form the colloidal sol by
simple addition of dispersion medium. Hence, these are irreversible in nature.
 MODERN'S abc + OF CHEMISTRY-All

These sols need some stabilising agents for their preservation. In case, the
dispersion medium is water, the lyophobic sol is called hydrophobic colloid.
For example, the solutions of metals like Ag and Au, hydroxides like Al(OH),,
Fe(OH),, metal sulphides like As,S,, etc.
Differences between Lyophilic and Lyophobic Colloids
The main differences between lyophilic and lyophobic colloids are summed
below :
Table 4. Distinction between lyophilic and lyophobic colloids.

Property Lyophilic colloids Lyophobic colloids

. Ease of preparation These are easily formed by direct These are formed only by special
mixing. methods.
. Particles nature The particles of colloids are true The particles are aggregates of many
molecules and are big size. molecules.
. Visibility The particles are not easily visible The particles are easily detected
even under ultramicroscope. under ultramicroscope.
. Stability These are very stable. These are unstable and require traces
of stabilizers.
. Action of electrolytes They are not easily precipitated by They are easily precipitated by the
small amount of electrolytes. Very addition of small amount of suitable
large quantities of electrolytes are electrolytes.
required to cause coagulation.
. Reversible or irreversible nature These are reversible in nature 1.e., These are irreversible in nature i.e.,
once precipitated can reform the once precipitated cannot form the
colloidal sol by simply remixing with colloidal sol by simple addition of
the dispersion medium. the dispersion medium.
. Charge on particles The particles do not carry any The particles move in a specific
charge. The particles may migrate direction 1.e., either towards anode or
in any direction or even not under cathode depending upon their charge.
the influence of an electric field.
. Hydration The particles of colloids are heavily The particles of colloids are not
hydrated due to the attraction for appreciably hydrated due to the
the solvent. hatred for the solvent.
. Viscosity The viscosity of the sols is much The viscosity is nearly the same as
higher than that of the dispersion that of the dispersion medium.
medium.
. Surface tension The surface tension is usually lower The surface tension is almost the
than that of the dispersion medium. same as that of the dispersion
medium.
. Tyndall effect They do not show Tyndall effect. They show Tyndall effect.
C. Classification Based on type of particles of dispersed phase
Depending upon the type of the particles of the dispersed phase, the
colloids are classified as :
(1) Multimolecular colloids
(it) Macromolecular colloids
(111) Associated colloids.
(i) Multimolecular colloids
When on dissolution, atoms or smaller molecules of substances (having
diameter less than 1 nm) aggregate together to form particles of colloidal
dimensions, the particles thus formed are called multimolecular colloids.
Therefore, in these sols the dispersed phase consists of aggregates of atoms or
molecules with molecular size less than 1 nm. For example, sols of gold atoms
and sulphur (S,) molecules. In these colloids, the particles are held together
by van der Waals forces.
SURFACE CHEMISTRY

(ii) Macromolecular colloids

These are the substances having big size molecules (called macro molecules)
caring Plus
which on dissolution form solution in which the dispersed phase particles @e Multimolecular colloids
have size in the colloidal range. Such substances are called macromolecular usually have lyophobic
colloids. These macromolecules forming the dispersed phase are generally character.
polymers having very high molecular masses. Naturally occurring Macromolecular colloids
macro-molecules are starch, cellulose, proteins, enzymes, gelatin, etc. Artificial usually have lyophilic
character.
macro-molecules are synthetic polymers such as nylon, polythene, plastics,
polystyrene, etc. Since these macromolecules have large sizes comparable to those
of colloidal particles, the solutions of such molecules are called macromolecular
colloidal solutions. Their solutions are quite stable and resemble true solution
in many respects. Thus, the common examples of macromolecular colloids are
starch, cellulose, proteins, plastics, etc.
(iii) Associated colloids
These are the substances which when dissolved in a medium behave as
normal electrolytes at low concentration but behave as colloidal particles at
higher concentration due to the formation of aggregated particles. The aggregate
particles thus formed are called micelles. For example, in aqueous solution,
soap (sodium stearate) lonises as :
C,,H,,;COONa == C,,H,.COO- + Nat
Sod. stearate (soap) Stearate ion

In concentrated solution, these ions get associated to form an aggregate

of colloidal size.
The colloidal behaviours of such substances is due to the formation of
aggregates or clusters in solutions. Such aggregated particles are called
micelles. Thus,
micelles are the cluster or aggregated particles formed by association
of colloids in solution.
The common examples of micelles are soaps and detergents. The formation of
micelles takes place above a particular temperature called Kraft temperature
(T,) and above a particular concentration called critical micellization
concentration (CMC). For example, CMC for soaps is about 10~* — 10-? mol
L-1. Different micelles have different values of CMC. On dilution, these colloids
revert back to individual ions. These coloids have both lyophobic and lyophilic
parts. The micelles may contain about 100 molecules or more.
Mechanism of Micelle Formation
Micelles are generally formed by the aggregation of several ions or
molecules with lyophobic as well as lyophilic parts. For example, sodium
stearate (C,,H,;,-COONa) is a typical example of such type of molecule. The
micelle may contain as many as 100 molecules or more. When sodium stearate Nat
is dissolved in water, it gives Nat and C,-H.-COO
17 35
ions.
Fig. 17. Aggregation of several ions
C,,H,,COONa == C,,H,.COO- + Na* to form ionic micelle
(—) represents
Sod. Stearate Stearate ion —COO group.
The stearate ions associate to form ionic micelles of colloidal size
(Fig. 17). The stearate ion, C,,H,.COO™ consists of two parts :
(4) a non-polar part which consists of long chain hydrocarbon part. It is
called non-polar ‘tail’. This part is insoluble in water but soluble in oil or
grease. It is also called water repelling or hydrophobic part.
(it) a polar group which consists of carboxylate ion, COO-. It is called
polar-ionic head. It is soluble in water and insoluble in oil or grease. It is
water attracting or hydrophilic part.
 MODERN'S abc + OF CHEMISTRY-All

These two parts of soaps are represented as :

O
CH, CH CH, CH, CH, CH, CH CH, ‘
CH,
L\S\S\S\S\S\S\S\CH,
CH, CH, CH, CH, CH, CH,
IS \q.,
CH, ONa
Ct
Sodium stearate (C,,H,,;COO Na’)
or simply as,

hy -

pet / Cet =,
~~ = a

Hydrophilic part
on-polar tall (Polar head)
For simplicity, it may be represented as :
+

Na

| ef
Hydrophilic head
Hydrophobic tail
The stearate ions are therefore, present on the surface with their COO-
groups in water and the hydrocarbon tail staying away from it and remains
at the surface. Inside water, these molecules have a unique orientation which
keeps the hydrocarbon portion out of water. At critical micelle concentration, the
anions are pulled into the bulk of the solution and form a cluster of molecules
in which the hydrocarbon tails are in the interior of the cluster and ionic ends
are at the surface of the cluster. This formation is called micelle formation
and the aggregate thus formed is known as ionic micelle (as shown in Fig.17).
These micelles may contain as many as upto 100 ions. When the concentration
of the solution is below its CMC (10-* mol L~), it behaves as normal electrolyte.
But above this concentration, it is aggregated to behave as micelles.
Some other examples of micelles are :
(1) Sodium palmitate (C,-H,,COONa)
(it) Cetyl trimethyl ammonium bromide CH, (CH,),. (CH), N Br
(it) Sodium lauryl sulphate [CH,(CH,),,S0,0 Na’]
Similarly in case of detergents, e.g., sodium lauryl sulphate,
CH,(CH,),, OSO, Na‘, the polar group is SO; along with the long hydrocarbon
chain. Therefore, the mechanism of micelle formation is same as that of soaps.
Differences between multimolecular colloids, macromolecular colloids and associated colloids.
Multimolecular colloids Macromolecular colloids Associated colloids
1. They consist of aggregates of | They consist of large size molecules They consist of aggregation of a
atoms or molecules which generally | (generally polymers) like rubber, nylon,| large number of ions which behave
have diameter less than 1 nm.| starch, proteins, etc. as colloidal size particles at higher
e.g., sols of gold, sulphur, etc. concentrations e.g., soap sols.
2. The atoms or molecules are held |The molecules are flexible and can They behave as normal electrolytes
by weak van der Waals forces. take any shape. at low concentrations and behaveas
colloidal only at high concentrations.
3. Their molecular masses are not They have high molecular masses. Their molecular masses are
very high. generally high.
3. They usually have lyophobic They usually have lyophilic character.) Their molecules contain both
character. lyophilic and lyophobic groups.
SURFACE CHEMISTRY 5/31 —

Cleansing action of soap

The cleansing action of soap is due to its tendency to act as micelle and form emulsions. A soap, for example,
sodium stearate is composed of long chain of alkyl group called tail and a polar part of COO ion called head.
CH, (CH,),<CH, — COO- Na*
Tail Head

HYDROCARBON (TAIL) ELECTRICALLY

CHARGED (HEAD)
This may be represented as the polar end which is water soluble and the non-polar end which is soluble in
organic solvents and oil.

(a) (b)
Grease on cloth Stearate ions
arranged around
the grease droplet

© ~ @)
Forming micelle Forming globules

Fig. 18. Cleansing action of soap.

Ordinarily, the dirt in the cloth is due to the presence of dust particles in fat or grease which stick to the cloth.
When the cloth is dipped in aqueous soap solution, the soap and the dirt come in contact with each other. The soap
molecules form micelle around the oil droplet in such a way that the hydrophobic part of stearate ions is in the
oil or grease droplet while the hydrophilic part projects out of the grease droplet like the bristles. In this manner,
each oil droplet is surrounded by a number of negatively charged carboxylate ions (Fig. 18). Since similar charges
repel each other, the oil droplets break up and form small droplets or globules. The negatively charged sheath
around the globules prevents them from coming together and form aggregates. These small droplets get dispersed
in water forming emulsion. The hand rubbing or the agitation due to the washing machine causes dispersion of
the oil or grease throughout the soapy water. These are washed away with water alongwith dust particles.

GENERAL METHODS OF PREPARATION OF SOLS

Lyophilic and lyophobic colloidal solutions (or sols) are generally prepared
by different types of methods. Some of the common methods are :
Preparation of Lyophilic Colloids
The lyophilic colloids have strong affinity between particles of dispersed
phase and dispersion medium. Therefore, these colloidal solutions are readily
formed by simply mixing the dispersed phase and dispersion medium under
ordinary conditions. For example, the substances like gelatin, gum, starch,
egg albumin etc. pass readily into water to give coloidal solution. They are
reversible in nature because these can be precipitated and directly converted
into colloidal state.
Preparation of Lyophobic Colloids
Lyophobic sols can be prepared by mainly two types of methods :
1. Condensation methods
2. Dispersion methods.
1. Condensation Methods
In these methods, smaller particles of dispersed phase are condensed suitably
to be of colloidal size. This is done by the following methods :
 MODERN'S abc + OF CHEMISTRY-All

(a) By chemical reactions.

(i) Oxidation. A colloidal sol of sulphur is obtained by bubbling H,S
gas through the solution of bromine water, sulphur dioxide, nitric acid, etc.
HS + Br, —— > 2HBre + 5&8
(sol)
2H,5 + SO, ——> 2H,0 ~ me
(sol)
H,S + 2HNO, ——-> 2H,O + 2NO, +5
(sol)
(ii) Reduction. The colloidal solutions of metals are obtained by reduction
of their compounds. For example, a solution of AuCl, is reduced with SnCl.,,.
2AuCl, + 385nCl,——~+ 35nCl, + 2Au
Gold sol
The reaction can also be carried out with formaldehyde, tannic acid or
hydrazine.
2AuCl, + 3HCHO +3H,O ——+ 2Au + 3HCOOH + 6HCI
Gold sol
or 4AuCl,+3NH,NH, ©——> 4Au + 3N, + 12HCl
Hydrazine Gold sol
The gold sol, thus prepared, has a purple colour and1s called purple of cassius.
Colloidal sols of platinum, silver, etc. can also be prepared in a similar
manner.
2PtCl, + 4S5nCl, ———> 4SnCl, + 2Pt
Sol
(iii) Hydrolysis. A colloidal solution of ferric hydroxide is prepared when
a concentrated solution of ferric chloride is added drop wise to hot water.
FeCl, +3H,O ——> Fe(OH), + 3HCl
(iv) Double decomposition. As,S, sol is obtained by passing H,S through
dilute solution of arsenious oxide in water.
As,O, + 3H,S ——> As,S, + 3H,O
Colloidal sol
(b) By excessive cooling. A colloidal solution of ice in an organic solvent
like ether or chloroform can be prepared by freezing a solution of water in
the solvent. The molecules of water which can no longer be held in solution,
separately combine to form particles of colloidal size.
(c) By exchange of solvent. Colloidal solution of certain substances
such as sulphur, phosphorus which are soluble in alcohol but insoluble in
water can be prepared by pouring their alcoholic solution in excess of water.
For example, alcoholic solution of sulphur on pouring into water gives milky
colloidal solution of sulphur.
(d) By change of physical state. Sols of substances like mercury and
sulphur are prepared by passing their vapours through
a cold water containing a suitable stabilizer such as
ammonium salt or citrate.
Suspension

: 4— Driving belt
2. Dispersion Methods
In these methods, larger particles of a substance
(suspension) are broken into smaller particles. The following
methods are employed:
(a) Mechanical dispersion. In this method, the
substance is first ground to coarse particles. It is then
Discharg ischarge
“a TUTTI TTT yy; aa mixed with the dispersion medium to get a suspension. The
: =e aa suspension is then grinded in a colloidal mill (Fig. 19). It
Metal discs rotating in opposite directions
consists of two metallic discs nearly touching each other
Fig. 19. Colloidal mill. and rotating in opposite directions at a very high speed
(about 7000 revolutions per minute).
SURFACE CHEMISTRY

The space between the discs of the mill is so adjusted that coarse suspension
is subjected to great shearing force giving rise to particles of colloidal size. Metal
Colloidal solutions of black ink, paints, varnishes, dyes, etc. are obtained by electrodes
this method.
(b) By electrical dispersion or Bredig's arc method. This method is
used to prepare sols of metals such as platinum, silver, copper or gold.
The metal whose sol is to be prepared is made as two electrodes immersed in
dispersion medium such as water (Fig. 20). The dispersion medium is kept cooled
by surrounding it with a freezing mixture. An electric arc is struck between the
electrodes. The tremendous heat generated by the arc vapourises the metals
which are condensed immediately in the liquid to give colloidal solution. The
colloidal solution prepared is stabilised by adding a small amount of KOH fo it.
(c) By peptization. The process of converting a freshly prepared precipitate
into colloidal form by the addition of a suitable electrolyte is called peptization. Fig. 20. Bredig's arc method.
The electrolytes used for the purpose are called peptising agents.
Cause of peptization. When an electrolyte is added to a freshly prepared
precipitate, the suitable ions from the added electrolyte are adsorbed by the
particles of the precipitate. The charged particles repel one another and form
colloidal solution. For example, treating a precipitate of iron (IIT) oxide with a
small amount of FeCl, solution, gives a reddish brown coloured colloidal solution.
In this case, Fe** ions from ferric chloride are adsorbed by Fe(OH), precipitate :

Fe(OH), ~ Fe** ——>» Fe(OH),. Fe**

Precipitate Electrolyte Colloidal sol

Fe(OH), }+ Fe* —-5 +

From
Precipitate — electrolyte
of Fe (OH); FeCl, Colloidal
particles of
Fe(OH),

Fig. 21. Preparation of colloidal sol by peptisation.

Similarly, a precipitate of silver chloride can be peptised by shaking with

a dilute solution of silver nitrate to give a colloidal solution of silver chloride.

AgCl + Agt (@m® Asc. Ag‘

Precipitate From Colloidal sol
electrolyte

PURIFICATION OF COLLOIDAL SOLUTIONS

The colloidal solutions prepared by the above methods usually contain
impurities especially electrolytes which can destabilize the sols. These impurities
must be eliminated to make the colloidal solutions stable. The following methods
are commonly used for the purification of colloidal solutions.
1. Dialysis
The process of separating the particles of colloids from those of
crystalloids by means of diffusion through a suitable membrane
is called dialysis.
Its principle is based upon the fact that colloidal particles cannot pass
through a parchment or cellophane membrane while the tons of the electrolyte
can pass through it. The colloidal solution is taken in a bag made of cellophane
or parchment. The bag is suspended in fresh water. The impurities slowly
 MODERN'S abc + OF CHEMISTRY-All

diffuse out of the bag leaving behind pure colloidal solution Fig. 22. The
distilled water is changed frequently to avoid accumulation of the crystalloids
otherwise they may start diffusing back into the bag. Dialysis can be used for
removing HC] from the ferric hydroxide sol.
Electrodialysis. The ordinary process of dialysis is slow. To increase the
process of purification, the dialysis is carried out by applying electric field.
This process is called electrodialysis and is shown in Fig. 23.

Cathode

—-» Water + crystalloid

'
Water +
crystalloid

Crystalloid Parchment Sol particle

Crystalloid Parchment Sol particle
membrane
membrane

Fig. 22. Dialysis. Fig. 23. Electrodialysis.

9. Ultra-filtration
/R U Curious... ®
It is the process of removing the impurities from the colloidal
O Some patients have to solution by passing itt through graded filter papers called ultra-
undergo dialysis. How does filter papers.
| it help ?
These filter papers are permeable to all substances except colloidal particles.
|» Kidneys in the human body
Colloidal particles can pass through ordinary filter paper because the size of
act as dialysers to purify
the pores is too large. However, the size of the pores of filter paper can be
blood which is of colloidal reduced by impregnating them with colloidion or gelatin solution to stop the
nature. The most important fiow of colloidal particles. The colloidion solution generally used is 4% solution
application of dialysis process of nitrocellulose in a mixture of alcohol and ether. An ultra-filter paper may
is the artificial kidney machine be prepared by soaking the filter paper in a colloidion solution, hardening
used for the purification of by dipping in formaldehyde solution and then finally drying it. A series
blood of the patients whose of graded ultra-filter papers may be obtained by using the impregnating
kidneys have failed to work. The solutions of different concentrations. With these ultra-filter papers impurities
artificial kidney machine (called of different sizes can be effectively removed. In this method, sol is poured
dialyser) work on the principle over the ultrafilters which allow solution of impurities to pass through but
of dialysis. It takes blood from retain the colloidal particles. The colloidal particles left on the ultra-filter
the artery and the dialysis paper are then stirred with fresh dispersion medium (solvent) to get a pure
membrane in the machine colloidal solution. This is a slow process and to speed up the process, pressure
allows small particles of excess or suction is applied.
ions and waste products to pass 3. Ultra-centrifugation
through while it does not allow In this method, the colloidal sol is taken in a tube which is placed in an
the colloidal size particles such ultra centrifuge. On rotation of the tube at high speeds, the colloidal particles
as haemoglobin to pass through. settle down at the bottom of the tube and the impurities remain down in the
Therefore, blood of the patient solution called centrifugate.
is purified and after purification
The settled colloidal particles are mixed with an appropriate dispersion
it is sent back to veins.
medium to regenerate the sol.
SURFACE CHEMISTRY

PROPERTIES OF COLLOIDAL SOLUTIONS

The main characteristic properties of colloidal solutions are discussed
below :
1. Physical Properties
(a) Heterogeneous character. The colloidal solutions are heterogeneous
in nature consisting of two phases : (1) dispersed phase and (ii) dispersion
medium. Because of the small particle size, the colloidal solutions generally
appear to be homogeneous to the naked eye but their heterogeneity can be
confirmed by seeing under electron microscope.
(b) Stable nature. The colloidal solutions are quite stable. Their particles
are in a state of motion and do not settle down at the bottom of the container.
However, particles of certain colloidal sols, which have comparatively large
size may settle down but very slowly.
(c) Filtrability. The colloidal particles can pass through ordinary filter
papers because the size of the colloidal particles is lesser than the size of the
pores of filter paper. However, they cannot pass through animal and vegetable
membranes and ultrafilter papers. This forms the basis of separation of colloidal
particles from those of crystalloids.
2. Colligative Properties
The colloidal particles being bigger aggregates have very high molecular
masses so that the number of particles per litre of the sol is relatively very small
than in a true solution. Therefore, they have very low colligative properties. As
a result, the sols boil and freeze at almost the same temperature as the pure
dispersion medium and lowering in vapour pressure 1s also negligible. However,
the osmotic pressure of colloidal solutions, though smaller than true
solutions is the only colligative property which has been determined
with a reasonable degree of accuracy. It gives information regarding the
number of particles present per kilogram of the dispersion medium and this
can be used to determine the average molecular masses of colloidal particles.
3. Mechanical Properties
(a) Brownian movement. When colloidal solutions are viewed through
a powerful ultramicroscope, the colloidal particles are seen to be in a state
of continuous zig-zag motion. This motion was first observed by the British
botanist, Robert Brown in 1827. He discovered that the pollengrains suspended
in water do not remain at rest but move about continuously and randomly
in all directions. Later on, it was observed that the colloidal particles also
are moving at random in a zig-zag motion as shown in Fig. 24. This type of
motion is called Brownian movement after the name of its discoverer, Robert
Brown. The Brownian motion is independent of the nature of the colloid but
depends on the size of the particles and viscosity of solution. Smaller the size
and lesser the viscosity, faster is the motion.
Cause of Brownian movement. The Brownian movement has been
explained to be due to the unbalanced bombardment of the particles by the
molecules of the dispersion medium. The molecules of the dispersion medium
are constantly colliding with the particles of the dispersed phase. It was stated
by Wiener in 1863 that the impacts of the dispersion medium particles are
unequal, thus, causing a zig-zag motion of the dispersed phase particles. When
a molecule of dispersion medium collides with a colloidal particle, it is then
displaced in one direction. Then another molecule strikes it, displacing it to
another direction and so on. This process gives rise to a zig-zag motion. Thus,
Brownian movement has a stirring effect which does not allow the particles to
settle down and hence is responsible for the stability of the sols. However, if
the size of the dispersed phase particles increases, then the chances of unequal
bombardment decrease. This can be confirmed by the fact that the suspensions Fig. 24. Brownian movement of
do not show any such movement due to large molecular size. colloidal particles.
 MODERN'S abc + OF CHEMISTRY-All

Thus, it may be noted that

() Brownian movement provides a direct demonstration of the ceaseless
motion of molecules as postulated by kinetic theory.
(iz) The Brownian movement explains the force of gravity acting on
colloidal particles. This helps in providing stability to colloidal sols by not
allowing them to settle down.
(iit) It has also helped in the determination of Avogadro's number.
(b) Diffusion. The sol particles diffuse from higher concentration to lower
concentration region. However, due to bigger size, they diffuse at a lesser speed.
(c) Sedimentation. The colloidal particles settle down under the influence
of gravity at a very slow rate. This phenomenon is called sedimentation and
is used to determine the molecular mass of macromolecules.
4. Optical Properties
(a) Tyndall effect
When a strong beam of light is passed through a true solution placed
in a beaker, in a dark room, the path of the hght does not become visible.
However, if the light is passed through a sol, placed in the same room, the
path of the light becomes visible when viewed from a direction at right angle
to that of the incident beam. The colloidal solutions appear reasonably clear or
translucent by the transmitted light but they show a mild to strong opalescence
when viewed at right angles to the passage of light i.e., the path of beam gets
Wluminated by a bluish light.
This phenomenon was first observed by Faraday and later studied in detail
by Tyndall and therefore, it is called Tyndall effect. The cause of Tyndall effect
is the scattering of light by the colloidal particles 1.e., these particles scatter light
in all directions in space. The scattering of light illuminates the path of beam
in the colloidal dispersion. The particles in true solution are too small in size
to cause any scattering i.e., the Tyndall effect is not observed in true solutions.
Thus,

the phenomenon. of scattering of light by colloidal particles as a result

of which the path of the beam becomes visible is called Tyndall effect.

Light beam Light beam visible Microscope

not visible
Scattered light
Scattering of Light

Source of
light Colloidal SS Colloidal solution
solution solution = + ;

Fig. 25. Tyndall effect.

The illuminated path of the beam is called Tyndall cone.

The Tyndall effect confirms the heterogeneous nature of the colloidal solutions.
The Tyndall effect can be observed due to scattering of dust particles, when
a beam of sunlight enters a dark room through a slit. You must have noticed
during the projection of picture in the cinema hall due to scattering of light
by dust and smoke particles present there.
Tyndall effect is observed only when the following two conditions are
satisfied :
(4) The diameter of the dispersed phase particles is not much smaller than
the wavelength of light used.
(it) The refractive indices of the dispersed phase and the dispersion medium
differ largely in magnitude.
SURFACE CHEMISTRY

Importance of Tyndall effect

The Tyndall effect has been used to devise an instrument called
Tyndall effect can be used to
ultramicroscope which was designed by Zsigmondy in 1913. In this instrument, distinguish between a true solution
an intense beam of light is focussed on the colloidal solution contained in and a colloidal solution. A strong
a glass vessel. The focus of light is then viewed with a microscope at right beam of light is passed through
angles to the beam. It is observed that individual colloidal particles appear the given solution. If the path of
as spots of bright light against a dark background. It may be noted that ultra the light gets illuminated, the
microscope does not make the actual colloidal particles visible but only the solution is a colloidal solution. On
light scattered by the colloidal particles can be seen through a microscope. the other hand, if the path of the
Thus, ultramicroscope does not provide any information about the size and light does not get illuminated, it is
shape of colloidal particles. a true solution.
(6) Colour Thus,
The colour of colloidal solutions depends on the wavelength of the light Colloidal solutions = show
scattered by the dispersed particles. The wavelength further depends on the Tyndall effect
size and nature of the particles. It has been observed that the colour of colloidal True solutions => donot show
solutions also changes with the manner in which the observer receives the light. Tyndall effect.
For example, a mixture of milk and water appears blue when viewed by the It may be noted that among
reflected light but if transmitted light 1s viewed it is red. Similarly, gold sol is colloids, lyophilic colloids do not
red in colour when the particles are fine but as the size of the particles increases, show Tyndall effect but lyophobic
its colour changes to purple, then blue and finally golden. colloids show Tyndall effect.
5. Electrical properties
The particles of the colloidal solutions possess electrical charge, positive or
negative. The presence of charge is responsible for the stability of these solutions.
It may be noted that only the sol particles carry some charge while the dispersion
medium has no charge. For example, the colloidal solutions of gold, arsenious
sulphide (As,S,) are negatively charged while those of Fe(OH), and Al(OH),
have positive charge. In the case of silver chloride sol, the particles may either
be positively or negatively charged.
Origin of charge
Various views have been put forward regarding the origin of charge on the
colloidal particles.
(4) Due to frictional electrification. It is believed that the frictional
electrification due to the rubbing of the dispersed phase particles with that of
dispersion medium results in some charge on the colloidal particles. But the
dispersion medium must also get some charge because of the friction. Since it
does not carry any charge, the theory does not seem to be correct.
(it) Due to dissociation of the surface molecules. Consider, for example,
an aqueous solution of soap (sod. palmitate) which dissociates into lons as :
C,,H,,COONa == C,,H,,COO-+ Na*
Sod. palmitate
The cations (Na*) pass into the solution while the anions (C,.H,,COO)
have a tendency to form aggregates due to weak attractive forces present in
the hydrocarbon chains.
(iit) Due to selective adsorption of ions. The particles constituting the
dispersed phase adsorb only those ions preferentially which are common with
their own lattice ions. For example, if a dilute solution of silver nitrate is added
to an aqueous solution of potassium iodide, the precipitated silver iodide will
adsorb negative ions (common ions) from the dispersion medium to form a
negatively charged sol. This is shown in Fig. 26 (a).
Agl + I. oe AgIl: I
Dispersion Negative sol.
medium (from KT)
In this case, the left out ions (K*) will remain in the dispersion medium
thereby giving equal and opposite charge (positive) to the dispersion medium.
However, if silver iodide is formed by adding a dilute solution of potassium
iodide to silver nitrate solution, the sol will be positively charged due to the
adsorption of Agt ions (common ions) present in the dispersion medium.
 MODERN'S abc + OF CHEMISTRY-All

Ac] + Agt — > AgliAg*

Dispersion Positive sol.
medium (from AgNO,)
The left out ions (NO,-) will remain in the dispersion medium thereby giving
equal and opposite charge (negative) to the dispersion medium [Fig. 26 (b)].
Thus ?

the ion which is common with their own lattice ions is preferentially
adsorbed.

Similarly, if ferric chloride is added to excess of hot water, a positively

charged sol of hydrated ferric hydroxide is formed. This is because of adsorption
of Fe** ions. However, when ferric chloride is added to sodium hydroxide (NaOH)
solution, a negatively charged sol is obtained due to the adsorption of OH7 ions.
FeCl, + H,O (excess) ——> Fe,O,.xH,0 iFe**
Positively charged sol

FeCl, + NaOH (aq),—_} Fe, 0,.xH,O (OH

Negatively charged sol
Based on the nature of the charge, the colloidal solutions have been classified
into positively charged and negatively charged colloids. Some common examples
are listed in Table 5.
Table 5. Some common positively and negatively
charged colloidal solutions.
Agi | Ag* Sol
Positively charged sols Negatively charged sols
NO,- ions remain in dispersion medium
Hydrated metallic oxides e.g., Al,O,.xH,O, | Metallic particles e.g., Cu, Ag,
(b)
Cr,0, +H,O, Fe Gaalgy etc. Au, Pt, sols
Fig. 26. Selective adsorption of ions
on Agl. Metal hydroxides e.g., Fe(OH),, Al(OH,), | Metal sulphides e.g., As,S,, CdS,
Cr(OH),, Ca(OH),. Sb,S,, etc.
Basic dye stuffs like methylene blue, | Acidic dyes like eosin, congo red,
prussian blue etc.
Haemoglobin (blood) Sols of starch, gum, gelatin, clay,
Oxides e.g., TiO, sol. charcoal, etc.

Learning Plus
THEORY OF ELECTRICAL DOUBLE LAYER
Colloidal dispersions possess electrical properties which are due to their
ability to adsorb from solution ions, molecules of medium or both. The adsorbed
phase controls the stability of the sol and its behaviour in electric field. To
explain this, a theory of electrical double layer was first proposed by Helmholtz
in 1879. According to this theory, when a solid comes in contact with a liquid
(e.g., a solution of an electrolyte) it preferentially adsorbs one type of ions on
its surface. This forms a fixed layer. To counter balance this charge, oppositely
charged ions are attracted to the surface to form a double layer of charges. For
example, as explained above, AgI sol becomes positively charged or negatively
charged by selective adsorption on the surface of the colloidal particles. This
layer attracts the counter ions from the medium forming a second layer as
shown below :
AglI Tr kK or Agl Ag* NO,-
Fixed layer Mobile layer Fixed layer Mobile layer
Such an arrangement of charges is called Helmholtz double layer
Fig. 27 (a) and leads to a difference of electric potential between the solid and
the liquid. In this theory, the charges next to the surface were considered to be
SURFACE CHEMISTRY

fixed while the compensating charges in the liquid were thought to be mobile.
— + =k -—+4+=-+-+
—~it — i: + ae ea
-i+ — +] to = +
it ee oe as
aes 4 — + i az + + = ai

=it+ oe x | oa
m |-i+ fm i-T! 4 +
—Se |—|-i+ Liquid
ici a|x|
|- ; _ - + i“
w am + to = Sees . ee

o |- ® |-_} Liquid —
Ee mj ti <
me |i + me j- ui Ft 7+
= Se = = r = +

om |-i+
— 2
em |-be + ca = OEY ed
—i+ — +; 2
=| + / Movable = Pil 2
=it
—i+
eth
-ti
g_ @- oea 4
Fixe Fixed
Movable
(a) Helmholtz double layer (6) Diffuse double layer
Fig . 27
However, according to modern views, some of the compensating charges are
held in the stationary liquid layer adhering to the surface. The remaining charges
are distributed next to this layer 'in the form of a diffuse or mobile layer as shown
in Fig. 27. (b). This mobile layer along with the fixed layer (containing charges fixed
on the surface as well as some compensating charges) constitute diffuse electrical
double layer. The potential difference that exists between the stationary layer of
compensating charges and the diffuse layer (present in the body of the solution)
is called electrokinetic or zeta potential. This is involved in various nonstatic
electrical properties of solid-liquid interfaces and is also responsible for the
electrical effects observed in colloids.

The electrical properties of colloidal solutions are related with two phenomena:
(4) Electrophoresis
(11) Electroosmosis
(1) Electrophoresis : The presence of the charge on the sol particles
and its nature whether positive or negative can be determined with the help
of a phenomenon known as electrophoresis. In this experiment, the colloidal
particles move towards positive or negative electrodes depending upon their
charge under the influence of electrical field.
The phenomenon of movement of colloidal particles under an applied
electric field is called electrophoresis.
If the particles accumulate near the negative electrode, the charge on the
particles is positive. On the other hand, if the sol particles accumulate near the
positive electrode, the charge on the particles is negative. (a) Before electrophoresis
The apparatus consists of U-tube with two platinum electrodes in each limb
(Fig. 28). Take a sol of As,S, in the U-tube. The intensity of the colour of the
sol in both the arms 1s same. Now pass the current through the sol. After some
time, it is observed that the colour of the sol near the positive electrode became
intense than the initial colour. This indicates that the As,S, particles have
accumulated near the positive electrode. In other words, the particles of As,S,
are negatively charged and they move towards oppositely charged (positive) particles get
electrode and accumulate there. | accumulated
Similarly, when an electric current is passed through positively charged
Fe(OH), sol, it is observed that they move towards negatively charged electrode
and get accumulated there.
Thus, by observing the direction of movement of the colloidal particles, the
sign of the charge carried by the particles can be determined.
(it) Electro-osmosis : When the movement of the colloidal particles is (b) After electrophoresis
prevented by some suitable means and the molecules of the dispersion medium
are allowed to move under the influence of applied potential, the phenomenon Fig. 28. Process of electrophoresis.
is called electro-osmosis.
 MODERN'S abc + OF CHEMISTRY-All

Thus, electro-osmosis is the phenomenon of the movement of the

molecules of the dispersion medium under the influence of electric field
whereas colloidal particles are not allowed to move.
The electroosmosis can be observed by a simple apparatus as shown in
Fig. 29. The colloidal solution is placed in a compartment A separated
from compartments B and C by semipermeable membranes D and D'. The
compartments B and C are filled with water up to the marks indicated by the
side arms. When a potential is applied across the two electrodes placed near
the membranes in B and C, the liquid level is observed to fall on one side and
rise on the other side due to the passage of water through membrane D and
D'. The direction of the flow of water depends on the charge of the colloid. For
positively charged sols the medium is negatively charged, and hence the flow
will take place from C to B. On the other hand, for negatively charged sols, the
reverse will occur and the level on the C side will rise.

‘ F Colloidal
| sol

D '

Semipermeable
membrane

Fig. 29. Process of electro-osmosis.

COAGULATION OF COLLOIDAL SOLUTIONS

We know that a small amount of an electrolyte is necessary for the stability of
the colloidal sol. The ions of the electrolytes are adsorbed on the sol particles and
impart them some charge; positive or negative. The charged colloidal particles
repel one another and are prevented from coming close together to unite into
bigger particles (Fig. 30). If, somehow, the charge is removed, the particles will
come nearer to each other to form aggregate (or coagulate) and settle down
under the force of gravity. For example, in the presence of a large excess of the
electrolyte, the charge on the particles of the dispersed phase is neutralised and
as a result, they come closer, grow in size and ultimately form precipitates. This
is called precipitation or coagulation. Thus,
the phenomenon of precipitation ofa colloidal solution by the addition
of excess of an electrolyte is called coagulation or flocculation.
Mechanism of coagulation. The particles of the dispersed phase i.e.,
colloids bear some charge. When an electrolyte is added to the sol, the colloidal
particles take up ions carrying opposite charge from the electrolyte. As a result,
their charge gets neutralised and this causes the uncharged particles to come
closer and to get coagulated or precipitated. For example, if BaCl, solution is
added to As,S, sol, the Ba** ions are attracted by the negatively charged sol
particles and their charge gets neutralised. This leads to coagulation.
Hardy Schulze rule.
The coagulation tendency of different electrolytes is different. It depends
upon the valency of the active ion called flocculating ion., which is the ion
Fig. 30. Repulsion between colloidal
carrying charge opposite to the charge on the colloidal particles. According to
particles gives stability.
Hardy Schulze rule, greater the valency of the the active ion or flocculating
ton, greater will be tts coagulating power.
SURFACE CHEMISTRY

Thus, according to Hardy Schulze rule :

(t) The tons carrying the charge opposite to that of sol particles are effective in
causing coagulation of the sol.
(it) Coagulating power of an electrolyte is directly proportional to the fourth
power of the valency of the active tons (ions causing coagulation). Greater is
the valency of the oppositely charged ton of the electrolyte being added, the
faster ts the coagulation.
For example, to coagulate negative sol of As,S,, the coagulating power of
different cations has been found to decrease in the order as :
Al** > Mg?* > Nat
Similarly, to coagulate a positive sol. such as Fe(OH),, the coagulating
power of different anions has been found to decrease in the order :
[Fe(CN),]* > PO,* > 50,2 > Cl
The minimum concentration of an electrolyte in millimoles which ts
required to cause the coagulation or flocculation of one litre of a sol
is known as coagulation value or flocculation value.
It is usually expressed as millimoles per litre. Thus, smaller is the coagulation
value of an electrolyte, greater is its coagulation or flocculation power. For
example, the coagulation values (in millimoles/litre) for the coagulation of positively
charged Fe(OH), sol and negatively charged As.S, sol are given in Table 6.

Table 6. Coagulation values (in millimoles/litre) of common electrolytes.

Ferric hydroxide (+) sol Arsenic sulphide (-) sol
Electrolyte Active ion Coagulation value Electrolyte Active ion Coagulation value
(anion) (millimoles/litre) (cation) (millimoles/litre)

KBr
Kel
KNO,
Ks0,
Na,C,O, C,0,7°
K,[Fe(CN),] [Fe(CN),]>-
The above table shows that the coagulating power is inversely proportional
to coagulation value or flocculation value. The relative coagulating powers may
be compared as :
REMEMBER
Coagulating power of electrolyte 1 | Coagulating value of electrolyte 2
Smaller is the coagulation or
Coagulating power of electrolyte2 | Coagulating value of electrolyte 1 flocculation value of an electrolyte,
For example, for coagulation of negatively charged As,S, sol. greater is its coagulation or
Coagulating power of AICI, Coagulating value of NaCl flocculation power.
Coagulating power of NaCl ~ Coagulating value of AICl,
51
= —— = 548
0.093
Thus, AlCl, has 548 times more coagulating power than NaCl.
A few other methods for coagulation
Apart from the addition of the electrolyte, the coagulation of a colloidal
sol can be affected by the following methods :
(1) By mutual precipitation. When two oppositely charged sols are
mixed in equimolar proportions, they mutually neutralise their charge and both
get coagulated. For example, if positively charged Fe(OH), sol and negatively
charged As,S, sol are mixed, both the sols get coagulated.
(it) By electrophoresis. We have seen in the electrophoresis that the
particles of the dispersed phase move towards the oppositely charged electrodes.
If the process is carried for a long time the particles will touch the electrode,
lose their charge and get coagulated.
 MODERN'S abc + OF CHEMISTRY-All

(iit) By persistent dialysis. The stability of colloidal sols is due to the

presence of a small amount of electrolyte. Ifthe electrolyte is completely removed
by repeated dialysis, the particles left will get coagulated.
(iv) By heating or cooling. In certain cases, the sols get coagulated on
heating. For example, coagulation of butter. Similarly, In some cases cooling
the sol also results into its coagulation. For example, coagulation of milk 7.e.,
on cooling milk fats start floating on the surface.
Coagulation of Lyophilic sols.
Lyophilic sols are more stable than lyophobic sols. The stability of lyophilic
sols is due to two factors :
(1) Charged and
(it) Solvation of the colloidal particles.
When these two factors are removed, a lyophilic sol can be coagulated. This
can be done (7) by adding electrolyte and (ii) by adding suitable solvent. For
example, when solvents such as alcohol or acetone are added to hydrophilic sols,
it results into dehydration of dispersed phase. Under this condition, a small
quantity of electrolyte can cause coagulation.

| SOLVED EXAMPLES = =
LJ} Example6
In a coagulation experiment, 5 mL of As,S,is mixed with distilled water and
0.1 M solution of an electrolyte
AB so that total volume ts 10 mL. It was found
that all solutions containing more than 4.6 mL of AB coagulate within 5
minutes. Whatis the flocculation value of AB for As,8, sol. ?
Solution : A minimum of 4.6 mL of AB is required to coagulate the sol. The moles
of AB in the sol is
4.6 x0.1
=
—H=0.046 moles
10
This means that a minimum of 0.046 moles or 0.046 x 1000 = 46 millimoles are
® Competition lus required for coagulating 1 litre of sol.
~. Flocculation value of AB for As,9, sol. = 46
At isoelectric point of colloids,
the lyophilic colloids, are expected to
have minimum mobility. For detail,
PROTECTION OF COLLOIDS
refer Competition File, (Page 65). Lyophobic sols such as those of metals like gold, silver etc. can be easily
precipitated by the addition of a small amount of electrolytes. They can be
prevented from coagulation by the previous addition of some stable lyophilic
colloids like gelatin, albumin, etc. This is because when a lyophilic sol is added
to the lyophobic sol, the lyophilic particles form a layer around the lyophobic
particles and this protects them from electrolytes as shown in Fig. 31. For
example, if a small amount of gelatin is added to gold sol, it is not readily
precipitated by the addition of sodium chloride. This process of protecting the
lyophobic colloidal solutions from precipitation by the electrolytes due to the
previous addition of some lyophilic colloid is called protection. The colloid which
is added to prevent coagulation of the colloidal sol is called protecting colloid.
The protecting power of different protective (lyophilic) colloids is expressed
~s Lyophilic in terms of gold number.
) protecting Gold number. The different protecting colloids differ in their protecting
Lyophobic f colloid powers. Zsigmondy introduced a term called gold number to describe the
particles protective power of different colloids. This is defined as
the minimum amount of the protective colloid in milligrams required
to just prevent the coagulation of a 10 mL of a given gold sol when
I mL of a 10% solution of sodium chloride is added to it.
The coagulation of gold sol is indicated by change in colour from red to
Fig. 31. Protection of colloid. blue. The gold numbers of a few protective colloids are as given in Table 7.
SURFACE CHEMISTRY

Table 7. Gold numbers of some protective colloids.

REMEMBER
e The smaller the value of gold
Gelatin 0.005 — 0.01 number, greater will be the
Casein 0.01 — 0.02 protecting power of the protective
Haemoglobin 0.08 — 0.07 colloid 2.e.,
Egg albumin 0.1 -—0.2 e Protective power of a colloid is
Gum arabic 0.15 — 0.25 reciprocal of the gold number.
Starch 20 — 25
Dextrin 6 — 20

It may be noted that smaller the value of the gold number, greater will
be protecting power of the protective colloid. Therefore, reciprocal of gold
number its a measure of the protective power of a colloid. Thus, out of
the list given above, gelatin is the best protective colloid.

SOLVED EXAMPLES

L) Example7
The coagulation of 100 mL ofa colloidal solution ofgold is completely prevented
by the addition of 0.25 g of starch toit before adding 1 mL of 10% NaCl solution.
Calculate the gold number of starch. (Ar. S.B,2004)
Solution : Amount of starch added to 100 mL of gold sol required to prevent
coagulation of 1 mL of 10% NaCl solution
= 0252
Congo Rubin Number
or = 250mg
It may be noted that sometimes
Starch required to be added to 10 mL of gold sol. to completely prevent coagulation the protective action of a lyophilic
by 1 mL of 10% NaCl solution colloid is expressed as Congo Rubin
Number instead of gold number. It
= ce x 10 = 25 mg
100 was suggested by Ostwald and is
expressed as the minimum amount
-. Gold number of starch = 25 of the protective colloid in milligrams
that prevents the colour change of
EMULSIONS 100 mL of 0.01% congo rubin dye to
Emulsions are the colloidal solutions in which both the dispersed which 0.16 gram equivalent of KC]
phase and the dispersion medium are liquids. is added.
In other words, emulsions are liquid-liquid colloidal systems i.e., the
dispersion of finely divided droplets in another liquid. Any two immiscible liquids
form an emulsion. For example, milk is a naturally occurring emulsion in which
the particles (or globules) of liquid fats are dispersed in water.
Emulsions are generally prepared by vigorously shaking two liquids or by
passing the mixture through a colloid mill, called the homogenizer. Since the
two do not mix well, the emulsion is generally unstable and the two liquids may
separate out on standing for some time. Therefore, to form stable emulsions,
small quantities of certain other substances are added during their preparation.
The substances which are added to stabilize the emulsions are called emulsifier
or emulsifying agent. The substances that are commonly used as emulsifying
agents are gum, soap of different forms, gelatin, albumin, etc.
Role of emulsifier. The stabilisation of an emulsion by means of emulsifier
is called emulsification.
The main function of the emulsifier is to reduce the interfacial
tension between the two liquids forming the emulsion. Emulsifiers are
generally long chain molecules having polar groups.
 MODERN'S abc + OF CHEMISTRY-All

The role of emulsifier can be explained by taking the example of soap as

an emulsifier. As already studied, the soaps are sodium or potassium salts of
= Polar group
higher fatty acids such as sodium palmitate (C,-H,,COONa), sodium stearate
(C,-H,.COONa), etc. A molecule of soap consists of two parts : hydrocarbon
non-polar part (e.g., C,-H,., C,/H,-, etc.) which is soluble in oil and the polar
oa Hydrocarbon group (—COO Na’*) which is soluble in water.
=] non-polar group
R-—COO Nat
When a drop of oil is surrounded by soap solution, R-part of the soap remains
in oil and the COO Nat part remains in water as shown in Fig. 32. As a result, soap
Fig. 32. Role of soap as an emulsifier. molecules get concentrated over the surface of the drop of oil and therefore form
protective film around each oil drop. As a result, the interfacial tension between
oil and water decreases and therefore they are intermixed to form the emulsion.
Casein (a protein), a lyophobic colloid present in milk acts as an emulsifying
agent as it forms a protective layer around fat molecules dispersed in water.
Therefore, milk is a fairly stable emulsion.
Oil
droplets Types of Emulsions. These are of two types :
(i) Oil-in-water (o/w type) emulsions. In this case, oil acts as the
dispersed phase (small amount) and water as the dispersion medium (excess)
[Fig. 33 (a)]. For example, milk is an emulsion of soluble fats in water and here
casein acts as an emulsifier. Vanishing cream is another example of this class.
Such emulsions are called aqueous emulsions.
(ii) Water-in-oil (w/o type) emulsions. In this case, water acts as the
dispersed phase while the oil behaves as the dispersion medium [Fig. 33 (0)].
Oil in water For example, butter, cod liver oil, cold cream, etc. Such types of emulsions are
called oily emulsions.
It may be noted that the two types of emulsions can be interconverted by
simply changing the ratio of the dispersed phase and dispersion medium. For
example, an oil-in-water emulsion can be converted to water-in-oil emulsion by
simply adding excess of oil in the first case.
Identification of emulsions
The oil in water or water in oil type emulsions can be identified by the
following tests :
Water in oll
(D) (i) Dilution test. Add water to the emulsion. If the emulsion can be
diluted with water, this means that water acts as the dispersion medium and
Fig. 33. Types of emulsions.
it is an example of oil-in-water emulsion. In case, it is not diluted, then oil acts
as dispersion medium and it is an example of water-in-oil emulsion.
(ii) Dye test. An oil soluble suitable dye is shaken with the emulsion.
If colour is noticed on looking at a drop of the emulsion, it is oil-in-water type
emulsion. In case the entire background is coloured, it is an example of water
in-oil type.
R U Curious... %
Applications of emulsions
e Both vanishing cream and cold (i) Concentration of ores in metallurgy. The concentration of the
cream are emulsions. Are these sulphide ore of a metal by froth floatation process involves the use of some oil
different or same ? such as pine oil. The oil forms emulsion with ore particles. When air is bubble
O Vanishing cream is an emulsion through the emulsion, it rises to the surface as foam and is skimmed off.
of oil-in-water whereas cold
(ii) In medicine. The various pharmaceuticals and cosmetics available
cream is an emulsion of in liquid form such as cod-liver oil, B-complex, ointments etc. are emulsions of
water-in-oil. Cold cream is water-in-oil type. These are readily adsorbed in the intestines.
used for dry skin as the base
(iii) Cleansing action of soaps. The cleansing action of soap is based
(dispersion medium) in this
upon the formation of oil-in-water type emulsion.
is oll.
(iv) Milk. Milk which is an important constituent of our diet is an emulsion
of fat in water.
SURFACE CHEMISTRY

Demulsification. It is the process of decomposing an emulsion back into

its constituent liquids. The demulsification can be done by centrifugation,
filtration, boiling, freezing and some chemical methods. For example : Colloidal sol of gold in water is
(1) Cream from milk is separated by centrifugation. called purple of cassius.
(it) Fat can be removed from milk by cooling it in a refrigerator. Colloidal sol of silver is called
argyrol and is used as eye
Properties of emulsions lotion.
(1) Emulsions show all the characteristic properties of colloidal solution Colloidal antimony is used for
such as Brownian movement, Tyndall effect, electrophoresis, etc. curing kalazar.
(7i) These are coagulated by the addition of electrolytes containing Colloidal Fe(OH), is given to
polyvalent metal ions indicating the negative charge on the globules. a person having poisoning due
(111) The size of the dispersed particles in emulsions is larger than those in to arsenic because it absorbs
arsenic and then can be vomited
the sols. It ranges from 1000 A to 10,000 A. However, the size is smaller than
out.
the particles in suspensions.
Colloidal solution of graphite in
(tv) Emulsions can be broken (or converted) into two separate liquids by
water is called aqua dag and
heating, centrifuging, freezing, etc. This process 1s also known as demulsification.
that in oil is called oil dag.
GELS Collodion is a 4% solution of
A gel is a colloidal system in which a liquid is dispersed in a solid. Under cellulose nitrate in a mixture of
ethyl alcohol and ether.
certain conditions, the lyophilic sols may be coagulated to give a semi solid jelly
like mass which encloses all the liquid present in the sol. The process of gel Substances such as soaps which
possess surface activity 1.e.,
formation is called gelation and the colloidal system formed is called gel. The
exhibit the property to lower the
common examples of gel are : gum arabic, gelatin, processed cheese, silicic acid,
surface tension of the liquid and
ferric hydroxide, etc.
therefore, increase its surface
Gels may be classified into two types : are called surfactants.
(t) Klastic gels (it) Non-elastic gels.
(i) Elastic gels. These are the gels which possess the property of elasticity.
They readily change their shape on applying force and return to original shape
when the applied force is removed. They change to solid mass on dehydration
which can again be converted into gel by addition of water followed by heating
and cooling. When these gels are placed in contact with water, they absorb water
and swell. This property is called imbibition. Common examples are gelatin,
agar, starch etc.
(ii) Non-elastic gels. These are the gels which are rigid and do not have
the property of elasticity. They change into solid mass on dehydration which
becomes rigid and cannot be converted into original form by heating with water.
Unlike elastic gels they do not show the phenomenon of imbibition. For example,
silica gel.
COLLOIDS AROUND US
We come across many phenomena of colloids in our day to day life. Some
of these are:
1 Blue colour of the sky and sea. Blue colour of the sky is due to the
scattering of light by colloidal dust particles present in the air (Tyndall effect).
These dust particles alongwith water suspended in air scatter blue light which
reaches our eyes and therefore, sky looks blue to us. This is because blue colour O Sky looks blue!
of white sunlight has minimum wavelength and hence shows more intense Sky looks blue dueto scattering of
scattering. Similarly, sea water looks green due to scattering of light by the light by colloidal dust particles.
colloidal impurities present in sea water. Since blue colour of sunlight has
2. Fog, mist and rain. When a large mass of air containing dust particles
minimum wavelength, it shows
is cooled below its dew point, the moisture present in the air condenses on the
more intense scattering. The
surface of these particles and form fine droplets. These droplets are colloidal in
nature and continue to float in the air in the form of mist or fog. scattered blue light reaches our
Clouds are aerosols having small droplets of water being suspended in air. eyes and, therefore, sky looks
Because of condensation in the upper atmosphere, the colloidal droplets of water blue to us.
become bigger and bigger in size till they fall down in the form of rain. Sometimes,
the rainfall occurs when two oppositely charged clouds collide.
 MODERN'S abc + OF CHEMISTRY-All

3. Food articles. Many food articles such as milk. butter, ice-creams fruit
juices, fruit jellies, whipped cream, etc. are colloidal in nature.
4. Soils. Fertile soils are also colloidal in nature. In the soil, the humus acts
as a protective colloid. Because of colloidal nature soils adsorb moisture and
other nourishing substances.
5. Dyeing. In the dyeing of fabrics, the fabric is first treated with a colloidal
suspension of a substance called mordant (e.g., aluminium hydroxide). The
mordant should be such that it gets strongly adsorbed on the fabric and then
the dye gets strongly adsorbed on it. As a result, the dye sticks fast to the fabric.
6. Varnishes, paints, enamels, resins, cellulose gums, glues, soaps, detergents,
etc. are all colloidal in nature.
7. Asphalt emulsified on water is used for building roads without the
necessity of melting the asphalt is colloid.
8. Formation of delta. River water is muddy and contains charged colloidal
particles of clay, sand and many other materials. Sea water contains in it a
number of dissolved electrolytes. When the river water comes in contact with
the sea water, the electrolytes present in sea water coagulate the suspended
colloidal particles which ultimately settle down at the point of contact. As a result,
the level of the river bed rises. As a result, water adopts a different course and
delta is formed in due course of time at the point where the river enters the sea.
High voltage source (30,000V) 9. Tail of comets. Tail behind a comet is seen as Tyndall cone due to
scattering of light by the tiny solid particles of colloidal range left by the comet
in its path.
To chimney 10. Blood. It is a colloidal solution of an albuminoid substance. Bleeding
eeeP(coses free stops when alum and ferric chloride solution is applied to a bleeding part. The
from dust)
styptic action of alum or ferric chloride is due to coagulation of blood by an
electrolyte forming a blood clot which stops further bleeding.
APPLICATIONS OF COLLOIDS
Colloids play a vital role in our daily life. The applications, in general, are
based upon the presence of the charge on the colloidal particles.
1. Electrical precipitation of smoke. In big cities, the factories work
round the clock and the smoke coming out of the chimneys contain a lot of unburnt
Precipitated ash carbon particles. Smoke is a colloidal solution of solid particles such as carbon,
arsenic compounds, dust, etc. in air. These are quite injurious to health and have
to be precipitated from the smoke. In fact, smoke is a colloidal system in which
Fig. 34. Cottrell smoke precipitator. the carbon particles are suspended in air. The carbon particles are charged in
nature and they do not get coagulated or precipitated.
The charge on the carbon particles is neutralised by bringing them in contact
STEM AND TECHNOLOGY with the oppositely charged metal plate. They thus, get precipitated and the
Colloidal particles in a sol are very smoke coming out of the chimney is free from dust. This precipitation of smoke
small and most of them are not particles is carried out by Cottrell smoke precipitator shown in Fig. 34. In
visible through an ultramicroscope this method, the smoke is allowed to pass through a chamber having a series of
or light microscope. Recently, new plates charged to very high potential (20,000 to 70,000 V). Charged particles of
techniques have been developed to smoke get attracted by charged plates, get precipitated and the gases coming
determine the size and shape of the out of chimney become free of charged particles.
colloidal particles. These are : 2. Sewage disposal. The sewage disposal contains particles of dirt, rubbish,
(1) Scanning Electron Microscope etc. suspended in water. They are, therefore, colloidal in nature and are also charged.
(SEM) These particles do not settle down easily. The particles can be removed by discharging
them at electrodes. The dirty water is either placed in big tanks or passed through
(it) Transmission Electron Microscope
a tunnel fitted with metallic electrodes which are maintained at high potential
(TEM)
difference. The colloidal particles migrate towards the oppositely charged electrodes
A modified form of the above methods
where their charge is neutralised and they get coagulated. The coagulated mass can
has also been developed. It is called
be used as a manure and the water left behind is used for irrigation.
Scanning Transmission Electron
3. Purification of drinking water. The water coming from natural sources
Microscope (STEM). All these
often contains suspended impurities. The drinking water can be purified by
techniques are superior to the light
precipitation of suspended colloidal particles . For this purpose, a small amount
microscope because they have greater
of alum [K,SO, Al, (SO,),. 24H,O] is added. The Al** ions neutralise the charge
resolving power. on the particles and they get coagulated.
SURFACE CHEMISTRY

4. Colloidal medicines. A wide variety of medicinal and pharmaceutical

preparations are emulsions. The colloidal medicines are quite effective on account
of their easy assimilation and adsorption. A few important medicines are colloidal
gold, manganese, sulphur, antimony, etc. For example,
(4) Argyrol is a silver sol used as an eye lotion.
(it) Colloidal antimony is used for curing disease kala azar.
(iit) Milk of magnesia, an emulsion is used for stomach disorders.
(tv) Colloidal gold is used for intramuscular injection. Colloidal medicines
are more effective because these have large surface area and therefore, are easily
assimilated with blood, which is colloidal.
(v) Ferric chloride is quite effective to stop bleeding from a minor cut. It
coagulates the blood due to its charged nature.
5. Tanning. Animal hides are colloidal in nature and have positively charged
particles. Tannin, which is obtained from plants contains negatively charged colloidal
particles. When animal hides are soaked in tannin, their mutual coagulation takes
place. This results in hardening of leather. This process of hardening of leather is
called tanning. Chromium salts are also used in place of tannin.
6. In disinfectants. The disinfectants such as dettol and lysol give emulsions
of the oil-in-water when mixed with water.
7. Photographic plates and films. These are thin glass plates or celluloid
films coated with gelatin containing a fine suspension of silver bromide. The
particles of silver bromide are colloidal in nature.
8. Chemical warfare. Smoke or mist screens are formed by the dispersion of
harmful substances by explosion of bombs, etc. They are very injurious to health.
Gas masks are essential to filter out the toxic smokes. These masks contain in
them colloidal animal charcoal to adsorb the poisonous gases.
9. Artificial rain. Artificial rain can be caused by spraying oppositely
charged colloidal dust or sand particles over a cloud from an aeroplane. The
colloidal water particles present in the cloud will get neutralised and will
coagulate to form bigger water drops causing artificial rain.
10. Rubber industry. Latex is a colloidal solution of negatively charged
colloidal rubber particles. Rubber can be obtained from latex by coagulation.
These rubber particles can be deposited over articles (wares or handles of
different tools) to be rubber plated by electrophoresis. The article to be rubber
plated is made the anode in the rubber plating bath. Rubber gloves are formed
by rubber plating on suitable templates.
11. In metallurgical operations. Emulsions play an important role in
industry. The metal ores are concentrated by froth-floatation process which
involves the treatment of the pulverised ore in emulsion of pine oil.

add on
» Why are lyophilic colloidal sols more stable than lyophobic colloidal sols ? (D.S.B. 2015)
. The lyophilic colloidal sols. are more stable because they are highly hydrated in solution.
. Give one test to distinguish whether the given emulsion is oil in water type or water in oil type emulsion.
. It can be identified by dilution test. In this method, the emulsion is diluted with water. If the emulsion gets diluted
with water, this means that water acts as the dispersion medium and it is an example of oil in water emulsion. If,
it is not diluted than oil acts as dispersion medium and it is an example of water in oil emulsion.
. What is observed when sodium chloride is added to a colloidal solution of ferric hydroxide ?
. When sodium chloride is added to ferric hydroxide sol., the sol. gets coagulated. This is because the Cl ions from
NaCl neutralie the +ve charge on Fe(OH), sol.
. Give an example of (7) micelles system (ii) macromolecular colloid.
5 (z) Sodium stearate (C,,H,,.COO Na’). (iz) Proteins.
 MODERN'S abc + OF CHEMISTRY-All

Q. 5. What is the difference between a sol and a gel ? (D.S.B. 2017)

Ans. In a sol, dispersion medium is liquid and dispersed phase 1s solid. On the other hand, in a gel, dispersion medium
is solid and dispersed phase 1s liquid.
Q. 6. What is the difference in the nature of a dilute soap solution and a concentrated soap solution ?
Ans. Dilute soap solution behaves like a true solution whereas concentrated soap solution behaves like a colloidal solution.
Q. 7. What happens when a colloidal sol of Fe(OH), and As,O, are mixed ?
Ans. Their mutual precipitation takes place.
Q. 8. The conductance of an emulsion increases on adding common salt. What type of emulsion is this ?
Ans. Oil in water type emulsion.
Q. 9. What happens when a freshly precipitated Fe(OH), is shaken with little amount of dilute solution of
FeCl, ? (Hr. S.B. 2004)
Ans. A reddish brown colloidal solution of Fe(OH), is obtained. This process is called peptization.
The Fe** ions from FeCl, are adsorbed on the surface of the precipitate and form positively charged colloidal solution.
FeCl, ———> Fe? +2CL
Fe (OH), + Fe** ——— ___ [Fe(OH),] Fe**
Colloidal solution
. What type of colloid is formed when a liquid is dispersed in a solid? Give anexample. (A./.S.5. 2017)
. Gel
For example: Cheese
. What does reciprocal of gold number indicate ?
. Reciprocal of gold number is a measure of protective power of a colloid. Smaller the value of gold number, greater
will be its protecting power.
. 50 mL of standard gold sol. needs 0.05 mg of gelatin for its protection from coagulation. Calculate gold
number of gelatin.
. 50 mL of gold sol. require gelatin for protection from coagulation = 0.05 mg
10 mL of gold sol. will require gelatin for protection from coagulation = 0.005 mg
.. Gold number of gelatin = 0.005.
.» 100 mL of a colloidal solution is completely precipitated by addition of 5 mL of 1 M NaCl solution.
Calculate the coagulation value of NaCl. (Hr. S.B. 2004)
. Coagulation value is the millimoles of an electrolyte that must be added to 1 L of a colloidal solution for complete
coagulation.
1
-.5mLof1M NaCl= x 5 = 0.005 or 5 m moles.
1000

100 mL of a colloidal solution require NaCl for complete coagulation = 5 m moles

“. 1 Lof colloidal solution require NaCl for complete coagulation = 50 m moles
~. Coagulation value of NaCl = 50.
Q. 14. What is the charge on the colloidal particles in the following:
(1) Fe(OH), sol (i1) As,S, sol (111) Colloidal sol of silver ?
Ans, (1) Fe(OH), sol : +ve
(iz) As,5, sol : -ve
(112) Colloidal sol of silver : —ve.
Q. 15. Which of the following is most effective electrolyte in the coagulation of Fe,O,.H,O/Fe* sol ?
KCl, AICI, MgCl, K,[Fe CN),] (CBSE Sample Paper 2011)
Ans. Since Fe(OH), sol is positively charged, the anion having highest charge will be most effective i.e., [Fe(CN),]*-.
Q. 16. Peptizing agent is added to convert precipitate into colloidal solution. Explain.
(CBSE Sample Paper 2011)
Ans. Peptisation is a process of converting a freshly prepared precipitate into colloidal form by the addition of an
electrolyte called peptising agent. The suitable ions from the peptising agent (electrolyte) are adsorbed by the
particles of the precipitate giving it positive or negative charge. The charged particles repel one another and break
up the precipitate into smaller particles of the size of the colloid. Therefore, it results into the formation of colloid.
For example, on treating a precipitate of iron (III) oxide with a small amount of FeCl, solution gives a reddish brown
coloured colloidal solution.
SURFACE CHEMISTRY 5/49 =

Fe(OH), + Fe** —> Fe(OH), Fe*+

Precipitate Electrolyte Colloidal solution
Q. 17. Cottrell’s smoke precipitator is fitted at the mouth of chimney used in factories. Give reasons.
(CBSE Sample Paper 2011)
Ans. Smoke coming out of chimney of a factory 1s a colloidal solution of soild carbon particles which are charged in nature.
The mouth of the chimneys used in factories 1s fitted with Cottrell smoke precipitator. In this method, the smoke
is allowed to pass through a chamber having a series of plates charged to very high potential (20,000 to 70,000 V).
Charged particles of smoke get attracted by charged plates, get precipitated and the gases coming out of chimney
become free of charged carbon and dust particles.
Q. 18. Why is colloidal gold used for intramuscular injection ? (CBSE Sample Paper 2011)
Ans. Colloidal gold is more effective because of larger surface area and therefore, is easily assimilated with blood which
is colloidal.
Q. 19. What is colloidion ? (CBSE Sample Paper 2011)
Ans. 4% solution of nitrocellulose in a mixture of alcohol and ether.
Q. 20. Differentiate between peptization and coagulation. (CBSE Sample Paper 2011, A..S.B.2017)
Ans. Peptization is the process of converting a freshly prepared precipitate into collodial form by the the addition of a
suitable electrolyte. The electrolytes used for the purpose are called peptizing agents. On the other hand, coagulation
is the phenomenon of precipitation of a collodial solution by the addition of excess of an electrolyte.
Q. 21. Why is ferric chloride preferred over potassium chloride in case of a cut leading to bleeding ?
Ans. Fe** is a better coagulating ion than K* due to larger positive charge on it.
Q. 22. Explain:
(1) Sky appears blue in colour.
(ii) Afreshly formed precipitate of ferric hydroxide can be converted to a colloidal sol by shaking it
with a small quantity of ferric chloride. (CBSE Sample Paper 2011)
Ans. (i) Dust particles alongwith water suspended in air scatter blue light which reaches our eyes and therefore, sky
looks blue to us.
(71) When we add FeCl, to a freshly formed precipitate of Fe(OH),, peptisation occurs. The Fe** ions are adsorbed
on the surface of the precipitate which ultimately breaks down into smaller particles of colloidal size.
Q. 23. Leather gets hardened after tanning. Why? (D.S.B. 2015)
Ans. Animal hide is colloidal in nature and has positively charged particles. When it is soaked in tanin which has
negatively charged colloidal particles, it results in mutual coagulation. This results in the hardening of leather.
Q. 24. It is necessary to remove CO when ammonia is prepared by Haber’s process. Explain. (D.S.B. 2015)
Ans. Carbon monoxide acts as a poison for the catalyst in Haber’s process and therefore, it will lower the activity of the
catalyst. Thus, CO must be removed when ammonia is obtained by Haber’s process.
Q. 25. Addition of alum purifies water. Why? (A.LS.B. 2015)
Ans. Alum coagulates the impurities present in water by neutralising the charge.
Q. 26. Out of MgCl, and AICI, which one is more effective in causing coagulation of negatively charged sol
and why? (D.S.B. 2016)
Ans. According to Hardy Schulze rule, for negatively charged sol, greater the valency of the positive ion of the electrolyte
added, greater is its coagulating power. Thus, AlCl, (Al** ion) is more effective in causing coagulation of negatively
charged sol than MgCl, (Mg** ions).
Q. 27. Out of sulphur sol and proteins, which one forms multimolecular colloids? (D.S.B. 2016)
Ans. Proteins are macromolecules which cannot form multimolecular colloids while sulphur sol has smaller S$, molecules
which can coagulate to form multimolecular colloids.
Q. 28. Write the dispersed phase and dispersion medium of milk. (A.LS.B. 2017)
Ans. Dispersed phase: Liquid
Dispersion medium: Liquid
Q. 29. Write the chemical method by which Fe(OH), sol is prepared from FeCl.,. (A.LS.B. 2017)
Ans. FeCl,(s) + 3H,0 —““** 5 Fe(OH), (sol) + 3HCl
 MODERN'S abc + OF CHEMISTRY-All

@ Adsorption. The phenomenon of higher concentration of molecular species (gases or liquids) on the surface of a solid than
in the bulk.
Occlusion. The adsorption of a gas on the surface of a metal.
Adsorbent. The substance on which adsorption takes place.
Adsorbate. The substance adsorbed.
Colloidal solution. A heterogeneous solution which contains particles having diameters between 1 to 1000 nm. These are
intermediate between true solutions and suspensions.
Lyophilic colloids. The colloidal solutions in which the particles of the dispersed phase have a great affinity for the
dispersion medium.
@ Lyophobic colloids. The colloidal solutions in which the particles of the dispersed phase have no affinity for the dispersion
medium.
Micelles. These are the cluster or aggregated particles formed by association of colloids in solution.
Dialysis. It is the process of separating particles of colloids from those of crystalloids by means of diffusion through a membrane.
Brownian movement. The random zig zag motion of colloidal particles.
Electrophoresis. The phenomenon of movement of colloidal particles under an applied electric field.
Coagulation. The process of changing the colloidal particles in a sol. into the insoluble precipitate by the addition of some
suitable electrolytes is known as coagulation.
Peptisation. Conversion of a freshly precipitated substance into colloidal sol. by shaking with a suitable electrolyte is
called peptisation.
@ Gold number. The minimum number of milligrams of a lyophilic sol. needed to protect 10 mL of gold sol. by the addition
of 1 mL of 10% NaCl is called gold number. Protective power is the reciprocal of gold number.
@ Emulsions are colloidal systems in which both dispersed phase and dispersion medium are liquids.
@ Emulsification. The process of making emulsion is called emulsification.
@ Gel. A colloidal system in which a liquid is dispersed in a solid.

QUICK CHAPTER ROUND UP!

ADSORPTION > For adsorption,
higher conc. of any species at the AH —ve, AS =-ve
surface than in the bulk AG AH-TAS
= —-ve — T(-ve)
For AG to be -ve (spontaneous) AH > TAS

Physical adsorpti Chemical adsorption

e weak van der Waals forces e strong chemical forces

¢ low enthalpy of adsorption e high enthalpy of adsorption
* reversible * irreversible
¢ related to ease of liquefication e not related to ease of liquefication » Higher the critical temperature of a gas
of gas of gas ereater is its adsorption.
* not very specific * highly specific e.g., NH, > CO, > CH, > CO>N, > H,
¢ forms multimolecular layers e forms mono-molecular layer
SURFACE CHEMISTRY 5/51 —

Freundlich adsorption isotherm

At low pressure At high pressure

> Plot of log “vs log P gives slope = 7 and intercept = log &
m.

CATALYSIS
i ® A catalyst provides a new pathway
of lower activation energy.

+ Catalysts donot change

AHorAG
) ® Catalysts are highly specific.

® Catalyst in the same ® Catalyst in different phase

phase as reactants (han the cesctants >Promoters: The substances which
m increase the activity of a catalyst.
»Catalytic poisons: The substances
ENZYME CATALYSIS which decrease the activity of a catalyst.

Biological catalysts produced by living cells.

> high efficiency
» needed in extremely © CH, 0, oe » 2C,H,OH (aq) + 2CO, optimum temperature (310 K
igs P (
> optimum pH (5-7)
small quantities Glucose
Prvertase » regulated activity
oe °C,,H,.0,;(aq) + HO —“*2y C5H,,0, + CgH,,0,
Sucrose Glucose Fructose

SIZES OF PARTICLES OF SOLUTIONS

True solutions Colloids

<10°m 10” m to 10° m

< 1pm 1 nm — 1000
nm

COLLOIDS

Based on Nature of Interactions between Dispersed

Phase and Dispersion Medium

Lyophilic Colloids e Component present in small Lyophobic Colloids

e particles of dispersed phase have great proportion =Dispersed phase _ ®* particles of dispersed phase have no affinity
affinity for dispersion medium e Component present in large for the dispersion medium
¢ not easily visible even under ultramicroscope proportion >Dispersion ® easily detected under ultramicroscope
¢ reversible in nature medium ® irreversible in nature
e very stable * unstable
 MODERN'S abc + OF CHEMISTRY-All

Based on Type of Particles of Dispersed Phase

Multimolecular Macromolecular Associated

* consist of aggregates of atoms * consist of large molecules generally * consist of aggregation of a larger number of
or molecules (have diameter less polymers ions which behave as colloidal size particles
than 1 nm) > rubber, nylon, starch at higher concentrations
> Sols of gold, sulphur > soap sols

Colloidal solutions are heterogeneous consisting of two phases

Colloidal solutions show:

» Brownian movement >» Tyndall effect =» Electrical properties >» Have charge

+ vely charged Sols - vely charged Sols

Electrophoresis helps
* metallic hydroxides; Fe(OH)z, ® metallic particles Cu, Ag, Au, Pt
to study the charge
Al(OH),, Cr(OH), * sulphides As,S,, Sb,S, carried by the particles.
« metallic oxides; Al,O,.«H,O

The minimum number of millimoles

of the electrolyte required for
coagulation of 1L of colloidal sol
is called coagulation value or
® ion carrying charge opposite to sol particles coagulate the sol flocculation value.

For negative sol like As,5, For positive sol like Fe(OH), The smaller is the coagulation
Al#+ > Mo?* > Nat [Fe(CN) J > PO = vor ae ie value of an electrolyte, greater
is its coagulation power.

GOLD NUMBER EMULSIONS GEL

* minimum amount of protective * Colloidal solution in which dispersed phase ¢ colloidal system in which a
colloid required to prevent and dispersion medium are liquids liquid is dispersed in a solid.
coagulation > Oil in water type e.g., gelatin, processed cheese,
e smaller the value of gold e.g., milk, vanishing cream gum arabic
number, greater is the protective > Water in oil type e.g. butter, cold cream
power of protective colloid.
e Protective power of a colloid is
reciprocal of gold number

Important Graphs

rT : Saturation
Physical
adsorption
Chemical
adsorption

y¥pressure
SURFACE CHEMISTRY

. NCERT FI a Solved
n-text Questions //
Q.1. Why are substances like platinum and palladium Q.5. Why is the ester hydrolysis slow in the beginning
often used for carrying out electrolysis of aqueous and becomes faster after sometime ?
solutions ?
Ans. This is because of the process of autocatalysis. Ester on
Ans. Platinum and palladium are often used for carrying out hydrolysis gives an acid which starts acting as a catalyst
electrolysis because these are inert in nature and the after sometime and therefore, the reaction becomes fast.
products of electrolysis easily get adsorbed or deposited
over these metals. Therefore, products can be easily
Q.6. What is the role of desorption in the process of
catalysis ?
collected.
Q.2. Why does physisorption decrease with the increase Ans. In the process of catalysis, when desorption occurs from
of temperature ? the surface of the catalyst, the surface becomes ready to
adsorb fresh reactants and act as a catalyst.
Ans. In physisorption, the attractive forces between adsorbent
and adsorbate molecules are weak van der Waals forces. Q.7. What modification can you suggest in Hardy Schulze
When temperature is increased, the kinetic energy of law ?
the molecules of the gas increases and they can easily Ans. The Hardy Schulze law considers the coagulation of
leave the surface of adsorbent because of weak forces of sols because of neutralization of their charges. Since
attraction. coagulation can also occur by mixing two oppositely
Q.3. Why are powdered substances more effective charged sols, it should also include
adsorbent than their crystalline forms ? “when oppositely charged sols are mixed in proper
Ans. This is because powdered substances have more surface proportions to neutralize the charges of each other, the
area as compared to their crystalline forms. Greater the coagulation of both the sols occurs”.
surface area, greater is the adsorption. Q.8. Why is it essential to wash the precipitate with
Q.4. Why is it necessary to remove CO when ammonia water before estimating it quantitatively ?
is obtained by Haber’s process ? Ans. The precipitates may be contaminated with the adsorbed
Ans. Carbon monoxide acts as a poison for the catalyst in particles of some other substances (impurities) which
Haber process and therefore, it will lower the activity of might have been used or formed during precipitation.
the catalyst. Thus, CO must be removed when ammonia Therefore, it 1s essential to wash the precipitate to remove
is obtained by Haber’s process. these adsorbed particles.

Textbook Exercises //
Q.1. Distinguish between the meaning of the terms Q.5. What is an adsorption isotherm ? Describe
adsorption and absorption. Give one example of Freundlich adsorption isotherm.
each, Ans. Adsorption isotherm represents the variation of the
Ans. Adsorption is a phenomenon in which there is higher mass of the gas adsorbed per gram of the adsorbent with
concentration of another substance on the surface than pressure at constant temperature.
in the bulk. Absorption is a phenomenon in which the For Freundlich adsorption isotherm, refer Text
molecules of a substance are uniformly distributed Page 9.
throughout the body of the other substance. Q.6. What do you understand by activation of adsorbent?
For example, silica gel adsorbs water vapour while How is it achieved ?
anhydrous calcium chloride absorbs water. Ans. Activation of adsorbent means the increasing of the
Q.2. What is the difference between physisorption and adsorbing power of the adsorbent. For detail see Text
chemisorption ? Page 8.
Ans. Refer Text Page 6. Q.7. What role does adsorption play in hetero-geneous
Q.3. Give reason why a finely divided substance is more catalysis?
effective as an adsorbent. Ans. In heterogeneous catalysis, the reactants are generally
Ans. Finely divided substance has larger surface area and gases while catalysts are solids. The reactant molecules
hence greater adsorption. are adsorbed on the surface of the solid catalyst by
Q.4. What are the factors which influence the adsorption physical adsorption or chemical adsorption. As a result,
of a gas on a solid ? the concentration of the reactant molecules on the surface
of the catalyst increases and hence the rate of reaction
Ans. Refer Text Page 7. also increases.
 MODERN'S abc + OF CHEMISTRY-All

Alternatively, one of the reactant molecules undergo Q.14. How are colloids classified on the basis of
fragmentation on the surface of the catalyst producing (a) physical states of components, (6b) nature of
active sites which make the reaction fast. The product dispersion medium, and (c) interaction between
molecules, on the other hand, have no affinity for the dispersed phase and dispersion medium ?
solid catalyst and therefore, undergo desorption leaving . (a) Classification of colloids on the basis of physical
the surface free for further fresh adsorption. This theory states of components. The colloids can be classified
is called adsorption theory. on the basis of physical state of dispersion medium
Q.8. Why is adsorption always exothermic ? and dispersed phase. For detail, refer Text Section
Ans. Adsorption occurs because of attraction between adsorbate Page 26.
and adsorbent molecules and therefore, energy is always (6) Classification on the basis of nature of dispersion
released during adsorption. Hence adsorption is an medium. Depending upon the nature of the dispersion
exothermic process. medium, the colloidal solutions are classified as :
Q.9. How are the colloidal solutions classified on the (t) Aquasol or hydrosol : when dispersion medium
basis of physical states of the dispersed phase and is water.
dispersion medium ? (11) Aleosol : when dispersion medium is alcohol.
Ans. Refer Text Page 26. (iit) Benzosol : when dispersion medium is benzene.
Q.10. Discuss the effect of pressure and temperature on (iv) Aerosol : when dispersion medium is alr.
the adsorption of gases on solids. (c) Classification on the basis of nature of
Ans. Refer Text Page 8. interactions between dispersed phase and
dispersion medium. These may be classified as
Q.11. What are lyophilic and lyophobic sols ? Give one
example of each type. Why is lyophobic sols easily (t) Lyophilic sols and (ii) lyophobic sols.
coagulated ? For detail refer Page 27 type B.
Ans. The lyophobic sols are less stable because their stability is Q.15. Explain what is observed
due to charge only. If the charge is removed, the particles (1) when a beam of light is passed through a
will come nearer to each other to form aggregates i.e., colloidal sol., (ii) an electrolyte, NaCl is added to
they will coagulate and settle down. On the other hand, hydrated ferric oxide sol. (iii) electric current is
the stability of lyophilic sols is due to charge as well as passed through a colloidal sol. ?
solvation of colloidal particles. Therefore, these are not Ans. (1) Scattering of light by colloidal particles takes place
easily coagulated. and path of light becomes visible (Tyndall effect).
Q.12. What is the difference between multimolecular and (it) The positively charged colloidal particles of Fe(OH), get
macromolecular colloids ?
coagulated by the oppositely charged Cl ions provided
Give one example of each. How are associated colloids by NaCl.
different from these two types of colloids ? (111) On passing electric current, the colloidal particles move
Ans. The important differences between multimolecular and towards the oppositely charged electrode where they lose
macromolecular colloids are :
their charge and get coagulated. This is electrophoresis

Multimolecull
process.
For details of these, refer Text Page 39-40.
1. The colloidal particles The colloidal particles are Q.16. What are emulsions? What are their different
consist of aggregates of macromolecules having very types ? Give one example of each type.
a large number of atoms large molecular mass. Ans. Refer Text Page 45-44.
or molecules having Q.17. What is demulsification ? Name two demulsifiers.
diameter less than Inm. Ans. The process of separation of constituent liquids of an
. Particles are held by They consist of macro- emulsion is called de-emulsification.
weak van der Waals molecular particles held by
forces. chemical bonds. De-emulsification can be done by (z) boiling or
(11) centrifugation.
The common example of multimolecular colloid is sulphur Q.18. Action of soap is due to emulsification and micelle
sol, which consists of particles of S, molecules. The formation. Comment.
common example of macromolecule is starch.
Ans. Refer Text Page 31.
The associated colloids are substances which behave as
Q.19. Give four examples of heterogeneous catalysis.
normal electrolytes at low concentrations but behave as
colloidal particles at higher concentration. For example, Ans. Refer Text Page 16.
soap and detergents. Q.20. What do you mean by activity and selectivity of
They differ from multimolecular and macromolecular catalysts ?
colloids in the sense that they behave as normal Ans. Activity means the ability of catalysts to increase the
electrolytes at low concentrations but exhibit colloidal chemical reaction. A common example of activity is the
state properties at higher concentrations due to the reaction H, and O, to form water in the presence of
formation of aggregated particles called micelles. platinum. Without the presence of the catalyst, the mixture
Q.13.What are enzymes ? Write in brief the mechanism of H, and O, can be safely stored. But in the presence of
of enzyme catalysis. catalyst, the reaction occurs with explosive voilence. In
Ans. Enzymes are complex nitrogeneous organic compounds some cases the catalyst can accelerate the reaction to as
produced by living cells which catalyze the biochemical high as 10° times.
reactions occurring in living organisms. These are also The selectivity means the ability of the catalyst to direct
called biological catalysts or bio-chemical catalysts. reaction to give particular products. For example, n-heptane
For detail Refer Text Pages 19-22. in the presence of platinum catalyst gives toluene.
SURFACE CHEMISTRY

Q.24. Give four uses of emulsions.

n C,H,, —— C,H,CH, Ans. Refer Text Page 44.
Similarly, propylene (CH,CH=CH,) reacts with O, in the Q.25. What are micelles ? Give an example of a miceller
presence of bismuth molybdate catalyst to selectively system.
give acrolein (CH,=CHCHO). Ans. Refer Page 29.
Q.21. Describe some features of catalysis by zeolites. Q.26. Explain the terms with suitable examples :
Ans. Zeolites are microporous aluminosilicates of the general (1) Aleosol (ii) Aerosol and (111) Hydrosol.
formula M,,, [(AIO,), (Si0,),] mH,O. These are most Ans. (1) Aleosol. It is a collodial sol of a solid in alcohol as
important oxide catalysts. These are used in petrochemical dispersion medium.
industries for cracking of hydrocarbons and isomerization. (iz) Aerosol. It is a collodial dispersion of a liquid in a gas
The reactions in zeolites depend upon the size of the e.g., fog.
cavities (cages) or pores (apertures) present in them. The (iii) Hydrosol. It is a colloidal sol of a solid in water as
most remarkable feature of zeolite catalysis 1s the shape dispersion medium.
selectivity. Therefore, the selectivity of catalyst depends Q.27. Comment on the statement that “colloid is not a
on the pores structure. It has been observed that the substance but a state of substance”.
pore size in zeolites generally varies between 260 pm to Ans. Colloid is not a substance but it is a state of substance.
740 pm. Depending upon the size of the reactants and This statement means a particular substance may exist
products compared to the size of the cages or pores of as a colloid under certain conditions and as a crystalloid
zeolite, reactions proceed in specific manner. under other conditions. For example, sodium chloride in
A zeolite catalyst called ZSM-5 converts alcohols to water behaves as a crystalloid while in benzene, it behaves
gasoline, by first dehydrating the alcohol by loss of water. as a colloid. Similarly, dilute soap solution behaves like
Q.22. What is shape selective catalysis ? a crystalloid while the concentrated solution behaves as
Ans. The catalysis by zeolites 1s called shape selective catalysis. a colloid (called associated colloid). It is the size of the
For details refer Text Page 25. particle that decides the state in which the substance
Q.23. Explain the following terms : (i) Electrophoresis exists. If the size of the particles lies in the range of
(ii) Coagulation (iii) Dialysis (iv) Tyndall effect. 10 nm to 100 nn, it is in the colloidal state.
Ans. Refer Text.

Exemplar Problems //
Subjective Questions

. Gelatin which is a peptide is added in ice creams.

What can be its role ?
. Why is it important to have clean surface in surface . Ice creams are emulsions which get stabilised by
studies ? emulsifying agents such as gelatin.
. Clean surface facilitates the adsorption of desired species . What is collodion ?
and help in surface studies. . Itisa 4% solution of nitrocellulose in a mixture of alcohol
. Why is chemisorption referred to as activated and ether.
adsorption ? . Why do we add alum to purify water ?
. Chemisorption involves formation of bond between . The colloidal impurities present in water get coagulated
gaseous atoms or molecules and the solid surface. This by added alum. This makes water potable.
requires high activation energy. Thus, it is referred to as
. What happens when electric field is applied to
activated adsorption.
colloidal solution ?
. What type of solutions are formed on dissolving
. The charged colloidal particles start moving towards
different concentrations of soap in water ?
oppositely charged electrodes.
Ans. At lower concentration soap forms a normal electrolytic
10. What causes brownian motion in colloidal
solution with water. After a certain concentration
called critical micelle concentration, colloidal solution is dispersion?
formed. . Unbalanced bombardment of the particles of dispersed
. What happens when gelatin is mixed with gold phase by molecules of dispersion medium causes Brownian
sol? motion. This stabilises the sol.
Ans. Gold solis a lyophobic sol. Addition of gelatin stabilises the 11. A colloid is formed by adding FeCl, in excess of hot
sol. water. What will happen if excess sodium chloride
. How does it become possible to cause artificial rain is added to this colloid?
by spraying silver iodide on the clouds ? Ans. Positively charged sol of hydrated ferric oxide is formed
Ans. Clouds are colloidal in nature and carry charge. Spray and on adding excess of NaCl, negatively charged chloride
of silver iodide, (an electrolyte) on the clouds results in ions coagulate the positively charged sol of hydrated ferric
coagulation leading to artificial rain. oxide.
 MODERN'S abc + OF CHEMISTRY-All

12. How do emulsifying agents stabilise the emulsion ? 22. Why does the white precipitate of silver halide
Ans. The emulsifying agent forms an interfacial layer between become coloured in the presence of dye eosin?
suspended particles and the dispersion medium thereby Ans. The dye eosin is adsorbed on the surface of silver halide
stabilising the emulsion. precipitate. Therefore, the precipitate is coloured.
138. Why are some medicines more effective in the 2a. What is the role of activated charcoal in gas mask
colloidal form ? used in coal mines ?
Ans. Medicines are more effective in the colloidal form because of Ans. Activated charcoal acts as an adsorbent for various
large surface area and are easily assimilated in this form. poisonous gases present in the coal mines.
14 Why does leather get hardened after tanning ? 24, How does a delta form at the meeting place of sea
and river water ?
Ans. Animal hide is colloidal in nature and has positively
charged particles. When it is soaked in tanin which River water is muddy and contains charged particles of
has negatively charged colloidal particles, it results in clay, sand and other materials. When the river water comes
mutual coagulation. in contact with sea water, the electrolytes present in sea
water coagulate the suspended colloidal particles which
15. How does the precipitation of colloidal smoke take
ultimately settle down at the point of contact. The point
place in Cottrell precipitator ?
at which river and sea meet is the site for coagulation. The
Ans. In Cottrell precipitator, charged smoke particles are deposition of coagulated clay results in delta formation.
allowed to pass through a chamber having a series of
20. Give an example where physisorption changes to
plates charged to very high potential (20,000 to 70,000
chemisorption with rise in temperature. Explain
V) opposite to the smoke particles. Smoke particles lose
the reason for change.
their charge on the plates and get precipitated. Therefore,
Ans. The process of physisorption for example that of H,
the gases coming out of the chimney become free of
on finely divided nickel, involves weak van der Waals’
charged particles.
forces. With increase in temperature, hydrogen molecules
16 How will you distinguish between dispersed phase dissociate into hydrogen atoms which are held on the
and dispersion medium in an emulsion ? surface by chemisorption.
Ans. On adding dispersion medium, emulsions can be diluted 26. Why is desorption important for a substance to act
to any extent. The dispersed phase forms a separate layer as good catalyst ?
if added in excess. Ans. After the reaction is complete between adsorbed reactants,
17. On the basis of Hardy-Schulze rule explain why the the process of desorption 1s important to remove products
coagulating power of phosphate is higher than chloride. and further create space for the other reactant molecules
Ans. The minimum quantity of an electrolyte required to to approach the surface and react.
cause coagulation of a sol is called its coagulating value. 27 What is the role of diffusion in heterogenous catalysis ?
According to Hardy-Schulze rule, greater the charge on Ans. The gaseous molecules diffuse on to the surface of the
flocculating ion and smaller is the amount of electrolyte solid catalyst and get adsorbed. After the required
required for precipitation, higher is the coagulating power chemical changes the products diffuse away from the
of coagulating ion. surface of the catalyst leaving the surface free for
18 Why does bleeding stop by rubbing moist alum ? more reactant molecules to get adsorbed and undergo
Ans. Moist alum coagulates the blood and forms blood clot. This reaction.
stops bleeding. 28. How does a solid catalyst enhance the rate of
19 Why is Fe(OH), colloid positively charged, when combination of gaseous molecules ?
prepared by adding FeCl, to hot water ? When gaseous molecules come in contact with the
surface of a solid catalyst, the gaseous molecules are
Ans. The adsorption of positively charged Fe** ions by
held with the surface of the catalyst by weak forces
the sol of hydrated ferric oxide results in positively
on the surface. This increases the concentration of
charged colloid.
reactants on the surface. Different molecules adsorbed
20 Why do physisorption and chemisorption behave
side by side have better chance to react and form
differently with rise in temperature ?
new molecules. This increases the rate of reaction.
Ans. Physisorption involves weak van der Waals forces which Moreover, adsorption is an exothermic process. The
decrease with rise in temperature. The chemisorption heat released in the process of adsorption 1s utilised
involves formation of chemical bond involving activation in increasing the reaction rate.
energy and is favoured by rise in temperature like any 29 Do the vital functions of the body such as digestion
other chemical reaction. get affected during fever ? Explain your answer.
21. What happens when dialysis is prolonged ? Ans. The optimum temperature range for enzymatic activity
Ans. When dialysis is prolonged, the traces of electrolyte which is 298-310 K. When the temperature is below or above
stabilises the colloids are removed completely. This this temperature range, enzymatic activity gets affected.
makes the colloid unstable and therefore coagulation Thus, during fever, when temperature rises above 310 K,
takes place. the activity of enzymes may be affected.
SURFACE CHEMISTRY sis7]

COUSS §=Memory TrEst MW

8. .............15 the process of separating the crystalloids from

eu Say True or False colloids using an animal membrane.
1. Physical adsorption increases with rise in temperature 9. Colloidal solution of gold in water is called ..............
whereas chemical adsorption decreases with rise in 10. In whipped cream, the dispersion medium is ......... es
temperature. and dispersed phaseIs .............
11. In benzosol, the dispersion etum er i —
2. Chemisorption is irreversible while physisorption is
12. The size of particles of colloidal solution is in he range
reversible. of pees
3. Selbetivity is the ability of a catalyst to direct the reaction fai wk arash a ame the amttfat of gas adsorbed per gram of
to give a particular product. the absorbent and equilibrium pressure of the adsorbate
4, At low pressure, the extent of adsorption is directly at constant temperature is called ......... ny
proportional to pressure at constant temperature. 14. The rate of adsorption in general is ............. in the
5. Al(NO,), has higher coagulating power than MgSO, for beginning and then ............. till equilibrium is attained.
Fe(OH), sol. 15. The formation of micelles takes place above a particular
6. Gel is a system in which liquid is the dispersed phase concentration called ............. .
and solid is the dispersion medium.
7. Greater the gold number of a protective colloid, greater wy Choose the correct alternative
is its protecting power. 1. Adsorption is exothermic/endothermic process.
8. Greater the flocculation value of an electrolyte, greater 2. Chemisorption always form unimolecular/multimolecular
is Its coagulating power. layer.
9. es is always multimolecular. 3. According to Freundlich adsorption isotherm, x/m
10. Colloidal sols are always heterogeneous. becomes independent of pressure at low/high pressure.
Hal Complete the missing links 4. The size of colloidal particles is less/more than that of
true solution particles.
1. Milk is an example of. ............. im ............. emulsion. 5. Substances like gum, starch form lyophilice/lyophobic sols.
2. The process in which adsorption and absorption take 6. The formation of micelles occurs only above/below Kraft
place simultaneously is called ............. temperature.
3. The nature of forces involved in physical adsorption are 7. Multimolecular colloids have lyophilic/lyophobic
eee character.
4. The formation of micelles takes placgfbove a pagyeular 8. Colloidal solutions form homogeneous/heterogeneous
temperature called ............... an etaeee
5. The movement of colloidal particles under the influence _ ee , ,
: : | 9. When ferric chloride is added to sodium hydroxide
of an electric field 1s called ............. :
solution, negative/positive sol is formed.
6. The scattering of light by colloidal particles is called
a 10. Gelatin (gold number 0.005-0.01) has more/less
7. The swelling of gel in water is called ............. protecting power than albumin (gold number 0.1—0.2).

Cues Memory Test WW

9, False. Physisorption is multimolecular but chemisorption
Say True or False
is unimolecular.
1. False 2. True o. True 4, True
10. True.
5. False. Fe(OH), is a positive sol. and therefore, SO,?-
ion (MgSO,) has higher coagulation power than |e Complete the missing links
NO, ion [Al(NO,),]. 1
» liquid, liquid 2. sorption
6. True. 9
. vander Waals forces 4. Kraft temperature
7. False. Protecting power varies inversibly
as gold number. 5 . electrophoresis
8. False. Greater the flocculation value of an electrolyte, 6 . Tyndall effect
lesser is 1ts coagulating power. 7 » imbibition
 MODERN'S abc + OF CHEMISTRY-All

8. dialysis
Choose the correct alternative
9. purple of cassius 10. liquid, gas
11. benzene 12. 1,1000 1. exothermic 2. unimolecular
13. adsorption isotherm 3. high 4, more
14. high, decreases 5. lyophilic 6. above
15. critical micelle concentration 7. lyophobic 8. heterogeneous
9. negative 10. more.

Higher Order Thinking Skills

& Advanced Level
s QUESTIONS WITH ANSWERS
Q.1.Sn0O, forms a positively charged colloidal solution Ans. A colloidal state has larger surface area of sol particles
in acidic medium and a negetively charged colloidal and therefore, are more effectively adsorbed. Therefore, the
solution in basic medium. Explain. medicines in colloidal state aremore easily assimilated or adsorbed
Ans. SnO, is amphoteric in nature and reacts with acids and are more effective.
as well as bases. It reacts with acids, e.g., HCl to form SnCl, in Q.5. On passing H,S through an aqueous solution of
solution. The common Sn* ions are adsorbed on the surface of SO,, a yellow turbidity is formed. Why ?
SnO, forming positively charged sol : Ans. On passing H,S through an aqueous solution of SO,,
Ssn0O,+4HCl —-> SnCl,+2H,0 oxidation of H,5 takes place.
2H,5+S50,—> 35 + 2H,0O
SnO,+Sn* —-» SnO, :Sn*
Colloidal
Positive sol
The particles of sulphur formed get condensed to be in the
SnO, reacts with a base e.g., NaOH to form sodium stannate colloidal range. Therefore, milky solution containing colloidal
(Na,SnO,) in the solution. The stannate ions are adsorbed on the particles of sulphur is formed.
surface of SnO, to form negatively charged sol. Q.6. A colloidal solution of AgI is prepared by two
snO,+2Na0QH —> Na,5SnO, + H,O different methods as shown below:
Sodium stannate AgNO, KI
SnO, + Sn0O,7- — > Sn0O, :SnOz-
Negative sol
Q.2. Why is chemical adsorption unimolecular while
physical adsorption is multimolecular ?
Ans. Chemical adsorption takes place as aresult of chemical
reaction between adsorbent and adsorbate. When the surface of
adsorbent is covered with one layer, no further reaction can take
place. Therefore, chemical adsorption is unimolecular. On the (1) What is the charge of colloidal particles in the two
other hand, physical adsorption is due to van der Waals forces test tubes (A) and (B) ?
between adsorbent and adsorbate molecules. So any number (11) Give reasons for the origin of charge.
of layers can be formed one over the other on the surface of the Ans. (7) (A) negative sol
adsorbent. Therefore, physical adsorption is multimolecular.
(B) positive sol
Q.3. Adsorption of a gas on the surface of solid is
(it) The origin of charge is the selective adsorption of ions
generally accompanied by decrease in entropy, stillitisa
from the dispersion medium. The particles constituting the
spontaneous process. Explain. dispersed phase adsorb only those ions preferentially which are
Ans. The molecules of adsorbate are held on the surface of common with their own lattice ions. For example, if silver nitrate
adsorbent and therefore, they have lesser tendency to move freely. solution is added to an aqueous solution of potassium iodide, the
Therefore, its entropy decreases and AS is —ve, which opposes silver iodide formed will adsorb negative I- ions (common ions)
the process. However, adsorption is an exothermic process and from the dispersion medium to form a negatively charged sol.
therefore, AH is—ve. The magnitude of AH is more than TAS so that Agl + [ —-+ Agi: TD
AG = AH-TAS=(-)-T(-) Dispersion Negative sol.
if AH > TAS, AG = -ve medium
Therefore, there is decrease in free energy and hence, it 1s a However, if silver iodide is formed by adding potassium
spontaneous process. 1odide to silver nitrate solution, the sol will be positively charged
Q.4. Why are medicines more effective in colloidal due to the adsorption of Ag* ions (common ions) present in the
state ? dispersion medium.
SURFACE CHEMISTRY

Agl + Agt ——> Agl: Ag* Amount adsorbed = 6.3-—3.78=2.52¢

Dispersion Positive sol. Amount adsorbed per gram of charcoal
medium = 2.52x2=5.04¢g
Q.7. Why does the sun looks red at the time of
Q.10. One gram of a water insoluble substance of
setting ? Explain on the basis of colloidal properties.
density 0.8 g cm™ is dispersed in 1L of water forming a
Ans. At the time of sun setting, the sunis at the horizon. The colloidal solution having 10!" particles of spherical shape
sun's rays have totravel alarger distance through the atmosphere. per mm. Calculate the radius of the particle.
When the light emitted by the setting sun passes through the Ans. 1mm? of sol contains particles= 101°
blanket of dust present in the atmosphere, the blue part of the light
1 cm? of sol contains particles= 1017 x 107=101
1s scattered away by the dust particles and hencered partis visible.
1 Lofsol contain particles= 101° x 103
Q.8. In an adsorption experiment, a graph between
= 10" particles
log (=) and log P was found to be linear with a slope Mass of substance dispersed= lg
m
Density = 0.8gcem™?
of 45°. The intercept on the log(x/m) axis was found to
be 0.3010. Calculate the amount of the gas adsorbed per Volume of dispersed substance = - =1.25em"
gram of the adsorbent under a pressure of 0.5 atmosphere.
Ans. According to Freundlich adsorption isotherm, 1.25
Volume of 1 particle = oo 9 1.25x107-cm®
7 =fn
it
Now Volume = =ar8 = 1.25 x 107 cm?

or log ~ =logk + Es
m n rs = ae 1.25x10-” wae
4 22
Plot of log(=|vs log P is linear with slope = ee and = 29.8x107!cm?
m. n
r= (29810) =3.1x 10" cm
intercept = log &. Thus, = 310x10°m=310nm
Q.11. 20% surface sites have adsorbed N,. On heating N,
Slope = = =tan45°=1 gas evolved from sites and was collected at 0.001
n
atm and 298 K in a container of volume 2.46 cm*.
m= 1 Density of the surrounding sites is 6.023 x 10-4 em
and surface area is 1000 cm?. Calculate the number
Intercept log &= 0.3010
of surface sites occupied per molecule of N,.
or pao (LET. 2005)
Ans. Applying ideal gas equation
* =ppu pV = nkRT

Oe is
it

=2~x(0.5)'=1.0 or n= pr

Q.9. 50 mL of 1M oxalic acid is shaken with 0.5 g of p = 0.001 atm,

wood charcoal. The final concentration of the solution
V = 2.46 cm? = 2.46 x 10°L
after adsorption is 0.6 M. Calculate the amount of oxalic
T = 298K
acid adsorbed per gram of charcoal.
-3
Ans. Amount of oxalic acid present can be calculated from — 0.001x 2.46 x10 ascii
the relation : 0.0821 x298
Molarity = Rion
leet / ce No. of N, molecules = 6.023 x 107? x 1 x 10- = 6.023 x 107°
M x V(in mL)
Total sites available = 6.023 x 101* x 1000 = 6.023 x 101”
or 7 —ae
Molarity x M x Van
eeemL) Surface sites used to adsorb N,
1000
Amount of oxalic acid present initially = x 6.023 x 101
100
_ 1x126x50_ 64, 12.04 x 1076
1000 .. Sites occupied per molecule of N,
Amount of oxalic acid present after adsorption
SurfacesitesusedtoadsorbN, _ 12.04 «10** _
0.6x126*50 _
3.78 g Moleculesof N, 6.023 x10”
1000
 MODERN'S abc + OF CHEMISTRY-All

=} Revision Exercises
25. Given an example of shape selective catatyst.
S Very Short Answer Questions [carrying 11mark || <4
(D.S.B. 2010, A..S.B. 2011)
1. Is adsorption exothermic or endothermic in nature ? 26. What is the effect of temperature on chemisorption ?
. state Hardy Schulze rule. (7.P.S.B. 2018) (A.LS.B. 2014)
. How is Brownian movement responsible for the stability of 27. Why is adsorption always exothermic? (A.J.S.B. 2014)
sols ? (C_.B.S.E. Sample Paper 2017-18) 28. What are the dispersed phase and dispersion medium in milk?
. Does the adsorption of a gas on the surface of solid increases (A.S.B. 2014)
or decreases with rise in temperature ? 29. Write a method by which lyophobic colloids can be coagulated.
. What causes Brownian movement in a colloidal solution ? (A.LS.B. 2015)
(D.S.B. 2008) 350. Write the main reason for the stability of colloidal sols.
. What is adsorption isotherm? (Meghalaya S.B. 2017) (D.S.B. 2016, A.I.S.B. 2016)
. Write Freundlich adsorption isotherm equation at low ol. What type of colloid is formed when a solid is dispersed in
pressure. (Pb.S.B. 2011) liquid? Give an example. (A..S.B. 2017)
. Write Freundlich adsorption isotherm at intermediate 3o2. CO (g) and H,(g) react to give different products in the
pressure. (Pb.S.B. 2011) presence of different catalysts. Which ability of the catalyst
. What form will Freundlich adsorption isotherm equation is shown by these reactions? (A...S.B. 2018)
take at high pressure ?
(Pb. S.B. 2011, Uttarakhand S.B. 2012) MCQs from State Boards’ Examinations
10. What is occlusion ? (Pb. S.B. 2012) oo. Movement of dispersion medium under the influence of
11. Name the type of emulsion to which milk belongs to. electric field is known as
(Pb S.B. 2012, H.P.S.B 2012) (a) electrodialysis (6) electrophoresis
12. Name the type of emulsion to which butter belong to. (c) electroosmosis (d) cataphoresis.
(H.P.S.B. 2012) (H.P.S.B. 2013, Meghalaya S.B. 2016)
135. Between absorption and adsorption, which one is surface oA, At CMC (Critical Micellization Conc.) the surface molecules
phenomenon ? (Uttarakhand S.B. 2013) (a) associate
14. Give one example each of lyophobic sol and lyophilic sol. (6) dissociate
(D.S.B. 2014) (c) decompose
15. Give one example each of sol and gel. (D.S.B. 2014) (d) become completely soluble.
16. Give one example each of ‘oil in water’ and ‘water in oil’ (H.P.S.B. 2013, Meghalaya S.B. 2016)
emulsion. (D.S.B. 2014) aoe Milk is an example of
17. Out of BaCl, and KC] which one is more effective in causing (a) emulsion (b) suspension
coagulation of negatively charged colloidal sol. Give reason. (c) foam (d) sol. (Ar.S.B. 2013)
(D.S.B. 2015) ob. Tyndall effect is due to
18. Write one similarity between physisorption and chemi- (a) electric charge (6b) scattering of light
sorption. (D.S.B. 2017) (c) absorption of light (d) none of these.
19. Which enzyme is used to convert glucose into ethyl alcohol? (Ar.S.B. 2013)
(H.P.S.B. 2017)
ods Fog is a colloidal system of
20. Define positive and negative catalysis. (Hr. S.B. 2017) (a) liquid dispersed in a gas(b) gas dispersed in a gas
21. Give one example of a biochemical catalyst. (c) solid dispersedin gas (d) solid dispersed in liquid
(Assam S.B. 2017)
(Ar.S.6. 2013, Mizoram S.B. 2015, Nagaland S.B. 2018)
22. What are the dispersed phase and dispersion medium in
oo. Blood may be purified by
soap lather? (W.B.S.5. 2018)
(a) coagulation (6) dialysis

»> CBSE QUESTIONS <4 (c) electro-osmosis (d) filtration

(Ar.S.B. 2013, H.P.S.B. 2018)
Zoe Which will be adsorbed more readily on the surface of og. Blue colour of water in sea is due to
charcoal and why : NH, or CO ? (A.J.S.B 2004) (a) refraction of blue hight by impurities in sea water
. Of physisorption and chemisorption, which type of (6) scattering of light by water
adsorption has higher enthalpy of adsorption ? (c) refraction of blue sky by water
(A.S.B. 2008, D.S.B. 2008, A..S.B 2013) (ad) None of these (Mizoram S.B. 2014)
SURFACE CHEMISTRY

40. The cause of Brownian movement is (a) High pressure (6) —-AH
(a) heat change in liquid state (c) High temperature (d) None of these
(6) attractive force between colloidal particles and (Hr. S.B. 2017)
dispersion medium 53. Which property of colloids is not dependent on the charge
(c) bombardment of the colloidal particles by the molecules on colloidal particles?
of the dispersion medium (a) Coagulation (6) Electro-osmosis
(d) interaction of charged particles
(c) Tyndall effect (d) None of these
(Meghalaya S.B. 2014)
(Hr. S.B. 2017)
Al, Emulsifying agent present in milk that makes it stable is
54. Tyndall effect is observed in
(a) maltose (6) casein
(c) lactose (d) none of these (a) True solution (6) Precipitate
(Ar. S.B. 2015) (c) Colloidal solution (d) Vapour (H.P.S.B. 2018)
42. Cloud is an example of 55. In the coagulation of solution As,5, which has maximum
(a) liquid dispersedin gas (6) solid dispersed in gas coagulating value
(c) solid dispersed in liquid (d) none of these (a) NaCl (6) KCl
(Ar. S.B. 2015) (c) BaCl, (d) AIC], (H.P.S.B. 2018)
. The colour of sky is due to 56. Which one has the highest coagulating power for ferric
(a) absorption of light (6) transmission of light hydroxide sol?
(c) scattering of light (d) all of these (a) KCl (6) K,SO,
(Ar. S.B. 2015) (c) Na,PO, (dq) NaCl (W.B.S.B. 2018)
. Which of the following is lyophobic colloid?
(a) Starch in water
(c) Soap in water
(6) Gum in water
(d) Gold sol » ea iti Teel <i tm icarrying 2 or 3 marks <<
(Kerala S.B. 2015) . Distinguish between adsorption and absorption with
45. At high concentration of soap in water, soap behaves as examples. (Pb. S.B. 2012, H.P.S.B. 2011, 2014,
(a) molecular colloid (6) associated colloid Nagaland S.B. 2016, Jammu S.Z. 2018)
(c) macro molecular colloid 2. (a) What do you understand by true solution, colloidal
(d) lyophilic colloid (Meghalaya S.B. 2015) solution and suspension ? Give their differences.
46. The efficiency of a protective colloid is described in terms (6) “Colloid is not a substance but a state of substance.”
of Justify.
(a) gold number (6) flocculation number 3. How are colloids classified on the basis of charge ? How will
(c) valence of counter ion (d) Tyndall effect. you account for the charge on these particles ?
(Nagaland S.B. 2015) 4, (a) How are colloids classified on the basis of attraction
47. The function of enzymes in the living system is to between dispersed phase and dispersion medium ?
(a) maintain pH (6) How will you prepare a colloidal solution of gold ? How
(6) catalyse biochemical process is it stabilised ?
(c) provide immunity 5. Explain electrophoresis. How is it helpful in causing
(d) transport oxygen (Meghalaya S.B. 2016) coagulation of colloidal solutions ?
. Theultrafiltration process of purification of colloidal solutions 6. Physical and chemical adsorptions respond differently
is based on: to rise in temperature. What is this difference and why
is it so ? (A..S.B. 2000, Uttarakhand S.B. 2012)
(a) optical properties of colloids
7. Explain Hardy Schulze rule and peptization.
(6) electrical properties of colloids
(H.P.S.B. 2011, 2014, 2018, Chhatisgarh S.B. 2012)
(c) magnetic properties of colloids
(d) size of colloids (Mizoram S.B. 2016) 8. Explain the following observations :
49, In physical adsorption the forces associated are
(a) Ferric hydroxide sol gets coagulated on addition of
sodium chloride solution
(a) ionic (6) covalent
(6) Cottrell's smoke precipitator is fitted at the mouth of
(c) van der Waals (dq) hydrogen bonding
the chimney used in factories.
(Meghalaya S.B. 2016)
(c) Physical adsorption is multilayered, while chemisorption
50. The colloidal system where liquid is dispersed in solid is is monolayered.
(a) Gel (b) Aerosol 9. What are lyophilic and lyophobic sols ? Give one example
(c) Emulsion (d) Foam of each type. Which one of these two types of sols is easily
(Mizoram S.B. 2017) coagulated and why? (D.S.B. 2008)
ol. Which one of the following has minimum gold number? 10. Give four differences between lyophilic and lyophobic
(a) Gelatin (6)
Starch colloids.
(c) Gum arabic (d)
Sodium oleate (A.P.S.B. 2011, Chhatisgarh S.B. 2011, Pb. S.B. 2015,
(Hr. S.B. 2017) Nagaland S.B. 2017)
o2. Which of the following is not a favourable condition for 11. (2) How will you justify that milk is an emulsion of oil
physical adsorption? in water with the help of dye test? (Pbd.S.B. 2011)
 MODERN'S abc + OF CHEMISTRY-All

(it) How will you justify that milk is an emulsion of oil in 24, Write the dispersed phase and dispersion medium of the
water with the help of dilution test ? (Pb.S.B. 2011) following colloidal systems:
12. Explain the following: (z) Smoke
(t) Tyndall effect (Hr. S.B. 2011, 2018, H.P.S.B. 2015, (iz) Milk
Mizoram S.B. 2017) Or
(it) Dialysis (Ar.S.B. 2011, Mizoram S.B. 2016, What are lyophilic and lyophobic colloids ? Which of these
Assam S.B. 2016) sols can be easily coagulated on the addition of small
(iit) Electrophoresis amounts of electrolytes ? (D.S.B. 2013)
(A. P.S.B. 2015, Assam 2016, Mizoram S.B. 2016) 205. What is the difference between oil/water (o/w) type and
water/oil (w/o) type emulsions ? Given an example of each
(iv) Coagulation (A. P.S.B. 2015, Assam S.B. 2016,
type. (D.S.B. 2013)
Mizoram S.B. 2017, Hr. S.B. 2018)
26. (a) Whatis adsorption isobar? Draw the adsorption isobar
(v) Peptization (Mizoram S.B. 2016, Hr. S.B. 2018)
for physical adsorption and chemical adsorption.
(vt) Emulsification (Assam S.B. 2016) (Mizoram S.B. 2018)
(vit) Brownian movement (Hr. S.B. 2018) (6) Give one example each of oil in water emulsion and
13. What do you understand by activity and selectivity of water in oil emulsion. (Meghalaya S.B. 2018)
catalysts ? (Ar.S.B. 2011, Nagaland S.B. 2017) 27. (a) Write any two differences between lyophilic and
14. Explain how the phenomenon of adsorption finds application lyophobic colloids.
in each of the following processes : (d) What is heterogeneous catalysis? Give an example.
(1) Production of vacuum (c) Give an expression for Freundlich adsorption
isotherm. (Karnataka S.B. 2018)
(11) Heterogeneous catalysis
28. (a) What is Tyndall effect ?
(it) Froth floation process.
(5) Define the following :
Or
(1) Kraft temperature.
Define each of the following terms : (11) Critical micelles concentration.
(1) Micelles (iz) Peptization (211) Desorption (c) What happens when Fe(OH), sol and As,O, sol are
(D.S.B. 2011) mixed with each other ? (Meghalaya S.B. 2014)
15. What is Tyndall effect ? Give its reasons and importance. 29. (a) In reference to Freundlich adsorption isotherm write
(Pb. S.B. 2011, Hr. S.B. 2012, 2017, the expression for adsorption of gases on solids in the
Uttarakhand. S.B. 20135, Jammu S.B. 2016) form of an equation.
16. What is meant by coagulation of a colloidal solution ? (d) Write an important characteristic of lyophilic sols.
Describe briefly any three methods by which coagulation (c) Based on type of particles of dispersed phase, give one
of lyophobic sols can be carried out. (D.S.B. 2012) example each of associate colloid and multimolecular
colloid. (D.S.B. 2014)
17. Describe a conspicuous change observed when
30. (a) Why does physisorption decrease with increase of
(1) a solution of NaCl is added to a sol of hydrated ferric oxide.
temperature?
(it) a beam of light is passed through a solution of NaCl (6) Why are powdered substances more effective
and then through a sol. (D.S.B. 2012)
adsorbents than their crystalline forms?
18. Define enzyme catalysis. What is the reason for its specific (c) Give the decreasing order of flocculating power of the
action ? (Uttarakhand S.B. 2012) following ions in the coagulation of a negative sol.
19. Differentiate between homogeneous and heterogeneous Nat, Ba?* , Al?* (Assam S.B. 2018)
catalysis with one example of each. ol. (a) Describe briefly Brownian movement.
(Manipur S.B. 2012, Meghalaya S.B. 2016. Hr. S.B. 2018) (6) Describe one method of purification of colloidal
20. Taking two examples of heterogeneous catalytic reactions, solution. (Ar.S.B. 2015)
explain how a heterogeneous catalyst helps in the reaction. oe (a) Explain the cleansing action of soaps.(Hr.S.B. 2015)
(Uttarakhand S.B. 2012) (b) Classify the type of colloidal sol in the following based
on the basis of physical state:
21. What are protective colloids ? How are the colloids stabilised?
Explain the term gold number. (Chhatisgarh S.B. 2012) smoke, milk, pumice stone, foam, rubber, cheese, gem
stones. (Pb.S.B. 2015)
22. (a2) Give two differences between macromolecular colloids
aoe (a) state Hardy Schulze law.
and associated colloids.
(d) What are differences between physisorption and
(6) Explain the term dialysis. How can it be increased? chemisorption. (Mention at least two differences).
(Pb.S.B. 2018) (c) How does bleeding from a wound stop by applying
23. What are associated colloids? How are they different from alum? (Meghalaya S.B. 2015)
multimolecular and macromolecular colloids? 34. What are adsorption and absorption processes? Give one
(Meghalaya S.B. 2016) example to show the distinction between the two.
SURFACE CHEMISTRY

Or (111) Name the promoter used in the Haber's process for

Define homogeneous and heterogeneous catalysis. Give the manufacture of ammonia.
one suitable example of each of the two catalysis. (C_.B.S.E. Sample Paper 2017-18)
(Assam S.B. 2015, Hr. S.B. 2018)
51. (a) Indicate a chemical reaction involving homogeneous
oo. Give reasons for the following observations:
catalyst.
(i) Leather gets hardened after tanning.
(6) What is Brownian movement?
(tt) Lyophilic sol is more stable than lyophobic sol
(c) Comment on the following statement :
(tit) It is necessary to remove CO when ammonia is
Colloid is not a substance but a state of substance.
prepared by Haber’s process. (D.S.B. 2015)
(Meghalaya 8.5. 2018)
ob. Write any two features which distinguish between
52. (a) State Hardy-Schulze rule with the help of example.
physisorption and chemisorption.
(Jharkhand S.B. 2016, Kolkata S.B. 2016)
(b) Why are lyophilic colloids used as protective colloids?
(Kerala S.B. 2018)
Od. Explain why the solid catalyst is used in a finely divided

38.
form as heterogeneous catalysis. (Kolkata S.B. 2016)
(1) Differentiate between adsorption and absorption. » CBSE QUESTIONS <4
(ii) Out of MgCl, and AICI1,, which one is more effective oe (a) In which of the following does adsorption take place
In causing coagulation of negatively charged sol and
and why ?
why?
(z) Silica gel placed in the atmosphere saturated with
(ti1) Out of sulphur sol and proteins, which one forms
water.
multimolecular colloids? (D.S.B. 2016)
39. (a. How will you differentiate between physical and
es
(71) Anhydrous CaCl, placedin
the atmosphere saturated
chemical adsorption? Give at least four points of with water.
difference. (6) Give an example of shape selective catalysis.
(b) Define gels. (..P.S.B. 2017) (c) What are micelles? How do they differ from ordinary
40). (a) Briefly explain Tyndall effect. Give its importance. colloidal particles ? Give two examples of micelles
(b) Define adsorption. Give one example. forming substanes. (A.L.S.B. 2006, H.P.S.B. 2011)
(Hr. S.B. 2017) od, (a) How can colloidal solution and true solution of the same
41. Define Tyndall effect. Differentiate between electrophoresis colour be distinguished from each other ?
and electroosmosis. (Pb.S.B. 2017)
(0) List four applications of adsorption.
42. Define coagulation. Differentiate between physical
Or
adsorption and chemical adsorption. (Pb.S.B. 2017)
. Define colloidal solution. Differentiate between lyophilic Explain the following observations :
colloids and lyophobic colloids. (Pb.S_B. 2017) (t) Lyophilic colloid is more stable than lyophobic
44, (a) How do the size of particles of adsorbent and pressure colloid.
of the gas influence the extent of adsorption? (iz) Coagulation takes place when sodium chloride solution
(b) Define the following giving an example of each: is added to a colloidal solution of ferric hydroxide.
(¢) Coagulation (ii) Tyndall effect. (111) Sky appears blue in colour. (A.L.S.B. 2006)
(Manipur S_B. 2017) Oo. Classify colloids where the dispersion medium is water.
. Explain the following observations : (any three) State their characteristics and write an example of each
(1) Sky appears blue in colour. of these classes.
(i) Deltas are formed where river meets the sea.
Or
(iit) Alum/ferric chloride solution is applied to stop
bleeding. Explain what is observed when
(iv) Mist or fog is formed im winter. (Assam S.B. 2017) (t) an electric current is passed through a sol.
46. (a) What is peptization? What is the cause of peptization? (it) a beam of light is passed through a sol.
(b) What happens when an electric field is applied to (zit) an electrolyte (say NaCl) is added to ferric hydroxide
a colloidal solution? (Meghalaya S.B. 2017) sol. (A..S.B., 2009, 2011, Assam S.B. 2012)
47, (a) Differentiate between physisorption and chemisorption. o6. Write three distinct features of chemisorption which are
(Hr. S.B. 2018) not found in physisorption. (A.IS.B. 2012)
(d) Write any two applications of adsorption. o7. What are the characteristics of the following colloids ?
(Kerala S.B. 2017)
Give one example of each.
. Write one difference in each of the following:
(1) Lyophobic sol and lyophilic sol (1) Multimolecular colloids
(it) Solution and colloid (11) Lyophobic sols
(111) Homogeneous catalysis and heterogeneous catalysis (iit) Emulsions (A.S.B. 2013)
(D.S.B. 2017) . Define the following terms giving an example of each :
49, Write one difference between each of the following: (c) Associated colloids
(t) Multimolecular colloid and macromolecular colloid (it) Lyophilic sols
(zi) Sol and gel
(iit) Adsorption (A..S.B. 2013)
(iit) O/W emulsion and W/O emulsion _(D.S.B. 2017)
50. (1) Write the expression for Freundlich's equation to og”. Give reasons for the following observations:
describe the behaviour of adsorption from solution. (1) Physisorption decreases with increase in temperature.
(11) What causes charge on sol particles?
 MODERN'S abc + OF CHEMISTRY-All

(it) Addition of alum purifies the water.

>> Long Answer Questions <4
(11) Brownian movement provides stability to the colloidal
solution. (A..S.B. 2015) 1. Define the terms physical adsorption and chemical adsorption
60. Define the following: and give any four points of differences between them.
2. (a) What is catalyst ? How does the phenomenon of
(1) O/W Emulsion
adsorption explain the role played by catalyst ?
(11) Zeta potential (6) What is electrophoresis ? What is its significance ?
(iit) Multimolecular colloids (A..S.B. 2016) Or
61. Write one difference in each of the following: (a) Discuss the phenomenon ofdialysis and electrodialysis?
(a) Multimolecular colloid and Associated colloid (6) What are protective colloids ? (Pb. S.B. 2012)
(6) Coagulation and Peptizaton 3. (a2) What do you understand by activity and selectivity of
(c) Homogeneous catalysis and Heterogeneous catalysis a catalyst ? Give one example of each.
(6) What is Tyndall effect ? What is its significance ?
Or
Or
(a) Write the dispersed phase and dispersion medium of (a) What is an emulsion ? Discuss the types of emulsions
milk. by giving example of each.
(6) Write one similarity between physisorption and (6) What do you mean by peptisation ?
chemisorption. (Pb. S.B. 2012)
4. (a) What is homogeneous and heterogeneous catalysis ?
(c) Write the chemical method by which Fe(OH), sol is Give one example of each.
prepared from FeCl.,. (A./2.S_B. 2017) (6) What is Brownian movement ? What is its cause ?
62. What happens when Or
(a) a freshly prepared precipitate of Fe(OH), is shaken (a) What are multimolecular, macro molecular and
with a small amount of FeCl, solution? associated colloids ? Give one example of each.
(6) persistent dialysis of a collodial solution is carried out? (6) What do you mean by gold number? (Pb. S.5. 2012)
(c) an emulsion is centrifuged? (A..S.B. 2018)

Hints & Answers

| Revision Exercises QA
16. Oil in water : Milk, Water in Oil : Butter
Very Short Answer Questions |
17. BaCl, because greater the valency of the coagulating ion
1 . Exothermic (positive lon), greater is its tendency to coagulate.
21. Invertase
A, Decreases with rise in temperature
22. Gas and liquid
6 . Chemisorption
23. NH,
TP ~ =P 24, Chemisorption
25. Zeolites e.g., zeolite ZSM-5
|
3e
= kP'" (n is a whole number) 26. Withincreasein temperature, chemisorption first increases
and then decreases.
27. Because of attraction between adsorbate and adsorbent,
=kP° =k
3|
Sie energy is released during adsorption.
10. The adsorption of gases on the surface of metals is called 28. Liquid (dispersed phase), Liquid (dispersion medium)
occlusion. 29. By addition of electrolyte. 31. Gel, cheese
32. Selectivity of a catalyst. It is the ability of a catalyst to
11. Oul-in-water type selectively form a particular product.
12. Water-in-oil
type 33. (b) 34. (a) 35. (a) 36. (5) 37. (a)
18. Adosorption is a surface phenomena 38. (b) 39. (a) AO. (c) Al, (bd) A2, (a)
43. (c) 44, (d) 45. (b) 46. (a) AZ, (b)
14. Lyophobic : As,S,, Lyophilic : Gelatin
48. (d) AQ. (c) 50. (a) 51. (a) 52. (c)
15. Sol: As,S,, Gel : Gum arabic 53. (c) 54. (c) 55. (d) 56. (c)
SURFACE CHEMISTRY

Competition Filo Additional Useful Information and Objective Questions

OO
—eeeeeerererr—SCCSCSC(‘(‘CD.OCtétC(
ida

ADDITIONAL USEFUL INFORMATION

0 ISOELECTRIC POINT OF COLLOIDS. The H* ions dimension less than 100 nm (1 nm = 10° m). These
concentration at which the colloidal particles are neither possess unique optical, conductance, magnetic, electrical
positively charged nor negatively charged (i.e., are and other properties which are different from those of
electrically neutral) is known as isoelectric point of a their bulk counterparts because of their small particle
colloid. For example, for gelatin, isoelectric point is at size. These properties have great impact in electronics,
pH = 4.7. At this point the colloids do not migrate under medicines and other fields.
the influence of electric field. At this point, the lyophilic The common examples of nanomaterials are gold,
colloids are expected to have minimum stability. carbon (fullerene), metals, metal oxides, metal alloys,
4H SYNERESIS AND THIOXOTROPY OF GELS etc. Due to their unique properties, the nanomaterials
@ When gels are allowed to stand for a long time, they give are gaining importance in different fields. These are
out small amount of trapped liquid which accumulates widely used in a number of industrial processes as well as
on its surface. This phenomenon is called syneresis or consumer products such as cosmetics, sun screens, stain
weeping of gels. resistant and wrinkle free textiles, electronics, paints
and varnishes, etc. These are finding use as important
@ Some gels like gelation are semisolid when at rest and
constituents of mass media storage devices. These are
change to liquid sol. on agitation. This reversible sol. gel
also used as heterogeneous catalysts because they provide
transformation is called thioxotropy.
large surface area. In the field of biology and medicine,
0 NANOMATERIALS nanomaterials are used as Magnetic Resonance Imaging
Nanomaterials are the materials having at least one (MRI), contrast agents, etc.

OBJECTIVE TYPE QUESTIONS

S
Multiple Choice Questions |
(c) Adsorption is more for specific substance
‘ cw (d) It is reversible reaction.
tor" with only one correct answer
AS. According to adsorption theory of catalysis, the speed of
Adsoprtion and Catalysis the reaction increases because :
(a) the concentration of the reactant molecules at the active
Al. Which of the following statements is not correct regarding centres of the catalyst becomes high due to adsorption.
physical adsorption ?
(a) It is not specific (6b) in the process of adsorption, the activation energy of
(6) It forms monomolecular layers the molecules becomes large.
(c) It has low heat of adsorption (c) adsorption produces heat which increases the speed of
(d) It is reversible. the reaction.
A2,. Which of the following is adsorbed by charcoal to maximum
extent ? (dq) adsorption lowers the activation energy of the
(a) N, (b) CO, reaction.
(c) CL, (d) Q,. AG. Which of the following characteristics is not correct for
A3. For adsorption of a gas on a solid, the plot of log x/m vs log physical adsorption ?
P is linear with a slope equal to (n being a whole number) (a) Adsorption increases with increase in temperature.
(a) R (b) logk (6) Adsorption is spontaneous.
(ec) n (d) 1/n. (c) Both enthalpy and entropy of adsorption are negative.
A4,. Which of the following is not correct regarding the (d) Adsorption on solid is reversible.
adsorption of a gas on the surface of a solid ?
Al. Rate of physisorption increases with
(a) On increasing temperature, adsorption increases
(a) decrease in temperature
continuously
(6) increase in temperature
(6) Enthalpy and entropy changes are negative
(c) decrease in pressure

AnswerAl. (5) A2. (6) AS. (d) Ad, (a) A5. (d) AG.
(d) decrease in surface area.

(a) AZ. (a)

 MODERN'S abc + OF CHEMISTRY-All

A8. The volumes of gases H,, CH,, CO, and NH, adsorbed by . Which of the following electrolytes will be most effective
1 gm of activated charcoal at 298 K are in the order. in causing the coagulation of a positively charged ferric
(a) H,> CH, > CO, >NH, hydroxide sol ?
(6) CH, > CO, > NH, > H, (a) K,SO, (6) K,Fe(CN),
fc) CO, > NH, > Ho > CH, (c) KCl (d) K,CO,.
(2) NH > CO,> CH= 4H,
. Soaps essentially form a colloidal solution in water and
remove the greasy matter by
(e) CO,.> NH, > CH, > H,
(a) coagulation (6) emulsification
A9. Adsorption is accompanied by
(c) adsorption (d) absorption.
(a) decrease in enthalpy and increase in entropy . Which of the following is an example of associated colloid?
(6) increase in enthalpy and increase in entropy (a) Protein + Water (6) Soap + Water
(c) decrease in enthalpy and decrease in entropy (c) Rubber + Benzene (d) As,O, + Fe(OH).
(d) increase in enthalpy and decrease in entropy . Alums purify muddy water by
Al10. The enthalpy of physical adsorption is about
(a) Dialysis (6) Adsorption
(a) zero (b) 20-50 kJ mol?
(c) 200-500 kJ mol"? (d) very high (c) Coagulation (dq) Forming a true solution.
. Which type of property is the Brownian movement of
Colloids
colloidal sol ?
All. The colloidal system in which the disperse phase and (a) Electrical (6b) Optical
dispersion medium are both liquids is known as (c) Mechanical (d) Colligative.
(a) a gel (6) an aerosol
(c) an emulsion (d) a foam. . When KI is added to silver nitrate solution, the sol formed
A112. Freshly prepared precipitates can be easily dispersed by may be written as:
shaking it with dispersion medium. This process is called (a) Agi T- (b) Agl Agt
(a) Peptisation
(c) Dispersion
(6b) Electrophoresis
(d) Dialysis.
(c) Agl NO> (d) NO,- Agi Ag*.
A113. The presence of electric charge on the colloidal particles . Which of the following reaction gives a colloidal sol ?
is Indicated by the experiment (a) MgCO, ———>MgO + CO,
(a) Osmosis (b) Electrolysis (6) 2Na + 2H,O ——> 2NaOH + H,
(c) Dialysis (d) Electrophoresis. (c) 2HNO, + 3H,S———>3S + 4H,O + 2NO
Al4, The number of phases in a colloidal system is
(a) 1 (b) 2
(d) Cu + CuCl,—>Cu,Cl,.
(c) 3 (d) 4. . Blue colour of water in sea is due to
Al15. The process of separation of colloids by passing through (a) refraction of blue light by impurities in sea water
semi-permeable membrane is called (6) scattering of light by water
(a) Filtration (b) Electrophoresis
(c) refraction of blue sky by water
(c) Dialysis (d) Ultrafiltration.
(d) none of these.
A116. The size of colloidal particles is in the range of
(a) 0.1-—1nm (6) 1nm—- 100 nm . Alum helps in purifying water by
(c) 100 nm — 1000 nm (dz) 1000 — 10000 nm. (a) forming silicon complex with clay particles
A17. An example of micelle is : (6) sulphate part which combines with dirt and romoves it
(a2) Sodium stearate (6) Gold sol.
(c) aluminium which coagulates the mud particles
(c) Solution of NaCl (d) Ruby glass.
(dq) making mud water soluble.
A18. Which of the following is most effective electrolyte in
causing the flocculation of a negatively charged arsenious . The coagulating power of an electrolyte for arsenious
sulphide solution ? sulphide sol decreases in the order :
(a) KCl (6) MgCl, (a) Na*> Al?*+ > Ba** (b) PO, > S0,7 > Cl
(c) K,Fe(CN), (d) AlCl, (c) Cl >80,7 > PO? (d) Al?* > Ba?* > Nat
A19. Colloidal particles exhibit Tyndall effect due to (e) Na*> Ba** > PO,
(a) polarisation of light (6) scattering of light . The disease kala azar is cured by
(c) reflection of light (d) refraction of light. (a) colloidal antimony (6) milk of magnesia
(c) argyrols (d) colloidal gold

HE A8. (d) AS. (c) AlO. (6) All. (c) Al2 (a) Als. (qd) Al3. (d) Al4. (6) Al15. (c) Al6. (6)
Al7. (a) <Al8 (d) AIS. (6) A220. (5b) A221. (5) A22, (6) A223. (c) A224. (c) A225. (6) A226. (c)
A27. (a) A228. (c) A229. (d) A380. (a)
SURFACE CHEMISTRY

B
B8. Which property of colloids is independent of the charge on
MULTIPLE CHOICE QUESTIONS colloidal particles ?
from competitive examinations (a) Electrophoresis (6) Electro-osmosis
(c) Tyndall effect (d) Coagulation
AIPMT & Other State Boards’ (A..P.M.T. 2015)
Medical Entrance B9. Fog is a colloidal solution of
(a) solid in gas
Bl. A plot of log x/m versus log p for the adsorption of a gas (b) gas in gas
on a solid gives a straight line with slope equal to (c) liquid in gas
(a) n (b) I/n (d) gas in liquid (NEET 2016)
(c) log K (d) —log K B10. The coagulation values in millimoles per litre of the
(C.B.S.E.P.M.T. 2006) electrolytes used for the coagulation of As,S, are given:
B2. The Langmuir adsorption isotherm is deduced using the I. (NaCl) = 52, IL (BaCl,) = 0.69, IIT. (MgSO,) = 0.22. The
assumption correct order of their coagulating power is
(a) The adsorbed molecules interact with each other (a) I> II >HI (6) II>1>I
(6) The adsorption takes place in multilayers. (c) Il>Ii>I (dq) WIl>1I>I1 (NEET 2016)
(c) The adsorption sites are equivalent in their ability to B11. On which of the following properties does the coagulating
adsorb the particles. power of an ion depend?
(d) The heat of adsorption varies with coverage. (a)
The magnitude of the charge on the ion alone
(C_.B.S_E.P.M.T. 2007) (b)
Size of the ion alone
B3. If is amount of adsorbate and m is amount of adsorbent, which (c)
Both magnitude and sign of the charge on the ion
of the following relations is not related to adsorption process ? (d)
The sign of charge on the ion alone
(a) x/m =f (p) at constant T (NEET 2018)
(6) x/m =f (T) at constant p B12. In an electrical field, the particles of a colloidal system
(c) p=f(T) at constant (x/m) move towards cathode. The coagulation of the same sol is
(d) =pxT (A.L.P.M.T. 2011) studied using K,SO,(1), Na,PO, (II), K,[Fe(CN,)] (IIL) and
Ba4. The protecting power of lyophilic colloidal sol is expressed NaCl (IV). Their coagulating power should be
in terms of (a) (D> U1) >U0)> UV) (6) (ID > UD > (D2 > (IV)
(a) coagulation value (6) gold number (c) (ID >) >UD> UV) (d) (IV) > UID > (D > dD
(c) critical miscelle concentration (e) (IV) > (I) > UD > UID (Kerala P.M.T. 2008)
(d) oxidation number (A.LLP.M.T. 2012) B13. The formation of micelles takes place only above
B5. In Freundlich adsorption isotherm, the value of 1/n is (a) Inversion temperature
(a) between 0 and 1 in all cases (6) Boyle temperature
(b) between 2 and 4 in all cases (c) Critical temperature
(c) 11n case of physical adsorption (d) Kraft temperature
(d) 1 1n case of chemisorption (A.LP.M.T. 2012) (e) Wein temperature (Kerala PMT 2010)
B14, Colloidion is a 4% solution of which one of the following in
B6. Which one of the following statements is incorrect about
alcohol-ether mixture ?
enzyme catalysis ?
(a) nitroglycerine (6) celluloseacetate
(a) Enzymes are mostly proteious in nature.
(c) glycoldinitrate (d) nitrocellulose
(6) Enzyme action is specific.
(e) methylcellulose (Kerala PMT 2010)
(c) Enzymes are denatured by ultraviolet rays and at high
temperature. B15. In the adsorption of a gas on solid, Freundlich isotherm
(d@) Enzymes are least reactive at optimum temperature.
is obeyed. The slope of the plot is zero. The extent of
adsorption is
(A.I_P.M.T. 2012)
(a) directly proportional to the pressure of the gas
B7. Which of the following statement is correct for the
(6) inversely proportional to the pressure of the gas
spontaneous adsorption of a gas ?
(c) directly proportional to the square root of the pressure
(a) AS is negative and therefore, AH should be highly positive
of the gas
(b) AS is negative and therefore, AH should be highly negative
(d) inversely proportional to the square root of the pressure
(c) AS is positive and therefore, AH should be negative
of the gas
(d) AS is positive and therefore, AH should be highly positive
(e) independent of the pressure of the gas
(A..P.M.T. 2014) (Kerala P.M.T. 2012)

Answets
Bl. (0) B2. (c) B3. (d) B4. (5) B5. (a) B6. (d) B7. (5) B8. (c) B9. (c) B10. (ce)
Bll. (c) B12. (5) B13. (d) B14. (d) B15. (e)
 MODERN'S abc + OF CHEMISTRY-All

B16. Which one of the following is not explained by adsorption? B21. Gold numbers of protective colloids A, B, C and D are 0.50,
(a2) When acetic acid solution is shaken with charcoal, 0.01, 0.10 and 0.005 respectively. The correct order of their
the concentration of the acid decreases. protective powers 1s
(b) The white precipitate of Mg(OH), attains blue colour (a) B< D<A<C (6) De A<C<B
when precipitated in the presence of magneson (fc) CeB<D<A (dq) A<C<B<D
reagent. (A.._ELE.E. 2008)
(c) The air becomes dry in the presence of silica gel. B22. Which of the following statements is incorrect regarding
physisorption ?
(d@) An aqueous solution of NaOH attains pink colour with
(a) It occurs because of van der Waals forces
a drop of phenolphthalein.
(b) More easily liquefiable gases are adsorbed readily
(e) When animal charcoal is shaken with coloured (c) Under high pressure it results into multimolecular
methylene blue solution, the solution turns colourless. layer on adsorbent surface
(Kerala PMT 2014) (d) Enthalpy of adsorption is low and positive.
B17. The correct ascending order of adsorption of the (A.LE.ELE. 2009)
following gases on the same mass of charcoal at the same B23. According to Freundlich adsorption isotherm, which of the
temperature and pressure 1s following is correct ?
x er,
(a) CH, < H, < 50, (6) H, < CH, < SO, (a) —_« p? (6) —x p™
Ft ITD
(c) SO, < CH, < H, (d) H, < SO, < CH,
xX
(ge) CH, < SO, < H, (Kerala PMT 2015) (ci — o 7
IT
B18. Which of the following statements is incorrect about
(d) All the above are correct for different ranges of
physisorption?
pressure. (A.D B.B.E. 2012)
(a) It is reversible in nature. B24. The coagulating power of electrolytes having ions Nat, Al**
(6) It forms multilayer. and Ba** for arsenic sulphide sol increases in the order
(c) It involves high activation energy. (a) Al?* < Nat < Ba**
(d) The extent of physisorption decreases with increase of (6) Al?* < Ba** < Nat
temperature. (c) Nat < Ba* < Al**
(e) It increases with increase in surface area. (d) Ba®* < Na* < Al** (JEE. Main. 2013)
(Kerala PMT 2015) B25. 3g of activated charcoal was added to 50 mL of acetic acid
solution (0.06 N)1in a flask. After an hour it was filtered and
JEE (Main) & Other State Boards’ the strength of the filtrate was found to be 0.042 N. The
Engineering Entrance amount of acetic acid adsorbed (per gram of charcoal) is
(a) 42 mg (b) 54 mg
B19. Volume of a colloidal particle, Vas compared to the volume (c) 18 mg (dq) 836mg (JEE. Main 2015)
of a solute particle in a true solution, V, could be B26. For a linear plot of log (x/m) versus log P in a Freundlich
V V adsorption isotherm, which of the following statement is
(a) ae (b) ~~ correct? (k and n are constants).
§ s (a) both & and 1/n appear in the slope term.
V V (6) 1/n appears as the intercept.
(c:) — =10° (i) = TOY (c) Only 1/n appears as the slope.
va § (A.LLE.E.E. 2005) (d) log (1/n) appears as the intercept. (JEE Main 2016)
B20. In Langmuir's model of adsorption of a gas on a solid B27. Tyndall effect is observed only when following conditions
surface. are satisfied:
(a) the adsorption at a single site on the surface may (A) The diameter of the dispersed particles is much smaller
than the wavelength of the light used.
involve multiple molecules at the same time.
(B) The diameter of the dispersed particle is not much
(6) the mass of gas striking a given area of surface is
smaller than the wavelength of the light used.
proportional to the pressure of the gas.
(C) The refractive indices of the dispersed phase and
(c) the mass of gas striking a given area of surface is dispersion medium are almost similar in magnitude.
independent of the pressure of the gas.
(D) The refractive indices of the dispersed phase and
(d) the rate of dissociation of adsorbed molecules from the dispersion medium differ greatly in magnitude.
surface does not depend on the surface covered.
(a) (A) and (C) (6) (B) and (C)
(A.LE.E.E. 2006)
(c) (A) and (D) (d) (B) and(D)(JEE. Main 2017)

Answets
B16. (d) B17. (5) B18. (c) B19. (d) B20. (bd) B21. (dq) B22. (d) B28. (d) B24. (c) B25. (c)
B26. (c) B27. (d)
SURFACE CHEMISTRY

B28. On adding one mL of solution of 10% NaCl to 100 mL of (c) the charge on the particles
gold sol in the presence of 0.25 g of starch, the coagulation (d) Tyndall effect. (Karnataka CET 2013)
is Just prevented. The gold number of starch is B37. The amount of electrolytes required to coagulate a given
(a) 0.25 (b) 0.025 amount of AglI colloidal solution (—ve charge) will be in
(ec) 2b (d) 25 the order
(e) 250 (Kerala C_E.T. 2005, 2007) (a) NaNO, > AI(NO,), > Ba(NO,),
B29. When an excess and a very dilute aqueous solution of KI (6) Al(NO,), > Ba(NO,), > NaNO,
is added to a very dilute aqueous solution of silver nitrate, (c) Al(NO,), > NaNO, > Ba(NO,),
the colloidal particles of silver iodide which are associated (d) NaNO, > Ba(NO,), > Al(NO,), (WB JEE 2014)
with Helmholtz double layer are B3s. Gold sol can be prepared by
(a) Agl : Ag*: F (a) hydrolysis of gold(III) chloride
(oy. Ag) KR NO (6) oxidation of gold by aqua regia
(c) Agl : NOZ: Agt (c) peptization
(d) AgI: I-: Kt (J & K 2009) (d) treating gold(III) chloride with metallic zinc
B30. Which one of the following impurities present in colloidal (e) reduction of gold(III) chloride with formalin
solution cannot be removed by electrodialysis ? solution. (Kerala PET 2014)
(a) Sodium chloride (6) Potassium sulphate B39. For Freundlich isotherm, a graph of log * is plotted against
(c) Urea (d) Calcium chloride
log P. The slope of the line and its y-axis intercept
(e) Magnesium chloride (Kerala C_E.T. 2009)
respectively correspond to
B31. The dispersed phase and dispersion medium in soap lather
are respectively (a) n1k (b) log n+, k
(a) gas and liquid (6) liquid and gas
(c) solid and gas (d) solid and liquid (c) AY jog k (@) log =, lore
n n
(e) gas and solid (Kerala P.E.T. 2010)
(Karnataka CET 2014)
B32. The best coagulant for the precipitation of Fe(OH), sol is
B40. Which of the following colloids cannot be easily coagulated?
(a) Na,HPO, (6) NaNO,
(a4) Multimolecular colloids
(c) Na,PO, (d) Na,SO, (J.K-CET 2011)
(6) Irreversible colloids
B33. Which 1s correct about physical adsorption ? (c) Lyophobie colloids
(a) High temperature and high pressure favour adsorption. (@) Macromolecular colloids (Karnataka CET 2015)
(6) High temperature and low pressure favour adsorption. B41. The electrolyte having maximum flocculation value for
(c) Low temperature and high pressure favour adsorption. Ag/Ag* sol is
(d) Low temperature and low pressure favour adsorption. (a) Na,S (6) Na,PO,
(e) Temperature and pressure have no effect on (c) NaCl (d) Na,SO,
adsorption. (Kerala P.E.T. 2012) (Karnataka CET 2015)
B34, During the adsorption of a gas on the surface of a solid, B42. Which of the following curves is in accordance with
which of the following is true ? Freundlich adsorption isotherm?
(a) AG<0,
AH > 0, AS <0
(6) AG> 0, AH <0,AS <0
(c) AG<0, AH <0, AS <0
(a) #lz (b) x|£
(dq) AG<0, AH <0, AS +0 (Karnataka C.E.T. 2012)
Ey o
B35. Negatively charged colloidal solution of clay in water will
need for precipitation the minimum amount of
p—> log p——>
(a) aluminium sulphate
(b) potassium sulphate
(c) sodium hydroxide
(ad) hydrochloric acid (A.M.U. Engg. 2012) e o
B36. The stability of a lyophobic colloid is due to
(a) adsorption of covalent molecules on the colloid p—. log p ——»
(6) the size of the particles (Karnataka CET 2015)

HE B28. (d) B29. (d) B30. (c) B31. (a) B32. (c) B33. (c) B33. (c) B85. (a) B86. (c) B87. (d)
B38. (e) B39. (c) B40. (d) B41. (db) B42. (d)
 MODERN'S abc + OF CHEMISTRY-All

B43. Enzymatic reactions are given in Column I and enzymes (c) The forces operating in this are weak van der Waals'
in Column II forces
Column I Column IT (d) It forms multimolecular layers of gas molecules on the
(A) Maltose — Glucose (1) Zymase surface (J.K. CET 2018)
(6) Sucrose — Glucose + Fructose (it) Pepsin B50. Which of the following is the correct increasing order of
(C) Glucose > Ethyl aleohol + CO, (iz) Maltase coagulating power of electrolytes required to precipitate a
(D) Starch + Maltose (iv) Invertase negatively charged As,5, colloid?
(EZ) Proteins —-> Amino acids (v) Diastase (a) NaCl < BaCl, < AICI,
Choose the correct matching of enzymatic reaction and (6) BaCl, < AICI, < NaCl
enzyme that catalyses the correct reaction from the codes (c) AICI, < NaCl < BaCl,
siven below: (d) AICI, < BaCl, < NaCl (J.K. CET 2018)
(a) (A) — (iz), (B) — (iv), (C) —(v), (D) -— (ait), (EB) - (a) B51. Which of the following electrolyte will have maximum
(6) (A) — (ait), (B) — (tv), (C) — @), (D) - (v), (EB) - (iz) coagulating value for AgI/Ag* sol?
(c) (A) —(), (B)— (ev), (C) — Gz), @) — (2), GE) — (raz) (a) Na,S (6) Na,PO,
(c) Na,SO, (d) NaCl
(d) (A) —(v), (B) — (zit), (C) — (iv), (D) - (ai), (2) -— (a)
(Karnataka CET 2018)
(e) (A) — (Gz), (B) — (az), (C) — @), D) — (v), GE) — Gv)
B52. Gold sol is not a
(Kerala PET 2016) (a) lyophobic sol (6) negatively charged sol
B44, In which one of the following properties, physisorption and (c) macromolecular sol (d@) multimolecular colloid
chemisorption resemble each other? (Karnataka CET 2018)
(a) Force of attraction (6) Enthalpy of adsorption B53. Which of the following statement is true about the
(c) Temperature effect (d) Effect of surface area adsorption?
(e) Number of adsorption layers (Kerala PET 2016) (a) AH <0 and AS <0 (b) AH > 0 and AS <0
B45. Which of the following statement is incorrect w.r.t. (c) AH <0 and AS>0 (q@) AH=Oand
AS <0
physisorption? (ce) AH =O andAS >0 (Kerala PET 2018)

(a) The forces involved are van der Waals forces.

JEE (Advance) for ITT Entrance
(6) More easily liquefiable gases are adsorbed easily.
(c) Under high pressure it results into mutimolecular layer B54. Lyophilic sols are
on adsorbent surface. (a) reversible sols
() AH,gaoeption is low and +ve
B46. Reactions in zeolite catalyst depend on
(WB JEE 2016) (6) they are prepared from inorganic compound
(c) coagulated by adding electrolytes
(a) pores (6) apertures (d) self stabilizing (LET. 2005)
(c) size of cavity (d) all of these. B55. Among the following, the surfactant that will form micelles
in aqueous solution at the lowest molar concentration at
(Karnataka C.E.T. 2016)
ambient conditions is
B47. Which of the following is not a favourable condition for
(a) CH,(CH,),. N (CH,),Br™
physical adsorption?
(a) High pressure (6) Low temperature (6) CH,(CH,),,0SO,-Na™
(c) High temperature (c) CH,(CH,),COO Na*
(d) Higher critical temperature of adsorbate (d) CH,(CH,),,N(CH,),Br_ (LIT 2008)
(Karnataka CET 2017) B56. Among the electrolytes Na,SO,, CaCl,, Al,(SO,), and NH,Cl,
B48. The process which is responsible for the formation of delta at the most effective coagulating agent for Sb,S, sol is
a place where rivers meet the sea is (a) Na,SO, (6) CaCl,
(a) peptization (6) colloidal formation (c) AL(SO,), (d) NH,Cl UUT-JEE 2009)
(c) emulsification (d) coagulation B57. Methylene blue, from its aqueous solution, is adsorbed on
(Karnataka CET 2017) activated charcoal at 25°C. For this process, the correct
B49. Which of the statement is true regarding chemisorption of a statement is
gas on a solid surface? (a) the adsorption requires activation at 25°C.
(a) This type adsorption first increases with increase of (6) the adsorption is accompanied by a decrease in
temperature enthalpy.
(6) No compound formation takes place in this case (c) the adsorption increases with increase of temperature.
(d) the adsorption is irreversible. (JEE Advance 2013)
Aiaswets
B43. (5) B44, (d) B45. (d) B46. (d) B47. (c) B48. (dq) B49. (a2) B50. (a) B51. (d) B52. (c)
B53. (a) B54. (d) B55. (a) B56. (c) B57. (bd)
SURFACE CHEMISTRY

C7. Choose the correct reason(s) for the stability of the

lyophobic colloidal particles.
with more than one correct answers (a) Preferential adsorption of ions on their surface from
the solution.
Cl. Which of the following increases the activation of a solid (6) Preferential adsorption of solvent on their surface from
adsorbent ? the solution.
(a) subdividing the solid adsorbent (c) Attraction between different particles having opposite
(6) carrying out adsorption at very elevated temperature charges on their surface.
(c) blowing superheated steam through porous adsorbent (d) Potential difference between the fixed layer and the
(d) polishing the surface of solid adsorbent diffused layer of opposite charges around the colloidal
particles. (LLT. J.E_E. 2012)
C2. Which of the following statements are correct ?
(a) The protective power of a colloid may be measured by C8. The given graphs/data I, II, III and IV represent
reciprocal of gold number. general trends observed for different physisorption
and chemisorption processes under mild conditions of
(6) Agel is a colloidal system in which a solid is dispersed temperature and pressure. Which of the following choice(s)
in a liquid. about I, IT, III and IV is(are) correct ?
(c) For positively charged sol, the coagulating power of
coagulating ion decreases as : PO, > 80,7" > CI E (1) P constant
(d) In colloids, the particles constituting the dispersed
phase adsorb only those ions preferentially which are
:
13]
oA

opposite with the own lattice ions. Bb adsorbed

gas
3
C3. The macromolecular colloids :
(a) consist of aggregates of atom or molecules which
generally have diameter less than lnm.
E
(6b) have usually lyophobic character
(c) have molecules which are flexible and can take any shape
(d) have molecules containing both lyophilic and lyophobic igtance of molecule from
croups. the surface
hi AFI4, = 150kJ mol
C4, Which of the following is/are not true in Langmuir Energy
Potential
of
Amount
adsorption isotherm ? of
adsorbed
Amount
gas
(a) At high pressure, = =kP
(a) Lis physisorption and II is chemisorption
(6b) Plot of log (x/m) and log P is a straight line (6) Lis physisorption and III is chemisorption
(c) At low pressure, ~ =kP (c) IV is chemisorption and II is chemisorption
(d) in intermediate range of pressure, — = kP¥ (d) IV is chemisorption and III is chemisorption
(n = whole number) q (LL.T.J_ EE. 2012)
C5. Which of the following statements are not correct ? C9. When O, is adsorbed on a metallic surface, electron transfer
(a) A catalyst does not change AH of a reaction. occurs from the metal to O,. The TRUE statement(s)
(b) The enzymes are highly specific in nature. regarding this adsorption is (are)
(c) Generally, very large quantities of enzyme catalysts (a) O, is physisorbed
are required to increase the rates of reaction. (b) heat is released
(d) Oxidation of alcohol to acetic acid can be carried out (c) occupancy of Ton of O, is increased
by invertase enzyme. (d) bond length of O, isincreased. (JEE Advance 2015)
C6. The correct statement(s) pertaining to the adsorption of C10. The correct statement(s) about surface properties is (are)
a gas on a solid surface is (are) (a) cloud is an emulsion type of colloid in which liquid is
(a) Adsorption is always exothermic dispersed phase and gas is dispersion medium.
(6) Physisorption may transform into chemisorption at (6) the critical temperatures of ethane and nitrogen are
high temperature 563 K and 126 K, respectively. The adsorption of
(c) Physisorption increases with increasing temperature
ethane will be more than that of nitrogen on same
but chemisorption decreases with increasing
temperature. amount of activated charcoal at a given temperature.
(d@) Chemisorption is more exothermic than physisor- (c) adsorption is accompanied by decrease in enthalpy and
ption, however it is very slow due to higher energy of decrease in entropy of the system.
activation. (LT. 2011) (d) Brownian motion of colloidal particles does not depend

rE
on the size of the particles but depends on viscosity of
the solution. (JEE Advance 2017)

Cl. (a,c) C2.(a,c) C3.(b,c) C4. (6, d) C5. (c,d) C6. (a, 5, d) C7. (a,d) C8.(a,c) C9.(b,c,d) C10. (5, c)
 MODERN'S abc + OF CHEMISTRY-All

particles of dispersed phase gets neutralised and precipitation

based on the given passage/comprehension takes place. This process is also called coagulation.
The coagulation is given by Hardy Schulze rules. According
Passage I to these rules the ions carrying the charge opposite to that of
Thomas Graham in 1861, during his work on diffusion found sol particles are effective and coagulating power of an
that certain substances such as gelatin, albumin, glue, etc. electrolyte is directly proportional to the fourth power of the
diffused at very slow rate and were called colloids. The valency of the ion. Coagulation can also occur by mutual
colloid paticles have the size in the range of 1 to 100 nm
precipitation, by electrophoresis, by persistent dialysis or
consisting of dispersed phase and dispersion medium. The
by heating or cooling.
dispersed phase or dispersion medium may be solid, liquid
or even a gas. Depending upon the nature of dispersion Answer the following questions:
medium or dispersed phase, 8 types of systems are possible
D4. The charge of colloidal particles can be determined by the
except for a gas dispersed in another gas because the gases
phenomenon
are completely miscible with each other. The substances
which have strong interaction with the dispersion medium (a) electrodialysis
are called lyophilic colloids while those which donot pass (6) electrophoresis
into colloidal state readily are called lyophobic colloids. (c) Bredig's are method
Lyophobic sols are much less stable and are irreversible.
(d) electro-osmosis
Answer the following questions : D5. The flocculation values of NaCl and AICI, are 51 and 0.093
D1. The size of colloidal particles is millimoles/litre for arsenic sulphide sol. This means that
(a) less than those of true solution (a) AICI, has 51 times more coagulating power than NaCl
(6) more than those of suspension (b) NaCl has 548 times more coagulating power than AICI,
(c) in the range 10 pm to 10° pm (c) AIC, has 548 times more coagulating power than NaCl
(d) inthe range 10 Ato 1000 A (J&K C.E.T. 2006) (d) The ratio of coagulating power of AICI, : NaCl is
D2. Which of the following statements is not correct ? 51: 0.093
(a) Lyophobic sols can be easily prepared only by mixing. D6. Which of the following electrolyte is most effective for
(6) Lyophilic sols are stable and irreversible. coagulating Fe (OH), sol ?
(c) Lyophobic sols are unstable and are not reversible
(a) K,[Fe(CN),|
(d) The particles of lyophobic sol are heavily solvated
(6) Na,C,O,
D3. Which of the following is not true about lyophilie sols ?
(c) K,SO,
(a) They are stable
(d) KCl
(b) They are reversible
D7. The stability of colloidal solution is due to
(c) They are heavily hydrated or solvated
(a) size of colloidal particles
(d) They are not easily formed by direct mixing
(6) charge of colloidal particles
Passage IT (c) movement of colloidal particles under applied
The particles of colloidal solution possess electrical charge electric field
which is responsible for the stability of these solutions. (d) tendency to show Tyndall effect.
The charge on colloidal particles arises because of selective
Ds. Which of the following electrolyte requires maximum
adsorption of ions which are common with their own lattice.
concentration to cause coagulation of As,S, sol ?
The presence of charge on colloidal particles can be determined
with the help of a phenomenon known as electrophoresis. (a) AICI, (6) MgSO,
However, when some electrolyte is added, the charge on the (c) K,[Fe(CN),] (d) KCl

Arswets
Passage I. D1. (d) D2. (c) D3. (d)
Passage II. D4. (b) D5. (c) D6. (a) D7. (b) D8. (d)
SURFACE CHEMISTRY 5/73 —

3. Assertion : Small quantity of soap is required to

Assertion Reason Type Questions prepare a stable emulsion.
Reason : Soaps lowers the interfacial tension
The questions given below consist of an Assertion and the between oil and water.
Reason. Use the following key to choose the appropriate answer. 4, Assertion : Sea water looks blue.
(a) Ifboth assertion and reason are CORRECT and reason Reason : Due to seatting of light by colloidal
is the correct explanation of the assertion. impurities present in sea water.
(6) Ifboth assertion and reason are CORRECT, but reason 5. Assertion: For a negatively charged sol., the
is NOT THE CORRECT explanation of the assertion. coagulation value of NaCl and MgCl, are
(c) Ifassertion is CORRECT but reason is INCORRECT. p20 amp 1 respectively.
(d) If assertion is INCORRECT but reason is CORRECT. Reason : Greater charge of cation causes slower
(e) Ifboth assertion and reason are INCORRECT. coagulation.
6. Assertion : The micelle formed by sodium stearate in
1. Assertion : Physical adsorption of molecules on the water has — COO- groups at the surface.
surface requires activation energy. Reason : Surface tension of water is reduced by
Reason : Because the bonds of adsorbed molecules addition of stearate. (A..T.M_S. 2003)
are broken. 7. Assertion : The conversion of fresh precipitate to
2. Assertion : Activity of an enzyme is pH dependent. colloidal state is called peptization.
Reason : Changes in pH affects the solubility of the Reason : It is caused by addition of common ions.
enzyme in water. (A..T.M.S. 2003) (A.LI.M_S. 2007)

Answers 1. (e) 2. (b) 3. (a) 4, (a) 5. (c) 6. (a) 7. (8)

Matrix Match Type Questions Enemas pours

(A) Whipped cream | (p) Emulsion
Each question contains statements given in two columns, (B) Medicines (q) Sol —
which have to be matched. Statements in Column I are labelled (2) oe) tute (r) ae soc ipes Se CEreeset
as A, B, C and D whereas statements in Column II are labelled Ql. hecar (s) ee having liquid dispersion
as p,q, r ands. Match the entries of Column I with appropriate medium
entries of Column II. Each entry in Column I may have one or
more than one correct option from Column II. The answers to 2. Match
. the entries of Column I with appropriate entries
in Column II.
these questions have to be appropriately bubbled as illustrated
in the following example. Column I Column II
If the correct matches are A-q, A-r, B-p, B-s, C-r, C-s and (A) Lyphobiec colloids | (p) liquid fats dispersed in water
D-q, then the correctly bubbled matrix will look like the following: (B) Lyophilic colloids | (q) behave as normal electrolyte
Dp 6Cf, MAS at low concentration and
colloidal at high concentration
A (p) (r) (s) (C) Micelles (r) get coagulated by electrolytes
B ®) Oo ©) (D) Emulsions (s) show Tyndall effect.
3. Match the column I with type of colloid given in coloumn II
C (P) (q) (r) (s) Column I Column II

DIC) @ME) (A) Starch sol fo) Bees ied

(B) Soap sol (gq) Multimolecular
1. Match the example given in Column I with the type of (C) Gelatin sol (r) Macromolecular
colloid given in Column II. (D) Gold sol (s) Lyophilic

Li} > (a) — {5} (B) —(p), (s) (C) — (q), (s) ee
(2) : (A)-(), (s) (B) -—(r) (C) —(q) (D) —(p)
(3) : (A)—(r), (s) (B) —(p) (C) —(r), (s) Ie sp)
 MODERN'S abc + OF CHEMISTRY-All

Matching List Type Questions

Each question has matching lists. The codes for the lists have 2. Match list I of enzymatic reaction with enzyme given
choices (a), (6), (c) and (d), out of which ONLY ONE is correct. in list IT:

1. Match list I with lst II and select the correct answer List I List I
using the code :
Proteins —> Amino acid 1. Zymase
List I (Type of colloid) List Il (Example) Glucose —> Ethyl alcohol + CO, 2. Lacto bacilli
P. —_Liquid in solid 1. Hair cream Starch ——> Maltose 3. Pepsin
Q. Gas in liquid 2. Cheese Wao
Milk —> Curd 4. Diastase
R. —_Liquid in liquid 3. Fog
~~ GsR Ss
S. Liquid in gas 4. Whipped cream
(a) 3 4 1 7
P Q R S§ eee /sl 3s 2
(c) “oy 4 2 1
(a) 2 1 3 4
(d) 3 1 4 =
(b) 1 3 2 4

Araswets
1. (c) 2. (d)

Exemplar Problems ji
Objective Questions
»>» Multiple Choice Questions (Type-l) CG (6) decrease in temperature.
(c) decrease in surface area of adsorbent.
1. Which of the following process does not occur at the
(d) decrease in strength of van der Waals forces.
interface of phases ?
. Extent of adsorption of adsorbate from solution phase
(a) crystallisation
(6) heterogenous catalysis increases with
(c) homogeneous catalysis (a) increase in amount of adsorbate in solution.
(d) corrosion (6) decrease in surface area of adsorbent.
2. At the equilibrium position in the process of adsorption (c) increase in temperature of solution.
(d) decrease in amount of adsorbate in solution.
(a) AH>0 (b) AH=T AS . Which one of the following is not applicable to the
(c) AH > TAS (dq) AH< TAS phenomenon of adsorption ?
3. Which of the following interface cannot be obtained ? (a) AH > 0 (c) AG <0
(a) liquid-liquid (6) solid-liquid (c) AS <0 (d)
AH <0
(c) liquid-gas (d) gas-gas . Which of the following is not a favourable condition for
4, The term ‘sorption’ stands for physical adsorption ?
(a) absorption (6) adsorption (a) high pressure
(c) both absorption and adsorption (6) negative AH
(d) desorption (c) higher critical temperature of adsorbate
5. Extent of physisorption of a gas increases with (d) high temperature
(a) increase in temperature.

aswel
ie 2. (5) 3. (d) A, (c) 5. (5) 6. (a) 7. (a) 8. (d)
SURFACE CHEMISTRY

9. Physical adsorption of a gaseous species may change to (a) coagulation (6) electrolysis
chemical adsorption with (c) diffusion (d) peptisation
(a) decrease in temperature 18. Which of the following electrolytes will have maximum
(6b) increase in temperature coagulating value for AgI/Ag* sol ?
(c) increase in surface area of adsorbent (a) Na,s (6) Na,PO,
(d) decrease in surface area of adsorbent (c) Na,SO, (d) NaCl
10. In physisorption, adsorbent does not show specificity for
19. A colloidal system having a solid substance as a dispersed
any particular gas because
phase and a liquid as a dispersion medium is classified as
(a) involved van der Waals forces are universal.
(6) gases involved behave like ideal gases.
(a) solid sol (b) gel
(c) enthalpy of adsorption is low.
(d) 1t is a reversible process. (c) emulsion (d) sol
11. Which of the following is an example of absorption ? 20. The values of colligative properties of colloidal solution
(a) Water on silica gel are of small order in comparison to those shown by true
(6) Water on calcium chloride solutions of same concentration because of colloidal
particles
(c) Hydrogen on finely divided nickel
(dq) Oxygen on metal surface (a) exhibit enormous surface area.
12. On the basis of data given below predict which of the (6) remain suspended in the dispersion medium.
following gases shows least adsorption on a definite amount (c) form lyophilic colloids.
of charcoal ? (d) are comparatively less in number.
Gas CO, oO, CH, 4H,
21. Arrange the following diagrams in correct sequence of steps
Critical temp./K 304 630 190 33 involved in the mechanism of catalysis, in accordance with
(a) CO, (6) SO, (c) CH, (d) H, modern adsorption theory.
13. In which of the following reactions heterogenous catalysis
is involved ? (x) } |
(i) 280, (g) + O, (g) “CE > 280, (g)
(ii) 250, (g) —“-> 280, @)
“rT
® i 1 |
77 ===) —

(iii) N, (g) + 38H, (g) > 2NH, (g)

. | of
(iv) CH,COOCH, ()) + H,O () “> ii) @—O—O—O—

B--9-O-
CH,COOH (aq) + CH,OH (aq)
| | |
(a) (iz), (222) (6) (it), (tt), (wv)
(c) (z), (et), (cit) (d) (tv)
14. At high concentration of soap in water, soap behaves as a | | |
(it) @)—O—O—O—

B00
| | |
(a) molecular colloid (b) associated colloid
(c) macromolecular colloid
(ad) lyophilic colloid
(iv) P| |

ane
15. Which of the following will show Tyndall effect ?
(a) Aqueous solution of soap below critical micelle
concentration.
(6) Aqueous solution of soap above critical micelle = 1)
concentration. | ||
(c) Aqueous solution of sodium chloride.
| | | |
(d) Aqueous solution of sugar. (v) = )—2—b—
16. Method by which lyophobic sol can be protected. + | | |
(a) By addition of oppositely charged sol. 3) —0O—0—0—
(6) By addition of an electrolyte. | | |
(c) By addition of lyophilic sol. (a) 1 — > it —> tt —> tv —3 0
(d) By boiling. (b) 1 —> itt —> 11 —3 tv —3 v
17. Freshly prepared precipitate sometimes gets converted to
(¢) t — it —> 11 —3 v — WwW
colloidal solution by
(d) i —> it —> tt —> v —3 WW
Auswets
9. (b) 10. (a) 11. (5) 12. (d) 13. (a) 14, (b) 15. (b) 16. (c) 17. (d)
18. (b) 19. (d) 20. (d) 21. (b)
 MODERN'S abc + OF CHEMISTRY-All

22. Which of the following process is responsible for the (a) Absorption (6) Adsorption
formation of delta at a place where rivers meet the sea ? (c) Coagulation (@) Emulsification
(a) Emulsification
(c) Coagulation
(6) Colloid formation
(d) Peptisation »> Multiple Choice Questions (Type-ll)
<q
Note :/n the following questions two or more options may be
23. Which of the following curves is in accordance with
correct.
Freundlich adsorption isotherm ?
26. Which of the following options are correct ?
(a) Micelle formation by soap in aqueous solution is possible
at all temperatures.
(a) (b) (6b) Micelle formation by soap in aqueous solution occurs
x/m—
log x/m—
log above a particular concentration.
(c) On dilution of soap solution micelles may revert to
p- individual ions.
(d@) Soap solution behaves as a normal strong electrolyte at
all concentrations.
27. Which of the following statements are correct about solid
(c) (d)
catalyst ?
x/m—
log x/m—
log (a) Same reactants may give different product by using
different catalysts.
logp > log p>
(6) Catalyst does not change AH of reaction.
24, Which of the following process is not responsible for the (c) Catalyst is required in large quantities to catalyse reactions.
presence of electric charge on the sol particles ? (d) Catalytic activity of a solid catalyst does not depend
(a) Electron capture by sol particles. upon the strength of chemisorption.
(6) Adsorption of ionic species from solution. 28. Freundlich adsorption isotherm is given by the expression
(c) Formation of Helmholtz electrical double layer.
(ad) Absorption of ionic species from solution. = =kPn, which of the following conclusions can be drawn
25. Which of the following phenomenon is applicable to the
process shown in the figure ? from this expression.
1 m8
(a) When “- 0 , the adsorption 1s independent of pressure.

l
(6) When —=(O, the adsorption is directly proportional
n
to pressure.
(yellowish brown) x
(c) When = x vs P graph is a line parallel to x-axis.

(d@) When n = 0, plot of * vs P is a curve.

29. H, gas is adsorbed on activated charcoal] to a very little extent
in comparison to easily liquefiable gases due to .
(a) very strong van der Waals interaction.
(6) very weak van der Waals forces.
(c) very low critical temperature.
(d) very high critical temperature.
350. Which of the following statements are correct ?
(a) Mixing two oppositely charged sols neutralises their
charges and stabilises the colloid.
Colourless
re solution of (6) Presence of equal and similar charges on colloidal
sugar particles provides stability to the colloids.
(c) Any amount of dispersed liquid can be added to emulsion

arse
without destabilising it.
(¢@) Brownian movement stabilises sols.

22. (c) 23. {(c) 24, (d) 20. (5) 26. (5, c) a7. (a, &) 28. (a,c) 29. (6,c) 30. (5, d)
SURFACE CHEMISTRY

31. An emulsion cannot be broken by and (c) Film of lyophilic sol is formed over lyophobic sol.
(d@) Film of lyophobic sol is formed over lyophilic sol.
(a) heating 35. Which phenomenon occurs when an electric field is
(b) adding more amount of
dispersion medium applied to a colloidal solution and electrophoresis is
(c) freezing prevented ?
Gy sidiig akalinmensent (a) Reverse caniGeis takes place.

32. Which of the following substances will precipitate the (0) Hlecirooamosis tes piace.
negatively charged emulsions ? (c) aa moygn begins to oe
(a) KCI (ey alana (d) Dispersidn medium becomes stationary.
(ey Urea (d) NaCl 36. Ina a catalyst changes

ge. Which of the following colloids cannot be coagulated easily ? ere a, : y

; . (6) qualitatively
(a) Lyophobie colloids. (
7 : ; (c) chemically
(6) Irreversible colloids. _
a Saas (dq) quantitatively
tc) — -— 7 = 37. Which of the following phenomenon occurs when a chalk
(d) Lyophilic colloids. stick is dipped in ink ?
34, What happens when a lyophilic sol is added to a lyophobic (az) adsorption of coloured substance
sol? (6) adsorption of solvent
(a) Lyophobic sol 1s protected. (c) absorption and adsorption both of solvent
(6) Lyophilic sol is protected. (d) absoprtion of solvent

31. (6,d) 32. (a,d) 33. (c,d) 34. (a,c) 35. (b,c) 36. (a, 5) 37. (a, d)

» Matching Type Questions

<@
Note: Match the items of Column I and Column Il in the following questions.
38. Method of formation of solution is given in Column I. Match it with the type of solution given in Column II.

Column I Column IT
(a) Sulphur vapours passed through cold water (t) Normal electrolyte solution
(6) Soap mixed with water above critical micelle concentration (tz) Molecular colloids
(c) White of egg whipped with water (zit) Associated colloid
(d) Soap mixed with water below critical micelle concentration (tv) Macromolecular colloids

39. Match the statement given in Column I with the phenomenon given in Column II.

(a) Dispersion medium moves in an electric field (1) Osmosis

(6) Solvent molecules pass through semipermeable (11) Electrophoresis
membrane towards solvent side
(c) Movement of charged colloidal particles under (iit) Electroosmosis
the influence of applied electric potential towards
oppositely charged electrodes
(d) Solvent molecules pass through semipermeable (iv) Reverse osmosis
membranes towards solution side

Ansett 38. (a) — (it) ; (6) — (ait) ; (c) — (iv) ; (2) — (2) 39. (a) — (itz) ; (6) — (tv) ; (ec) — (at) ; (d) — (a)
a 5/78 MODERN'S abc + OF CHEMISTRY-All

; *
[pines s=

i
is
vt = ll ;

40. Match the items given in Column I and ColumnII.

(1) Protective colloid (a) FeCl, + NaOH

(it) Liquid - liquid colloid (6) Lyophilic colloids
(iit) Positively charged colloid (c) Emulsion
(iv) Negatively charged colloid (d) FeCl, + hot water

41. Match the types of colloidal systems given in Column I with the name given in Column II.

(a) Solid in quid (:) Foam

(6) Liquid in solid (it) Sol
(c) Liquid in hquid (zz) Gel
(d) Gas in liquid (iv) Emulsion
42, Match the items of Column I and Column II.

(a) Dialysis (:) Cleansing action of soap

(6) Peptisation (it) Coagulation
(c) Emulsification (iit) Colloidal sol formation
(d) Electrophoresis (iv) Purification
43. Match the items of Column I and Column II.

(a) Butter (t) dispersion of liquid in liquid

(6) Pumice stone (it) dispersion of solid in liquid
(c) Milk (iit) dispersion of solid in liquid
(d) Paints (tv) dispersion of liquid in solid

Aiaswecs
40. (a) — (ii) ; (b) — (iit) ; (c) — (iv) ; (d) — @) Al. (a) — (it) ; (6) — (iit) 3 (c) — (iv) ; (d) — (i)
42, (a) — (iv) ; (6) — (zit) ; (ec) — (Z) 3 (d) — (a) 43. (a) — (iv) ; (6) — (ait) ; (ec) — (2) ; (d) — (a)

»» Assertion and Reason Type Questions <@

Note : In the following questions a statement of assertion followed by a statement of reason is given. Choose the correct answer out
of the following choices.
(a) Assertion and reason btoth are correct and the reason is correct explanation of assertion.
(6) Assertion and reason both are correct but reason does not explain assertion.
(c) Assertion is correct but reason is incorrect.
(d) Both assertion and reason are incorrect.
(e) Assertion is incorrect but reason is correct.
44, Assertion: An ordinary filter paper impregnated with collodion solution stops the flow of colloidal particles.
Reason: Pore size of the filter paper becomes more than the size of colloidal particle.
45, Assertion : Colloidal solutions show colligative properties.
Reason: Colloidal particles are large in size.
46. Assertion : Colloidal solutions do not show brownian motion.
Reason : Brownian motion is responsible for stability of sols.
47. Assertion : Coagulation power of Al** is more than Na‘.
Reason : Greater the valency of the flocculating ion added, greater is its power to cause precipitation (Hardy Schulze rule).
48. Assertion : Detergents with low CMC are more economical to use.
Reason : Cleansing action of detergents involves the formation of micelles. These are formed when the concentration of
detergents becomes equal to CMC.

Arve 44, (c) 45, (5) 46. (e) A7. (a) 48. (a)
SURFACE CHEMISTRY

anatio ns for
Hints & Expl Difficult Objective Type Questions
B17. () : Higher the critical temperature of a gas, greater
A. mcq with only one correct answer is the amount of gas adsorbed. The critical
temperature of H, < CH, < SO,. Therefore, the
Al. (6): Physical adsorption may be multilayer.
order of adsorption will be H, < CH, < SO,,.
x B18. : It has very low activation energy.
(c)
A3. (d) : = RP’ or log = = log k + = ipae
| n B19. (d) : For a true solution, the diameter range is
Plot of log x/m vs log P will be a straight line with 1 to < 10 A, and for colloidal solution, diameter
1 range is 10 — 1000 A. Taking lower limits,
slope = —.
7 4
+r? 3
Ad, (a):On increasing temperature adsorption decreases
continuously in physical adsorption and firstly SD_py: . (7
increases and then decreases in case of chemisorption. % 4a fi
a #* a
Al8. (d): Cation having maximum positive charge i.e., Al**.
10
A225. (b): Agl : Ag* because AgNO, is present in excess. ro o= _ =5A, r_= - 05A
A28. (c) : Alum helps in purifying water by Al** ions which 2 bo
|

coagulate the negative mud particles. Vv 5 \° 108

A29. (d): As,S, 1s a negative sol and therefore coagulating v, {O05} 1
power decreases as Al?* > Ba** > Na*
B20. (5) : In Langmuir adsorption, the rate of condensation
B. meq from Competitive Examinations depends upon the pressure of the gas as according to
kinetic theory, the number of molecules striking per
Bl. (0) : When a graph is plotted between log x/m and unit area is proportional to the pressure of the gas.
log p, for Langmuir adsorption, a straight line is B21. (d) : Lesser the gold number of a protective colloid, better
obtained with a slope = 1/n. The equation of straight is 1ts protective power.
line is log x/m = log K + 1/n log p. A<C<B<D
x B22. (d) : For physisorption, AH is negative.
BS. (d) : — =p T 1s incorrect.
iL B23. (d ) : According to Freundlich adsorption isotherm :
B5. (a) : Freundlich adsorption isotherm is ad = ppm
a :

a kp'” where 7 is > 1 so that (1/7) hes between

m 1/n can have values between 0 to 1 over different
0 and 1. ranges of pressure.
B6. (d) : The rate of enzyme activity rises rapidly with B2a, (c) : As,S, is a negatively charged sol. Therefore,
temperature and becomes maximum at a definite coagulating power is proportional to the valency
temperature called the optimum temperature. On of the active (positive) ion (Hardy Schulze rule)
either side of the optimum temperature, the enzyme Al?* > Ba2?*>Na*™ or Na‘ < Ba® < Al®*
activity decreases. 0.06 x 50
B10. (c) : Lower is the coagulation value, higher is the
B25. (c) : Moles of acetic acid initially present =
1000
coagulation power. Therefore, coagulating power =3.0x 10°
is in the order : III (MgSO,) > II (BaCl,) > I (NaCl) 0.042 x40
Bll. (ce) : According to Hardy Schulze rule, the coagulating Moles of acetic acid after adsorption =
1000
power of an ion depends upon magnitude and sign =2.1x 10°
of the coagulating ion.
Moles of acetic acid adsorbed = 3.0 x 10°? -—2.1 x 10-3
B12. (b) : The given sol is positively charged because the
= 0.9 x 10° moles
colloidal particles move towards cathode. Its
Mass of acetic acid adsorbed = 0.9 x 10-3 x 60
coagulation can be caused by oppositely charged
anion. Therefore, the coagulating power is : =54x10%¢
Amount of acetic acid adsorbed per gram of charcoal
[Fe(CN),]* > PO, > SO,2> > Cr
54x10° :
B15. (e) 2. _ Un aa aa =18x 10°¢g=18mg
mo kp
x 1 B26. (c) : According to Freundlich adsorption isotherm,
In— = Ink+—Inp 1
m n
=kpn
Slope = a

Thus, ~*~
ee _ kp 0 or log —=logk + SNog bg
|e
3
S/R n
 MODERN'S abc + OF CHEMISTRY-All

Plot of log (x/m.) vs log P gives intercept = log k and B54. (d) : Lyophilic sols are self stabilizing because these
1 sols are reversible and are highly hydrated in the
slope = —. Therefore, only — appears as the slope. solution.
n n
B56. (c) : Sb,S, is a negatively charged sol. Hence Al,(SO,), is
B27. (d) : The conditions (B) and (D) are correct.
the most effective coagulating agent because higher
B28. (d) : Amount of starch in milligram added to 10 mL of
the magnitude of opposite charge (Al**), higher is
gold sol required to prevent coagulation of 1 mL of
the coagulating power.
10% NaCl solution = 0.25 g or = 250 mg.
B57. (bd) : The adsorption of methylene blue on activated
Amount of starch required to be added to 10 mL of
charcoal is physical adsorption. It is accompanied
gold sol. to completely prevent coagulation of 1 mL
of 10% NaCl solution. by a decrease in enthalpy.
250
— x10=25mg C.mcecq with more than one correct answer
100
C&. (a; 6) - In physisorption on increasing temperature at
Hence, gold number = 25
constant pressure, adsorption decreases while in
B29. (d) : On addition of KI to AgNO,, Agl is formed. Since KI chemisorption, adsorption will increase due to
is added in excess, the Agl formed adsorbs K* and requirement of activation energy for adsorption at
I- which form the Helmholtz electrical double layer. the same pressure. So, I is physisorption and II is
» (c) : Electrodialysis is used to remove electrolytes. Urea chemisorption.
is a non-electrolyte. III is physisorption because on increasing
: Fe(OH), is a positive sol. and therefore, the best temperature, extent of adsorption decreases.
coagulant is PO,*- ion. Graph IV represents enthalpy change during
chemisorption (due to bond formation). So, IV is
x 1 for chemisorption. Hence correct answer is (a,c)
» (c) : log — =logk + — logP
m n C10. (8, c): (6) Higher the critical temperature, higher will be
the extent of adsorption.
Intercept = log k, slope = —
n (c) For adsorption, AH = —ve (exothermic) and AS
B40. (d) : Macromolecular colloids are quite stable and = —ve (decrease in entropy)
resemble true solution in many respects. Therefore
these cannot be easily coagulated. NCERT Exemplar Problems : MCQs Type-I
B41. (d) : Ag|Ag* is a positively charged sol. It can be 40) 3 There is no interface in homogeneous catalysis.
coagulated by a negative ion. For its flocculation, . (6): At equilibrium position during adsorption, AG = AH —
PO,* ions have maximum flocculation power and TAS = 0 so that AH = TAS.
Cl ions have minimum flocculation power. Hence, « (ahs Gas-gas interface is not possible because gases are
NaC] will have maximum flocculation value. miscible.
B42. (d) : Freundlich adsorption isotherm is om 4 ee AH > 0 is not possible.
* = RPpin s Gr? Because physical adsorption decreases with increase
m in temperature.
or log ~ = lof Pa eP 12. (d) : Higher the critical temperature, large is the adsorption.
m n With decrease in critical temperature, adsorption
Hence plot of log vs log P will be straight line decreases.
m 17. (d): Peptisation 1s a process of converting freshly prepared
with intercept equal to log & (not zero as in () precipitate to a colloidal solution.
. (d) : Both physisorption and chemisorption increase with 18. (BD) : Because it contains highly charged precipitating ion
increase 1n surface area. (PO):
» (d) : In physisorption, AH SAcption 15 low and always 22. (c) : Delta is formed due to coagulation of electrolytes
negative. present in sea water.
- (a) : The coagulating power of an electrolyte depends NCERT Exemplar Problems : MCQs Type-Il
upon the charge on the oppositely charged ion of the
electrolyte. For negatively charge sol, the order is : 28. (a, c) : When Pai, ~ = ki.e., adsorption is independent of
Fi FFL
Nat < Ba** < Al®*
pressure.
» (b) : Agl/Ag* is positively charged sol and, therefore, When n =0,— vsp graph becomes parallel tox-axis
negative 1on will cause coagulation. The coagulation th

value decreases with increase in charge of the 32. (a, d) : because these contain positively charged
coagulating ion. Since CI ion has minimum charge, coagulating ions.
it will have maximum coagulation value. 36. (a, b) : A catalyst is recovered unchanged after the
reaction and therefore it changes only physically
. (a) : Adsorption is accompanied by evolution of heat
and qualitatively.
(AH<0) and decrease in randomness (AS<0).
LL)
 qi)
.

07575) DOs WAYS ) a ~*

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Ai materials found in the earth are composed of different elements.

As These elements are distributed in all the three main parts of the
earth; atmosphere, hydrosphere
and lithosphere. Among these,
& lithosphere constitutes the main source of most of the elements.
: The periodic table is dominated by metals because of all the
\ elements known about 80% are metals. In the present unit,
| we shall mainly emphasise on the isolation and extraction
_ of metals. A particular element may occur in a variety of
/ compounds. The extraction and isolation of an element from
its combined form involves various principles of chemistry.
f The entire scientific and technological processes used for
isolation of metal from its ores is called metallurgy.

~~. | >“ MODES OF OCCURRENCE OF ELEMENTS

The elements generally occur in the free state (called native state) or in the combined state. This is mainly
because of different chemical reactivities of elements.
1. Native State
The elements which have very low reactivity and are not attacked by oxygen or air, moisture, carbon dioxide or
other non-metals occur in the free state, called native state. For example, carbon, sulphur, nitrogen, noble gases,
metals like gold, silver, platinum, etc. occur in nature in the native state. Therefore, these elements are also called
native elements.
2. Combined State
The elements which are reactive and have a tendency to combine with oxygen or air, moisture, carbon dioxide
and non-metals like carbon, nitrogen, sulphur, phosphorus, arsenic, halogen, etc. occur in the combined state.
 MODERN'S abe + OF CHEMISTRY
-AXIl

Therefore, these elements occur in the crust of the earth in the form of their
compounds. In the combined state, the non-metals are usually found in the
reduced form and the metals in the oxidised form.
Among the metals, only a few metals, such as silver, gold, platinum, etc.
occur in native state.
Non-metals such as carbon and sulphur also occur in native state as well
as in combined state.
Abundance of Elements
Elements vary in abundances. The sixteen most abundant
elements in the earth’s crust and their percentages by weight
are shown in Fig. 1. Oxygen constitutes nearly half (49.5%)
ery ay and silicon about one quarter of the total mass of the elements
POTASSIUM 94] in the earth’s crust.
MAGNESIUM 1.9 Most metals occur in the combined states. The most
TITANIUM 0.6 : '
CHLORINE og | common forms of metals in the combined states are oxides,
PHOSPHORUS 0.1| carbonates, sulphides, silicates, halides, sulphates, arsenides,
MANGANESE 0.1] phosphates, ete.
OTHERS < 0.1
Among metals, aluminium is the most abundant. It is the
third most abundant element in earth’s crust (8.31% by wt).
It occurs widely as a constituent of rocks and soils. It is a major
Fig. 1. Distribution of elements in the earth's crust
component of many igneous minerals including mica and clays.
Iron is the second most abundant metal in earth’s crust. It forms
a variety of compounds which have various important uses. This makes
iron a very important element. Iron is also one of the essential elements in
biological systems.
OCCURRENCE OF METALS : MINERALS AND ORES
As already discussed, metals occur in native state and combined state.
Most of the metals have a tendency to react with moisture, oxygen, sulphur,
halogens, etc. and therefore, occur in the crust of the earth in the form of
Gem stones. Many gem stones are
their compounds such as oxides, sulphides, halides, silicates, carbonates,
impure forms of alumina (Al,O,) and
nitrates, phosphates, etc.
contain traces of metal ions as
impurities such as Cr** (in ruby), Co** The naturally occurring chemical substances in the form of which
(blue sapphire), Fe** (topaz or yellow the metals occur in the earth's crust are called minerals.
sapphire), Mn** (amethyst), etc.
The mineral, from which the metal can be economically and
conveniently extracted, is called an ore.
It may be noted that often a metal occurs in more than one form. The
type of mineral from which the metal can be extracted is decided on the
basis of profitability. For example, metals are not generally extracted from
silicate minerals because of the difficulties during the extraction. For example,
aluminium occurs in the earth’s crust in the form of two minerals, bauxite
(Al,O,.2H,O) and clay (Al,0,.2810,.2H,O). Out of these two, aluminium can
be conveniently and economically extracted from bauxite. Therefore, the ore of
aluminium is bauxite though both bauxite and clay are minerals of aluminium.
Similarly, iron occurs in the earth's crust as oxides, carbonates and
sulphides. Out of these minerals of iron, oxides of iron are taken for extraction
because these are most abundant and do not produce polluting gases (like
SO,, which is produced in case of iron pyrites, FeS,). For copper and zinc,
any of the minerals given in Table 1 may be employed depending upon their
availability and other relevant factors. Thus, it may be concluded that
All the ores are minerals but all the minerals are not ores.

The principal ores of some important metals are given in Table 1.

GENERAL PRINCIPLES AND PROCESSES OF ISOLATION OF ELEMENTS

Table 1. Principal ores of some important metals.

Composition

Bauxite JARO RCT Lee

(where 0 < x < 1)
Feldspar KAISi,0,
Cryolite Na, AIF,
Kaolinite Al,(OH),S8i,0,
(a form of clay)
Iron (Fe) Haematite Fe,O,
Magnetite FeO,
Siderite ee
Iron pyrites FeS,
Limonite Fe,O,.8H,O
Copper (Cu) Copper glance Cu,8
Copper pyrites CuFes,
Malachite CuCO,.Cu(OH),
Cuprite (ruby copper) Cu,O
Azurite 2 CuCQ,.Cu(OH),
Zine blende or Sphalerite “Ans
Calamine ZnCO,
Zincite “ZnO
Willemite 7n,910,
Franklinite £nO.Fe,O,
Manganese (Mn) Pyrolusite MnO,
Braunite MnO,
Calcium (Ca) Limestone CaCO,
Gypsum CaSO,.2H,0
Magnesium (Mg) Magnesite MgCo,
Dolomite CaCO,.MgCO,
Lead (Pb) Galena PbS
Cerrusite PbCO,
Silver (Ag) Argentite or Silver glance Ago©
Horn silver AgCl
Ruby silver Ag,©.5b,5,5
Mercury (Hg) Cinnabar Hgs

OLVED EXAMPLES
LJ Example 1 LJ Example 3.
In general, which metals do you expect to occur in Name two examples each of the following types of
native state in nature ? Give examples. Ores -
Solution: In general, the metals which lie below hydrogen (a) Oxides (6b) Sulphides (c) Carbonates (d) Silicates
in electrochemical series occur in native state in nature because Solution: (a) Oxides
these are not attacked by oxygen, moisture and CO, present
(t) Haematite : Fe,O, (zz) Bauxite : AL,O,.2H,O
in the atmosphere. Common examples are Cu, Ag, Au, Pt, ete.
(6) Sulphides
L] Example 2.
(1) Copper glance : Cu,S (iz) Zine blende : ZnS
Why do metal sulphides occur mainly in rocks and
metal halides occur mostly in lakes and seas ? (c) Carbonates
Solution : Metal sulphides are insoluble in water and (t) Siderite : FeCQ, (zz) Dolomite : CaCO,.MgSO,
therefore, they occur mostly in rocks. On the other hand, metal (d) Silicates
halides are highly soluble in water. Therefore, they get dissolved
(i) Willemite : Zn,SiO, (ii) Feldspar : KAISi,O,
in rain water and are carried to lakes and seas.
 MODERN'S abe + OF CHEMISTRY
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EXTRACTION OF METALS : METALLURGY

The process of extracting metals from their ores is called metallurgy.
The ores mined from the earth’s crust are never pure. These are generally
contaminated with earthly or undesired materials (impurities). These are
called gangue or matrix. The process of metallurgy depends upon the nature
of the ore and the impurities present in it. Therefore, it is not possible to have
a single universal method which may be applicable to all the metals. Thus,
the extraction of each metal involves an individual procedure. However, some
common steps involved in the metallurgical operations are :
1. Crushing and grinding of the ore
2. Concentration or benefaction of the ore
3. Hxtraction of crude metal from concentrated ore
4, Purification or refining of the metal
I. CRUSHING AND GRINDING OF THE ORE
The ores occur in nature as huge lumps. They are broken to small pieces
with the help of crushers or grinders. These pieces are then reduced to fine
powder with the help of a ball mill or stamp mill. This process is called
pulverisation.

Il. CONCENTRATION OF ORE OR ORE BENEFACTION

The ores are usually found mixed up with large amounts of non-metallic
impurities such as, sand, mica, limestone, felspar, earthly and rocky impurities.
These unwanted impurities are called gangue or matrix and have to be
removed before extracting the metals.
The process of removal of unwanted impurities (1.e., gangue or matrix)
from the ore is called ore concentration or ore dressing or ore benefaction.
Before the ore is subjected to metallurgical processes for extraction of
metal from the ore, it is essential to concentrate the ore. The powdered ore is
concentrated by one of the following methods depending upon the differences
in physical properties of the compound of the metal present and the impurities
(gangue) present in the ore.

1. Hand picking.
Quite often, the ore is separated from the main stock in a sufficient degree
of purity by simply picking it by hand and then breaking away the adhering
rocky materials with a hammer.
2. Gravity separation or Levigation.
This method is based on the differences in the specific gravities of
metallic ores and the gangue particles. Therefore, this method is known as
gravity separation. This method is frequently used when the ore particles are
heavier than the earthy or rocky gangue particles. For example, this method is
commonly used for oxide ores such as haematite, tin stone and native ore
of Au, Ag, etc.
The process by which lighter earthly particles are removed from
heavier ore particles by washing with water is called hydraulic
washing or gravity separation or levigation.
The powdered ore is fed into a stream of running water when the lighter
impurities are washed away and the heavier ore particles are left behind. This
method is used only on a small scale. In order to concentrate the ores in bulk,
two commonly used methods of gravity separation are :
GENERAL PRINCIPLES AND PROCESSES OF ISOLATION OF ELEMENTS

(4) Wilfley washing

(77) Hydraulic washing or Levigation
(4) Wilfley’s washing. A Wilfley table is a wooden table having a
slanting floor on which long wooden strips called riffles or cleats are fixed
(Fig. 2). The powdered ore is mixed with water and introduced at one end of
the table. The table is given regular rocky motion.
The heavier ore particles are obstructed by the riffles while the lighter
impurities are carried away by the stream of water. The heavier ore particles
which get collected behind the riffles move to one side as a result of motion
of the table and are collected.
This method is particularly useful for the concentration of native gold ore
or cassiterite (SnO,).
(74) Hydraulic washing or Levigation. The hydraulic classifier consists of
a large conical reservoir fitted with an ore inlet at the top and water inlet at the
bottom. There is a provision to remove light gangue particles from the side near
the top and concentrated ore from the bottom as shown in Fig. 3. In this method,
the powdered ore is dropped through a hopper into the hydraulic classifier from
the top. A powerful stream of water is forced into it through the pipe at the
bottom of the reservoir. The lighter particles of the gangue are carried up by the
current of water and pass out alongwith water flowing out from the outlet near
the top. The heavier particles of the ore get collected at the base of the cone.
The conical shape of the reservoir helps in reducing the velocity of water
and this prevents the ore particles from being carried away along with the
stream of water.

Powdered ore / Powdered ore

Suspension
of the ore

Concentrated ore
a
Concentrated ore

Fig. 2. Wilfley washing table. Fig. 3. Hydraulic classifier.

3. Electromagnetic separation
This is based on the differences in magnetic properties of the ore
components. If either ore or the gangue (one of these two) is attracted by
a magnet then ore can be separated from the impurities with the help of
magnetic separation method. For example, the magnetic impurities such as
iron and manganese tungstates (FeWO,, MnWO,) present in tin stone (SnO,,
non-magnetic) are separated by this method. Similarly, chromite (FeO.Cr,O,)
is magnetic and it can be separated from non-magnetic silicious gangue by
this method. This method is also used for the concentration of haematite
(Fe,O,) or magnetite (Fe,O,), pyrolusite (MnO,), ilmenite (ore of titanium),
etc. It consists of a brass or leather belt moving over two rollers, one of which
 MODERN'S abe + OF CHEMISTRY
-AXIl

is Magnetic in nature as shown in Fig. 4. Powdered ore is

dropped over the moving belt at one end. At the other end,
the magnetic portion of the ore is attracted by the magnetic
roller and falls nearer to the roller while the non-magnetic
impurities fall farther off.
4. Electrostatic concentration
This method is used for the separation of ores which
are good conductors of electricity from those which
are poor conductors of electricity. It is based on the
principle that when an electrostatic field is applied, the ore
Leather belt
particles which are good conductors of electricity become
electrically charged and are consequently repelled by
Magnetic particles
electrode having the same charge and are thrown away.
Non-magnetic particles This method is used for the concentration of lead sulphide
(PbS) and zinc sulphide (ZnS) ores occurring together in
Fig. 4. Magnetic separation process. nature. The powdered ore is fed upon a roller in a thin
layer and subjected to the influence of an electrostatic
field. Lead sulphide being a good conductor, gets charged immediately and
is thrown away from the roller whereas zinc sulphide being a poor conductor
falls vertically from the roller.
5. Froth floatation
This method is based on the principle of difference in the wetting properties
of the ore and gangue particles with water and oil. It is used for the extraction
of those metals in which the ore particles are preferentially wetted by oil and gangue
by water. This method has been used for the concentration of sulphide ores, such
@ Collectors: pine oil, eucalyptus as galena (PbS), zine blende (ZnS), copper pyrites (CuFeS,), etc. The sulphide ore
oil, xanthates; enhance the particles are preferentially wetted by oil and gangue particles by water.
non-wettability of mineral In this method, the powdered ore is mixed with water to form a suspension
particles. in a tank (Fig. 5). To this suspension small quantities of collectors and froth
Froth stabilizers: aniline, stabilizers are added. Collectors (e.g., pine oil, eucalyptus oil, fatty acids,
geret) EAL LE xanthates, etc.) enhance the non-wettability of the mineral particles and froth
stabilizers (e.g., cresols, aniline) help in stabilization of the froth. The mineral
ore particles become wet by oil while
the gangue (impurities) particles by
water. The suspension is agitated
by a rotating paddle or by blowing
Rotating paddle
air violently, when froth (or foam) is
formed.
Powdered ore During the process, the ore
+ Oil + Water Light ore particles which are preferentially
particles in froth | wetted by the oil become lighter. The
froth carries the lighter ore particles
along with it to the surface. The heavier
impurities are left behind in water
and these sink to the bottom. Since
the ore particles float with the froth
at the surface, this process is called
froth floatation process. The froth is
(ome | either skimmed off from the surface
Paddle draws | is < ‘ f = or transferred into another tank. The
heir cules JL == = 7) froth is broken by adding some acid
mld and ore particles are separated by
filtration and dried.
Fig. 5. Froth floatation process.
GENERAL PRINCIPLES AND PROCESSES OF ISOLATION OF ELEMENTS

Separation of two sulphide ores : Froth floatation method can also be

used for separating one sulphide ore from another by adjusting the
proportion of oil to water. Sometimes, depressants are used to prevent
certain types of particles from forming the froth with air bubbles. For example,
sodium cyanide can be used as a depressant in the separation of zinc sulphide
ore (ZnS) and lead sulphide ore (PbS). Sodium cyanide forms a layer of zinc
complex, NaJZn(CN),/ on the surface of ZnS and therefore, prevents it from
forming the froth. Therefore, tt acts as a depressant.
4ANaCN + “ZS — > Na,[Zn(CN),] + Nas
Depressant Ore Sodium tetracyanidozincate(II)
However, NaCN does not prevent PbS from forming the froth. Thus, it
selectively prevents ZnS from coming to the froth but allows PbS to come with
the froth. Thus, the two ores can be separated by the use of a depressant.

6. Leaching
This is a chemical method of concentration and is useful in case the ore is
soluble in a suitable solvent. In this method, the powdered ore is treated
with certain reagents which can selectively dissolve the ore but not
the impurities. The impurities left undissolved are removed by filtration.
Leaching method is used for concentrating ores of aluminium, silver, gold,
etc. For example:
(1) Leaching of alumina from bauxite ore : Pure alumina (AI,O,) is
obtained from principal ore of aluminium, bauxite by Baeyer’s process. The
bauxite ore is usually contaminated with impurities of silica (S10,), iron oxides
(Fe,O,), titanium oxide (Ti0,), etc. Concentration is carried out by digesting
the powdered ore with a concentrated solution of sodium hydroxide at 473-5238
K and 35-36 bar pressure. In this process, Al,O, dissolves in alkali to form
soluble sodium aluminate and silica (Si0,) dissolves as sodium silicate, leaving
behind the impurities.
A1,0,-2H,0 (s) + 2NaOH (aq) + 3H,O (2) “88% _,Na[Al(OH),] (aq)
Alumina 5odium aluminate
“ 473 — 523 K ‘
910, + 2NaQ0H —————— Na,810, (ag) + HO (f)
Silica Sodium silicate
The resulting solution is filtered (to remove impurities), cooled and its pH
is adjusted downward by dilution or by neutralisation with carbon dioxide. It is
agitated for two to three hours when Al,O, gets precipitated. It may be noted
that seeding with a little freshly prepared samples of hydrated Al,O, quickens
the process.
2Na[Al(OH),] (aq) + 2CO, (g¢) —————>. Al,,0,..xH,,0 (s) + 2NaHCO, (aq)
The sodium silicate remains in the solution and the precipitated hydrated
alumina is separated by filtration. It is dried and upon heating to 1470 K gives
pure alumina.
A1,0,.xH,0 (s) —————
1470 K
AI,0, (s) + xH,O @)
Pure alumina
This process is known as Baeyer’s process.
(11) Leaching of silver and gold ores : Leaching is also used to concentrate REMEMBER
silver and gold ores. The ore containing native metal (silver or gold) is treated
@® Leaching of bauxite ore to get pure
with a dilute solution (0.5%) of NaCN or KCN in the presence of atmospheric alumina
oxygen. As a result, silver and gold get oxidised which then combine with CN-
=» Baeyer’s process
ions forming their respective soluble complex cyanides while the impurities
Leaching to concentrate silver and
remain unaffected and are filtered off. The metal dissolves in the solution as gold ores
a complex.
» MacArthur Forrest Cyanide
4M (s) + 8CN- (ag) + 2H,O (@) + O, (g¢) ——> 4 [M(CN),J (aq) + 40H (aq) Process
Air Soluble complex
 MODERN'S abe + OF CHEMISTRY
-AIl

The metal is obtained by replacement reaction as :

2[M(CN),} (aq) + Zn (s) ———> [Zn(CN),]* (aq) + 2M (s) metal
(where M = Au or Ag)
For example,
(1) Silver is leached as:
4Ag + 8NaCN + 2H,O + O, ———+ 4NalAg (CN),] + 4NaOH
Sodium dicyanidoargentate(1)
(Soluble complex)
Ifinstead of native silver, silver glance or argentite (Ag.S) 1s used for leaching
of silver, the initial reaction forming the soluble complex is reversible.
Ag.s + 4NaCN 2Nal[Ag(CN),] + Na,S
Sodium dicyanidoargentate(1) (Soluble complex)
Sodium sulphide, thus formed is oxidised to sodium sulphate by blowing
air into the solution. This helps the reaction to occur in the forward direction.
4Na,S + 50, (air) + 2H,O ——~+ 2Na,SO, + 4NaOH + 28
The above solution after filtration and removing insoluble impurities is
heated with zinc to get silver.
2NalAg(CN),] + Zn .——~+ Na,[Zn(CN),] + 2Ag
Complex
(11) Gold is also extracted in a similar way.
4Au + 8KCN + 2H,0+ 0, ——Y—> 4KIAu(CN),] + 4KOH
Potassium dicyanidoaurate(I)
(Soluble complex)
2K[Au(CN),] + Zn —W—>_ K,[Zn(CN),] + 2Au
Potassium tetracyanidozincate(II)
(Soluble complex)
This process is known as Cyanide Process or Mac Arthur Forrest
Cyanide Process.
I. EXTRACTION OF CRUDE METAL FROM CONCENTRATED ORE
The process of working of the concentrated ore to extract metal depends
upon the nature of the ore as well as the nature of the impurities present in
the ore. This involves oxidation and reduction reactions. The concentrated ore
must be converted into a form which is suitable for reduction. Generally, the
sulphide ores are converted to oxides before reduction because oxides are easily
reduced. The main operations for the working of the ore involves two steps :
(A) Conversion of the concentrated ore to its oxide form (oxidation or
de-electronation)
(B) Conversion of the oxide to the metal (reduction or electronation)
(A) Conversion of the concentrated ore to its oxide form (Oxidation
or de-electronation)
The concentrated ore is either a hydrated oxide, a carbonate or a sulphide.
It can be converted into its oxide form by the following two methods :
(4) Calcination
(i) Roasting
These are discussed below :
(4) Calcination
Calcination is a process of heating the ore strongly below its melting
point either in a limited supply of air or in the absence of air.
During calcination, the following changes take place:
(4) moisture is removed
(ii) the volatile impurities are removed
(iit) the ore becomes porous and hence becomes easily workable in the
subsequent steps.
(iv) water from hydrated oxides is removed
GENERAL PRINCIPLES AND PROCESSES OF ISOLATION OF ELEMENTS

(v) carbonates decompose to oxides.

For example, hydrated oxide and carbonate ores are generally calcined
to give oxides.
(a) Zine occurs as zinc carbonate in calamine (ZnCO,). The ore is calcined
1.e., heated strongly in the absence of air to convert it to zinc oxide. During
calcination, carbon dioxide is expelled.
ZnCO, (s) Calcination , ZnO (s) 4 Co, (g)

“ine carbonate Aine oxide

(Calamine ore)
Similarly,
CaCO, (s) Salcination, CaO (s) + CO, (g)

CaCO,.MgCO,(s) 8H, Cad (s) +MgO(s) + 2C0,(g)

Dolomite

CuCO,.Cu0OH), > e2Ccu0 + H,O(s) +00,

Malachite Cupric oxide

(6) Aluminium occurs as Al,O,:2H,O in its bauxite ore. When the bauxite
ore is calcined, water vapours are expelled and anhydrous aluminium oxide
is obtained.
Calcination
AL,O,.2H,0 =" ALO, + 2H

(c) Water of hydration are removed from limonite (Fe,O,.3H,0O).

2Fe,0,.3H,O —Ht , 2Fe,0,4°3H5O

Lamonite

(71) Roasting
Roasting is the process of heating the ore strongly in the presence
of excess of air at a temperature below the melting point of the metal.
This methods is mainly employed in case of sulphide ores. As a result
of roasting, the moisture and volatile impurities are removed and the ore is
converted to oxide. For example, impurities of sulphur, arsenic and phosphorus
are, removed as their volatile oxides, SO,, As,O,, P,O,, respectively.
S, +80, A—=>»88S0,1
4As + 30,/. ——>, 2As,0,1
P, +50, =—~ 2P,0,T
The ores of the metal are converted into their oxides. For example, the
sulphide ore of the metal is roasted to give oxide. REMEMBER
27n5 + 80, > BFnO + 250, e Calcination is a process of
Zine sulphide ine oxide converting an ore into its
2Pb5 +80, ———> 2PbO + 250, metallic oxide either in the
Lead sulphide Lead oxide absence or limited supply
2Cu,8 +80, ——> 2Cu,0 + 250, of air.
Copper sulphide Copper (I) oxide Roasting is a process of
converting an ore into its
metallic oxide in the presence
of excess air.
Sometimes, the oxidation of sulphides takes place only to the sulphate Calcination is generally used
stage. For example, for ores containing carbonates
PbS + 20, — PbSO, and hydrated oxides.
Roasting 1s generally done for
405 + 20, —______ > A4nSO A sulphide ores.
 MODERN'S abe + OF CHEMISTRY
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Both calcination and roasting are generally carried

Charge hopper
Tie-rod Charge hopper in a reverberatory furnace. The modern furnace is shown
Hangers in Fig. 6. In this type of furnace, the fuel does not come
| in direct contact with the charge. The flames are directed
from the roof of the furnace on the charge and air supply
can be controlled by vents. The intensely hot flames melt
the charge. There are tap holes along the walls for crude
metal and slag. Such type of furnace can melt about 10°
Air and oil kg of charge per day.
In case of roasting, the air holes are kept open
while in case of calcination, the air holes are partially
or completely closed. The reverberatory furnace can be
used both for oxidation and reduction.
Silica

Fig. 6. Modern reverberatory furnace.

If the calcined or roasted ore still contains non-fusible
impurities of earthly matter, then during reduction, an
additional substance called the flux is also added to the ore. It combines with
impurities to form easily fusible product known as slag.
Impurities + Flux——> _ Fusible product (slag)
(present in the ore)
Slag is not soluble in molten metal. Being lighter, it can be easily skimmed
off from the surface of the molten metal. Therefore, removal of gangue becomes
easier. Thus,
flux is a substance which chemically combines with gangue (earthly
impurities) which may still be present in the calcined or roasted
ore to form easily fusible material called the slag.
Types of fluxes: There are two types of fluxes : Basic fluxes and acidic fluxes.
The choice of flux depends upon the nature of impurities present in the
ore. For example,
(a) If the ore contains acidic impurities such as Si0,, P,O,, etc., then
the basie fluxes like lime (CaO), limestone (CaCO,), magnesite (MgCO,)
haematite (Fe,O,), etc. are used.
SiO, + CaO —> CaSiO,
Acidic impurity Basic flux Calcium silicate (slag)

SiO, + CaCO, —>» CaSiO, + CO,

Acidic impurity Basic flux Calcium silicate (slag)

SiO, + MgCO, —> MgSiO, +CO,

Acidic impurity Basic flux Magnesium silicate (slag)

(6) If basic impurities are present in the ore such as CaO, FeO, MgCO,,
etc., then acidic fluxes like sand (Si0,) or borax (Na, B,O,.10H,O) are used.
FeO + SiO, — FeSiO,
Basic impurity Acidic flux Ferrous silicate (slag)

CaO + SiO, — CaSiO,

Basic impurity Acidic flux Calcium silicate (slag)

(B) Conversion of the oxide of the metal to the metallic form

(Reduction or electronation)
The metal oxides are usually reduced to free metals by using a suitable
reducing agent such as carbon, carbon monoxide or even another metal. The
reduction process involves electron gain or electronation.
The process of extraction of metal by heating the metal oxide
with a suitable reducing agent is called thermal reduction or
pyrometallurgy.
GENERAL PRINCIPLES AND PROCESSES OF ISOLATION OF ELEMENTS
ant]
Some metals are easily reduced (i.e., reduction occurs at low temperatures)
while others are reduced with difficulty (i.e., reduction occurs at high
temperatures). However, it may be noted that heating is always required for
reduction. The choice of the element which will suit as a reducing agent for a
civen metal oxide and the optimum temperature at which reduction will proceed
smoothly, can be understood in terms of basic thermodynamic concepts as
discussed later. Depending upon the nature of the oxide and metal, the extraction
of metal can be carried out by the following reducing agents:

(t) Reduction with C or CO: In the metallurgy of Fe,

Cu, Pb, Sn, 4n, Mg, Co, etc.
(it) Reduction with Na, Al, Mg or hydrogen : In the
metallurgy of Mn, Cr, Ti, Mo, W, etc.
(iti) Reduction with water gas (CO, H,): Inthe metallurgy
of Ni.
(zu) Self reduction or Auto-reduction : In the metallurgy
of Pb, Hg, Cu, etc.

These methods are discussed below :

(4) Reduction with carbon and carbon monoxide. The oxides of
metals like zinc, copper, tin, lead, etc. can be reduced by using carbon as
reducing agent.
The process of extraction of metal by reduction of its oxide with
carbon (in the form of charcoal, coke or carbon monoxide) is
called smelting.
In this process, the roasted ore is mixed with a suitable amount of carbon
(coke or coal) or carbon monoxide and heated to a high temperature above the
melting point of the metal in a furnace. Carbon or carbon monoxide (produced
by incomplete combustion of carbon) reduces the oxide to free metal.
M,O, + yo ——— «wM + yCO
For example,
ZnO + Cc ——- “Zn + CO
PbO + C —~@— Ps + CO
Fes. + 3c S— )S=ZBe + 3CO
Fe,0, + 300 —85, oFe + 300,
FeO + co —S) Fe + CO,
| 1600K._
nO + AQ“ Zn + CO,
The carbon reduction process is generally carried out in a blast furnace.
For example, the extraction of the most important industrial metal, iron, is
carried out in a blast furnace.
(ii) Reduction by hydrogen. Certain metal oxides are reduced by
hydrogen. Because of the inflammable nature of hydrogen, it is used in very
few cases. For example, molybdenum and tungsten oxides are reduced by a
current of hydrogen at higher temperature (1270-1470 K).
wo, + SH, W + 3H,0
Tungsten trioxide Tungsten
MoO, + 38H, —M-,> Mo + 38H,O
Molybdenum trioxide Molybdenum
NiO + H, ———> Ni + 4H,0O
Nickle oxide Nickel
ena MODERN'S abe + OF CHEMISTRY

(iii) Reduction by aluminium: aluminothermy. Many oxides, like Cr,O,,

-AXIl

Mn.0O,, etc. are not reduced easily by carbon or CO. These metal oxides are
reduced by strongly electropositive metals such as aluminium. The process
of reduction of a metal oxide to the metal with the help of aluminium
powder is called aluminothermy.
For example,
Cr,0, + 2Al —— > 2Cr + Al,O,
3Mn,0, + sAl ———» 4AL0, + 9Mn
The above reaction is highly exothermic and therefore, the metals are
produced in the molten state.
The above process is also known as Goldschmidt thermite process.
Similarly, Fe,O, can be reduced to metallic iron by aluminium :
Fe,O, + 2Al —f/s4F> 2 + ALO,
The molten iron produced by thermite process can be used to weld broken
parts of heavy machinery of all kinds such as rail, girders, etc. This process
is also called thermite welding.
(iv) Reduction by sodium or magnesium or calcium. Certain metal
halides are reduced to pure metal state by reduction with Na, Mg or Ca, in
a closed vessel on heating. For example, titanium, zirconium, or vanadium
metals are obtained by reduction of their halides with Na or Mg at higher
temperatures (1070-1170 K).
TiCl, + 4Na ——> Ti + 4NaCl
VCl, + 2Mg —— > V + 2MgCl,
(v) Reduction with water gas. Nickel oxide (NiO) is reduced to nickel
by heating carefully in a tower at 600 K in which a current of water gas
(CO + H,) is passed. In this case both CO and H, present in water gas act
as reducing agents.
NiO” + CO ——>» Ni + CO,
NiO + H, ——— Ni + 4H,O
(vt) Self reduction or Auto-reduction. Reduction can also be carried
out by self reduction or auto-reduction in which the anions associated with the
metal help in the reduction. This is used for the reduction of sulphide ores of
certain less electropositive metals like those of Pb, Hg and Cu. In this method,
Learning Plus the metal is heated in air to bring about the conversion of a part of sulphide
Kroll Process ore into its oxide or sulphate which then reacts with the remaining sulphide
Rutile ore (Ti0,) is mixed with to give the metal and SO,,. In this case, no reducing agent is required.
carbon and heated to about 900°C For example, mercury is directly obtained by the roasting of its ore cinnabar
and then a current of chlorine is (HgS) in air as:
passed when vapours of titanium HgS + o ——» de + 80,
tetrachloride are produced. Cinnabar
2T10, + 3C + 4Cl,——> or HgS + 380, —> 2HgO + 250,
Rutile 2HgO —— 2H¢g + O,
2TiCl, + 2CO + CO rs
and 2HgO + HgsS —— > 3Hg + 80,
TiCl, and other volatile chlorides
Copper is also obtained by reducing Cu,S by partly converted Cu,O in
are subsequently separated by
this way during smelting.
continuous fractional distillation.
TiCl, is reduced by passing it in 2Cuss + 80, —-> 2Cu,0 + 250 Pe
vapour state over magnesium Cu,sS + 2Cu,0 ———+ 6Cu + SO,
heated to 800— 850°C ina stainless Copper pyrite
steel retort. The reduction can be carried out in reverberatory furnace (Fig. 6) as
TiCl, + 2Mg ——> Ti + 2MgCl, described earlier.
GENERAL PRINCIPLES AND PROCESSES OF ISOLATION OF ELEMENTS

| SOLVED EXAMPLES
lL) Example 4. L} EKxample 5
How does sodium cyanide act as depressant in What is flux ? How is it useful ? (7.P.S.B 2016)
preventing ZnS from forming the froth ?
Solution: Flux is a substance which combines with gangue
Solution : Sodium cyanide combines with ZnS to form a
(ampurities) present in roasted ore to form easily fusible
complex Na,[Zn(CN),] on the suface of ZnS and therefore,
it prevents it from forming the froth. raatera) Cale. Bag:
ZnS + 4NaCN ——-> Na,[Zn(CN),] + Na,S Flux + Cygne ——> Slag
Sodium Thus, flux helps to remove impurities from the roasted or
tetracyanidozincate (ID) calcined ore.

THERMODYNAMIC PRINCIPLES OF METALLURGY

The extraction of metals from their oxides by using a particular reducing
agent can be predicted by some basic concepts of thermodynamics. As we
have learnt in thermodynamics, the feasibility of a process can be predicted
in terms of Gibbs energy change (AG) at any specified temperature. This is
related to enthalpy change (AH) and entropy change (AS) as:
AG = AH — TAS eel)
where T is the absolute temperature at which process is carried out.
AH is a measure of energy changes while AS is a measure of randomness or
disorder during the process.
For any reaction, the Gibbs energy change is also related to equilibrium
constant (K) of the reactant-product system at the temperature T as
AG® = —RT In K
For a spontaneous process or reaction, the energy change (AG) must be
negative. This also implies positive value of K and can happen only when
reaction proceeds towards products. On the basis of these basic concepts, we
can make the following conclusions :
1. For any reaction to occur, the value of AG must be negative. This will
be possible if AH is negative and AS is positive. On increasing temperature
(T), the value of TAS would increase and then AG will become more negative
and the reaction will be feasible. It may be noted that even if AH is positive,
the AG will become negative after certain temperature as T increases
(AH < TAS).
2. [f reactants and products of two reactions are put together in a system
and the net AG of the two possible reactions is negative, then the overall
reaction will occur. This involves coupling of two reactions, getting the sum
of their AG values taking into account their magnitude and sign. This means
that a reaction with positive AG can also be made to occur by coupling it
with another reaction having large negative AG so that the net AG of the
two reactions is negative.
Such coupling can be easily understood by plotting a graph between
Gibbs energy (AG) versus temperature (T) for the formation of oxides. The
graphical representation showing the variation of Gibbs energy with increase
of temperature for the formation of oxides (i.e., oxidation of metals to their
oxides) was first used by H.J.T. Ellingham and is known as Ellingham
diagram.
a 6/14 MODERN’S abc + OF CHEMISTRY-XII

Ellingham diagram.
Ellingham diagram provides a sound basis for considering the choice of reducing agent in the reduction of
oxides. These diagrams help us in predicting the feasibility of thermal reduction of an ore. The basic criterion of
feasibility is that at given temperature, Gibbs energy change of the reaction must be negative. The Ellingham
diagram for the oxidation of metals to metal oxides per mole of O, is given in Fig. 7.
The diagram has the following significant features :
1. Ellingham diagram gives graphical representation of plots of A,G° vs T for formation of oxides of elements.
The reaction may be represented as :
2xM (s) + O,@) —>2M,_0 6)
In terms of Gibbs energy of formation, the reaction may be written as :
xM(s) + =O, ——>M,0(s) 4G°(M, M,O)
In this reaction, dioxygen is used up in the course of the reaction. As we know, gases have more randomness
(or disorder) than liquids and solids and therefore, gases have higher entropy than liquids or solids. Therefore,
entropy of the reaction decreases and hence AS for the above oxidation process would be negative. With increase
in temperature TAS term would become more and more negative and thereby AG would become less and less
negative with increase in temperature. Thus, the Gibbs energy change increases or becomes less negative with an
increase of temperature.
Therefore, AJG° vs T lines have positive slopes for most of the reactions involving the formation of metal oxides,
M,.O(s). This is clear from Fig. 7. It may be noted that in Fig. 7, the plots are shown for A,G° vs T per mole of O,.
2. The AG vs T graphs are straight lines unless some change in phase occurs i.e., the materials melt or vaporise
(i.e., Change from solid ——> liquid or from liquid ——> gas). The temperature at which such change occurs is
indicated by an increase in slope on positive side. This is because there is a large change in entropy when the
metals undergo fusion (solid ——sliquid) or vaporisation (liquid ——> gas) because solids have less entropy than
liquids which have less entropy than gases. This increase changes the slopes of ASG° vs T considerably.
For example, in the Zn—ZnO plot, at the boiling point of zinc (907°C or 1180 K), there is an abrupt increase
in the +ve slope of the curve. Similarly, the slope of Mg—MgO curve increases abruptly at the boiling point
of Mg (1120°C or 1893 K), Reactions for different
and that of Hg—-HgO curve curves
at 356°C (or 623K) where
Hg boils. The melting points Ag : 4Ag + O, —> 2Ag,0
Hg : 2Hg + O, —> 2HgO
and boiling points of other
metals are indicated by e dots
“phe Sanne | for 2Cu + 0, —> 2Cu0
3. When the temperature is a
raised, a point would be reached .
where the A,G° vs T graphs Sa ew Fe : 2Fe + O, —> 2FeO
cross the AG =0 line. Below this
temperature, AG is negative , SL Qe Zn : 27n + 0, —> 2Zn0
and hence the oxide is stable. << O
Above this temperature, the ‘ad ee Cr 2 Cr+0O, —>5.Cr,0;
Gibbs energy change is positive
and the oxides formed would,
therefore, be unstable and | A
a
would decompose to give metals Alia Al+ 0,— =Al,0,
and oxygen. Thus, according to :
Ellingham diagram, all oxides | Mg : 2Mg + 0, —> 2MgO
would decompose to give the Ca: 2Ca + O, —> 2CaO
metal and oxygen provided the 800 1200 1600 2000 2400
temperatures are sufficiently 273 K 673K 1073K 1478K 1873K 2273K 2673 K

high at which AG becomes Temperature —>

positive. However in practice, Fig. 7. Gibbs energy change (A,G*) vs T plots for formation of some metal oxides
such high temperatures are not (Ellingham diagram)
GENERAL PRINCIPLES AND PROCESSES OF ISOLATION OF ELEMENTS 6/15 —

easily attained. It has been observed that the Ag-Ag,O, Au—Au,O and Hg—HgO lines cross the AG° = 0 line at
temperatures which are attainable (Fig. 7). Thus, the oxides of Ag, Au and Hg are the only oxides which
can be decomposed at temperatures which are attainable and therefore, these metals are extracted by
thermal decomposition or reduction (called pyrometallurgy) of these oxides.
4. In Ellingham diagram, the plots of some reducing agents such as carbon and carbon monoxide are also
civen. The coupling or combination of oxidation and reduction reactions helps in interpreting whether the given
reducing agent can be useful or not.
§. Similar diagrams are also constructed for sulphides and halides. These diagrams show as to why reduction
of MS is difficult in which AG of MS is not compensated.
Limitations of Ellingham Diagram
(i) The Ellingham diagram simply indicates whether a reaction is possible or not i.e., it shows the tendency
of reduction with a reducing agent. This is because it is based only on the thermodymanic concepts. It does not
predict the kinetics of the reduction i.e., rate or time taken for reduction to occur or how fast it could be.
(iz) The interpretation of AG° is based on the equation.
ee hee
Thus, it is presumed that the reactants and products are in equilibrium as:
MO+A_, = 2M + A0
This is not always true because the reactant or product may be solid. However, it explains satisfactorily how
the reactions are slow when every species is in solid state and smooth when the oxide ore melts. It is interesting
to note that AH and AS values for any chemical reaction remain nearly constant even on changing temperature.
Therefore, the only dominant variable in equation [AG = AH — TAS] is T. However, AS depends much on the
physical state of the compound. Since the entropy depends upon the degree of disorder or randomness in the
system, it will increase if a compound melts (s > /) or vaporises (J — g) because the degree of molecular randomness
increases on changing the phase from solid to liquid or from liquid to gas.
Let us understand the use of Ellingham diagram for some reducing agents.
1. Metals act as reducing agents
In a number of processes, a metal is used to reduce the oxide of another metal. For example, aluminium is
used to reduce Cr,O, to Cr in a well known
thermite process. With the help of Ellingham
diagram, it is evident that metals for which
Gibbs energy of formation of their oxides 1s
more negative can reduce those metal oxides
for which the Gibbs energy of formation of their
respective oxides is less negative. In other words,
a
O
any metal would reduce the oxides of other metals S
—
which lie above itin Ellingham diagram because rr;

the Gibbs energy change of the combined reaction

will become more negative by an amount equal
-
to the difference between the two graphs at that
particular temperature.
The part of Ellingham diagram showing
variation of A,G° vs T for Al and Cr is shown 1273K
in Fig. 8. The A,G° vs T line for Al lies below
the ° vs T line for Cr, at all temperatures. 500 1000 1500 2000
In other words, Gibbs energy for aluminium is
more negative than that of chromium. Therefore, Temp (K) |
aluminium should reduce chromium (IID at all Fig. 8. Ellingham diagram for Cr and Al.
temperatures.
For example, at 1273 K(1000°C), the AG® values for Al and Cr are —827 kJ mol! and —540 kJ mol respectively.
Adding these together, we get an overall value for AG = —287 kJ mol".
= Cr + O, —~> - Cr,O, AG = —540 kJ mol senh)

= 5, ——— =Al,O, AG =-827kJ mol __....(ii)

a 6/16 MODERN’S abc + OF CHEMISTRY-XII
Subtracting equation (z) from (iz), we get :
:ae 2 €.0, — “Cr + =AL0, AG =-827—(— 540) kJ mol4...Gii)
: = — 287 kJ mol
So, the reaction (zii) is feasible or Al can reduce Cr,O,. Similarly, it can be shown that Al can reduce NiO
or FeO also which lie above the line for Al—A1,O,. (Fig. 7).
Let us see whether Cr can reduce Al,O, or not. Subtracting equation (ii) from equation (7), we get

4 Cee 2Al,0, —— + : Cr,0, + = Al AG = 540 — (827) = +287 kJ mol

Since AG for the reaction is positive, therefore, the above reaction would not occur. i.e., Cr would not reduce
Al,O, to Al. Similarly, AG° vs T curve for Mg lies below AG? vs T line for Al. This means that Al cannot
reduce MgO to Mg at temperature below 1623 K but Mg can reduce Al,O, to Al.
Alternatively, without going into calculation for A.G°, we can still predict the feasibility of a reduction process
from the Ellingham diagram. In Ellingham diagram, if the AG°, vs T curves for two metals intersect at a point
(making AG = 0), then we can easily predict the feasibility of reduction of metal oxide by another metal. Below
this intersection temperature (corresponding to AG = 0), the AG is —ve and hence the oxide is stable. Above this
temperature, AG = +ve, and hence its oxide is unstable and it would give metal and oxygen. For example, the
intersection point of Al — Al,O, and Mg — MgO in A,G° vs T curves is approximately 1350°C (or 1623 K, marked I).
Therefore,
® below 1623 K, MgO is stable and hence Mg can reduce Al,O, to Al. But
@ above 1623 K, Al,O, is stable and hence Al can reduce MgO to Mg.
2. Reduction by carbon or carbon monoxide
The process of extracting a metal by reduction of tts oxide with carbon (in the form of coke, charcoal or carbon
monoxide) is called smelting.
If the reduction is carried out by carbon, two reactions are possible for the reaction of carbon and oxygen :
(a) C(s) + - O, (g) +> CO @) AG (C, CO) a)
(b) CO (g) + - 0 Key We AG (CO, CO,) di)
If carbon is taken, it may also undergo complete oxidation to CO, as
1 1 | 1 1 one
(c) m C (s) + 902 (g) ————> Or (g) GAG (c; Cos) beleEE)

The variation of A,G° vs T for these reactions is shown

in Fig. 9. It may be noted that in Fig. 9, AG° vs T plots I boS =

are drawn per mole of O,,.

When metal oxide is reduced, the reducing agent form
are | fs=
its oxide. The basic role of reducing agent is to provide AG° =
negative and large enough so that the sui of AG° of 2
the two reactions (oxidation of reducing agent and 5<] I coSo =

reduction of metal oxide) is negative. Let us illustrate

this by taking example of C and CO as reducing agent. 273
Temperature (K)
Fig. 9. Ellingham diagram showing the variation of AG
with temperature for three reactions involving carbon.
During reduction, metal oxide decomposes as :
M,O(s) ———> «xM(sor) + 50,@) iv)
The reducing agent takes away the oxygen as
See Gey, ————> xM(sorl) + CO(g) ee big
MOOS) 7 CC) Ge) a xM (sor!) + CQO,@) aE)

M,O(s) + 3C(s) ——> Mor) + 5CO,@) ...(vii)

GENERAL PRINCIPLES AND PROCESSES OF ISOLATION OF ELEMENTS 6/17 =

The AG° values for these reactions can be obtained by subtraction of the corresponding A,G° values, of metal
oxide and reducing agent. Since we have learnt that heating (increasing T) favours a negative value of A.G°,
therefore, the temperature is so chosen such that the sum of A_G° in the two combined redox reactions 1s negative.
For example, if at a temperature C, CO line lies above the metal oxide line in Fig. 7, the AG° (M, M_O) is more
negative than AG° (C, CO). At this temperatures, AG° (C, CO) — AG° (M, M,O) is positive so the reaction (v) is
not spontaneous. However, for temperatures for which C, CO line lies below the metal oxide line, the reduction
of metal oxide by carbon is spontaneous, Similarly, we can explain the reduction of metal oxide by equations (v7)
and (vii) on the basis of carbon oxidation lines whether they lie above or below the metal oxide line.
To sum up
For temperature at which C, CO line lie below the metal oxide line, carbon can be used to reduce metal
oxide and it itself gets oxidised to CO. If the difference is large, reduction is easier.
= It is clear from Ellingham diagram that the two lines for C ———> CO, or C ——-— CO cross at about
710°C or 983 K.
® Below this temperature, carbon reduces metal oxides to metals in Ellingham diagram, carbon being oxidised
to CO,.
® Above 710°C or 983 K reduction of oxides results in the formation of CO. In other words, below 710°C
(or 983 K) the formation of CO, is preferred and above 710°C (or 983 K) the formation of CO is
preferred.
In other words, below 9838 K both C and CO ean act as a reducing agent but since CO can be more
easily oxidised to CO, than C to CO,, therefore, below 983 K, CO is more effective reducing agent than
C. However, above 983K CO is more stable and hence its oxidation to CO, is less rapid than that of
C to CO,. Therefore, above 983 K carbon is better reducing agent than CO.

It may be noted that many metals occur as sulphides. However, we cannot reduce metal sulphides with
carbon. As we have learnt that AG° vs T line for CO has negative slope at higher temperatures. Therefore
carbon can reduce metal oxides at higher temperatures. However, there is no compound CS analogous to CO for
which AG vs T graphs slope downwards. Therefore, sulphide ores are first converted to oxides before reducing
with carbon as:
2MS + O, ~f wm “SMO + 250,
In a similar way, we can interpret from Ellingham diagram that hydrogen is not commonly used as a reducing
agent for extracting metals from their oxides. This is because of two reasons :
(1) AG vs T graph for the oxidation of hydrogen
2H, + JO, ——af?> 2H,0
has a positive slope and runs parallel to most of the metal-metal oxide lines above the hydrogen line so that only
a few metals having metal-metal oxide lines above the hydrogen line can be reduced by hydrogen. Moreover, the
increase in temperature will not be of any use because AG does not vary with temperature.
(11) Hydrogen reacts with many metals forming hydrides.

Applications of Ellingham Diagram

The Ellingham diagram has been used to understand the extraction of
metals such as iron, copper and zinc from their respective oxides as discussed
later in their extraction.
ELECTROCHEMICAL PRINCIPLES OF METALLURGY
The thermodynamic principles can also be applied for the reduction of
metal ions in solution or molten state. The reduction occurs by electrolysis
or by adding some reducing element.
The reduction of a molten metal salt is done by electrolysis. This method
is based on electrochemical principles. The Gibbs energy change is related to
electrode potential of the redox couple formed in the system as:
AG? = — nFE®
where 7 is the number of electrons taking part in the redox reaction and
F is the Faraday of electricity. More reactive metals have large negative
values of the electrode potential and therefore, their reduction is difficult. If
the difference of two E° values of a redox system corresponds to a positive K°
value and consequently negative AG° in equation (iv), then the less reactive
ene MODERN'S abe + OF CHEMISTRY

metal will come out of the solution and more reactive metal will go into the
-AXIl

solution. For example, the electrode potential of two electrodes are :

Fe** (ag) + 2e ——> Fe(s) E°=-0.44V
Gut® — @e- +» Cuts BP = 4+ 0.84V
In this more active metal iron will go into the solution while less reactive
metal copper will come out of the solution as :
Cu** (aq) + Fe (s} ————~> Cu(s) + Fe* (aq)
In simple electrolysis, the M”* ions are discharged at negative electrode
(cathode) and deposited there.
M"* (ag) + ne~ M—— Ms)
During electrolysis, precautions are taken considering the reactivity of the
metal produced and suitable materials are used as electrodes. Sometimes, a
flux is also added for making the molten mass more conducting.
The process of extraction of metals by electrolysis of their fused
salts is called electrometallurgy.
This method is discussed later in the metallurgy of Al and Cu.

:
lL] Example 6. L} Kxample 8
Out of C and CO which ts a better reducing agent for ZnO ? Copper can be extracted by hydrometallurgy but not
N.C.E.R.T. zine, Explain. WNCERT

Solution: Carbon is a better reducing agent for ZnO. Solution: Zinc is more electropositive (E° = — 0.76V) and
therefore, is highly reactive metal. Hence, it cannot be easily
Taide ess gaa CO
displaced from its solution of ZnSO,. On the other hand, copper
Example 7.
is less electropositive (E° = +0.34 V) and can be readily displaced
A part of Ellingham diagram for some metal oxides from its solution by some more active metal such as zinc.
(based upon 1 mole of O,) and carbon ts shown.
Zn (s) + Cu** (ag) —> Zn** (aq) + Cu (s)
L} Kxample 9
Free energies of formation (AG) of MgO (s) and CO (g)
at 1273 K and 2278 K are given below
(AG) [MgO (s)] = — 941 kJ/mol at 1273 K
(AG) [MgO (s)] = — 314 kJ/mol at 2273 K
(AG) [CO (g)] = —439 kJ/mol at 1273 K
(kJ
AG
O,)
mol
per (AG) [CO (g)] = — 628 kJ/mol at 2273 K
0 p00 1000 1500 2000 On the basis of above data, predict the temperature
Temp (°C) —> at which carbon can be used as a reducing agent for
In figure A, B, C and D represent curves for metal MgO(s). (CBSE Sample Paper 2007)
oxides and a, b, c, d, eand fare temperatures. Answer Solution: The reduction of MgO with carbon is expressed as :
the following : MgO (s) + C (s) —3 Mg (s) + CO (@)
(i) Will B oxide reduce metal oxide of A or C or Free energy (AG) for the reaction may be calculated as :
both ? AG = AG [CO(g)] — AG [Mg0(s)]
(11) Which metal can be reduced thermally ? At 12738 K AG = — 439 —-(-941) = + 502 kJ/mol
(111) Will oxide of B be reduced by coke above
At 2273 K AG = — 628 —(-314) =- 314 kJ/mol
temperature c or below temperature c ?
Since AG is negative at 2273 K, the reduction is feasible at
(tv) Will the formation of CO or CO, be preferred
this temperature. Hence, carbon can be used as a reducing
above temperature f ?
agent at 2273 K.
(v) What does temperature ‘a’ represent ?
Solution: LJ Kxample 10
(z) Metal oxide of C (11) Metal oxide of B The value of AG for the formation of Cr,O0, 1s — 540 keJ
(zit) Above temperature c (av) CO mol and that of Al,O, is — 827 kJ mol. Is reduction
(v) The change in state (at fusion or vaporisation) of Cr,O, possible with Al ?
GENERAL PRINCIPLES AND PROCESSES OF ISOLATION OF ELEMENTS

Solution: The two equations are: L) Example 11

(z) =Al(s) +O, (g) + =A,0, (s) Why is the reduction of a metal oxide easter tf the
metal its formed in liquid state at the temperature of
AG° (Al, Al,O,) =—827 kJ mol
.., 4 2 reduction ?
(i1) aut (s) + O,(g) —> 3 Cr,O, (s) N.C.E.R.T) (Hr. S.B. 2012, Kerala S.B. 2013)
A,G® (Cr, Cr,O,) =— 640 kJ mol Solution: The entropy of a metal is higher in its liquid
Subtracting eqn. (iz) from eqn (2), we get state than 1n its solid state. Therefore, entropy change, AS of the
“Al (s) + =Cr,0, (s) —> =Al,O, (s) + < Cr (s) reduction process is more on the positive side when the metal
formed is in liquid state and metal oxide being reduced is in
A.G° =— 287 kJ mol
the solid state. Since the value of TAS increases and that of AH
Since A_G* for the combined reaction is —ve, therefore, the
remains constant, therefore, the value of AG becomes more on
above reaction, i.e. reduction of Cr,O, by Al is possible.
negative side and therefore, reaction becomes easier.

EXTRACTION OF NON-METALLIC ELEMENTS BY OXIDATION

Non-metatllic elements are extracted from their combined states by
oxidation. The common example of extraction based on oxidation is the
extraction of chlorine from brine. Chlorine is most abundant in sea water as
common salt. Chlorine can be obtained by the oxidation of Cl ions in water :
2CI (aq) + 2H,O (1) ——> 20H" (aq) + H, @) + Cl, &)
The AG®° for the reaction is 422 kJ. The minimum potential difference
required for oxidation can be calculated as:
AG? = —nFE°
a 422 x 1000 J = — 2 x 96500 C x EP
ge = _242x1000 _ 5196 - oo
2x 96500
However, the oxidation of Cl ions cannot be carried out by ordinary
chemical methods. The oxidation of Cl can be done by electrolysis.
Thus, we will require an external e.m.f greater than 2.2 V for electrolysis.
This is because the electrolysis requires an excess potential to overcome
some other hindering reactions such as liberation of gases. The extra voltage
required is called overvoltage. Thus, chlorine is obtained by the electrolysis
giving out H, and aqueous NaOH as by-products. Similarly, fluorine can be
extracted by electrolysis.
Electrolysis of molten NaCl can also be carried out but in this case Na
metal is produced at cathode and Cl, at the anode.
EXTRACTION OF METALS BOTH BY OXIDATION AND REDUCTION
Extraction of gold and silver
As already studied, the extraction of gold and silver involves leaching of
metals present in the ore with CN- ions. This is also an oxidation reaction
because during the leaching process, Ag is oxidised to Agt and Au is oxidised to
Aw’ which then combine with CN ions to form their respective soluble complexes.
4Ag(s) + 8CN(aq) + 2H,OW) + Og) —> 4[Ag(CN),]- + 40H (aq)
milver soluble complex
4Au(s) + 8CN-(aqg) + 2H,0@) + 0g) —> 4[Au(CN),]- + 40H-(aq)
Gold soluble complex
The metals are then recovered from these complexes by reduction or
displacement method using a more electropositive zinc metal.
2[Ag(CN),](aq) + Zn(s) —~> 2Ag(s) + [Zn(CN),]? (aq)
2[Au(CN),] (aq) + Zn(s) —— 2Au(s) + [Zn(CN),]* (aq)
In these reactions, zinc acts as a reducing agent.
This process is called hydrometallurgy. Thus,
the process of extraction of metals by dissolving the ore in a suitable
chemical reagent followed by the precipitation or displacement of
the metal by a more reactive or more electropositive metal is called
hydrometallurgy.
Copper is also extracted from low grade ores by hydrometallurgy (as
discussed later).
"eo IV. REFINING OF METALS
MODERN'S abe + OF CHEMISTRY-AIl

The metal obtained by any of the above methods is usually impure and
is known as crude metal. Therefore, the crude metal is to be purified. The
impurities may be in the form of
(4) unreduced oxides of the metals
(ii) non-metals like C, Si, P, As, 5, etc.
(iii) foreign metals
(7v) slag or flux.
The process of purifying the crude metal is called refining.
Some of the common methods of refining are :
1. Distillation. This method is useful for low boiling metals like zinc
and mercury. In this method, the impure metal is heated in an iron retort
and the vapours are condensed in a separate receiver. The pure metal distils
over and is collected as distillate leaving behind the
non-volatile (having higher boiling points) impurities
in the retort.
2. Liquation
This method is used for refining the metals having
=—— Impurities low-meilting points than those of impurities such as
tin, lead, bismuth, etc. In this method, the impure
metal is placed on the sloping hearth (Fig. 10) of the
reverberatory furnace and is gently heated in an inert
atmosphere of carbon monoxide. The metal melts and
flows down leaving the non-fusible impurities (called
dross) on the hearth. The pure metal is collected at
the bottom of the sloping hearth in a receiver.
3. Electrolytic refining
Fig. 10. Liquation process.
This is most general method for the refining of
metals and is based upon the phenomenon of electrolysis.
In this method, the impure metal is made to act as
anode. A strip of the same metal in pure form is used
as cathode. Both anode and cathode are placed in a
suitable electrolytic bath containing soluble salt of
the same metal. On passing current, metal ions from
the electrolyte are deposited at the cathode in the
form of pure metal while equivalent amount of metal
dissolves from the anode into the electrolyte in the
form of metal ions. The impurities fall down below
Impure the anode as anode mud. The reaction occurring at
copper as
inae the electrodes are:
anode
At cathode : M"* + ne- .M

Copper is refined using an electrolytic method

Copper sulphate
Anode mud
solution
(Fig. 11). In this method crude copper is made anode,
a thin sheet of pure copper is made cathode and
Fig. 11. Electrolytic refining of copper acidified solution of copper sulphate is used as an
' electrolyte. On passing electric current, metal ions
from the electrolyte are deposited at the cathode in
the form of pure metal. On the other hand, an equivalent amount of metal
dissolves from the anode into the electrolyte in the form of metal ions. The
reactions occurring at electrodes are :
At cathode: Cu** + 2e —— Cu
At anode: Cu — 2e ——~ Cu
The impurities settle down below the anode in the form of anode mud. The
anode mud may contain antimony, selenium, tellurium, silver, gold and platinum.
The recovery of these elements may meet the cost of refining.
Zine may also be refined by this method.
GENERAL PRINCIPLES AND PROCESSES OF ISOLATION OF ELEMENTS

4. Zone refining Fe Oe
This method is used for metals KKK
which are required in very high purity.
For example, extremely pure silicon,
germanium, boron, gallium and indium 4d Noble gas atmosphere i
are refined by this method. This method is
based on the principle that the impurities
are more soluble in the melt than in Pure metal Bet = Impure metal
the solid state of the metal. Therefore,
an impure metal on solidification will Metal roZ XK) > > >
deposit crystals of pure metal and the Molten zone
Induction coil Direction of movement of
impurities will remain behind in the (containing impurities) molten zone and impurities
moving heaters
molten part of the metal. In this method,
the impure metal is cast into a thin bar. Fig. 12. Zone refining of metals.
A circular mobile heater is fixed at on
end of the rod of impure metal. One zone of the bar is melted by a circular
mobile heater in the atmosphere of an inert gas like argon. At the heated
zone, the metal melts (Fig. 12) and forms a molten zone or the melt. As the
heater moves forward slowly, the pure metal crystallises out of the melt and
the impurities pass on into the adjacent molten zone. The process is repeated
several times and heater is moved in the same direction till the impurities
are completely driven to one end of the rod. In this way, the impurities are
made to move into one end which is finally cut off and discarded. Thus, we
get completely pure metal by this method. This method is specially useful
for producing semiconductors of very high purity. Germanium, for example,
purified by this method contains impurities only upto 7—10 ppm.
5. Vapour phase refining
This method is based on the fact that certain metals are converted to their
volatile compounds while the impurities are not affected during compound
formation. The compound formed decomposes on heating to give pure metal.
Thus, the two requirements are :
(i) The metal should form a suitable compound with a suitable reagent.
(it) The volatile compound should be easily decomposable so that the
metal can be easily recovered.
For example, nickel is refined by this technique and the method is known
as Mond process. In this method, nickel is heated in a steam of carbon
monoxide to form volatile nickel tetracarbonyl, Ni(CO), complex.
The carbonyl vapours when subjected to higher temperature (450-470 K)
undergoes thermal decomposition giving pure nickel.

Ni + 4co —20-350K, Nico), “OSPR, Mi + 400

Impure Nickel tetracarbonyl Pure
6. Van Arkel Method
This method is similar to above method. It is very useful for removing
all the oxygen and nitrogen present in the form of impurity in certain metals
such as zirconium and titanium for getting ultra pure metals. In this method,
the metal is converted to a volatile unstable compound (e.g., iodide) taking
care that the impurities are not affected during compound formation. The
compound thus obtained is decomposed to get the pure metal. For example,
the crude zirconium is heated in an evacuated vessel with iodine at 870 K.
The covalent volatile zirconium tetraiodide thus formed is separated. It is
then decomposed by heating over a tungsten filament at 2075 K to give pure
zirconium.
Zr + 870 K
21, ———=— Zr, _
207K,
—ainesten filament Zr + 2I,()
Impure Vapour Vapour Pure
Similarly,
523 K 1700 K
Ti(s) + a1} ——— Til, @) ————7 Ti(s) + 21, (g)
Impure Vapour Pure
lene 7. Chromatographic method
MODERN'S abe + OF CHEMISTRY
-AXIl

This is a modern method of separation or purification. It is based on

the principle that different components of a mixture are differently
adsorbed on an adsorbent. The mixture is put in a liquid or gaseous medium
(called moving phase) which is moved through a porous medium (adsorbent
called stationary phase). Different components of the mixture are adsorbed
at different levels in the column. After the separation, the different adsorbed
components are extracted from the adsorbent with suitable solvent. This process
of recovery or extraction of the adsorbed components is called elution. Thus,
the technique consists of two phases, the stationary phase and the moving
phase. The stationary phase may be a solid (such as alumina, silica gel) or
tightly bound liquid on a solid support (such as paper in which liquid water
is held by the solid cellulose). On the other hand, the moving phase may be a
liquid or gas. The mobile phase and the stationary phase are chosen such that
components of the sample have different solubilities in the two phases. Depending
upon the physical states of two phases and also on the process of passage of
moving medium, the chromatographic technique is given
different names such as column chromatography, thin
Mixture layer chromatography, paper chromatography, and gas
+

Solvent chromatography. These are discussed in previous class.

Adsorbent Column chromatography is an important technique
(stationary) in which an adsorbent (e.g., alumina, Al,O.) is packed
in a glass column. The mixture to be separated or
purified is taken in a suitable solvent and is applied
on the top of the column. Because different components
of the mixture are adsorbed to different extents, they
get adsorbed on the column at different places. The
component which is adsorbed strongly gets adsorbed at
the top. The other components with decreasing orders of
(a) Adsorbent their adsorbabilities are held up at different zones down
column
the column in the form of bands. Consider for example,
a mixture of three components A, B and C. Let their
tendencies to get adsorbed on a solid surface are in the
(c) Elution
order A > B > C when these are dissolved in a solvent
(a) Laboratory method.
and passed through the column. The component A, which
is most strongly adsorbed by the adsorbent will be held
by the solid to a greater extent than the others. It will
be adsorbed at the top. As this solution goes down, the
concentration of A becomes less and more of B will be
adsorbed (adsorbing power of B is more than that of C).
After this C will be adsorbed. Thus, a separation of the
mixture takes place (Fig. 13 (a)). After the separation,
the substances are extracted with a suitable solvent
(called eluent). The commonly employed eluents are
petroleum ether, carbon tetrachloride, benzene, alcohol,
acetone, etc. The eluent acts as a mobile phase. The
eluent dissolves different components selectively. The
weakly adsorbed component will be eluted more rapidly,
followed by the more strongly adsorbed component and so
on. The process of elution is repeated a number of times
Solvent tank
to achieve complete separation. Different components
of the mixture are collected in the form of different
(b) Industrial method fractions in separate conical flasks. The components
from the eluent are separated by simple methods such
Fig. 13. Column chromatography | as distilling off solvent or separating with the help of
separating funnel.
GENERAL PRINCIPLES AND PROCESSES OF ISOLATION OF ELEMENTS

This method is especially suitable for the elements which are available only
in minute quantities and the impurities are not very much different in their
chemical behaviour from the element to be purified. A schematic diagram for
the separation of three components in a mixture (A, B and C) using column
chromatography is shown in Fig 13(q).
The industrial method of chromatography is shown in Fig. 18(0).
The flow sheet of the metallurgical process has been given below :

Step I
CRUSHING AND
GRINDING Powdered Ore

Step 2 Levigation
CONCENTRATION Electromagnetic separation
OF THE ORE Electrostatic concentration
Froth floatation
Leaching
Concentrated Ore

Roasting Conversion into

Caleination metal oxide
(oxidation)
Step 3 Smelting
WORKING OF THE Hydrogen reduction
CONCENTRATED ORE Auto reduction ' Conversion of
(OXIDATION AND Hydrometallurgy oxide to metal
REDUCTION Electrolytic reduction | (reduction)
PROCESSES)

Crude Metal

Step 4 Distillation
PURIFICATION AND Liquation
REFINING Poling
Electrolytic refining
Zone refining
Vapour phase refining

Pure Metal

APPLICATIONS OF THERMODYNAMIC AND ELECTROCHEMICAL

PRINCIPLES OF METALLURGY FOR EXTRACTION OF METALS
Let us discuss extraction of some important metals such as iron, copper, zinc
and aluminium by applying the thermodynamic and electrochemical principles
of metallurgy.
1. Extraction of Iron
Iron is the second most abundant metal occurring in the earth’s crust.
It is a reactive metal and does not occur in the free state. In combined state
occurs as oxides, carbonates and sulphides. The common ores of iron are :
(1) Haematite FeO, (red oxide of iron)
(it) Magnetite FeO, (magnetic oxide of iron)
(iit) Limonite Fe,O0,.3H,O (hydrated oxide of iron)
(iv) fron pyrites Fes,
(v) Siderite FeCO,
Though iron pyrites (FeS,) is abundantly available in the earth's crust, but
because of its higher sulphur content, it is not used for the production of iron.
Iron is usually extracted from its oxide ore (haematite). This process
involves the following steps :
ene MODERN'’S abe + OF CHEMISTRY

1. Concentration. The ore is crushed in jaw crushers and is broken to

-AXIl

small pieces of about 1 inch in size. The crushed ore is concentrated by gravity
separation process in which it is washed with water to remove clay, sand, etc.
2. Caleination. The concentrated ore is then calcined (heated strongly
in the presence of a limited supply of air) in a reverberatory furnace. During
this process, the following changes take place :
(t) Moisture is removed.
(it) The impurities such as sulphur, phosphorus and arsenic are converted
to their gaseous oxides which are volatile and escape.
S + 0, —— gm
4As + 80, ——> /2As,0,1
P, + 50, ——>» P,O,, T
If some ferrous carbonate is present, it changes to oxide.
FeCO, —~—> FeO +CO,
(iit) Ferrous oxide if present gets oxidised to ferric oxide.
4FeOQ + Of > Barc.0,
Ferric oxide
This prevents the loss of iron due to the formation of ferrous silicate
(slag) during smelting.
(iv) The entire mass becomes porous which helps in the reduction
process at a later stage.
3. Smelting. The calcined ore is reduced with carbon 1.e., smelted in the
blast furnace (Fig. 14). It is a tall cylindrical furnace made of steel lined with
fire bricks. It is narrow at the top and has cup and cone arrangement for
the introduction of the charge and outlet for waste gases. The cup and cone
arrangement prevents the exit of gases during the charging process. At the
base of the furnace, it is provided with
(i) tuyeres arrangement for the introduction of hot air,
(ii) a tapping hole for withdrawing molten iron and
(iit) an outlet through which slag can be flown out.
The calcined ore (8 parts) is mixed with coke (4 parts) and limestone
(1 part) and is introduced from the top
Charge (Ore + limestone
+ coke) through cup and cone arrangement. At
the same time, a blast of air preheated at about
Cup and cone 1000 Kis blown upwards with the help of tuyeres
arrangement arrangement. The added coke serves as a fuel
as well as a reducing agent while added lime
serves as a flux.
The burning of coke to carbon dioxide
Fire bricks —» Exhaust gases supplies most of the heat required for the working
(CO, CO,) temperature of the furnace and give temperature
Spongy iron
formed Reduction begins upto 2200 K at the bottom of the furnace. As
Slag formed Z\ 3Fe,0, + CO > 2Fe,0,+CO,| the gases move up, they meet the descending
CaCO, + CaO + CO, EF Fr Fe,0, + 4CO — 3Fe + 4CO, charge and the temperature falls gradually. At
CaO + SIO, — CaSiO, fa Por Fe,0, + CO — 2FeO + CO, the bottom, the temperature is about 2200 K,
(slag) Frq Sl — pediiction completes in middle it is about 1300 K and near the top,
4 FeO + CO > Fe + CO, it is between 700-900 K. It may be noted that
C+ CO, — 2CO at the bottom of the furnace, the reducing
lron melts and Carbon burns agent is carbon itself but at the top part of
dissolves G, Si
GC +0, GO, the furnace, the reducing agent is carbon
and P
FeO + C > Fe + CO monoxide.
Hot ai The following reactions take place in the
alr
isch furnace :
(1) Combustion zone. At the base, coke burns
to produce CO, which starts rising upward during
Slag
the reaction. The reaction is exothermic and heat
Molten tron produced raises the temperature to about 2170
K. This region is called combustion zone.
Fig. 14. Blast furnace for the manufacture of cast iron.
C +O, ——> CO,; AH = — 393.4kJ
GENERAL PRINCIPLES AND PROCESSES OF ISOLATION OF ELEMENTS

(it) Fusion zone. As carbon dioxide rises upward, it comes in contact with
layers of coke and gets reduced to carbon monoxide.
CO, + C —>2CO; AH = +163.2 kJ
This is an endothermic reaction and therefore, the temperature is lowered
to about 1570 K. The iron produced in the upper region melts here. Any
Fe,O, if present undergoes reduction by hot coke to iron. This region is called
fusion zone.
Fe,O, + 83C —> 2Fe + 3CO + Heat
(iit) Slag formation zone. In the middle portion of the furnace, the
temperature is about 1270 K. In this region limestone decomposes to produce
lime (CaO) and carbon dioxide (CO,). The lime thus produced acts as a flux
and combines with silica (present as an impurity) to produce slag. Commercial Varieties of Iron
CaCO, — CaO + CO, There are three commercial varieties
(Limestone) of iron :
1. Cast iron or pig iron. It contains
CaO +810, —~ CaSi0,
2 to 4.5% of carbon, alongwith
(Lime) Calcium silicate (slag)
impurities such as sulphur, silicon,
The molten slag forms a separate layer (being lighter) above the molten phosphorus, manganese, etc. It is the
iron. This region is called slag formation zone. least pure form of iron. It is brittle
(iv) Reduction zone. The temperature near the top of the furnace is of and cannot be welded.
the order of 500-875 K. The oxides of iron are reduced by carbon monoxide 2. Wrought iron. It is the purest
to iron. form of iron and contains carbon
FeQ + CO ——> Fe + CQ, and other impurities not more than
3Fe,0, + CO ——> 2Fe,0, + CQO, 0.6%. It is malleable and can be
Iron ore easily welded.
he), + 4CO ——> 3Fe + 4CO, 3. Steel. It contains 0.5 to 1.5%
carbon alongwith small amounts of
Fe,O, + CO ——> 2Fe0 + SG
other elements such as manganese,
This region of the furnace is called reduction zone. The spongy iron chromium, nickel, etc. and other
produced in the reduction zone moves down slowly and melts in the fusion impurities. It comes in between cast
zone. At the lower hotter part, the main reaction is : iron and wrought iron and exhibits
FeO + C —- Fe + CO intermediate properties.
It dissolves some carbon, silicon, phosphorus and manganese and forms
the lower layer at the base of furnace. It is removed from tapping hole from
time to time. The iron, thus obtained is called pig iron and cast into variety
of shapes. Cast iron is different from pig iron and is made by melting pig
iron with scrap iron and coke using hot air blast. It has slightly lower carbon
content (about 3%).
It expands slightly on solidifying and, therefore, reproduces the shape of
the mould. It is extremely hard but brittle. The melting point of cast iron is
about 1473 K.

Thermodynamic concept of reduction of iron oxide in metallurgy of iron : Ellingham diagram.

Thermodynamics helps us to understand how coke reduces the oxide and why this furnace is chosen for this
process. The main reduction reaction is :
FeO (s) + C (s) —— Fe(sorl) + CO fw) ee,
This reaction is a combination of two simple oxidation-reduction reactions. In one reaction, reduction of FeO is
taking place and in the other carbon is being oxidised to CO as:
FeO (s) —— > Fe(s) + 50> &) AG.(FeO, Fe) ve(2E)
Cs) +50, ——> CO®) AG (C, CO) -.=(EE5)
When both the reactions (77) and (iii) take place to give equation (7) the net Gibbs energy change is :
AG (C, CO) + AG(FeO, Fe) = AG
The net reaction [Eq. (2)] will occur when the resultant AG is negative. The Ellingham diagram for formation
of FeO from Fe, CO from C and CO, from CO is shown in Fig. 19. As we notice in Ellingham diagram, AG vs T plot
representing Eq. (ii) goes upward while that representing the change C ——> CO (i.e., C, CO line) goes downward.
At temperature above 1073 K (approx.), the C, CO line falls below Fe, FeO line IGic., coy < AG geo, Fel This means
ene MODERN'S abe + OF CHEMISTRY
-AXIl

that in this temperature range, coke can reduce FeO to Fe and it will itself be oxidised to CO. Similarly,
it can be observed from Ellingham diagram, (Fig. 19), that at temperature below 1073 K the CO, CO, line lies
below Fe, FeO line. Therefore, below 1073 K, CO reduces the oxides of
iron (i.e. FeO
903, Fe;0,).
In blast furnace, the reduction of oxides takes place at different
temperature ranges. For this, hot air is blown from the bottom of the
furnace and coke is burnt to give temperature up to 2200 K in the
lower portion. The burning of coke therefore, supplies most of the heat “eu
Oo
required for the working temperature of the furnace. The CO and heat c=)
E
moves to upper part of the furnace. In upper part, the temperature is 5
a4
lower and the iron oxides (Fe,O, and Fe,0,) coming from the top are .
oO
reduced to FeO in steps. Thus, the reduction reactions occurring in the =

lower temperature range and in the higher temperature range depend

on the points of corresponding intersections in the A.G vs T plots. It is
observed that at the bottom of the furnace (higher temperature range)
the reducing agent is carbon itself but at the top of the furnace (lower
273 K 673K 1073K 1473K
temperature range) the reducing agent is carbon monoxide. These Temp (K) ——>
reactions are summarised below :
Fig. 15. Ellingham diagram for formation of
At lower temperature range in the blast furnace (500 — 800 K) FeO from Fe. CO from C and CO, from CO.
3Fe,0, + CO — > are 47 CO,
Fe,0, + 4CO ——> 3Fe + 4CO,
Me. + CO — > 2FeO “- CO,
At higher temperature range (900-1500 K) in the blast furnace
C + CO, an
FM US — sre wee
Preparation of Wrought Iron
Wrought iron is the pure form of iron and contains less than 0.5%
impurities. The cast iron obtained above contains about 2.5-5% carbon and
other impurities such as S, P, Si and Mn. In order to convert cast iron into
wrought iron, the percentage of carbon and that of other impurities has to be
decreased. This is done by heating the cast iron on the hearth of a reverberatory
Passive Iron
furnace (known as puddling furnace) with haematite (Fe,O.,). The haematite
When a piece of iron is dipped in supplies the oxygen and oxidises carbon, silicon, manganese and phosphorus
concentrated nitric acid, a reaction
present in the cast iron to carbon monoxide (CO), silica (S10,), manganese
takes place which stops completely
oxide (MnO) and phosphorus pentoxide(P.,O,) respectively.
after some time. The iron does not
appear to undergo any change in Thus,
appearance but it becomes inactive. Fe,O, + 3C Heat. 2Fe + 38CO
We know that ordinary iron liberates 351 + 2Fe,0, ——> 3810, + 4Fe
H, from dilute acids and displaces
35 + 2Fe,0,——> 3580, + 4Fe
copper from CuSO, solution. However,
this iron does not liberate hydrogen Whereas CO and SO, escape, MnO and silica (Si0,) combine to form
from dilute acid and cannot displace manganous silicate (MnSi0,) as slag.
copper from copper sulphate solution. MnO + SiO, Heat, Mnsio,
The tron in this form is said to be Manganous silicate (slag)
passive and the process is called Similarly, phosphorus pentoxide combines with Fe,O, to form ferric
passivation of iron. The loss of phosphate slag.
chemical activity of tron is called
passivity. The passivity of iron is due
2Fe,0, + P,O
0. —— 4FePO,
Ferric phosphate (slag)
to the formation of a thin insoluble
and invisible iron film on surface Sometimes, limestone is added as a flux. This also helps to remove S10,
which prevents its further reactions. as CaSiO, slag.
The film is due to the formation of The metal is removed and freed from slag by passing through rollers.
Fe,O,. The passivity can be removed Wrought iron thus prepared contains about 0.5% impurities of which about
by scratching, scrubbing or by half is carbon. The melting point of wrought iron is about 1673 K and it can
dissolving out in iodine solutions. be welded at about 1273 K. It is tough, malleable and ductile and can be used
The passivity of iron is important in for making chains, bolts, frameworks, etc. For structural purposes, wrought
preventing corrosion of iron.
iron has been largely replaced by mild steel.
GENERAL PRINCIPLES AND PROCESSES OF ISOLATION OF ELEMENTS

2. Extraction of Copper
Copper does not occur abundantly in nature (about 1 x 10+ % of the earth's
crust). It occurs as native copper as well as in combined state. The main ores
of copper are:
(4) Copper glance Cus
(it) Copper pyrites CuFes,
(iit) Malachite Cu(OH),.CuCO,
(wv) Cuprite or GRubby copper) Cu,O
(v) Azurite 2CuCO,.Cu(OH),
Extraction of copper from cuprous oxide [Copper (I) oxide]
The Ellingham diagram for the formation of cuprous oxide (Cu,O) from
copper and formation of CO from C, CO, from C and CO, from CO is shown in
Fig. 16. Inspection of graph AG° vs T shows that Cu—Cu,0O line is almost at the
top. Therefore, it is quite easy to reduce oxides of copper to copper directly by
heating with coke. It is learnt that both the lines of C, CO and C,
CO, are at much lower positions in the graph particularly, after
500—600 K. However, most of the ores of copper are sulphide
ores. These (after concentration by froth floatation process) are
first converted to oxides. oO *

rc) fe? C + 0, CO,

2Cu,8 + 30, —> 2Cu,0 + 250, = ce SS TT

The oxide can then be easily reduced to metallic copper

=~
©<|
with coke. “5S Co

Cu,0 + C —— 2Cu + CO a,

However, in actual practice copper is extracted from its

sulphide ore, copper pyrites CuFeS,,. It is concentrated by froth °73 500 1000 1500 2000
floatation process and then roasted 1.e., heated strongly in the Temp (K) ——>
presence of excess air in a reverberatory furnace. In the furnace Fig. 16. Ellingham diagram for formation of Cu,O from
copper pyrite is converted to ferrous sulphide (FeS), cuprous | Gy @O from C, CO, from C and CO, from C and CO.
sulphide (Cu,S) which are partially oxidised
2CuFeS, + O, —— Ses/ + 2FeS + SO,
Copper pyrites
2FeS + 30, fewe SFcO + 250,
2Cuss + 80, —> 2Cu,0 + 250,
The roasted ore is mixed with some powdered coke and sand and is heated
strongly in a blast furnace. The blast furnace is made up of steel and is lined
inside with fire bricks. A blast of hot air is introduced at the lower part of the
furnace. The following changes occur :
(4) Since iron is more reactive than copper, FeS is preferentially oxidised to
FeO than Cu,S to Cu,O. Therefore, most of the ferrous sulphide gets oxidised
to ferrous oxide which combines with silica (flux) to form fusible slag.
2FeS) + = 380, ——> 2FeO + 250,
FeO + Si0, —> FeSi0,
Flux Ferrous silicate (slag)
The slag being lighter floats and forms the upper layer. It is removed through
the slag hole from time to time.
(iz) During roasting or in the blast furnace if any oxide of copper is formed,
it combines with FeS and is changed back into its sulphide.
2Cu,S - 380, —— 2Cu,0 + 250,
Cu,O + FeS —> Cu,5 + FeO
i 6/28 MODERN'S abe + OF CHEMISTRY-AXIl

Ferrous oxide thus formed again combines with silica to form more slag.
FeO + S10, ——> FesiO,
Slag
As a result of smelting, two separate layers are formed at the bottom of
the furnace. The upper layer consists of slag and is removed as a waste. The
lower layer of molten mass contains mostly cuprous sulphide and some traces
of ferrous sulphide. It is called copper matte and is taken out from the taping
hole at the bottom.
Recovery of copper from copper matte.
The molten matte from the blast furnace is transferred into a Bessemer
converter (Fig. 17). It is a pear shaped furnace made up of steel and is lined
inside with lime or magnesium oxide. It is mounted on a horizontal axel and
can be tilted in any position. It is fitted with small pipes called tuyeres through
which a blast of hot air mixed with sand is blown into the molten
matte. During this process:
(1) traces of ferrous sulphide present in the matte is oxidised
to FeO which combines with silica to form slag.
2FeS - a), “7 > 2FeO + 280,
FeO + Si0, ——— FeSi0, (slag)
(iz) copper sulphide is partially oxidised to cuprous oxide which
further reacts with remaining copper sulphide to form copper and
sulphur dioxide.
2Cu,5 + 30, ——> 2Cu,0 + 250,
Cus ~ 2Cu,0 ——-> 6Cu + SO,
After the reaction has been completed, the converter is tilted
and the molten copper is poured into sand moulds. On cooling,
Fig. 17. Bessemer converter.
sulphur dioxide, nitrogen and oxygen escape from the metal. The
copper thus obtained is about 99% pure and is known as blister
copper. The name blister comes from the fact that as the metal solidifies, the
dissolved SO,, escapes producing blisters on the metal surface.
Refining. The blister copper is purified as follows :
(4) Poling. The blister copper is purified by heating it strongly in a
reverberatory furnace in the presence of excess of air. The impurities are either

reduced back to copper by stirring the molten metal with green

poles of wood. The hydrocarbons present in these freshly cut
poles reduce cuprous oxide to copper which is about 99.5% pure.
Further purification is done by electrolyic refining.
f; (it) Electrolytic refining. The crude copper is further
me hie Pa an ob hoe. purified by electrolytic method. In this method, a thin sheet of
or metal is made as cathode and the block of crude metal is made
as anode. Both the electrodes are placed in an acidified copper
Copper sulphate
Ainodeamud to , Saige sulphate solution (Fig. 18). When electric current is passed
| through the solution, impure copper from anode goes into the
Fig. 18. Electrolytic refining of copper solution and pure copper from the solution gets deposited on
the cathode.
At anode Cu—2e- ——> Cu**
At cathode Cu*+ + 2e- ——> Cu
The impurities of zinc, nickel, iron, etc. get collected below the anode as anode
mud.
GENERAL PRINCIPLES AND PROCESSES OF ISOLATION OF ELEMENTS

Alternatively, prolonged exposure of copper pyrites to air and rain leads to

the formation of dilute solution of copper sulphate. Copper can be precipitated
from this solution by the addition of scrap iron. It is then refined electrolytically.
Copper from low grade ores and scraps
Copper is extracted by hydrometallurgy from low grade ores. It is leached
out using acid or bacteria. When copper is treated with an acid in the presence
of air, it goes into the solution as Cu** ions :

Cu(s)+ 2H’ (aq) + 50;(g) —> Cu™ (aq) +H, OW)

The solution containing copper ions (Cu**) is treated with scrap iron or H, as:
Cu** (ag) + Fe(s) ———> Cu(s) + Fe* (aq)
Serap iron
Cu** (aq) + H,(g) ————> Cu (s) + 2H* (aq)
Since E° of Fe**|Fe (—0.44 V) and that of H*|H,(0.0 V) redox couple is
lower than that of Cu** |Cu (40.34 V), therefore, iron or hydrogen can displace
copper from Cu** ions.
In this way, copper is obtained.

3. Extraction of Zine
Zine does not occur in native form because it is a reactive metal. The main
ores of zinc are:
(1) Zine blende Ans
(it) Calamine ZnCO,
(iit) Zincite AnO
(iv) Franklinite 4£nO.Fe,O,
(v) Willemite Zn,910 ,
The principal ore of zinc is zine blende. Thermodynamic concept of
reduction
Extraction. Zinc can be extracted from zinc blende by the following steps:
Figure 7 shows that the AG
1. Concentration. The ore is concentrated by froth floatation process as
vs T curve for Zn, ZnO is lower
already described.
than Cu, Cu,O curve but it is
2. Roasting. Concentrated ore is roasted in the presence of excess of air above C, CO curve. This means
at about 1200 K to convert zinc sulphide into zinc oxide. that ZnO can be reduced to metallic
24n5 +80, ——> 24n0 + 250, zinc at higher temperature (about
Zinc blende Aine oxide 1673 K) than in case of copper.
Sulphur dioxide gas evolved in this process may be used in the manufacture M0 +C —168K_,
an + Co
of sulphuric acid.
3. Reduction. Zinc oxide is reduced to zinc by heating
with crushed coke at 1673 K in vertical fire clay retorts.
Zn Qaim PEK, In + CO
(coke)

The vapours of zinc formed are collected and condensed.

The Ellingham diagram for the formation of ZnO from Zn,
CO from C, and CO, from C and CO is shown in Fig. 19. It is
clear that intersection of AG vs T curve for Zn—ZnO and C—CO O,)
(kJ/mol
AG?
curve lies at a higher temperature than that of Cu — Cu,O
curve and C, CO curve. Therefore, reduction of ZnO with coke
is carried out at a higher temperature than that of CuO.
It is also clear from the figure that all the three curves 273 500 1000 1500 2000
Temp (K) >
for the oxidation of carbon [i.e.; (C, CO); (C, CO,) and (CO,
CO,,)] lie above the oxidation curve of Zn till the boiling point | Fig. 19. Ellingham diagram for formation of ZnO from
Zn, CO from C, CO, from C and CO, from C and CO.
of zinc (1180 K) is reached. However, above 1180 K, A,G° for
eno MODERN’S abc + OF CHEMISTRY

the formation of CO decreases and that for the formation of ZnO increases,
-AXII

very rapidly and these intersect the C, CO, curve at 1270 K. This means that
above 1270 K, AG° for ZnO is higher than that of CO, and CO from carbon.
Therefore, above 1270 K, A.G° for the reduction of ZnO by carbon is negative
and hence ZnO is easily reduced by coke above 1270 K. For this purpose of
reduction, ZnO is made into brickettes with coke and clay and heated around
1673 K so that the reduction process goes to completion. Since the boiling point
of zinc is low (1180 K), the metal is distilled off and collected by rapid cooling.
It may be noted that A,G° of CO, from CO is always higher than that of
ZnO. Therefore, CO cannot be used for reduction of ZnO.
4. Refining. The impure metal is refined by fractional distillation or by
electrolytic method.
(1) By fractional distillation. Impure zinc contains impurities of cadmium
(b.p. = 1073 K), lead (b.p. 2024 K) and iron (b.p. 8273 K). The boiling point
of zinc is 1188 K. The impure metal is distilled when zinc and cadmium with
low boiling points distil over leaving behind lead and iron. The boiling points
of zinc and cadmium are also different and therefore, the mixture of zinc and
cadmium is again subjected to fractional distillation when low boiling cadmium
distils leaving behind zinc metal in the distillation flask.
(it) By electrolytic refining. In this process, the impure zinc is made anode
while a plate of pure zinc is made the cathode. The electrolyte is zinc sulphate
containing a small amount of dilute sulphuric acid. On passing current, zinc from
the electrolyte is deposited at the cathode while an equivalent amount of zinc
from anode goes into the electrolyte. Therefore, pure zinc is obtained on cathode.

It may be noted that bauxite Special types of zinc

ore is of two types. If the main Zine is also found in two special types (1) Zinc dust and (11) Granulated zinc.
impurities are oxides of iron, it is (1) Zine dust. It is prepared by melting zinc and then atomising it with blast
called red bauxite. On the other of air.
hand, if the main impurities are (iz) Granulated zinc. It is prepared by pouring molten zinc into cold water.
due to oxides of silicon, the bauxite
is called white bauxite. 4, Extraction of Aluminium
® The red bauxite is purified Aluminium oecurs widely as a constituent of rocks and soils. It is most
by Baeyer’s process. abundant element (8.31%) by weight) after oxygen and silicon. The main ores
of aluminium are:
® The white bauxite is purified
by Serpeck’s process. (1) Bauxite; Al,O,.2H,O
(ii) Cryolite; Na,AIF,
(vit) Feldspar; KAISi,0,
(iv) Mica; KAIS1,0,,(OH).
Extraction of Aluminium
Aluminium is normally extracted from bauxite ore, Al,O,.2H,O. .
Electrolysis of fused alumina
Copper clamp. Carbon rods (anode) Fused alumina is a bad conductor of electricity. In
aT
“a.1 ./, this method, purified alumina is mixed with molten cryolite
Powdered coke (Na,AlF,) or fluorspar (CaF) and is eleetrolysed in an
iron tank lined inside with carbon. The molten eryolite
Carbon lining (Na, AIF) decreases the melting point to about 1173 K
x
RR(sathode)
+,ee

lron tank
and also inereases the electrical conductivity. The
2. : : ‘ ;
process of electrolysis is carried in an iron tank having a
OOOO) F's lining of carbon as shown in Fig. (20) which acts as the
BAIA
Outlet for *
aA, te
hl
a
bP
.
cathode. The anode consists of a number of carbon rods
aluminium which dip in the fused electrolyte. The molten electrolyte is
covered with a layer of powdered coke to prevent oxidation
Fig. 20. Electrolysis of fused A an and loss of heat due to radiation. The overall reaction is
2Al,0, + 3C —> 4Al + 38CO,
GENERAL PRINCIPLES AND PROCESSES OF ISOLATION OF ELEMENTS

This process of electrolysis is called Hall Heroult process. During

electrolysis the following reactions occur :
At eathode : Al®* (melt) + 8e° = —> Al (D
At anode: C(s)+O* (melt) —> CO(g) + 2e-
C(s) + 207 (melt) ——> CO,(g) + 4e7
Therefore, aluminium is liberated at the cathode and gets collected at the
bottom of tank, from where it is removed periodically. The oxygen evolved at
the anode combines with the carbon of the anode to produce carbon monoxide.
CO either burns to CO, or escapes out. This way for each kg of aluminium
produced, about 0.5 kg of carbon anode is burnt away. Because of the reaction
of carbon anodes, these need to be replaced periodically.
The aluminium metal liberated at the cathode melts at the high temperature
(1178K) of the tank. The molten metal being heavier than the molten electrolyte
sinks to the bottom of the tank from where it is withdrawn periodically through
the tapping hole. The aluminium metal obtained by the electrolysis of alumina
is 99.95% pure. It can be further purified by electrolytic refining.
The summary of occurrence and extraction of some metals is given below :
Table 2. Summary of Occurrence and Extraction of some Metals.
Common method
of extraction
Bauxite, Al,O,.xH,O Electrolysis of Al,O, dissolved A good source of electricity is
Cryolite Na,Al ih in molten Na,AIF, required.
Haematite Braille Reduction of the oxide ore with Temperature of the order 2170 K
Magnetite Fe.0, CO and coke in blast furnace is required.
Iron pyrites Fed,
miderite FeCO,

Copper pyrites CuFes, Roasting of sulphide partially It is self reduction in a specially

Copper glance Cu,5 and followed by reduction designed converter.
Cuprite Cu,O 2CHZO + Cu,5 —> 6Cu + SO, The reduction takes place easily.
Malachite CuCOQ,.Cu(OH), In the hydrometallurgy of copper
from low grade ores, sulphuric acid
leaching is used.

fine blende Roasting followed by reduction Metal may be purified by fractional

or sphalerite ZnS with coke distillation.
“incite ZnO
Calamine ZnCO,

USES OF ALUMINIUM, COPPER, ZINC AND IRON

Uses of Aluminium
(4) Aluminium is used for making electrical transmission cables as it is
a good conductor of electricity.
(iz) Aluminium powder is used as a reducing agent in thermite welding.
(iit) In the form of finely divided powder, it is used in anti-rust paints
and lacquers.
(iv) Aluminium foils are used up for wrapping cigarettes, food stuffs,
chocolates, soaps, etc.
(v) It is used to remove dissolved oxygen during the extraction of
certain metals.
(vi) It is used in making household utensils.
(vit) Aluminium being highly reactive is used in the extraction of
chromium and manganese from their oxides.
(viit) It is also used in making certain alloys. These alloys are extensively
used for household purposes. Some of the common alloys of aluminium are :
lene Percentage Properties
MODERN'S abe + OF CHEMISTRY-AXIl

composition
Aluminium bronze a oe — Light strong alloy with golden Coins, utensils, jewellery, picture frame, etc.
lustre, resistant to corrosion.
Magnalium Al = 95, Mg=5 Light, tough and strong Light instruments, balance beams, pressure
cookers, etc.
Duralumin Alpaca Light, tough, ductile, resistant © Making aeroplanes, automobile parts,
Mg = 0.5, Mn = 0.5 ‘to corrosive action pressure cookers, etc.
Alnico Al = 12, Fe = 60 Strongly magnetic Permanent magnets
M—20,Co—s
Uses of Copper
After iron and aluminium, copper is probably the most important metal.
It is in great demand as an electrical conductor and for water and steam
piping. Its important uses are :
(4) Copper is used for making electric wires used in electrical industry
and for water and steam pipes. This is because of very high electrical
conductivity of copper.
(iz) Since it is not attacked by water or air, it is used for making utensils,
containers, kettles, evaporating pans, coins, etc.
(iit) It is used in electroplating and electrotyping industry.
(iv) It is used in several alloys which are tougher than metal itself. The
common alloys are brass, bronze, gun metal, coinage metal, etc.
(v) Copper is also used for alloying with gold and silver to make them
hard for the purpose of making ornaments and coins.
Some important alloys of copper are given in Table 3.
Table 3. Alloys of Copper
Percentage
composition
. Brass Cu = 60, Zn = 40 Utensils, condenser tubes, cartridge caps, etc.
. Bronze Cu = 90, Sn = 10 Coins, statues, control valves
. Aluminium bronze Cu = 90, Al = 10 Coins, picture frames, golden powder for paints, cheap jewellery
. Bell metal Cu = 80, Sn = 20 Bells, gongs
» Gun metal Cu = 88, Sn = 10, Zn = 2 Gears, bearings, castings.
.» German silver Cu = 26 — 60, “Zn = 26—3656 Utensils, resistance wire
Ni = 10 — 36
. Phosphor bronze Cu = 96, Sn = 4.8,P=0.2 Springs, electrical equipments

.» Monel metal C = 30, Mae OF Acid pumps and acid containers

Fe and Mn = 3
. Gold copper alloy Au = 90, Cu = 10 Gold coins, jewellery, watch cases, spectacle rims
. Constantan Cu = 60, Ni = AQ Electrical apparatus

Uses of Zinc
(4) Zine is widely used for galvanising iron.
(it) Zine is used in extraction of gold and silver by cyanide process.
(iit) Zine dust is used as a reducing agent in the laboratory It is also
used in the manufacture of drugs, dye stuffs paints and other chemicals, etc.
(iv) Zine is used in dry cells as electrodes.
(v) Itis used in the manufacture of many alloys such as brass, german
silver, etc.
Uses of Iron
(4) Cast iron which is the most important form of iron is used for casting
stoves, railway sleepers, gutter pipes, toys, etc.
(ii) It is used in the manufacture of wrought iron and steel.
(iit) Wrought iron is used in making wires, bolts, anchors, chains and
agricultural implements.
GENERAL PRINCIPLES AND PROCESSES OF ISOLATION OF ELEMENTS

(iv) Steel finds number of uses. Alloy steel is obtained when other metals
are added to it and find extensive uses. Different types of steels and their
uses are given in Table 4.
(v) Itis used in the manufacture of many alloys such as brass, german
silver, etc.
Steels obtained by the addition of some other one or more metals such as
chromium, vanadium, titanium, molybdenum, manganese, cobalt or nickel to
carbon steel are called alloy steels. The metals are added to obtain some special
properties of steel. Some special alloy steels, their composition, properties and
uses are given below :
Table 4. Some important alloy steels.

Percentage Properties
composition
. Stainless steel Fe = 73, Cr = 18, Resistance to rusting Utensils, cycle and automobile parts,
Ni= 8 cutlery.
. Nickel steel Fe = 96-98, Ni=2-4 Hard, elastic Cables, automobile and aeroplane
and rust proof parts, armour plates, gears.
. Invar Fe = 64, Ni = 36 Low expansion Metre scales, measuring
on heating instruments, clock pendulums.
. Chrome steel Fe = 98, High tensile Cutting tools such as files, cutlery.
Cr = 1.5 — 2.0 strength
. Tungsten steel Fe = 94,W=5 Hard, resistant High speed cutting tools, springs.
and C to corrosion
. Silicon steel Fe = 85 Hard and Pumps and pipes for carrying acids.
Si = 15 resistant to acids
. Alnico Fe = 60, Al = 12, Strongly Permanent magnets.
Ni = 20, Co =8 magnetic
. Manganese Fe = 86 Extremely hard, Rock crushers, burglar proof safes,
steel Mn = 18 and C resistant to wear and tear rail road trucks.

|SOLVED EXAMPLES |
LU) Example 12 (11) Haematite oxidises carbon to carbon monoxide
forming iron.
Ai a site, low grade copper ores are available and zinc
and iron scraps are also available. Which of the two Fe,0,+3C —-> 3CO+ 2Fe
scraps would be more suitable for reducing the leached Q Example 14
copper ore and why ? Explain the following :
Solution : Since zinc lies above iron in electrochemical (a) Although thermodynamucally feasible, in practice
series, 1t 1s more reactive than iron. As a result, if zinc scraps magnesium metal is not used for the reduction of
are used, the reduction will be fast. However, zinc is a costher alumina in the metallurgy of aluminium. Why ?
metal than iron. Therefore, 1t will be advisable and advantageous
(6) Why is zinc and not copper used for the recovery of
to use iron scraps.
silver from the complex [Ag(CN),| ?
LU) Example 13
(c) The extraction of Au by leaching with NaCN involves
(a) Give one example each of the following : both oxidation and reduction. Justify giving equations.
(1) Acidic flux (it) Basic flux (C_.B.S.E. Sample Paper 2011)
(6) What happens when (d) Lime stone is used in the manufacture of pig iron from
(1) Cu,O undergoes self reduction in a silica line haematite. Why?
converter Solution :
(11) Haematite oxidises carbon to carbon monoxide. (a) Inspection of Ellingham diagram (Fig. 13) shows that AG
(C.B.S.E. Sample Paper 2012) — vs T curves for Al,O, and MgO intersect at a point corresponding
Solution: to very high temperature of the order of 2000 K. This means
(a) (i) Acidic flux: SiO, (ii) Basic flux : CaO above this temperature, AG for the reaction :
(6) (z) Cu,O undergoes self reduction to form blister copper Al, O, + 3Mg ——-> 2Al + 3MgO
as:
would become negative and hence reduction will be feasible.
2Cu,0 + Cu,8 —> 6Cu + 50,
However, this temperature is very high so that the process is
Blister copper
uneconomical and technologically difficult.
ecu (6) Zine is stronger reducing agent (E° = — 0.76 V) and
MODERN’S abc + OF CHEMISTRY-XII

soluble complex, sodium tetracyanozincate (II).

more electropositive than copper (E° = + 0.34 V). Therefore,
zinc is used for recovery of Ag from [Ag(CN,)|- complex. 2Na[Au(CN),] (ag) + Zn (s) ——> 2Au (s) + Na,[Zn(CN),]
(Sodium
(c) During leaching process, gold (Au) 1s first oxidised by tetracyanozincate (IT)
O, of the air to Aut which then combines with CN™ ions to (Soluble complex)
form the soluble complex, dicyanoaurate (I). Thus, extraction of gold by leaching with NaCN involves
4Au (s) + 8NaCN (aq) + O, (g) + 2H,O (1) ——> both oxidation and reduction.

4Na[Au(CN),] (aq) = ANaOH (aq)

(d) Haematite is an ore of iron and contains silica (SiO,)
as the main impurity. The purpose of limestone is to remove
Sodium dicyanidoaurate (1)
(Soluble complex) 510, as calcium silicate (CaSi0O,) slag.
CaCO, Jaen} CO,
Goldis then extracted from this complex by displacement method
Limestone
by using a more electropositive zinc metal. In this method, zinc
acts as a reducing agent and it reduces Au* to Au. Zinc itself CaO + S10, fs CasiO,
gets oxidised to Zn** ions which combine with CN ions to form Basic flux

Concept uestions

Q.1. Which method of refining is generally used when a metal of high degree of purity is needed?
(Pb. S.B. 2016)
Zone refining method.
Q.2. Name the metal used as a reducing agent in aluminothermic process. (Pb. S.B. 2016)
» Aluminium.
Q.3. What is basic difference between calcination and roasting ?
. During calcination, the concentrated ore is heated either in the absence or in the limited supply of air. On the
other hand, roasting is carried out in excess of air.
Q.4. Which is the cheapest and most abundant reducing agent which is used in the extraction of metals ?
» Carbon in the form of coke.
Q.5. Why does CaO react with 510, to form a slag ?
- CaO is basic oxide whereas SiO, is acidic oxide. Their reaction is acid-base reaction as :
CaO + 510, ——> CaSi0,
Slag
Q.6. Why is the formation of sulphate in calcination sometimes advantageous ?
Ans. Sulphates are usually water soluble and the gangue remains insoluble. Therefore, the desired metal is
leached away as soluble sulphate from insoluble gangue.
Q.7. Why cannot aluminium be reduced by carbon ? (H.P.S.B. 2010)
Ans. Aluminium is stronger reducing agent than carbon and therefore, cannot be reduced by it.
Q.8. How does NaCN act as a depressant in preventing ZnS from forming the froth ?
Ans. NaCN forms a layer of zinc complex, Na,[Zn(CN),] on the surface of ZnS and thereby prevents it from the
formation of froth.
Q.9. Which is better reducing agent at 983 K, C or CO?
Ans. Carbon.
Q.10. Indicate the temperature at which carbon can be used as a reducing agent for FeO,
Ans. Above 1123 K.
Q.11. Which metals are generally extracted by electrolytic process? Which positions these metals generally
occupy in the periodic table ?
. Electrolytic process is used for the extraction of active metals like Na, Ca, Mg, Al, etc. These metals belong to
p-block elements.
Q.12. What is the composition of copper matte? (D.S.B. 2013, Tripura S.B. 2016)
Ans. Copper matte contains cuprous sulphide (Cu,S) and iron sulphide (Fes).
Q.13. What is cupellation ?
Ans. Cupellation is a method used for refining of those metals which contain impurities of other metals which form
volatile oxides. For example, removal of last traces of lead from silver.
GENERAL PRINCIPLES AND PROCESSES OF ISOLATION OF ELEMENTS 6/35 —

Q.14. What type of ores are roasted?

Ans. Sulphide ores.
Q.15. How is granular zinc obtained ?
Ans. Granular zinc is obtained by pouring molten zinc in cold water.
Q.16. What is Kroll process ?
Ans. The production of titanium metal at 900K from TiCl, by reduction with Mg in argon atmosphere.
TiCl,() + 2Mg ———> Ti(s) + 2MgCl, (@)
Q.17. The iron produced in the blast furnace is called .......... peeuditeennuadnentie
Ans. pig iron.
Q.18. What is the role of a stabilizer in froth floatation process ? Give examples.
Ans. In froth floatation process stabilizer stabilizes the froth. For example, aniline, cresol, etc.
Q.19. Name three forms of iron. How do these three forms differ ?
Ans. Three forms of iron are : cast iron, wrought iron and steel. These differ in their carbon content.
Q.20. What is the actual reducing agent of haematite in blast furnace ?
Ans. Carbon monoxide, CO.
Q.21. An ore sample of galena (PbS) is contaminated with zinc blende (ZnS). Name one chemical which
can be used to concentrate galena selectively by froth floatation method. (CBSE Sample Paper 2007)
Ans. NaCN (sodium cyanide) is used as depressant.
Q.22. Name the method used for refining of
(1) Nickel (77) Zirconium (CBSE Sample Paper 2007)
Ans. (1) Mond's process (it) Van Arkel method
Q.23. Pine oil is used in froth floatation method. Why ? (CBSE Sample Paper 2007)
Ans. Pine oil is added in froth floatation method because it enhances the non-wettability of the mineral particles.
Q.24. Giving examples differentiate between roasting and calcination. (S5ithar 8.B. 2012, J.K.S.B. 2012)
Ans.

1. In calcination, the ore is heated in the absence of air. | In roasting the ore is heated in regular supply of air
- below the melting point of metal.
Fe,0,.xH,O (s-—>_ Fe,0, (s) + x H,O@) 2708 + 30, ——> 2%Zn0 + SO,
Heat
ZnCO, (s) —— ZnO (s) + CO, (g) 2C0o + 3),—§$—> 20,0 + 280,
CaCO,.MgCO, (s) —“> CaO (s) + MgO (s) + 2CO, 2PbS + 30, ———> 2PbO + 2S0,
2. It is used for carbonate and oxide ores. It is used for sulphide ores.
3. Moisture and organic impurities are removed. Volatile impurities are removed as oxides,
SO,, P,O,, As,O,, ete.
Q.25. What is meant by benefaction process ? (Hr. S.B. 2017)
Ans. The process used to concentrate an ore is called benefaction process.
Q.26. Write the overall reaction taking place in the process used for the electrolysis of alumina by
Hall-Heroult process. (CBSE Sample Paper 2011)
Ans. 2Al1,0, + 3C ——-+ 4Al + 38CO,
Q.27. Why is the froth floatation method selected for the concentration of sulphide ores?
(CBSE Sample Paper 2011)
Ans. Froth floatation process is selected for the concentration of sulphide ores because sulphide ore particles are
preferentially wetted by oil and the impurities by water.
Q.28. Write a non-exothermic reaction taking place in the blast furnace during extraction of iron.
(CBSE Sample Paper 2011)
Ans. CaCO, —224> CaO + CO,
Q.29. Why can’t aluminium be reduced by carbon ? (CBSE Sample Paper 2011)
Ans. Aluminium cannot be reduced by carbon because it 1s a stronger reducing agent than carbon.
Q.30. What is a flux ? What is the role of flux in the metallurgy of iron and copper ?
(CBSE Sample Paper 2011)
Ans. Flux is a substance which combines with gangue which may still be present in the calcined or roasted ore to
form an easily fusible material called the slag.
Flux + Gangue t——> Slag (fusible)
In the metallurgy of copper, most of the ferrous sulphide present as impurity gets oxidised to ferrous oxide
which combines with silica (flux) to form fusible slag.
FeO + S10, ———> FeS10,
ene MODERN'S abe + OF CHEMISTRY
-AXIl

The slag being lighter floats and forms the upper layer which is removed from the slag hole from time to time.
In the blast furnace for metallurgy of iron, lime acts as a flux and combines with silica present as impurity to
form slag.
CaO + 810, ———> Casi0,
Slag
Q.31. Out of C and CO which is a better reducing agent for FeQ.
(4) In the lower part of blast furnace (Higher temperature)
(it) In the upper part of blast furnace (Lower temperature) (CBSE Sample Paper 2011)
Ans. (1) C is better reducing agent at higher temperature (lower part of blast furnace).
(iz) CO 1s better reducing agent at lower temperature (higher part of blast furnace).
Q.32. Name the method of refining of metals such as germanium. (D.S.B. 2016)
Ans. Zone refining.
Q.33. In the extraction of Al, impure Al,O, is dissolved in conc. NaOH to form sodium aluminate and
leaving impurities behind. What is the name of the process. (D.S.B. 2016)
Ans. Al,O, + 2NaOQH + 3H,O ——- 2Na [AI(OH),]
This process is called leaching.
Q.34. Name the method of refining which is based on the principle of adsorption. (ALL S.B. 2016)
Ans. Chromatography.
Q.35. What is the role of limestone in the extraction of iron from its oxides? (A.LS.B. 2016)
Ans. Limestone decomposes to form lime (CaO) and carbon dioxide (CO,). The lime, thus, produced acts as a flux
and combines with silica (present as impurity in oxides of iron) to produce slag.
CaCO, —-> CaO + CO,
Limestone
CaO + 810, ——> CaSi0,
Lime Calcium silicate (slag)
Q.36. What is role of coke in the extraction of iron from its oxides? (D.S.B. 2016)
Ans. The coke serves as a fuel as well as a reducing agent. It burns to produce CO, and heat which raises the
temperature to about 2200 K (in combustion zone).
La), > Lu, AH = —393.4kJ
It also reduces Fe,O, to iron.
Fe,O, + 3C ——> 2Fe + 3CO + Heat

Q.37. Out of PbS and PbCO, (ores of lead), which one is concentrated by froth floatation process preferably?
(D.S.B. 2017)
Ans. PbS.
Q.38. What is the role of collectors in the froth floatation process? Give an example of a collector.
(ALLS.B. 2017)
Ans. The collectors enhance the non-wettability of the mineral particles in the froth floatation process. For example:
Pine oil.
Q.39. What is the role of depressants in the froth floatation process? (A.LS.B. 2017)
Ans. The depressants in the froth floatation process, selectively prevent one of the sulphide ores from forming the
froth with air bubbles.

Calcination. It is a process of heating the ore strongly in the absence or limited supply of air.
Roasting. It is a process of heating the ore in the presence of excess air.
Ore. The minerals from which the metals are conveniently and economically extracted.
Gangue or matrix. The unwanted earthy and silicious impurities associated with the ores.
Concentration of ore or ore dressing. The process of removal of gangue or matrix from the ore.
Flux. The substance which combines with gangue which may still be present in the calcined or roasted ore to form easily
fusible material.
Slag. The fusible material formed by the combination of flux and gangue.
Ore refining. The process of purifying the crude metal.
GENERAL PRINCIPLES AND PROCESSES OF ISOLATION OF ELEMENTS 6/37 =

QUICK CHAPTER ROUND UP

All ores are minerals but all minerals

are not ores.

Crushing & grinding

POWDERED ORE

removal of unwanted
—» | Concentration (dressing or benefaction)
impurities (gangue or matrix)

Gravity separation or Electromagnetic Froth floatation Leaching

Levigation separation e Differences in wetting e Ore is treated with
e Based on the e If either ore or gangue is properties of ore and certain chemical
differences in specific attracted by the magnet gangue particles with reagents which can
gravities of metallic ores » for chromite (FeCr,O,), water and oil selectively dissolve ore
and the gangue particles magnetite (Fe,O,) > for sulphide ores such but not impurities
>» for oxides ores of Fe, Sn as ZnS, CuFesS,, PbS > for bauxite, Ag and Au.
and native ores Au, Ag

Extraction of Crude Metal

A. Conversion into metal oxide (oxidation)

e Calcination. Heating the ore in a limited * Roasting. Heating the ore in the presence
supply of air or absence of air. of excess air.

op, 2nCO, nation | 70 + COL e.g., 2ZnS + 30, ——> 27nO + 280,

B. Conversion of oxide into metal (reduction)

e By heating the metal oxide with a suitable reducing agent (C or CO or some other metal)
e.g., 4nO + C ——+ Zn + CO
Fe,O, + CO——> 2Fe + Jas
NiO + H, ——— Ni+H,0O
Cr,O, + 83Al ——-> 2Cr + AIO, (called aluminothermy or Goldschmidt thermite process)

Purification and refining

Distillation Liquation Electrorefining Zone refining

* For low boiling liquids ¢« For metals of low m. pts. ¢ By passing electric « Impurities are more
>» low boiling metals Hg, >» tin, lead, bismuth current soluble in melt than in
“n » Cu solid state
© impure metal—anode > Si, Ge, Ga
pure metal—cathode
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* Vapour phase refining eee

Ni + 4COQ ————} Ni(CO),
Ni( CO), 450-470 K Ni + 4CO

o20 K 1700 K
« Van Arkel method Ti(s) + 21, @) ee aay Ti L(g) 2 Tits) + 21
Pure

870 K 2075 K
Zr + 21,
(g) ————> fel (eg) ——_—_> “rs ol ip)
Pure

« Chromatography Different components of a mixture are differently adsorbed on a adsorbent

Ores are: Haematite (Fe,O,), magnetite (Fe,O,), iron ¢ Ores are: Copper glance (Cu,5), copper pyrites (CuFesS,),
pyrites (FeS,) malachite [Cu(OH),.(CuCO,)], cuprite (Cu,O)
Iron is extracted from haematite ¢ Copper is extracted from copper pyrites
Calcined (to remove moisture etc.) 2C teh 7+ O, —> Cu,5 + 2FeS + SO,
Reduced with C (smelting) in blast furnace Sye5 +30, —> 2FeO + 2850,
O Fusion Zone weg te, dd ol,
CO, + C—> 2CO; AH = 163.2k<J
Fe,O, + 3C —- 2Fe + 3CO + heat

0 Slag formation Fes is preferentially oxidised

CaCO, —> CaO + CO, et eae
CaO + 810, —> CasSi0, ee ee
O Reduction zone Flux Slag
f|Me je ese ie) ge
During roasting if any oxide of copper is formed, it combines
Fe,O, + 4CO —-> 3Fe + 4CO,
a (IE sp LNoe eee with FeS
FeO + C— + Fe + CO 2 ee ole oe
We get pig iron Molten mass contains Cu,S and Fes (called copper matte)
0 Wrought iron is the purest form of iron 2Pep - a0, >
— 2het) 7 25,
|e Ors LO ee tse)
LOC) FT)
2Cu,5 + 30, —> 2Cu,0 + 250,
Cu,5 + 2Cu,0 —> 6Cu + SO,
Blister
copper

Blister copper is purified by electrolytic refining

* Ores are: Bauxite (Al,O,. 2H,O) cryolite (Na,AIF,,), feldspar. * Ores are. Zinc blende (ZnS), calamine (ZnCO,), Zincite
(KAI S1,0,) (ZnO), Franklinite (ZnO.Fe,O,)
« Aluminium is extracted from bauxite by electrolysis * Yinc is extracted from zinc blende.
2AL,0, + 3C —> 4Al + 3CO, ¢ Jtis concentrated by froth floatation process
Process is called Hall-Heroult process 27nS + 30, —Rate5 27n0 + 280,
Cathode: Al** (melt) + 3e- —> Al (2)
Amode: (isi, Cr — =» LO (a) 4 gan nO + CS754 CO
C(s) + 207° —-> CO, (g) + 4e7 Zine vapours are collected and condensed
Alis liberated at cathode
GENERAL PRINCIPLES AND PROCESSES OF ISOLATION OF ELEMENTS

\ NCERT F LE \ Solved
Intext Questions /!
» Which types of ores can be concentrated by magnetic Gibbs energy value. Why does it not take place at
separation method ? Give two examples. room temperature ?
. The ores in which one of the components (either the ore Ans. The reaction is thermodynamically favourable. Sincein the
or the impurity) 1s magnetic in nature can be separated given redox reaction, all the reactants and the products are
from the non-magnetic components by magnetic separation solids at room temperature, therefore, it does not occur at
method. For example, room temperature. However, at high temperature when
(t) Haematite (Fe,O,) (it) Magnetite (Fe,O,) chromium melts, the reaction proceeds rapidly. Thus,
Q.2. What is the significance of leaching in the extraction heating is required for this reaction to start.
of aluminium ? . Isit true that under certain conditions magnesium
Ans. The principal ore of aluminium is bauxite (AI1,Q,). can reduce SiQ, and silicon can reduce MgO? What
It contains 510,, iron oxides and titanium oxide as are those conditions ?
impurities. The significance of leaching in the extraction . Below the melting point of silicon (1693 K), the AG? curve
of aluminium from bauxite is to remove the impurities for the formation of 510, lies above the A,G° curve for
from the ore. MgO. Therefore, below 1693 K, Mg can reduce 510, to
Q.3. The reaction : 51. However, above 1693 K, the ° curve for MgO hes
Cr,O, + 2Al ——_+AlIL,0, + 2Cr ; AG® = - 421 kJ is above AG° curve for 510, and therefore, at temperatures
thermodynamically feasible as is apparent from above 16938 K, Si can reduce MgO to Mg.

Textbook Exercises //
Q.1. Copper can be extracted by hydrometallurgy but Moreover, there is no CS analogous to CO for which
not zine. Explain. AG® vs T graphs slope downward. Therefore, extraction
Ans. Refer Solved Example 8. (Page 18) of copper from pyrite ore (Cu,S) 1s difficult.
Q.2. What is the role of depressant in froth floatation Q.4. Explain (7) zone refining (11) column chromatography.
process ? (A.FS.B. 2076) . Refer Text page 21 and 22.
Ans. The depressants are used to prevent certain types of Q.5. Out of C and CO, which is better reducing agent
particles from forming the froth with bubbles in froth at 673 K ?
floatation process. This helps to separate two sulphide Ans. At 673 K, the AG® vs T line for CO, CO, is lower than
ores. For example, in case of an ore containing zinc that of C, CO line. Therefore, CO can be used as better
sulphide (ZnS) and lead sulphide (PbS), sodium cyanide reducing agent at 673 K.
(NaCN) is used as a depressant. It forms a layer of zinc .6. Name the common elements present in the anode
complex Na,[Zn(CN),] with ZnS on the surface of ZnS and mud in electrolytic refining of copper. Why are
therefore, prevents it from forming the froth. Therefore, they so present?
it acts as a depressant. Ans. The anode mud in the electrolytic refining of copper
ZnS + 4NaCN —— Na,[Zn(CN),] + Na,5 contains antimony, selenium, tellurium, silver, gold and
Sodium platinum. These are present as impurities in blister
tetracyanidozincate (I1) copper. These are less reactive and are not affected by
However, NaCN does not prevent PbS from forming the CuSO, — H,SO, solution and hence settle down under
froth and allows it to come with the froth. anode as anode mud.
Q.3. Why is the extraction of copper from pyrite difficult . Write down the reactions taking place in different
than that from its oxide through reduction ? zones in the blast furnace during the extraction
of iron.
Ans. The graph of A.G° vs T in Ellingham diagram for the
. In blast furnace, reduction of iron oxides takes place in
formation of oxides shows that the copper-copper oxide
different temperature ranges. The lower part of the blast
line is almost at the top. Therefore, it is very easy to
furnace has high temperature of the order of 2200 K
reduce oxide ores of copper directly to metal by heating (called combustion zone) and the top of the furnace has low
with coke. This is because, AG° vs T lines for CO has temperature of the order of 500-800 K (called reduction
negative slope at higher temperature and therefore, zone). The reduction occurring in the lower temperature
can easily reduce Cu,O to copper. However, the Gibbs range (upper part) is by carbon and in the higher
energies of formation of most sulphides are greater than temperature range (lower part) is by carbon monoxide.
that for CS,. In fact, CS, 1s an endothermic compound. At lower temperature range (500-800 K) in upper part
of furnace the reactions occurring are :
Teuo 3dFe,0, + CO —— 2Fe,0, + CO,
MODERN'S abe + OF CHEMISTRY-AXIl

(111) The mechanical stability of stationary phase must

Fe,0O, + 4 CO ——* 3Fe + 4CO, be high to prevent the formation of dust which might
Fe,O, + CQ —— 2FeO + CO, be deposited in the channels of packing.
At higher temperature range (900-1500 K) in lower part (zv) It should not react chemically either with the sample
of furnace the reactions occurring are: components or with the eluting solvents.
C + CQ, — 2C0 (v) It should be pure.
FeO +CO —— Fe+ CO, Q.12. Describe a method for refining nickel.
In the middle portion (at about 1270 K), limestone . For refining nickel, nickel is heated in a stream of carbon
decomposes to give lime (CaO) and CO,. Lime acts as a monoxide forming volatile complex (nickel tetracarbony]l).
flux and combines with silicate impurity to form slag.
Ni + 4CO —330:350K., Ni(CO),
CaCO, ——> CaO + CO, The carbonyl is subjected to high temperature so that
CaO + SiO, — > CaSiO0 . the complex decomposes to give the pure metal.
Lime Impurity Calcium silicate (slag)
Ni(CO), Ames ee, Bh + ACO
Slag is in the molten state and separates out from iron.
This process is called Mond process.
Q.8. Write chemical reactions taking place in the
extraction of zinc from zinc blende. Q.13. How can you separate alumina from bauxite ore
associated with silica ? Give equations.
Ans. (t) The concentrated zinc blende ore (ZnS) is roasted in
the presence of excess air at about 1200 K to convert it . Bauxite, a principal ore of aluminium contains silica,
to zine oxide. ‘ iron oxide and titanium oxide as impurities. The ore
is digested with a concentrated solution of NaOH at
2/n5 + 30, — 2ZnO + 280,
Ainc blende “inc oxide 473-623 K and 35-36 bar pressure. Al,O, is leached out
as sodium aluminate and silica as sodium silicate while
(11) Zine oxide is reduced to zinc by heating with crushed
impurities are left behind.
coke at 1673 K.
ALO, (s)+2NaQOH (aq)+3H,O ——> 2Na[Al(OH),] (aq)
ZnO + C —#S'., Zn + CO
(zit) The impure copper 1s refined by electrorefining method. The aluminate in the solution is neutralised by passing
In this method, the impure zinc is made anode and a CO, gas and hydrated Al,O, is precipitated.
plate of pure zinc 1s made cathode in an electrolytic bath 2NalAl(OH),] (aq) + CO, (¢) ——> Al,O,.xH,O +
containing zinc sulphate and a small amount of dilute 2NaHCoO, (aq)
H,5O,. On passing current, the following reactions occur: The sodium silicate remains in the solution while hydrated
At anode Zn —— Zn** + 2e7 alumina is filtered and dried.
At cathode : Zn** + 2e° ——> Zn The hydrated alumina thus precipitated is filtered, dried
The zine gets deposited on cathode and is collected. and heated to give back pure alumina.
Q.9. State the role of silica in the metallurgy of copper. Al,O,.*xH,O —1473K_. ALO, (s) + xH,O
(Pb. S.B. 2010, Assam S.B. 2012) Hydrated alumina Alumina
Ans. During roasting, the copper pyrites are converted into a Q.14. Giving examples, differentiate between roasting
mixture of FeO and Cu,O. and calcination.
2CuFeS, + O, _A_, Cu,S + 2FeS +80, . Refer Conceptual Questions. @).24. (Page 35).
Copper pyrites Q.15. How is cast iron different from pig iron?
2Cu,S + 30, _4 , 2Cu,0 + 280, (Assam S.B. 2012)
2FeS + 30, ———> 2FeO + 250, . The iron obtained form blast furnace is pig iron. It
contains about 4% of carbon and many impurities in
To remove FeO (basic), the roasted ore is mixed with
smaller amount (e.g., 5, P, Si, Mn, ete).
silica and heated. Silica acts as a flux and combines with
ferrous oxide present to form fusible slag of iron silicate. Cast iron is obtained by melting pig iron with scrap iron
and coke using hot air blast. It contains slightly lower
FeO + 810, —> > FeSi0,
carbon content (about 3%) and is extremely hard and
Flux Slag
brittle.
The slag being lhghter floats and forms the upper layer Q.16. Differentiate between “minerals” and “ores”.
and is removed through slag hole. Therefore, silica helps
(HP. S.B. 2011)
to remove FeO in the metallurgy of copper.
» Minerals are naturally occurring chemical substances in
Q.10. What is meant by the term chromatography ?
the earth’s crust obtainable by mining.
Ans. Chromatography is a technique for the separation and
The minerals from which a metal can be economically
purification based on the differences in the adsorbing
and conveniently extracted is ore.
tendencies of the metal and its impurities on a suitable
For example, Al occurs in the earth’s crust in the form
adsorbent. It 1s based on the principle that different
of two chemical substances bauxite (Al,O,.2H,O) and
components of a mixture are differently adsorbed on an
clay (Al,O,.2510,.2H,O). These are called minerals.
adsorbent.
However, Al can be conveniently and economically
Q.11. What criterion is followed for the selection of the
extracted from bauxite. Therefore, bauxite is an ore of Al.
stationary phase in chromatography ?
Ans. The stationary phase acts as adsorbent and may have Q.17. Why copper matte is put in silica lined converter?
the following characteristics: . The copper matte containing Cu,S and FeS is put in
(t) It should have high and selective adsorption power. silica lined convertor. Some silica is also added and hot
(tt) It should be finely divided to offer greater surface air blast is blown to convert remaining FeS to FeO, which
area for adsorption. is removed as slag with silica.
GENERAL PRINCIPLES AND PROCESSES OF ISOLATION OF ELEMENTS

2FeS +30, ———’

2FeO + 250, free energy of formation of their oxides is more negative
FeO + SiO, ——
FeSi0, can reduce those metal oxides for which the standard
Cu,5 or CuO gets converted to copper. free energy of formation of their respective oxides is
less negative. In other words, a metal will reduce the
2Cu,8 + 30, —— 2Cu,0 + 250, oxides of other metals which lie above it in Ellingham
2Cu,O + Cu,S —— 6 Cu+S0, diagram because the standard free energy change, (A G*)
Q.18. What is the role of cryolite in the metallurgy of of the combined redox reaction will be —ve by an amount
aluminium ?(H.P.S.B. 2010, Assam S.B. 2012, 2016) equal to the difference in AJG° of the two metal oxides.
Ans. Cryolite is added to bauxite ore before electrolysis because For example, both Al and Zn can reduce FeO to Fe but
of the following reasons: Fe cannot reduce Al,O, to Al or ZnO to Zn. Similarly,
(1) It acts as a solvent. C ean reduce ZnO to Zn but not CO. Thus, the choice of
(zz) It lowers the melting point of alumina to about a particular reducing agent depends on thermodynamic
1173 K. factor. For more details Refer Text.
(121) Addition of cryolite to alumina increases the electrical Q.24. Name the processes from which chlorine is obtained
conductivity. as a by product. What will happen if an aqueous
solution of NaCl is subjected to electrolysis ?
Q.19. How is leaching carried out in case of low grade
copper ores ? Ans. (t) Chlorine is obtained as a by product during electrolysis
of sodium chloride by Down's process for the manufacture
Ans. Copper is leached out from low grade copper by using
of sodium.
acid in the presence of air when copper goes into the
solution as Cu?* ions. NaCi({) —Hlectrolysis_, Nat (melt) + Cl (melt)
At anode : CI (melt) ——> Cl(g) + e~
Cu (s) + 2H* (ag) + - O, (g) —> Cu** (ag) + H,O Cl (g) + Cl (g¢) ——> Cl, @)
The solution containing Cu** ions is treated with scrap At cathode : Nat(melt) + e7 ———> Na (s)
iron or H,. (11) Electrolysis of brine solution in Castner Kellner cell
Cu** (aq) + H, (g) —— Cu (s) + 2H* (aq) for manufacturing sodium hydroxide (caustic soda).
Q.20. Why is zinc not extracted from zinc oxide through
Q.25. What is the role of graphite rod in the
electrometallurgy of aluminium ?
reduction using CO ?
Ans. The graphite rod is useful in the electrometallurgy of
Ans. In Ellingham diagram, the AG® vs T plot representing aluminium for reduction of alumina to aluminium.
CO, CO, lies above AG*° vs T plot of Zn, ZnO. Therefore, 2A1,0,+ 3C ——> 4Al + 8CO,
CO connot act as reducing agent for the reduction of ZnO. Q.26. Out line the principles of refining of metals by the
Q.21. The value of A,G° for formation of Cr,QO, is following methods:
-540 kJ mol-' and that of Al,O, is -827 kJ (1) Zone refining (11) Electrolytic refining
mol". Is reduction of Cr,O, possible with Al ? (411) Vapour phase refining
Ans. Refer Solved Example 10 (Page 18). Ans. Refer Text page 21 — 21.
Q.22. Out of C and CO which is better reducing Q.27. Predict conditions under which Al might be
agent for ZnO ? expected to reduce MgO.
Ans. C is better reducing agent for ZnO. Ans. The two equations are :

ZnO+C 3K. Zn £CO 2Mg + O, ——> 2Mg0O

Q.23. The choice of a reducing agent in a particular case
depends on thermodynamic factor. How far do you
*Al+0, —> 2 1,0,
It is clear from Ellingham diagram that AG®° vs T plot
agree with this statement? Support your opinion
with two examples. for Mg, MgO is below AG* vs T plot for Al. Therefore,
Al cannot reduce MgO to Mg. However, at the point of
Ans. The thermodynamic factor helps us in choosing a suitable
intersection (corresponding to temperature 1600K), the
reducing agent for the reduction of a particular metal
AG® for the combined reaction becomes zero. After this
oxide to metal. The feasibility of thermal reduction can be
point (1600 K),Mg, MgO curve, is higher than that for Al,
predicted on the basis of AG* vs T plots for the formation
Al,O, curve. Thus Al can reduce MgO at temperature
of oxides, known as Ellingham diagram. From the diagram,
higher than 1600 K. But there are practical difficulties
it can be predicted that metals for which the standard
to attain higher temperatures.

Exemplar Problems TI
Subjective Questions

Ans. For the reaction of extraction of Cl, from brine solution :

2CI (ag) + 2H,O (1) —> 20H (aq) + H, (g) + Cl, (@)
1. Why is an external emf of more than 2.2V required The value of AG? is +ve (422 kJ). For this the value of
for the extraction of Cl, from brine ? E® is
leuz AG? = —nFE®
MODERN'S abe + OF CHEMISTRY-AXIl

manganous silicate (MnSi0,) as slag.

o 3
or Kk = _AG __ 422x109 _ gon MnO + SiO, —“28t_, MnSiO,
nk 2x 96500 Manganous silicate (Slag)
Therefore, extraction of Cl, from brine solution will require 9. The mixture of compounds A and B is passed
an external e.m.f. more than 2.20 V for electrolysis process. through a column of Al,O, by using alcohol as eluant.
. At temperatures above 1073K coke can be used to Compound A is eluted in preference to compound
reduce FeO to Fe. How can you justify this reduction B. Which of the compounds A or B, is more readily
with Ellingham diagram? adsorbed on the column ?
Ans. From the Ellingham diagram, it is clear that at Ans. Since compound ‘A’ comes out before compound ‘B’, the
temperature above 1078 K, AG(C, CO) is less than AG compound ‘B’ is more readily adsorbed on column.
(Fe, FeO). Therefore, coke can reduce FeO to Fe. 10. Why is sulphide ore of copper heated in a furnace
after mixing with silica ?
. Wrought iron is the purest form of iron. Write a
Ans. Iron oxide present as impurity in sulphide ore of copper
reaction used for the preparation of wrought iron
forms slag which is iron silicate and copper is produced
from cast iron. How can the impurities of sulphur,
in the form of copper matte.
silicon and phosphorus be removed from cast iron ?
FeO + 510, ——> FeSi0,
Ans. The reaction is :
11. Why are sulphide ores converted to oxide before
Fe,O, + 3C —-> 2Fe + 3CO reduction ?
Limestone is added as flux and the impurities of sulphur, Ans. Sulphides are not reduced easily but oxides are easily reduced.
silicon and phosphorus change to their oxides and pass 12. Which method is used for refining Zr and Ti? Explain
into slag. with equation.
. How is copper extracted from low grade copper ores ? Ans. Van Arkel method is used for refining Zr and T1. In this
Ans. Copper is extracted by hydrometallurgy from low grade method crude metal is heated with iodine to form volatile
ores. It is leached out using acid or bacteria. The solution unstable compound. The compound is then decomposed
containing copper ions (Cu**) is treated with scrap iron, to get pure metal.
zinc or H, as : Zr
Impure
491, - OR. at 4
Cu** (aq) + H, (g¢) —> Cu (s) + 2H* (aq)
Cu*t + Fe (s) —> Cu (s) + Fe** (aq)
Zrl, Ok , Zr +21,
Pure
In this way, copper is obtained.
T 42. === 11@
. Write two basic requirements for refining of a metal Impure
by Mond process and by Van Arkel Method. Ti, —O* , Ti +21,
Ans. The basic requirements for refining a metal by Mond Pure
process and by Van Arkel method are : 13. What should be the considerations during the
(t) The metal should form a volatile compound with an extraction of metals by electrochemical method ?
available reagent. Ans. During extraction of metals by electrochemical method,
(it) The volatile compound should be easily decomposable, the following are considered so that proper precautions
so that metal can be easily recovered. can be taken :
. Although carbon and hydrogen are better reducing (1) reactivity of metal produced.
agents but they are not used to reduce metallic
(12) suitability of electrodes.
oxides at high temperatures. Why ?
14, What is the role of flux in metallurgical processes?
Ans. This is because at high temperature carbon and hydrogen
react with metals to form carbides and hydrides respectively. Ans. Flux is used for making the molten mass more conducting.
. How do we separate two sulphide ores by Froth Flux combines with impurities to form easily feasible
Floatation Method ? Explain with an example. product known as slag.
Ans. Two sulphide ores can be separated by adjusting proportion 15. How are metals used as semiconductors refined?
of oil to water or by using depressants. For example, in the What is the principle of the method used?
case of an ore containing 7nS and PbS, the depressant NaCN Ans. Semiconducting metal is produced by zone refining method
is used. It forms a layer of zinc complex Na,[Zn(CN),] on which is based on the principle that the impurities are
the surface of ZnS and therefore, prevents it from forming more soluble in melt than in the solid state of metals.
the froth. Therefore, it acts as a depressant.
16. Write down the reactions taking place in Blast
. The purest form of iron is prepared by oxidising
furnace related to the metallurgy of iron in the
impurities from cast iron in a reverberatory furnace.
temperature range 500-800 K.
Which iron ore is used to line the furnace ? Explain
by giving reaction. Ans. The following reactions take place in blast furnance during
Ans. Haematite (Fe,O,) 1s used. It supplies the oxygen and the metallurgy of iron in the temperature range 500 — 800 K.
oxidises carbon, silicon, manganese and phosphorus present 3dFe,0, + CO —-> 2Fe,0, + CO,
in the cast iron to CO, 510,, MnO and P,O, respectively. Fe,O, + 4CO —-> 3Fe + 4CO,
Fe,0: 4 80 = 4 9¥s 4300 Fe,O, + CO —-> 2FeO + CO,
351 + 2Fe,0, —-> 4Fe + 3510, 17. Give two requirements for vapour phase refining.
35 + 2Fe,0O, —> 350, + 4Fe Ans. (1) The metal should form a volatile compound with
CO and SO, escape and MnO and S10, combine to form
available reagent.
GENERAL PRINCIPLES AND PROCESSES OF ISOLATION OF ELEMENTS 6/43 =

(11) The volatile compound should be unstable and easily Ans. The following reactions occur :
decomposable so that the recovery is easy. 4Au (s) + 8CN(aq) + 2H,O (aq) + O, (¢) —>
18. Write the chemical reactions involved in the 4 [Au (CN),]" (aq) + 40H (aq)
extraction of gold by cyanide process. Also give 2[Au(CN),}- (ag) + Zn(s) —> 2Au(s) + [Zn (CN),]*" (aq)
the role of zinc in the extraction. In this reaction zinc acts as a reducing agent.

CUsS Memory Tesr “\

A. oad -witechange.cernsigWesarttcalemaith
onaearen
1. Copper is found both in free as well as in combined state are called -........
in nature. 9. Copper is extracted by ........ . from low grades ores.
2. All minerals are ores but all ores cannot be minerals. 10. Red bauxite is purified by ......... method.
3. The minerals siderite, magnetite and haematite contain 11. Sulphide ores are generally concentrated by ...... process.
iron. 12. Copper is extracted from copper pyrites by roasting the
4, Flux combines with slag to form gangue. ore partially and followed by ..........
5. In calcination, the ore is heated with calcium. Cc.
6. Silver is extracted by hydrometallurgy. ; f
; 1. Pine oil is added in froth floatation method because it
7. Zone refining method is used for alkali metals. increases the non-wettability/wettability of the mineral
8. Themetals Ag, Auand Hg are extracted by pyrometallurgy. particles.
9. The AG versus T line for Al lies below AG vs T line for =: For the recovery of silver from the complex [Ag(CN),],
Cr at all temperatures indicating that Al should reduce zinc/iron is used.
Cr (IIT) at all temperatures. 3. The iron produced in the Blast furnace is called
10. For temperature at which C, CO line lie below the metal pig iron/ wrought iron.
oxide line, carbon can be used to reduce metal oxide. 4. The better reducing agent at 983 K is C/CO.

B. 5. Carbon can be used for reduction of FeO above / below

1. The earthly and silicious impurities which generally 6. Substances which convert infusible impurities present 1n
occur with ores are called .......... ores into fusible substances during smelting are called
slags /fluxes.
2. The most abundant metal in earth's crust is ..........
i. heganedtiaal tends... , 7. Inthe electro-refining of copper, impure copper 1s made
anode / cathode.
4, The process involving reduction of metal oxide with coke
or carbon monoxide is called .......... a Na,AIF, is added to Al,O, for extraction of Al to
lower/raise the melting point.
" “irconium is best refined by ......... method.
9. Calcination is the process of converting an ore into its
oo. Above 1073 K, FeO is reduced to Fe by ......... and below
oxide by heating it in the limited /excess air.
1073 K, Fe,O, is reduced to Fe by ..... ae
7. Inthe Mond's process, ... is used to purify impure nickel.
10. Haematite is Fe,O,/Fe,0,,.

Memory Test \\\

Answers»)
4, False. Flux combines with gangue to form slag.
Say True or False
5. False. In calcination, the ore is heated in the absence or
1. True. limited supply of air.
2. False. The minerals from which the metal is convenientl
and economically extracted is called an ore. Thus, all al Se ee ares ee Deus
are minerals but all minerals are not ores.
3. True.
 MODERN'S abe + OF CHEMISTRY
-AXIl

| Complete the missing links Choose the correct alternative

1. non-wettability 2. zinc 3. pig iron
1. gangue 2. aluminium 3. wroughtiron 4. smelting
4. ¢ 5. above 6. fluxes 7. anode
5. Van Arkel 6. Coke,CO 7. CO 8. minerals
8. lower 9. limited 10. Fe,Og.
9. hydrometallurgy 10. Baeyer's
11. froth floatation 12. reduction

Higher Order Thinking Skills

& Advanced Level
QUESTIONS WITH ANSWERS
Q.1. Metals donot occur in nature as nitrates. Why ? these sulphides are more stable than those with carbon or
Ans. Nitrates of all metals are soluble in water. Therefore, hydrogen. Hence, neither carbon nor hydrogen can reduce metal
if metal nitrates are present in the crust of earth, these would be sulphides to metal. In contrast the standard free energies of
slowly and gradually washed by rain water into the sea. Therefore, formation of oxides are much lower than those of SO, and therefore
metals usually donot occur as nitrates. oxidation of metal sulphides to metal oxidesis thermodynamically
Q.2. Why the graphite rods in the extraction of favourable. Therefore, it is a common practice to roast sulphide
aluminium from molten Al,O, have to be replaced from ore to oxide ore before reduction.
time to time ? Q.7. Thermite process is quite useful for repairing
Ans. During the reaction, oxygen is evolved at anode which broken parts of machines. Explain.
reacts with carbon electrode to form CO and CO,,. This will result Ans. In the thermite process, oxides of metals like iron
in slow corrosion of carbon electrodes and therefore, these have are reduced by aluminium. This reaction is highly exothermic
to be replaced from time to time. and a large amount of heat is evolved during the reaction. As a
Q.3. Why is zinc and not copper used for the recovery result of large heat, the metal will be in the molten state. For
of metallic silver from its cyanide complex [Ag(CN),]- ? example,
Ans. Zinc is more electropositive than silver and therefore,
zine displaces silver from its solution.
Fe,O, +2Al(s) _Heat_. Al 0, (s) + 2Fe + Heat
Iron oxide Molten
2[Ag(CN),J' + Zn ——> [Zn(CN),)*> + 2Ag
Ifthe molten metalis allowedto fall between the broken parts
On the other hand, copper is less electropositive than silver and
of a machine, the gaps will be filled up. Therefore, the machine
therefore, cannot displace silver from its solution.
will be repaired.
Q.4. Galena (PbS) and cinnabar (HgS) on roasting
Q.8. The extraction of gold by leaching with NaCN
often give their respective metals but zinc blende (ZnS)
does not. Explain. involves both oxidation and reduction. Justify giving
equation.
Ans. On roasting sulphides are partly converted to their
respective oxides. Since the oxides of lead and mercury are Ans. During leaching process, (Au) is first oxidised by O,
unstable, these bring about the reduction of their respective of the air to Au* which then combines with CN7 ions to form the
sulphides to the corresponding metals. soluble complex, dicyanidoaurate (I).

PbS + 2PbO _Heat . 3Ph + SO, 4Au(s) +8 NaCN (aq) + O,(g) + 2H,O (1) —>
unstable 4ANalAu(CN),](a@q) + 4NaQH (aq)
HgS + 2HgO _Heat . sHg + SO, Sodium dicyanidoaurate (I)
unstable (Soluble complex)
However, zinc oxide is stable and it does not reduce Gold is then extracted from this complex by displacement
ZnS to Zn. method by using a more electropositive zinc metal. In
Q.5. Graphite is commonly used as an anode but not this method, zinc acts as a reducing agent and it reduces
diamond. Give reason. Aut to Au. Zine itself gets oxidised to Zn** ions which
Ans. Graphite is a good conductor of electricity due combine with CN- ions to form soluble complex, sodium
to the presence of free electrons within its layers. But in tetracyanido zincate (II).
diamond, no free electrons are present and therefore, it is a bad
conductor of electricity. Therefore, diamond is not used as an 2Na[Au(CN),] (aq) + Zn (s) —> 2Au(s) + Na,[Zn(CN),]
anode. Sodium tetracyanido
Q.6. Why is it advantageous to roast a sulphide ore to zincate(1IT)

the oxide before reduction ? (Soluble complex)

Ans. The standard free energy of formation (A,G*) of most of Thus, extraction of gold by leaching with NaCN involves
the sulphides are larger than those of CS, and H,8. Therefore, both oxidation and reduction.
GENERAL PRINCIPLES AND PROCESSES OF ISOLATION OF ELEMENTS

Q.9. Apart of Ellingham diagram is shown below : (iz) At the point of intersection of AL,O, and MgO curves, AG
becomes zero for the reaction:

=Al,O, + 2Mg—> 2MgO +=Al

Therefore, below this point, the curve of magnesium lies
below the curve for Al. Hence below this point, magnesium can
G(kJ)
reduce Al,O, to Al.
Q.10. In the metallurgy of copper partial roasting of
sulphide ore is done. Why ?
Ans. Partial roasting of sulphide ore forms some oxide which
then reacts with the remaining sulphide ore to form copper metal
by self reduction of the oxide and sulphide as:
(z) Will Cr,O, be reduced by Al or not ? 2Cu,5 + 80, —> 2Cu,0 + 250,
(14) Suggest a condition under which magnesium
2Cu,5 + Cu,S ——> 6Cu+S0,
could reduce aluminium.
Thus, to bring about self reduction process, sulphide ore of
Ans. (1) Since the AG vs T curve for Cr,O, lies above Al curve,
copper is partially roasted to Cu,O.
Al can reduce Cr,O,.

+ Revision Exercises
Very Short Answer Questions
23. What is the composition of copper matte ?
.» What is a mineral ? How does it differ from an ore ? (D.S.B. 2013, Tripura S.B. 2016)
. What are flux and slag? 24, Define calcination. (Pb. S.B. 2014)
Give the formula of the ores : haematite and bauxite. 25. Define roasting. (Pb S.B. 2014)
Mention two important ores of zinc. 26. What is Blister of copper? (H.P.S.B. 2016)
(Pb.5.58. 2015, Jammu S.B. 2015) 27. State and explain the term flux. (H.P.S.B. 2016)
. Write the names and formulae of two ores of aluminium. 28. Name the metal used as a reducing agentin Aluminothermic
(Pb.S.B. 2015) process. (Pb.S.B. 2016)
»>
he
PO
aOF . What is meant by native ore ? Name two metals which
occur in native state. CBSE QUESTIONS
. What is a depressant ? Give one example. 29. Whatis meant by the term pyrometallurgy?
Define aluminothermy. (A.L.S.B. 2009)
OOI© . What is the principle of chromatography ? 30. Differentiate between mineral and ore. (A./.S.B. 2011)
1 i . What types of ores are roasted ? 31. Why is that only sulphide ores are concentrated by froth
11. Which method is used when a metal of high degree of purity floatation process ? (A oso en)
is needed? (Pb.S.B. 2016) 32. What type of ores can be concentrated by magnetic
12. Name the sulphide ores of (7) zinc (iz) lead. separation method ? (ALS Boar?)
13. Which is better reducing agent at 983 K, C or CO? 33. What is the role of collector and froth stabilizer in froth
(Pb.S.B. 2016) floatation process ? (A.L.S.B. 2012)
14, Name two ores which are concentrated by froth floatation 34. Name the method used for refining of copper.
method. (A.L.S.B. 2013)
15. Write reduction reaction occurring in the blast furnace in 35. Name the method that is used for refining of nickel.
the metallurgy of iron at 900-1500 K.
(A.L.S.B. 2014)
16. What are ores? Name one sulphide ore. (Assam 8.5. 2016)
17. Why aluminium cannot be reduced by carbon ? 36. Whatis the role of zinc metal in the extraction of silver?
(A.P.S.B. 2010) (A..S.B. 2014)
18. What is the role of silica in the metallurgy of copper ?
(Pb.S.B.E. 2010) MC@Qs. from State Boards’ Examinations
19. Write the role of depressant in froth floatation process.
37. Cinnabar is an ore of
(Pb.S.B. 2010)
(a) Hg (6) Ag
20. Whatis the principle of zone refining? (Pb. 8.5. 2012)
21. What is the role of graphite in the electrometallurgy of
(c) Sn (dq) Al (Ar.S.B., H.P.S.B. 2013)
aluminium ? (D.S.B. 2012) 38. Pyrolusite is an ore of
22. Give an important ore each of zinc and magnesium. (a) Ag (6) Hg
(Pb. S.B. 2013) (c) Sn (d) Mn (Ar.S.B. 2013)
leu.
39. Malachite is an ore of
MODERN'S abe + OF CHEMISTRY
-AXIl

(6) What is the benefaction of the ores? Explain froth

(a) Hg (6) Cu (c) Sn = (d) Mn (Ar.S.B. 2013) floatation process? (Hr. SB. 2077)
40. The process employed for the concentration of sulphide (c) Write short note on calcination. (Hr. S.B. 2017)
are 18
. Name the important ores of iron. Give equations for the
(a) Froth floatation (5b) Roasting
chemical reactions occurring in different zones of blast
(c) Electrolysis (d) Calcination (.P.S.B. 2013) furnace.
41. Zone-refining is used for the
. Whatis froth floatation process ? Name the ores which are
(a) concentration of an ore
concentrated by froth floatation process. What is meant
(6) reduction of metal oxide
by a depressant ?
(c) purification of metal
10. List important steps for the extraction of zinc from zinc
(d) purification of an ore. (.P.S.B. 2013)
blende.
42. The metal always found in free state is
(a) Gold (b) Silver 11. Explain the basic principles of the following metallurgical
operations:
(c) Copper (d) Sodium (4.P.S.5. 2013, 2018)
43. Bauxite is an ore of (1) Zone refining
(a) aluminium (6) calcium (D.S.B. 2008, 2014, 2017, Ar.S.B. 2015, A.L.S.B. 2017)
(c) Copper (d) zine (Hr.S.B. 2015) (it) Froth floatation process
44, Most abundant element in earth’s crust is (D.S.B. 2008, 2014, A..S.B. 2017)
(a) O (b) Si (c) Al (d) Fe (iit) Refining by liquation (D.S.B. 2008)
(Ar.S.B. 2015, H.P.S.B. 2018)
(iv) Vapour phase refining
45. Which of the following ore is concentrated by the froth
floatation process? (D.S.B. 2008, 2011, 2014, 2017)
(a) Haematite (6) Magnetite (v) Electrolytic refining
(c) Copper pyrite (d) Bauxite (D.S.B. 2008, 2011, 2014, Hr.S.B. 2015)
(Jharkhand S.B. 2016) (vi) Chromatography (D.S.B. 2014, 2017, AI.S.B. 2017)
46. Common impurities present in bauxite ore: 12. Define the following terms :
(a) CuO (b) ZnO (a) Roasting (b) Electro metallurgy
(c) Fe,O, (d) None of these (Hr. S.B. 2017)
(c) Aluminothermy (Mizoram S.B. 2017)
A7. In which of the following minerals Al is not present?
135. Describe the role of the following :
(a) Cryolite (6b) Mica
(c) Feldspar (d) Fluorspar (Hr. S.B. 2017) (1) Depressant in Froth floatation process.
48. In the metallurgy of iron from haematite, limestone is (iz) Silica in the extraction of copper from copper pyrites
added to act as ore.
(a) flux (b) slag (iit) Cryolite in the metallurgy of aluminium.
(c) areducing agent (d) an oxidising agent (D.S.B. 2008)
(Manipur S.B. 2017) 14 (a) Differentiate between ore and mineral.
49, (z) Purest form of iron is
(Ar. S.B. 2017)
(a) cast iron (6) wrought iron
(6) Differentiate between calcination and roasting.
(c) steel (d) pig iron (H.P.S.B. 2018)
(Jharkhand S.B. 2016)
Short Answer Questions (c) Differentiate between gangue and flux.
(Pb.S.B. 2009, J_K.S.B 2012)
. Define metallurgy. Name the important metallurgical
operations. (Manipur S.B. 2017) 15. Describe how the following changes are brought about :
(1) Pig iron into steel.
» What is the function of reduction in the metallurgical
operations ? Discuss briefly the carbon reduction process. (it) Zine oxide into metallic zine.
(111) Impure titanium into pure titanium.
» Whatis meant by leaching? Explain leaching of aluminium
ore. (A. P.S.B. 2015, Jammu 8.24. 2018) Or
Describe the role of
. What is electrorefining ? Explain with one example.
(1) NaCN in the extraction of gold from gold ore.
oh (a) Why is zinc not extracted from zinc oxide through
reduction with CO ? (iz) 510, in the extraction of copper from copper matte.
(zit) Iodine in the refining of zirconium. (Pb.S.B. 2010)
(6) Is carbon a satisfactory reducing agent for all metal
oxides ? Give reasons. 16. What is the role of graphite rod in the metallurgy of
aluminium ? (Ar. S.B. 2011)
(a) Discuss gravity separation method for concentration
of ore. (Pb. S.B. 2017) 17. Explain the role of each of the following in the extraction
of metals from their ores :
(6) Discuss froth floatation process for concentration of
(1) CO in the extraction of nickel.
ores. (Pb. S.B. 2017, Hr. S. B. 2018)
(11) Zine in the extraction of silver.
(c) Whatis magnetic separation method for concentration
of ore? (Pb. S.B. 2017) (zit) Silica in the extraction of copper. (D.S.B. 2011)
(a) What is the role of depressant in froth floatation 18. (a) Why is reduction of a metal oxide easier if metal formed
process? (Ar. S.B. 2017) is in liquid state at the temperature of reduction ?
GENERAL PRINCIPLES AND PROCESSES OF ISOLATION OF ELEMENTS

(6) Explain magnetic separation with the help of diagram. 350. Explain with neat diagram the extraction of aluminium
(Ar. S.B. 2012) metal from molten aluminium?
19. Describe the principle involved in each of the following Or
processes : What type of ores can be concentrated by froth floatation
(a) Mond process for refining of nickel. process? Explain how can the process be carried out?
(6) Column chromatography for purification of rare (Nagaland S.B. 2015)
elements. (D.S.B. 2012) ol. Give the name and formula of two main ores of iron.
20. Describe the following : Describe the method to obtain cast iron from one of its
(a) The role of cryolite in electrometallurgy of aluminium. ores. Give chemical reactions also.
(6) The role of carbon monoxide in the refining of crude (Uttarakhand S.B. 2013, 2015)
nickel. (D.S.B. 2012) 32. (z) Indicate the principle behind the method used for the
21. (a) Differentiate between roasting and calcination. refining of zinc.
(6) How is cast iron different from pig iron ?
(11) What is the role of silica in the extraction of copper?
(Jharkhand S.B. 2016)
(211) Which form of the iron is the purest form of commercial
(c) Explain magnetic separation method 1n detail.
iron? (D.S.B. 2015)
(Ar. S.B. 2013)
22. (a) Which solution is used for the leaching of silver metal oo. (a) Why is zinc blende roasted before carbon reduction?
in the presence of air in the metallurgy of silver? Answer with balanced chemical equation.
(6) Out of C and CO, which is a better reducing agent at (6) What is malachite? Write down its formula.
the lower temperature range in the blast furnance to (Kolkata S.B. 2016)
extract iron from the oxide ore ? (D.S.B. 2013) 34, Explain with suitable diagram for the production of steel
23. (a) Give an example of zone refining of metals. by Bessemer process.
(6) What is the role of cryolite in the metallurgy of Or
aluminium ? (D.S.B. 2013) How is zine obtained from zinc blende? Give chemical
24, In the blast furnace, the reduction of Fe,O, by coke reactions. (Nagaland S.B. 2016, 2018)
(C) and carbon monoxide (CQO) takes place around
oo. (a) Name the ore from which aluminium is extracted and
1073 K. With the help of Ellingham diagram explain
write its composition.
which reducing agent converts Fe,O, to Fe below and above
1073 K? (Manipur S.B. 2014) (6) How is Ni purified by Mond’s process?
25. Draw labelled diagram of Hall-Heroult electrolytic cell (Meghalaya S.B. 2016)
for the extraction of aluminium. Write anode and cathode 36. (a) Name the role of Na,AlF’, in the electrolytic reduction
reactions. (Karnataka S.B. 2014) of alumina.
26. (a2) What are calcination and roasting ? In which type of (6) How does the FeO impurity present in sulphide ore of
ores are these processes used ? copper is removed? (Assam S.B. 2016)
(6) Which metals are generally extracted by electrolytic
of. (a) Name the method of refining of metals such as
processes ? What position do these metals occupy in
germanium.
the periodic table ?
(6) In the extraction of Al, impure AI,O, is dissolved
Or
in conc. NaOH to form sodium aluminate and
(c) What types of metals are likely to exist in native state
leaving impurities behind. What is the name of this
in nature ? Give examples.
process?
(d@) Writethe chemical reactions involvedin the blast furnace
(c) What is the role of coke in the extraction of iron from
during the extraction of iron from haematite.
its oxides? (D.S.B. 2016)
(Mizoram S.B. 2014)
38. What are minerals and ores? Comment on the statement,
27. (a2) What is the principle of zone refining?
“All the ores are minerals but all the minerals are not
(6) What is flux? Give one example each of an acidic flux ores . (H.P. S.B. 2017)
and a basic flux.
39. (a2) Name the main ore of iron.
(c) Why are metallic ores converted into oxide usually?
How is cast iron made from pig iron?
(d) Discuss the process of leaching with reference to the
(6) Mention the type of ore that can be concentrated by
extraction of aluminium.
froth floatation process. (Assam S.B. 2017)
(Meghalaya S.B. 2018)
40). Leaching is a process of concentration of ores. Explain the
28. Define the following terms:
leaching of alumina from bauxite. (Kerala S.B. 2017)
(2) Ore benefaction (it) Hydrometallurgy
Al. (a2) Name one important ore of aluminium. Give its
(111) Pyrometallurgy (Mizoram S.B. 2015) chemical composition.
29. How can you extract blister copper from copper pyrites ? (6) Give the Mond process for refining of nickel.
Give the chemical reactions involved in the process. Write
(c) How is copper extracted from low grade ore?
the names and formulae of two ores of copper. How can
you obtain pure copper from blister copper? (Assam S.B. 2018)
(Meghalaya S.B. 2015)
leu
42. (a) Write the principle of method used for the refining of
MODERN'S abe + OF CHEMISTRY
-AXIl

(1) Froth floatation method

(11) Electrolytic refining of metals
(6) Out of PbS and PbCO, (ores of lead), which one is
(121) Zone refining of metals
concentrated by froth floatation process preferably?
(A.L.S.B. 2010)
(c) What is the significance of leaching in the extraction
of aluminium? tse Describe the principle controlling each of the following
processes :
(D.S.B. 2017)
(1) Vapour phase refining of titanium metal.
43. Describe the role of (iz) Froth floatation method of concentration of a sulphide
(1) NaCN in the extraction of gold from its ore. ore. (A.LS.B. 2011)
(1) Cryolite in the extraction of aluminium from pure a4. Which methods are usually employed for purifying the
alumina. following metals :
(zzz) CO in the purification of nickel. (a) Nickel (6) Germanium
(C_B.S.E. Sample Paper 2017-18, Hr. S.B. 2018)
Mention the principle behind each one of them.
(A.LS.B. 2012)
44, (a) Explain Mond's process used for refining of nickel
50. Explain the role of each of the following :
(Pb.S.B. 2018)
(a) NaCN in the extraction of silver.
(6) Define leaching. Explain leaching of aluminium ore.
(6) S10, in the extraction of copper.
(Jammu S.Z. 2018)
(A.L.S.B. 2012, 2014)
45. (1) What is calcination? 56. (a) Name the method used for removing gangue from
(11) What is smelting ? sulphide ores.
(221) Name the ore of aluminium. (6) How is wrought iron different from steel?
(7.P.S.B. 2018) (A.LS.B. 2013)
57. Explain the principle of the method of electrolytic refining
46. (1) Name a metal refined by Van Arkel method. of metals. Give one example.
(11) Explain the process of obtaining "blister copper" from (A.LS.B. 2014)
“copper matte" with equation.
58. Write the principle behind the froth floatation process.
(Karnataka S.B. 2018)
What is the role of collectors in this process?
A7. (1) Explain zone refining method for refining of metals. (A.L.S.B. 2014)
(Hr.S.B. 2018) o9. (1) Name the method used for the refining of zirconium.
(11) Explain the van Arkel method for refining of metals.
(it) What is the role of CO 1n the extraction of 1ron?
(Hr.S.B. 2018)
(zit) Reduction of metal oxide to metal becomes easier if
48. Define the following terms: the metal obtained is in liquid state. Why?
(1) Leaching (iz) Levigation (zzz) Smelting (A.S.B. 2015)
(Mizoram S.B. 2018) (a) Name the method of refining which is based on the
49, Explain with neat diagram the extraction of aluminium principle of adsorption.
from molten alumina. (Nagaland S.B. 2018) (6) What is the role of depressant in froth floatation

»> <4
process?
CBSE QUESTIONS (c) What is the role of limestone in the extraction of iron
o0. What chemical principle is involved in choosing a reducing from its oxides? (A.LS.B. 2016)
agent for getting the metal from its oxide ore? Consider
61. Write the principle of the following:
the metal oxides, Al,O, and Fe,O, and justify the choice
of reducing agent in each case. (A.L.S.B. 2008) (a) Zone refining

ol. Describe the underlying principle of each of the following (6) Froth floatation process
metal refining methods : (c) Chromatography (A.15.5. 2077)
(1) Electrolytic refining of metals 62. (a) Write the principle of electrolytic refining.
(zt) Vapour phase refining of metals. (6) Why does copper obtained in the extraction from
(A.S.B. 2009) copper pyrites have a blistered appearance?
52. Describe the role of the following : (c) Whatis the role of depressants in the froth floatation
(1) NaCN in the extraction of silver from a silver ore process? (A.fL.S.B. 2017)
(11) lodine in the refining of titanium
635. Write the chemical reactions involved in the process of
(111) Cryolite in the metallurgy of aluminium
extraction of gold.
Or
Describe the principle involved in each of the following Explain the role of dilute NaCN and Zn in this process.
processes of metallurgy : (A.LS.B. 2018)
GENERAL PRINCIPLES AND PROCESSES OF ISOLATION OF ELEMENTS

What is refining ? Outline the principles of refining of

Cc
»»> Long Answer Questions <4 metals by the following methods :
1. (a) How does iron occur ? Discuss in detail the extraction (1) Zone refining.
of iron from haematite ore. (11) Electrolytic refining.
(d) What are steel alloys ? Give examples. (Ar. S.B. 2011, 2015)
(1) How is pure copper extracted from copper pyrites ? (a) Write the chemical reaction taking place in the
(iz) Give the chemistry of extraction of zinc from its ore. extraction of zinc from zinc blende.
(iit) List important uses of zinc and copper. (6) State the role of silica in the metallurgy of copper.
fe Write down the chemical reactions taking place in different (c) How is copper extracted from low grade copper ores?
zones in the blast furnace during extraction of iron.
(d) How is ‘pig iron’ different from ‘cast iron’?
Or
(Meghalaya S.B. 2017)

aa \\ Hints & Answers

yor Revision Exercises

Very Short Answer Questions res i. -

22. zinc blende (ZnS), magnesite (MgCQ,)
3. Fe,O,, Al,O,.2H,O 23. Cuprous sulphide and traces of ferrous sulphide
4. Zinc blende (ZnS), Calamine (ZnCQ,) 28. Aluminium
5. Bauxite Al(OH),., (0 <x < 1), Kaolinite Al,(OH),51,0, 3a. (1) Collector enhances non-wettability of the mineral
6. Gold, platinum. _ Berpeles -
10. Generally sulphide ores are roasted. , ~ (a panama etree
12. (i) Zine blende (ZnS), (ii) Galena (PbS) ag oP ye reining
30. Mond's process
een 37 38.(d) 39.(b) 40 41
rae
15. C+CO,——>
2CO; FeO + CO—_>
Fe + CO, 2.oan
. 43.)| “4.
~)| 45.
_- 46.
iam
47. (d) 48. (a) A9, (5)

Competition File ~osjecivecuestore

e, 6 a

> FA

Hite Choice Questions M. C. Q.

c

Multip

A
~ SS®MULTIPLE CHOICE QUESTIONS
4c :
=)
(c) ore
(0) slag
(d) catalyst.
<0V with only one correct answer 7 .
A3. During smelting an additional substance is added which
Cenierenes and Cdeacmeatinn of metals combines with impurities to form a fusible product which
is known as
Select the correct answers: (a) mud (6) slag
Al. Which of the following is not an ore of magnesium ? (c) flux (d) gangue.
(a) Gypsum (6) Dolomite A4. Roasting results in the production of metal in the case of
(c) Magnesite (d@) Carnallite. (a) iron pyrites (6) galena
A2,. A substance which reacts with gangue to form material (c) cinnabar (d) bauxite.
is called

Answers
Al. (a) A2. (a) As. (bd) AA, (ce)
aso MODERN'S abe + OF CHEMISTRY
-AXIl

AS. The method for the purification of impure metals which is (a) volatile unstable compound
based upon the phenomenon of electrolysis is called (6) volatile stable compound
(a) Electrorefining (6) Hydrometallurgy (c) non-volatile stable compound
(c) Polling (d) Liquation. (d) none of the above.
AG. Coke is used in metallurgical process chiefly as Al7. In which of the following, ore does not match with the
(a) flux (6) reducing agent metal ?
(c) slag (d) oxidising agent (a) Zine — Calamine (6) Lead — Gypsum
AZ. Zone refining has been employed for preparing ultra pure (c) Copper — Malachite (d) Aluminium — Bauxite
samples of
Al8. Smelting involves reduction of metal oxide with
(a) Cu (b) Na (c) Ge (d) Zn.
(a) Carbon (6b) Carbon monoxide
. Titanium can be obtained 1n a state of high purity by
(c) Magnesium (dq) Alumimum.
(a2) Van Arkel method (6) Poling
Al19. Out of the following metals that cannot be obtained by
(6) Cupellation (d) Electrorefining.
electrolysis of the aqueous solution of their salt is
. Copper pyrites are concentrated by
(a) Ag (6) Cu
(a) Electromagnetic method
(6) Froth flotation process
(c) Al (d) Cr.
(c) Gravity method . Which of the following reaction is used in thermite welding?
(d) All the above. (a) Ti0, + 4Na—> Ti + 2Na,O

Al10. Electrolytic reduction method is used in extraction of (dD) Cy), 4+ 2A] —-+ AL, 4+ 2Cr
(a) highly electronegative elements
(c) 3Mn,O, + 8Al—-> 4Al,0, + 9Mn
(b) metalloids (c) transition metals
(d) 2Al + Fe,O,
—-> Al,O, + Fe
(d) highly electropositive elements.
All. The purpose of smelting an ore is to ; AG° vs T plot in Ellingham diagram slopes downward for
(a) oxidise it the reaction:

(6b) reduce it (a) 2Ag + 502 > Ag,O

(c) obtain an alloy
(d) separate volatile impurities.
1
(6) CO + 0, —> C0,
A112. Which of the following metal is obtained by leaching the
(c)
1
C+ 92 —> CO
ore with dilute cyanide solution?
(a) Titanium (6) Silver
(d) Cut 502 —> CuO
(c) Zirconium (d@) Vanadium.
» Which of the following statement is not true ?
Al13. The ore having two different metal atoms is
(a) The Ellingham diagram show the plots of AG vs T.
(a) Haematite (6) Copper pyrites
(6) In froth floatation process depressants are added to
(c) Malachite (d) Magnetite
enhance the formation of froth.
Al4, Rocky impurities present in the mineral are called
(c) Extraction of zinc oxide is done by coke.
(a) flux (b) gangue
(d) CO 1s more effective reducing agent below 983K
(c) matte (d) slag.
A23. From the Ellingham graphs on carbon, which of the
A115. Which of the following metal cannot be extracted by carbon following statements is false ?
reduction process ? (a) CO, is more stable than CO at less than 983 K
(a) Pb (6) Al (c) Zn (d) Hg. (6) CO reduces Fe,O, to Fe at less than 983 K
Al6. Van Arkel method of purification of metals involves (c) CO 1s less stable than CO, at more than 983 K
converting the metal to a (d) CO reduces Fe,O, to Fe in the reduction zone of blast
furnace. (Karnataka C_E.T. 2012)

(oa
A5. (a) AG. (5) AZ. (c) A8. (a) AS. (5) Alo. (7) All. (6) AZ. (6) AS. (6) Ald. (6)
Al5. (5) Al6. (5) A177. (5) Al18. (a) A119. (c) A20. (f) <AZI. (ce) AZZ. (6) ABs. fc)
GENERAL PRINCIPLES AND PROCESSES OF ISOLATION OF ELEMENTS

Occurrence & Extraction of Fe, Cu, Zn and Al (a) Fusion (6) Reduction
(c) Sublimation (d) Roasting
A24, During roasting of zinc blende, 1t converts to
. Heating of iron pyrites in air to remove sulphur is called
(a) ZnO (6) ZnSO, (c) ZnCOQ, (d) Zn.
(a) calcination (6) fluxing
A25. Iron obtained from reduction zone of the blast furnace is
(c) smelting (d) roasting
(a) Cast iron (6) Spongy iron
. In the metallurgy of iron, when limestone is added to the
(c) Steel (d) Wrought iron.
blast furnace, the calcium ions end up in
A26. In blast furnace, iron oxide is reduced to iron by
(a) gangue (b) slag
(a) Carbon (6) Limestone
(c) metallic calcerum (d) calcium oxide
(c) CO (d) Zine
A30. In electrorefining, the impure metal is made
A27. The reduction of iron in a blast furnace involves all the (a) anode (b) cathode
steps except (c) anode or cathode (d) electrolyte.

A24,. (a) A225. (6) A226. (c) ABW (c) A228. (d) A29. (b) AsO. (a)

Bd. Aluminium is extracted from alumina (Al,O,) by

MULTIPLE CHOICE QUESTIONS electrolysis of a molten mixture of
from competitive examinations (a) Al,O, + HF + NaAlF,
(6) ALO, + CaF, + NaAlF,
AIPMT & Other State Boards'
(c) ALO, + Na, AIF, + CaF,
Medical Entrance (d) Al,O, + KF + Na, AIF, (A.LP.M.T. 2012)
Select the correct answers: B6. Which one of the following is a mineral of iron ?
Bl. Which of the following statements, about the advantage (a) Malachite (b) Cassiterite
of roasting of sulphide ore before reduction is not true ? (c) Pyrolusite (d) Magnetite
(a) The ASG? of the sulphide is greater than those for CS, (A.LLP.M.T. 2012)
and H,S Bi. Roasting of sulphides gives the gas X as a by product. This
(6) The AG* is negative for roasting of sulphide ore to is a colourless gas with choking smell of burnt sulphur and
oxide. causes great damage to respiratory organs as a result of
(c) Roasting of the sulphide to the oxide is thermodynami- acid rain. Its aqueous solution is acidic, acts as a reducing
cally feasible. agent and its acid has never been isolated. The gas X is
(d) Carbon and hydrogen are suitable reducing agents for (a) CO, (6) 50, (ec) HS (d) SO, (NEET 2013)
metal sulphides (C_B.S.E£.PMT. 2007) B8. In the extraction of copper from its sulphide ore, the metal
B2. Which of the following pairs of metals is purified by Van is finally obtained by the reduction of cuprous oxide with
Arkel method ? (a) copper (I) sulphide (Cu,5)
(a) Ga and In (6) Zr and Ti (6) sulphur dioxide (SO,)
(c) Ag and Au (d) Niand Fe (AIPMT 2011) (c) iron sulphide (FeS)
Bs. Which of the following elements is present as the impurity (@) carbon monoxide (CO) (A.LLP.M.T. 2012, 2015)
to the maximum extent in the pig iron ?
B9. “Metals are usually not found as nitrates in their ores”.
(a2) Manganese (6) Carbon
Out of the following two (A and B) reasons which is/are
(c) Silicon (d) Phosphorus true for the above observation?
(AIPMT 20117)
(A) Metal nitrates are highly unstable.
Ba4. Identify the alloy containing a non-metal as a constituent
(B) Metal nitrates are highly soluble in water.
in it.
(a) Invar (6) Steel (a2) A and B are false (6) Ais false but B is true
(c) Bell metal (d) Bronze (A.LP.M.T. 2012) (c) Ais true but B is false(d) A and B are true.
(A... P.M.T 2015)

Aaswets
B1. (d) B2. (5) Bs3. (5) BA. (5) B5. (c) B6. (d) B7. (d) B8. (a) B9. (5)
asa MODERN'S abe + OF CHEMISTRY
-AXIl

B10. Match items of Column I with the items of Column IJ and B18. Sphalerite is concentrated by
assign the correct code: (a) gravity separation (6) froth floatation

(1) Cyanide process

Column I
(a) Ultrapure Ge
(c) magneticseparation
(e) leaching.
(d) hydraulic washing
(Kerala PMT 2014)
(ii) Froth floatation process | (6) Dressing of ZnS B19. The following set of reactions are used in refining zirconium.
(iit) Electrolytic reduction (c) Extraction of Al 523 K
Zr(impure) + 21, —~~>—, 1800 K
Zrl, ————> Zr(pure) + 21,
(iv) Zone refining (d) Extraction of Au
This method is known as
(e) Purification of Ni
(a) distillation (6) liquation
Code:
(c) Hall-Heroult method (d) Van Arkel method
A B CG D
(e) Mond’s process. (Kerala PMT 2014)
(a) (2) (iz) (112) (iv)
(b) (zit) (iv) (v) (1) JEE (Main) & Other State Boards’
(c) (wv) (iz) (112) (1)
Engineering Entrance
(d) (iz) (iit) (z) (v) (NEETI 2016)
Bil. Extraction of gold and silver involves leaching with B20. During the process of electrolytic refining of copper some
CN ion. Silver is later recovered by metals present as impurity settle as “anode mud”. These
(a) distillation (6) zone refining are :
(c) displacement of Zn (d) liquation (NEET 2017)
(a) Sn and Ag (6) Pb and Zn
B12. Considering Ellingham diagram, which of the following
(c) Ag and Au (dq) Fe and Ni
metals can be used to reduce alumina?
(a) Fe (b) Zn (A. EEE. 2005)
(c) Mg (d) Cu (NEET 2018) B21. Heating Cu,O and Cu,5 will give :
B13. Which one of the following ores is concentrated by chemical (a) Cu+SO, (6) Cu+50O,
leaching method ? (ce) CuO + CuS (d) Cu,5O, (A.LE.E.E. 2005)
(a) Galena (6) Copper pyrite B22. In view of the sign of A.G° for the following reactions :
(c) Cinnabar (d) Argentite
PbO, + Pb —> 2PbO; A.G° <0
(e) Copper glance (Kerala P.M.T. 2009)
snO, + Sn —> 25nO; A.G° > 0
B14, Which of the following methods is used for obtaining
aluminium metal? which oxidation states are more characteristic for lead and
tin ?
(a) Electrolysing fused Al,O, and cryolite
(a) For lead + 2, for tin + 2
(6) By heating Al,O, with carbon
(6) For lead + 4, for tin + 4
(c) By heating Al,O, in Muffle furnace
(c) For lead + 2, for tin + 4
(d) By a process called pyrometallurgy (DUMET 2010)
(@) For lead + 4, for tin + 2 (A.LE.ELE. 2011)
B15. Which of the following reaction is an example of calcination
B23. Which method of purification is represented by the
process?
following equation ?
(a) 2Ag+2HCl+[O0]——> 2 AgCl+H,O 523 K 1700 K
(6) 27n+0, ——>2Zn0 Ti (s)+ 215 (g) ——— Til, (g) ——>Tis) + 21, (g)
(c) 2ZnS+30, ——>2Zn0+2S0, (a) Cupellation (6) Poling
(4) MgCO, ——>MgO+CO, (ALIMS 2010)
(c) Van Arkel (d) Zone refining
B16. Which one of the following is not a sulphide ore ?
(a) Magnetite (6) Iron pyrites (ALLELE. 2012)
(c) Copper glance (d) Sphalerite B24, In the context of the Hall-Heroult process for the extraction
(e) Galena (Kerala P.M.T. 2012) of Al, which of the following statements is false?
B17. Principle of paper chromatography is based on (a) Al®* is reduced at the cathode to form Al.
(a) solid-liquid partition chromatography (6) Na,AlF, serves as the electrolyte.
(6) liquid-liquid partition chromatography
(c) CO and CO, are produced in this process.
(c) liquid-solid adsorption chromatography
(d) liquid-liquid sorption chromatography (d) Al,O, is mixed with CaF, which lowers the melting
point of the mixture and brings conductivity.
(A.M.U. Med. 2013)
(JHE Main 2015)

Arswer
B10. (c) B11. (c) B12. (c) B13. (d) B14. (a) B15. (d) B16. (a) B17. (5) B18. (5)
B19. (d) B20. (c) B21. (a) B22. (c) B23. (c) B24. (5)
GENERAL PRINCIPLES AND PROCESSES OF ISOLATION OF ELEMENTS

B25. Which one of the following ore is best concentrated by froth B34. The statement that is not correct is
floatation method? (a) afurnace lined with haematite is used to convert cast
(a) Magnetite (b) Siderite iron to wrought iron.
(c) Galena (d) Malachite (6) collectors enhance the wettability of mineral particles
(JEE Main 2016) during froth floatation.
(c) in vapour phase refining the metal should form
B26. AG*® vs T plot in the Ellingham's diagram slopes downward
volatile compound.
for the reaction
(d) copper from its low grade ores is extracted by
Gy Migs 7O,—>MgO (6) 2Ag+ -0, —> Ag,O hydrometallurgy. (Karnataka CET 2014)
B35. Roasted copper pyrite on smelting with sand produces
() C+50,—+CO — (@) CO+ 0,+0, (a) FeSi0, as fusible slag and Cu,5 as matte
(6) CaSi0, as infusible slag and Cu,O as matte
(Karnataka CET 2006) (c) Ca,(PO,), as fusible slag and Cu,S as matte
B27. Identify the reaction that does not take place in a blast (d) Fe,(PO,), as infusible slag and Cu,5 as matte
furnace : (WB JEE 2015)
(a) 2Fe,O, + 83C ——-> 4Fe + 3CO, B36. Name the metal that is purified by placing the impure
(6) CO, + C —+2CO metal on sloping hearth of a reverberatory furnace and
heating that above its melting point in absence of air.
(c) CaCO, —> CaO + CO,
_ = (a) Mercury (6) Galium
(d) CaO + S10, —+CasSiO, (Karnataka C.E.T. 2008) (cMAZircomfutn (d) Copper (MH-CET 2015)
B28. In aluminothermic process, Al is used as B37. How is ore of aluminium concentrated?
(a) Reducing agent (6) Oxidising agent (a) roasting (b) leaching
(c) Catalyst (d) Electrolyte (c) froth floatation (d) using Wilfley table
(Orissa J_E_E 2009) (MH-CET 2015)
B29. The temperature of the slag zone 1n the metallurgy of iron B3s. Name the reagent that is used in leaching of gold:
using blast furnace is (a) Carbon (6) Sodium cyanide
(a) 1600—1600°C (6) 400—700°C (c) Carbon monoxide (d) Iodine. (MH-CET 2016)
(c) 800—1000°C (d) 1200-1500°C B39. Which metal is refined by Mond Process?
(Karnataka C.E.T. 2009) (a) Titanium (6) Copper
B30. In the electrolytic refining of zine, ............ (c) Nickel (d) Zine. (MH-CET 2016)
(a) graphite is at the anode B40. The composition of ‘copper matte’ is
(6) the impure metal is at the cathode (a) Cu,5 + FeS (6) Cu,S + Cu,O
(c) the metal ion gets reduced at the anode (c) Cu,5 + FeO (d) Cu,O + Fes
(d) acidified zinc sulphate is the electrolyte (Karnataka CET 2016)
(Karnataka CET 2010) B41. The complex formed when Al,O, is leached from bauxite
B31. Accordingto Ellingham diagram, the oxidation reaction of using concentrated NaOH solution is
carbon to carbon monoxide may be used to reduce which (a) NafAl(OH),] (6) NaAl,O,
one of the following oxides at the lowest temperature ? (c) Na,[Al(OH).] (d) Na,AlO,
(Karnataka CET 2016)
(a) ALO, (6) Cu,O (c) MgO . ae
(d) ZnO (e) FeO (Kerala PET 2010) B42. The metal extracted by leaching with cyanide is
B32. The function of potassium ethyl xanthate in froth floatation (a) Re .
process is to make the ore (c) Na eres (K taka CET 2017)
| | arnataka Cl |
im necres idee ay - om ssdae B43. Purification of aluminium by electrolytic refining is called
c) lighter fe sala on (a) Hall’s process (6) Froth floatation process
arnataka C.E.T. : (c) Baeyers process (d) Hoope’s process
B33. The first step in the extraction of copper from copper pyrites (e) Serpeck’s process (Kerala PET 2017)
a B44, Corundum is mineral of aluminium.
(a) reduction by carbon (5) electrolysis of ore (a) silicate (b) oxide
(c) roasting oforeinO, (d) magnetic separation (c) double salt (d) sulphate
(J_.K.C_E.T. 2012) (e) nitrate (Keral PET 2017)

B25. (c) B26. (c) B27. (c) B28. (a) B29. (c) B30. (d) B31. (d) B32. (5) B33. (c)
B34, (5) B35. (a) B36. (a) B37. (5) B3s. (5) B39. (c) B40. (a) B41. (a) B42. (6)
B43. (d) B44, (5)
as MODERN'S abe + OF CHEMISTRY
-AXIl

B45. Electrolytic refining is used to purify which of the following B48. Extraction of zinc from zinc blende 1s achieved by :
metals? (a) Electrolytic reduction
(a) Cu and Zn (b) Ge and Si (6) Roasting followed by reduction with carbon
(c) Zr and Ti (d) Zn and Hg (c) Roasting followed by reduction with another metal
(Karnataka CET 2018)
(d) Roasting followed by self reduction. (EET. 2007)
B46. The common impurity present in bauxite is B49. Oxidation states of the metal in the minerals haematite
(a) CuO (b) ZnO and magnetite, respectively, are
(c) Fe,O, (d) Cr,O,
(a) I, II haematite and IIT in magnetite
(Karnataka CET 2018) (6) I, I] in haematite and IT in magnetite
(c) ILin haematite and II, I] in magnetite
JEE (Advance) for ITT Entrance
(d) Ill in haematite and I, Wl in magnetite (L.-T. 2011)
B50. In the cyanide extraction process of silver from argentite
B47. In the process of extraction of gold,
ore, the oxidizing and reducing agents used are
Roasted gold ore + CN- + H,O a [X] + OH- (a) O, and CO respectively
[X] + 4n——-+ [Y] + Au (6) O, and Zn dust respectively
Identify the complexes [X] and [Y] (c) HNO, and Zn dust respectively
(d) HNO, and CO respectively (LET. JELE. 2012)
(a) X = [Au(CN),] ; Y = [Zn (CN),]?-
B51. Sulphide ores are common for the metals
(6) X = [Au (CN),]* ; Y = [Zn (CN),]?2-
(a) Ag, Cu and Pb (6) Ag, Cu and Sn
(c) X =[Au(CN),]; Y = [Zn (CN),]*
(c) Ag, Mg and Pb (d) Al, Cu and Pb
(d@) X = [Au (CN), )- -Y¥ =([4n (CN), 1° (LET. 2003)
(J.B. Advance 2013)

Answets
B45. (a) B46. (c) B47, (a) B48. (5) B49, (d) B50. (5) B51. (a)

(c) removal of copper impurity

(d) removal of iron impurity. (LT. 2011)
with more than one correct answers C7. Upon heating with Cu,5, the reagent(s) that give copper
metal is/are
Select the correct answers: (a) CuFes, (6) CuO
Cl. Leaching process can be used for concentration of ores of (c) Cu,O (dq) CuSO, JEE Advance 2014)
(a) aluminium (6) copper (c) gold (d) iron C8. Copper is purified by electrolytic refining of blister copper.
C2. Van Arkel method of refining is used for The correct statement(s) about this process is(are)
(a) zirconium (6) silicon (c) germanium (d) titanium (a) impure Cu strip is used as cathode
C3. Which of the following is/are not example of thermite (6) acidified aqueous CuSO, is used as electrolyte
reaction? (c) pure Cu deposits at cathode
(d@) impurities settleasanode-mud (JHE Advance 2015)
(a) 3Mn,O, + 8Al ——-> 4Al,0, + 9Mn
C9. Extraction of copper from copper pyrites (CuFeS,) involves
(6) Cr,O, + 2Al ——> Al,O, + 2Cr
(a) crushing followed by concentration of the ore by froth-
(c) 2Cu,0 + Cu,8 —-> 6Cu +50, floatation
(dq) 2HgO + Hes —-> 3Hg +50, (6) removal of iron as slag
C4, Which of the following oxide cannot be reduced to metal (c) selfreduction step to produce 'blister copper' following
by carbon ? evolution of SO,
(a) ZnO (6) Al,O; (c) CuO (d) MgO (d) refining of 'blister copper' by carbon reduction.
C5. The metals which cannot be obtained by electrolysis of (JEE Advance 2016)
aqueous solution of their salts are C10. The role of fluorspar, which is added in small quantities
(a) Ag (6) Mg (c) Cu (d) Al in the electrolytic reduction of alumina dissolved in fused
eryolite is
(B.H.U. 2006)
(a) as a catalyst
C6. Extraction of metal from the ore cassiterite involves (6) to make fused mixture conducting
(a) carbon reduction of an oxide ore (c) to lower the melting temperature of the mixture
(6) self-reduction of a sulphide ore (2d) to decrease the rate of oxidation of carbon at anode.
(WB JEE 2017)

Se
Cl.(a,c) C2.(a,d) Céa.(c,d) C4i(a,c) Ch.(6,d) Ch(b,d) C7. (6, c, d) C&é. (5,c,d) C9.(a,6,c) C10. (5, c)
GENERAL PRINCIPLES AND PROCESSES OF ISOLATION OF ELEMENTS

1. Assertion: Oxide and carbonate ores are concentrated by

Assertion Reason Type Questions froth floatation process.
Reason In froth floatation pine oil is used because it
The questions given below consist of an Assertion and preferentially wets the ore particles.
Reason. Use the following key to choose the appropriate answer. 2. Assertion: Gold and platinum occur in native state.
(a) Ifboth assertion and reason are CORRECT and reason Reason Gold and platinum are expensive metals.
is the CORRECT explanation of the assertion. o. Assertion: Aluminothermy is used for the extraction of
(b) If both assertion and reason are CORRECT but, reason Cr from Cr,Q,.
is NOT THE CORRECT explanation of the assertion. Reason Aluminium has a high melting point.
(c) Ifassertion is CORRECT but, reason is INCORRECT. 4, Assertion: Titanium can be purified by Van Arkel process.
(dq) If assertion is INCORRECT but, reason is CORRECT. Reason Titanium form volatile Til, unstable compound
(e) Ifboth assertion and reason are INCORRECT. 5. Assertion: In Mond process, nickel is heated 1n a stream
of CO forming a volatile complex.
Reason This is an electrolytic refining method.

See
1. (d) Z. (c) 3. (bd) A, (a) S. (ec)

1. Match the metal in Column I with the ores in Column II

Matrix Match Type Questions Column I Column II
(A) Aluminium (p) Siderite
Each question contains statements given in two columns, which (B) Zine (q) Malachite
have to be matched. Statements in Column I are labelled as A, (C) Copper (r) Sphalerite
(D) Iron (s) Bauxite
B, C and D whereas statements in Column II are labelled as
p. gq, r and s. Match the entries of Column | with appropriate 2. Match the extraction process in Column I with the metal
in Column II.
entries of Column IJ. Each entry in Column I may have one or
more than one correct option from Column II. The answers to Column I Column IT
these questions have to be appropriately bubbled as illustrated (A) Carbon reduction (p) Gold
(B) Self reduction (q) Copper
in the following example.
(C) Electrolytic reduction (r) Aluminium
If the correct matches are A-g, A-r, B-p, B-s, C-r, C-s and (D) Complex formation (s) Lead
followed by displac-
D-q, then the correctly bubbled matrix will look like the following: ement by metal

3. Match the anionic species given in Column I[ that are

A®) @O® present in the ore(s) given in Column II.

B}/® @O® Column

(A) Carbonate
I Column Il
(p) Siderite
crO@aO® (B) Sulphide
(C) Hydroxide
(qq)
(r)
Malachite
Bauxite
0}@2 @O® (D) Oxide (s) Calamine
(¢) Argentite

(J A.B. Advance 2015)

Auswers
ee Sy (B) —(r) (C) —(q) (D) —(p)
(2) : (A) —(q)(s) (B) —(q) (s) (C) —(r) (D) —(p)
(3) :(A)-(p)(q@)(s)_~—(B) -(@) (C) —(q) (r) (D) -(r)
ase MODERN'S abe + OF CHEMISTRY
-AXIl

4, Amongst the following the metals which can be refined by

Integer Type or Numerical Value Type Questions
vapour phase refining are:
#n, Cu Ti, Ni Co, Al, Zr
Integer Type: The answer to each of the following
question is a single-digit-integer ranging from 0 to 9. Numerical Value Type: Give the correct numerical
1. Amongst the following, total number of metals which occur value (in decimal notation truncated/rounded off to the
in native state in the earth's crust are: Pt, Ni, C, Hg, 5, second decimal place).
Zn, Au, Pb
2. Amongst the following the metals which are roasted to 5. Galena (an ore) is partially oxidized by passing air through
convert them into their corresponding metal oxides are: it at high temperature. After some time the passage of air
“ine blende, iron pyrites, alumina, calamine, copper is stopped, but the heating is continued in a closed furnace
pyrites, galena, pyrolusite, malachite such that the contents undergo self-reduction. The weight
se Amongst the following the oxide ores are: (in kg) of Pb produced per kg of O, consumed is
pyrolusite, haematite, bauxite, zincite, cinnabar, (Atomic weights in g mol! : O = 16, 5 = 32, Pb = 2017)
magnesite, cuprite, azurite, siderite
(JHE Advance 2018)

Answer
1. (2) 2. (4) 3. (5) . (3) 5. 6.47

Exemplar Problems //
Objective Questions
»>» Multiple Choice Questions (Type-l) <a
(c) different components of a mixture are differently
1. In the extraction of chlorine by electrolysis of brine adsorbed on an adosrbent.
(d) vapours of volatile compound can be decomposed in
(a) oxidation of Cl ion to chlorine gas occurs. pure metal.
(6) reduction of Cl ion to chlorine gas occurs. 6. In the extraction of copper from its sulphide ore, the metal
is formed by the reduction of Cu,O with
(c) for overall reaction AG® has negative value.
(a) FeS (6) CO
(d) a displacement reaction takes place.
(c) Cu,S (dq) SO,
. When copper ore is mixed with silica, in a reverberatory
7. Brine is electrolysed by using inert electrodes. The reaction
furnace copper matte is produced. The copper matte contains
at anode is
a 1 _ |
(a) sulphides of copper (II) and iron (II) (a) Cl (ag.) —> ache (g)+e; Fea = 136V
(6) sulphides of copper (II) and iron (IIT)
(c) sulphides of copper (I) and iron (ID) (6) 2H,O (J) —-> O, (g) + 4H* + 4er ; Een - 123 V
(d) sulphides of copper (I) and iron (IIT) (c) Na*(ag.) + e& —> Na(s) ; Bagi —-9.71V
» Which of the following reactions is an example of auto
1
reduction ? (d) H* (aq.) + e°
— —> ails (g);5 Ge
= a) _= 0-00 V

(a) Fe,O, + 4CO —-+ 3Fe + 4CO,

(6) Cu,O + C —-> 2Cu + CO 8. In the metallurgy of aluminium
(c) Cu** (aq) + Fe (s) ——> Cu (s) + Fe** (aq) (a) Al** is oxidised to Al (s).
(6) graphide anode is oxidised to carbon monoxide and
(d) Cu,0 +> Cu,S > 8Cu + SO, carbon dioxide.
.» A number of elements are available in earth’s crust but (c) oxidation state of oxygen changes in the reaction at
most abundant elements are : anode.
(a) Al and Fe (6) Al and Cu (d) oxidation state of oxygen changes in the overall reaction
(c) Fe and Cu (dq) Cu and Ag involved in the process.
. Zone refining is based on the principle that 9, Electrolytic refining is used to purify which of the following
(a) impurities of low boiling metals can be separated by metals?
distillation. (a) Cu and Zn (6) Ge and Si
(6) impurities are more soluble in molten metal than in (c) Zr and Ti (d) Zn and Hg
solid metal.

Arseets
ere, 2. (c) 3. (d) A, (a) 5. (3) 6. (c) me th) 8. (b) 9. (a)
GENERAL PRINCIPLES AND PROCESSES OF ISOLATION OF ELEMENTS

10. Extraction of gold and silver involves leaching the metal 14, At the temperature corresponding to which of the points
with CN- ion. The metal is recovered by in the given figure above. FeO will be reduced to Fe by
(a) displacement of metal by some other metal from the coupling the reaction 2FeO ——> 2Fe + O, with all of the
complex ion. following reactions ?
(6) roasting of metal complex. @) C+O,—+CO, (uz) 2C + O, —> 2CO and
(c) calcination followed by roasting.
(zit) 2CO + O, —> 2CO,
(d) thermal decomposition of metal complex.
(a) Point A (b) Pomt B
Note : Answer the questions 11-13 on the basis of figure given
(c) Point D (d) Point E
below :
15. Which of the following options are correct ?
(a) Cast iron is obtained by remelting pig iron with scrap
iron and coke using hot air blast.
(6) In extraction of silver, silver is extracted as cationic
complex.
(c) Nickel is purified by zone refining.
(d) Zr and Ti are purified by van Arkel method.
16. In the extraction of aluminium by Hall-Heroult process,
—->
mol"
AG/kKJ
0,
of purified Al,O, is mixed with CaF, to
(a) lower the melting point of Al,O,.
(6) increase the conductivity of molten mixture.
(c) reduce Al** into Al(s).
(d) acts as catalyst.
0 400 800 1200 1600 2000 17. Which of the following statements is correct about the role
Temperature (°C) —+
of substances added in the froth floation process ?
11. Choose the correct option of temperature at which carbon
(a) Collectors enhance the non-wettability of the mineral
reduces FeO to iron and produces CO.
particles.
(a2) Below temperature at point A.
(6) Collectors enhance the wettability of gangue particles.
(6) Approximately at the temperature corresponding to
(c) By using depressants in the process two sulphide ores
point A.
can be separated.
(c) Above temperature at point A but below temperature
(d) Froth stabilisers decrease wettability of gangue.
at point D.
18. In the Froth Floatation process, zinc sulphide and lead
(d) Above temperature at point A.
sulphide can be separated by .
12. Below point ‘A’ FeO can
(a) using collectors.
(a) be reduced by carbon monoxide only
(6) adjusting the proportion of oil to water.
(6) be reduced by both carbon monoxide and carbon.
(c) be reduced by carbon only. (c) using depressant.
(d) not be reduced by both carbon and carbon monoxide. (d) using froth stabilisers.
13. For the reduction of FeO at the temperature corresponding 19. Common impurities present in bauxite are
to point D, which of the following statements is correct? (a) CuO (6) ZnO
(a) AG value for the overall reduction reaction with carbon (c) Fe,O, (d) S10,
monoxide is zero. 20. Which of the following ores are concentrated by froth
(6) AG value for the overall reduction reaction with a floatation ?
mixture of 1 mol carbon and 1 mol oxygen 1s positive.
(a) Haematite (6) Galena
(c) AG value for the overall reduction reaction with a
(c) Copper pyrites (d) Magnetite
mixture of 2 mol carbon and 1 mol oxygen will be
positive. 21. Which of the following reactions occur during calcination?
(d) AG value for the overall reduction reaction with carbon (a) CaCO, ——> CaO + CO,
monoxide is negative.
(6) 2FeS, — 20: —— Fe,O, + 450,
Multiple Choice Questions (Type-lll)
(c) MOLLO —> AlL,O, + xH,0
Note: In the following questions two or more options may be
correct. (d) ZnS + =O, —> Zn0 + SO,

Answees
10. (a) ie id) 12. (a) 13. (a) 14, (6), (d) 15. (a),(d) 16. (a), (5) | ae
1S ote) I eiay 2 tote” “Siac!
ase MODERN'S abe + OF CHEMISTRY
-AXIl

22. For the metallurgical process of which of the ores calcined

ore can be reduced by carbon ? Coloured bands Zone refining
(a) haematite (6) calamine Impure metal to volatile Fractional
(c) iron pyrites (d) sphalerite complex distillation
23. The main reactions occurring in blast furnace during Purification of Ge and Si Mond Process
extraction of iron from haematite are Purification of mercury Chromatography
Liquation
(a) Fe,O, + 3CO —-> 2Fe + 3CO,
(6) FeO + S10, —> FeSi0, Code:
(c) Fe,O, + 3C —-> 2Fe + 8CO (a) AQ) B(2)C(4 D6), ©) A(4)B(3) C (1) D (2)
(dq) CaO + S10, ——> CaSi0, (c) AG) B(MCMDGA) dW Ab) B(4) C3) D (2)
29. Match items of Column I with the items of ColumnII and
24, In which of the following method of purification, metal is assign the correct code :
converted to its volatile compound which is decomposed
to give pure metal ?
(a) heating with stream of carbon monoxide. (A) Cyanide process Ultrapure Ge
(6) heating with 1odine. (B) Froth Floatation Process Dressing of ZnS
(c) liquation. (C) Electrolytic reduction Extraction of Al
(D) Zone refining Extraction of Au
(d) distillation. Purification of Ni
25. Which of the following statements are correct ?
Code:
(a) A depressant prevents certain type of particle to come
(a) A(4)B(2)C(@3) DQM) (©) Al) B(3)C(0)D()
to the froth.
(c) A(I)B(2)C(@3)D(4) (dd) ACS) B(4)C (6) D1)
(6) Copper matte contains Cu,S and Zns.
oO. Match the items of Column I with the items of Column II
(c) The solidified copper obtained from reverberatory and assign the correct code :
furnace has blistered appearance due to evolution of
SO, during the extraction.
(d) Zine can be extracted by self-reduction. (A) Sapphire (1) Al,O,
26. In the extraction of chlorine from brine (B) Sphalerite (2) NaCN
(a) AG® for the overall reaction is negative. (C) Depressant (3) Co
(d) AG® for the overall reaction is positive. (D) Corundum (4) ZnS
(c) E® for overall reaction has negative value. (5) Fe,0,
(d) E® for overall reaction has positive value.
Code:

»> Matching Type Questions

<@ (a) A(8) B (4) C (2) DQ)
(6) A(6) B (4) C (3) D (®)
Note: Match the items given in Column I and ColumnII in (c) A (2) B (8) C (4) D (&)
the following questions. (d) A(1) B (2) C (3) D (4)
27. Match the items of Column I with items of Column II and ol. Match the items of Column I with items of ColumnII and
assign the correct code: assign the correct code :

(A) Blsterred Cu (1) Aluminium

(A) Pendulum (1) Chrome steel
(B) Blast furnace (2) 2Cu,O0 + Cu,S — 6Cu +
(B) Malachite (2) Nickel steel
(C) Calamine (3) Na, AIF, 50 2

(D) Cryolite (4) CuCO,-Cu (OH), (C) Reverberatory furnace (3) Iron
(6) ZnCO, (D) Hall-Heroult process (4) FeO + 510, — FeSi0,
(6) 2Cu,5 +30, - 2Cu,0
Code:
+ 250
(a) A(1)B(2)C (38) D(4) (6) A(2)B(4) C (6) D3) 2

(c) A(2)B(38)C(4)D(6) (d) A(4) B(6)C(3) DQ) Code:

28. Match the items of Column I with the items of Column II
(a) A(2)B(3) C (4) D (1)
and assign the correct code :
(6) A(1) B (2) C (8) D (6)
(c) A(B)B(4)C (3) DQ)
(d) A (4) B (6) C (3) D (2)
Arswets
22.(a), (0) 23. (a),(d) 24. (a),(b) 25. (a), (e) 26. (5), (c) 27. (5) 28.(6) 29. (d) 30. (a) 31 (a)
GENERAL PRINCIPLES AND PROCESSES OF ISOLATION OF ELEMENTS 6/59 =

<@ 3c. Assertion : Zirconium can be purificed by Van Arkel

method.
Note : In the following questions a statement of assertion Reason : ZrI, is volatile and decomposes at 1800 K.
followed by a statement of PEGSOT 15 2 SUE. Choose the 34. Assertion : Sulphide ores are concentrated by Froth
correct answer out of the following choices. Wicteoneamethord
(a) Both assertion and reason are true and reason is the
correct explanation of assertion. Reason : Cresols stabilise the froth in Froth Flotation

(6) Both assertion and reason are true but reason is not rmptiind.
the correct explanation of assertion. 35. Assertion : Zone refining methodis very useful for producing
(c) Assertion is true but reason is false. Rermeernue thee .
(d) Assertion is false but reason is true. Reason : Semiconductors are of high purity.
(e) Assertion and reason both are wrong. 36. Assertion : Hydrometallurgy involves dissolving the ore
in a suitable reagent followed by precipitation by a more
32. Assertion : Nickel can be purified by Mond process. electropositive metal.
Reason: Ni(CO), is a volatile compound which decomposes Reason : Copper is extracted by hydrometallurgy.
at 460 K to give pure N1.

Arswets
32. (a) 33. (a) 34, (5) 35. (5) 36. (0b)

ations for |
Hints & Explan Difficult Objective Type Questions
B. meq from Competitive Examinations or Pb** is more stable than Pb®
AG® > 0 1.e. non-spontaneous
B4, (5): Steel is an alloy of carbon (non-metal) and iron
or Sn*+——>3 Sn**
(metal).
So that Sn** is more stable than Sn“.
B6. (d): Magnetite is Fe,QO,.
B7. (d): Roasting of sulphides gives SO,,. B23. (c) : This represents Van Arkel method.
B8. (a): Itis an example of autoreduction : B24. (6b) : In Hall-Heroult process for the extraction of
Cu, Sy 2Cu,O —s 6Cy + SO, aluminium, electrolyte is Al,O, dissolved in
B9. (6): Metal nitrates are usually not found as nitrates in Na, AIF, containing a —_ — of CaF.
their ores because these are highly soluble. B35. (a) : The roasted copper pyrites contain Cu,5 and FeO
B10. (c) : (a) Cyanide process—extraction of Au (iv) and some unreacted FeS. On smelting, the roasted
—
copper pyrites with sand give fusible ferrous silicate
(6) Froth floatation process—dressing of sulphide
ores, ZnS (ii) slag, FeS10, and Cu,5 as matte.
(c) Electrolytic reduction—extraction of Al (iz) FeO + 510, —~> _ FeSi0,
Silica Ferrous silicate
(d) Zone refining—ultrapure Ge (z) (slag)
Bll. (c) : Zine being more reactive than Au and Ag, displaces B43. (d) - Baeyer’s process, Hall’s process and Serpeck’s
them from their solutions. It is Mac Arthur or |
process are used for the extraction of aluminium.
cyanide process.
The aluminium obtained is then purified by Hoope’s
B13. (d): Ores of gold and silver are concentrated by chemical
electrolytic refining method.
leaching method. B b C acentachonid d
B15. (d): Conversion of carbonate into its oxide by heating 44, (6) : Ce eee
in the absence ofair is called calcination. B46. (c) : Aluminium is isolated from bauxite ore which is

B16. (a): Magnetite(Fe,O,), iron pyrites (FeS,), copper glance onan ecaguuaaial by impurities such as ferric
(Cu,), sphalerite (sulphide of Zn and Fe), galena eee TERE EE a .
(PbS). B49. (d): In haematite (Fe,O,) oxidation number of Fe is

B20. (c) : Agand Au donot react with CuSO, and H,SO, solution. 2x+3x(—2)=0-.x=3
B21. (2): Cu,S + 2Cu,O ——> 6Cu + SO, Magnetite (FeO y, is an equimolar mixture of FeO
and Fe,Q,.
fae
.
le
o ; A+ B+
Oxidation number of
iron
inFeO is 2 andinFe,O, is 3.
eco
B50. (5) : Silver ore is oxidised by using oxygen from air :
MODERN'S abe + OF CHEMISTRY-AXIl

w — 1000x207 _ g468.75¢
4Ag + 8NaCN + 2H,0 + O,(air) —> 32
ANalAg(CN),] + 4NaQH
or - 6.47kg
In this, Ag(0) is oxidised to Ag(+1).
Silver is precipitated from the solution by addition
of zinc powder. NCERT Exemplar Problems : MCQs Type-I
2Na[Ag(CN),] + Zn —-> Na,[Zn(CN),] + 2Ag
(c) : Matte consists of cuprous sulphide and some traces
Silver gets reduced from Ag(+1) to Ag(0).
2.

of ferrous sulphide.
B5l. (a) : Sulphide ores of Ag (Ag,S : silver glance), copper (6) : Zone refining method is based on the principle that
(CuFeS, : copper pyrites) and lead (PbS : galena). impurities are more soluble in molten metal than
in the solid state of the metal.
C.mcq with more than one correct answer (c) : 2Cu,O0 + Cu,5 > 6Cu + 5O,

C7. (0, c,d): CuFeS, + Cu,S —4_, No reaction (a) : At anode : Cl'(ag) > : Cl, (g) + e7

2CuO —4—> Cu,0 + = O, (6) : C(s) + O* (melt) — CO(g) + 2e-

2
: C(s) + 207 (melt) + CO,(g) + 4e7
2 Cu,O + Cu,S ——> 6Cu + SO, (a) : Cu and Zn are purified by electrolytic refining.
11. (d) : Above point A, A.G° (CO, CQ,) 1s always much lower
Cu,SO, ———> CuO + SO, + 50:
than A,G° (Fe, FeO) and therefore, above point A,
Both Cu,O and CuO on heating with Cu,5 give Cu. carbon reduces FeO to Fe forming CO.
C8. (6, c, d): Impure copper is made anode and a thin sheet of 12. (a) : Below point A, A,G° (CO, CO,) is always more
pure metal is made cathode. So, statement (q@) is incorrect negative than A,G° (Fe, FeO) and therefore, below
and (5, c, d) are correct.
point A, FeO will be reduced by CO only.
13. (a) : A-G° curve for the formation of FeO from Fe and that
Matrix Match Type Questions
of CO, from CO intersect at point D and therefore
oe (A) — (p), (q), (s) : Carbonate ores are A_G* for the overall reduction of FeO with CO 1s zero.
(p) Siderite : FeCO,
NCERT Exemplar Problems : MCQs Type-IT
(q) Malachite : CuCO,.Cu(OH),
(s) Calamine : ZnCO,
16. (a, b): CaF, mixed with purified Al,O, helps in lowering
(B) — (¢) : Sulphide ore is argentite : Ag,S the melting point of Al,O, and increases the conductivity
(C) — (q), (7) : Hydroxide ion 1s present of the molten mixture.
(q) Malachite : CuCO,.Cu(OH), 17. (a, c): Collectors such as pine oil, eucalyptus oil, etc.
(r) Bauxite : AIO(OH),4. increase the non-wettability of the mineral particles.
(where 0 <x < 1) Depressants are used to separate the two sulphide ores.
(D) — (r) : Oxide ore is bauxite, Al,Os. 18. (6, c): Zine sulphide and lead sulphide can be separated
by adjusting the proportion of oil to water and using
Integer Type or Numerical Value Type Questions depressant.
20. (6, c): Sulphide ores (galena, PbS and copper pyrites,
(2) : Pt, Au CuFes,).
(4) : Zine blende, iron pyrites, copper pyrites, galena 22. (a, 6): The oxides of metals can be reduced by carbon.
(3) : Ti, Ni, Zr
a(6.47): 2PbS + 830, ——> 2PbO + 250,
24, (a,b): Ni +4CO SS Ni(CO), 82". Ni + 4CO
Impure Pure
PbS + 2PbhO “——>°SPb + SO,,
Ti + 21, (g) 2" > Til, (¢) —™ > Ti + AL @®
Or 3Pb5+30, —-> 38Pb+ 350, Pure
Or PbS + O, — Pb+580, 26. (6, c) In the extraction of elements by electrolysis, AG°
Moles of O, consumed = Moles of Pb produced of the overall reaction is +ve while E° of the overall cell
reaction is —ve.
1000 _ w
ONO
92 207
GENERAL PRINCIPLES AND PROCESSES OF ISOLATION OF ELEMENTS

~ Unit Practice Test

(Surface Chemistry and General Principles and Processes of Isolation of Elements)

Time allowed : 2 Hrs. Maximum Marks : 85

Why is pine oil used in froth floatation method? (1)

Which is a better reducing agent at 983 K; carbon or carbon monoxide ? (1)
Define aluminothermy. (1)
How is adsorption of a gas related to its critical temperature ? (1)
What causes Brownian movement in a colloidal solution. (1)
What is Tyndall effect? Why do colloidal solutions show Tyndall effect? (2)
What are enzyme catalysts? Give two examples of enzyme catalysis reactions. (2)
>
eS
PP
FU Compare lyophilic and lyophobic sols 1n terms of
(t) Stability (12) Reversibility (2)
Giving examples differentiate between calcination and roasting. (2)
10. Explain the role of silica in the metallurgy of copper. (2)
11. Describe the role of the following:
(a) Iodine in the refining of titanium
(6) NaCN in the extraction of silver from a silver ore
(c) Cryolite in the metallurgy of aluminium (3)
12. Describe the underlying principle of each of the following metal refining methods:
(tz) Electrolytic refining
(it) Vapour phase refining
(zit) Zone refining (3)
135. Explain what is observed when
(z) an electric current is passed through a sol
(it) a beam of light is passed through a sol
(zz) an electrolyte (say NaCl) is added to ferric hydroxide sol. (3)
14, Define each of the following terms:
(1) Micelles
(it) Peptization
(zt) Electophoresis (3)
15. Explain how the phenomenon of adsorption find application in each of the following processes :
(t) Production of vacuum
(it) Heterogeneous catalysis
(zzz) Froth floatation process (3)
16. (a) What is Freundlich adsorption isotherm equation? What form will it take at high pressure and low pressure?
(6) Explain Hardy Schulze rule.
(c) What are emulsions? How are these classified? (5)

» To check your performance, see HINTS AND SOLUTIONS TO SOME QUESTIONS at the end of
Part I of the book.
 Building on..... Assessing..... Preparing, for Competition.....
@ Understanding Text 1 @ Quick Memory Test with @ Additional Useful Information 140
@ Conceptual Questions 44, 82,118 Answers 130 | @ Topicwise MCQs 142
@ HOTS & Advanced Level @ Competitive Examination Qs
CHAPTER SUMMARY & QUICK Questions with Answers 131 > AIPMT & Other State Boards’
Seer cater ee teas al 120 REVISION EXERCISES Medical Entrance 144
NCERT FILE (with Previous Years’ CBSE Qs > JEE (Main) & Other State
@ In-text Qs & Exercises with & Other State Boards Qs) 133 Boards’ Engineering Entrance 146
Solutions 123. @ Hints & Answers for Revision => JEE (Advance) for ITT Entrance
¢ NCERT Exemplar Problems with oo al te
Answers & Solutions (Subjective) 128 . NCERT Exemplar Problems
(Objective Questions) 153
UNIT , @ Hints & Explanations for
PRACTICH Ss oe Difficult Questions 156

a J the long form of the periodic table, the elements have been classified
into four blocks : s, p, d and f depending upon the subshell in which the
\ last electron enters. The elements in which the last electron enters the
i The cen of their outermost energy shell are called p-block elements.
Ne _ The elements belonging to groups 13 to 18 constitute p-block elements
and have the general configuration ns*np’*. The properties of the
\ p-block elements, like that of other elements, are greatly influenced
‘¢ © eo by variation in their atomic sizes, ionisation enthalpy, electron
| Ar) gain enthalpy and electronegativity. They follow the systematic
| | gradation in both periods and groups.
. © | Like other elements, the elements of second row also show a
number of differences in properties from the other members of
\ / their families because of the absence of d-orbitals. The importance
| / of p-block lies in the fact that it includes all the three types of
elements; metals, non-metals and metalloids which results in
interesting diversification in chemistry of elements of this block. We
Pa have already discussed the chemistry of groups 13 and 14 of p-block
elements in the previous class. In the present unit we will learn about
it, * the elements of group 15-18 of p-block.

GROUP 15 ELEMENTS.
It contains five elements namely nitrogen (N), phosphorus (P), arsenic (As), antimony (Sb) and bismuth (Bi). This
group is regarded as nitrogen family. Collectively, the group 15 elements are also called pnicogens and their
compounds as pniconides. The name is derived from the Greek word pnicomigs meaning suffocation.
OCCURRENCE
The elements of group 15, except phosphorus do not occur very abundantly in nature. Though molecular nitrogen
comprises about 78% by volume of the earth’s atmosphere, it is not very abundant in the earth’s crust. It is only
 MODERN'S abc + OF CHEMISTRY-XIl

thirty third most abundant element by weight in the earth's crust. Since
nitrates are very soluble in water so these are not widespread in the earth’s
crust. The only major nitrate minerals are NaNO, (sodanitre, Chile saitpetre)
and KNO, (nitre, Indian saltpetre). The major deposits of salt petre (KNO,)
occur in India. Nitrogen is also an important constituent of proteins, amino
acids and nucleic acids in plants and animals. The continuous interchange
of nitrogen between the atmosphere and biosphere is called nitrogen cycle.
Phosphorus is the eleventh element in order of abundance in
crustal rocks of the earth. It is very reactive element and therefore
it does not occur in free state in nature. All its known minerals are
orthophosphates. Major amounts of phosphorus occur in a single mineral
family known as apatites, which have the general formula, 3Ca,(PO,),
CaX, or Ca,(PO,),.CaX, or Ca,,(PO,),.X, where X = F, Cl or OH.
The common minerals of phosphorus are:
GROUP 15 (t) Phosphorite > Caf@o,),
N
(it) Fluorapatite : Caceonel or 8Ca,(PO,),.CaF,
—
(111) Chlorapatite : Ley £1 or 8Ca,(PO,),.CaCl,
phon (iv) Hydroxyapatite : Ca(PO,),0H or 38Ca,(PO,),.Ca(OH),

Large deposits of phosphate rocks are located in North Africa and North
America. In India, the phosphate rocks are mainly found in Rajasthan.

Phosphorus is essential for life, as a structural material in both animals

and plants. It is present in bones as well as in living cells. About 60% bones and
teeth are Ca,(PO,), or [3{Ca,(PO,).}.CaF,]. It also occurs in nucleic acids (DNA
and RNA) which control the hereditary effects in human beings. Phosphorus is
also found in ATP (adenosine triphosphate) and ADP (adenosine diphosphate)
which are of vital importance for production of energy in the cells. Phospho
proteins are present 1n eggs and milk.

The elements arsenic, antimony and bismuth are not very abundant.
Their important sources are sulphides occurring as traces in other ores e.g.,
arsenopyrites, FeAss; stibnite, Sb,S., bismuth glance, Bi,S,. These are obtained
as metallurgical by-products from roasting sulphide ores.

GENERAL CHARACTERISTICS OF GROUP 15 ELEMENTS

A. Electronic Configurations
The atoms of group 15 have five electrons in the outermost shell, two in
s and three in p subshell. The general electronic configuration of this group
may be expressed as ns2np*.
Table 1. Electronic configuration of group 15 elements.

Electronic
configuration

Nitrogen [He] 2872p?

Phosphorus 3 [Ne] 3573p?
Arsenic : [Ar] 3d1°4524p3

Antimony | [Kr] 4d?° 5s? 5p*

Bismuth : [Xe] 4/14 5d?" Gs? 6p?
p-BLOCK ELEMENTS

B. Atomic and Physical Properties

The important atomic and physical properties of group 15 elements are
given in Table 2

Table 2. Some important atomic and physical properties of group 15 elements.

Atomic number 15 33 51
Atomic mass (g mol"*) 30.97 74.92 121.75
Atomic radius covalent (pm) | 110 121 141
Ionic radius (pm) | 212 222 76
Leet (As?) (Sb?*)
Ionisation enthalpy 1012 947 834
(kJ mol) : 19038 1798 1595
2910 2736 2443
Electronegativity 3.0 21 2.0 1.9
m.p. (K) ol7.1 1089 904
(Molecular) (White P) (Grey o-form at 38.6 atm)
b.p. (K) hes 603.5 885 1860
(Molecular) (White P) (Sublimation temp.)
Density (g cm-?) at 298 K 0.879 1.823 5.778 6.697
(at 63 K) (Grey o-form)

The important trends of atomic and physical properties are discussed below: Aone a re ee
1. Atomie and ionic radii. The atomic and ionic radii of group 15 elements radius (pm) (pm)
are smaller than the atomic radii of the corresponding group 14 elements.
On going down the group, the atomic radii increase with increase in atomic number.
Explanation. The nuclear charge in case of elements of group 15 is larger
than in the case of elements of group 14. Due to increased nuclear charge, the
electrons are strongly attracted by the nucleus and therefore, atomic radii decrease.
Thus, the atomic radii of elements of group 15 are less than those of group 14.
On moving down the group, the atomic radii increase due to increase in
number of shells because of addition of a new principal shell in each succeeding
element. However, from As to Bi, only a small increase in covalent radius is
observed. This is due to the presence of completely filled d — and or f-orbitals
in the heavier members.
2. Ionisation enthalpies. The first ionisation enthalpies of the group
15 elements are higher than the corresponding members of the group 14 elements.
On going down the group, the ionisation enthalpies decrease. (kJ =
Explanation. The larger ionisation enthalpy is due to greater nuclear
charge, small size and stable configuration of the atoms of group 15 elements. i
The electronic configuration of atoms of group 15 are half filled, 3 np.7,
ia np.? ;
np," and are stable. Therefore, they have high ionisation enthalpies
eaa~o /. | -
The decrease 1n lonisation enthalpy, as we move down the group, is due
oe
to Increase in atomic size and screening effect which overweigh the effect of =
increased nuclear charge. 2736
As expected, the successive ionisation enthalpies of these elements (Table 2)
increase in the order :
AH, < AH, < AH,
3. Electronegativity. The electronegativity values of elements of group coe
15 are higher than the corresponding elements of group 14. On going down
the group, the electronegativity value decreases.
Explanation. The elements of group 15 have smaller size and greater
nuclear charge of atoms and therefore, they have higher electronegativity values.
 MODERN'S abc + OF CHEMISTRY-XIl

The decrease in electronegativity on going down the group is due to increase

Electronegativity in size of the atoms and shielding effect of inner electron shells on going down
the group. However, amongst the heavier elements, the difference is not that
much pronounced.
3.0 4. Metallic character. The elements of group 15 are less metallic.
However, on going down the group, the metallic character increases from N
2.1 to Bi. For example, N and P are non-metallic, As and Sb are partly non-metallic
while Bi is a metal.
2.0 N P As Sb Bi
—— S

Sb Non-metals Metalloids
1.9
Metallic character increases
Bi Explanation. Due to increased nuclear charge and higher electronegativity,
1.9 the elements of group 15 are less metallic than the corresponding elements of
group 14. On moving down the group, the atomic size as well as the screening
REMEMBER effect of the intervening electrons increases. As a result, the ionization enthalpy
@® Among group 15 elements, decreases and therefore, metallic character increases down the group.
bismuth is a metal. 5. Melting and boiling points. The melting points of group 15 elements
N and P are non-conductors of jirst increase from nitrogen to arsenic and then decrease to antimony and
heat and electricity. bismuth. However, the boiling points increase regularly on going from nitrogen
As 1s poor conductor. to bismuth.
Sb is good conductor whereas Bi Explanation. The melting points increase down the group due to increase
1s very good conductor of heat and in atomic size. However, the unexpected decrease in the melting points of Sb
electricity. and Bi is because of their tendency to form three covalent bonds instead of five
covalent bonds, due to inert pair effect. As a result, the attraction among
their atoms is weak and hence their melting points are low. Because of large
size of atoms, Bi has still weaker interatomic forces than Sb and therefore,
has still lower melting point.
The boiling points increase down the group from N to Bi because of increase
in their atomic size.
6. Catenation. The elements of group 15 also show a tendency to form
bonds with itself (self linking of atoms) known as catenation. All these elements
REMEMBER
show this property but to a much smaller extent than carbon. For example,
e The element having maximum hydrazine (H,NNH,) has two N atoms bonded together, hydrazoic acid (NH)
tendency for catenation in the
has three N-atoms, azide ion, N, has also three N atoms bonded together
periodic table is carbon.
Among the elements of group 15,
Hydrazoic acid, HN, : H_-N=N=N>
P has maximum tendency for
Azide ion, N, tN = N= NO
catenation.
Among the elements of group 15, phosphorus has the maximum
tendency for catenation forming cyclic as well as open chain
compounds consisting of many phosphorus atoms.
Diphosphine (P,H,) has two phosphorus atoms bonded together.
The lesser tendency of elements of group 15 to show catenation in comparison
to carbon is their low (M—M) bond dissociation enthalpies.

Bond C—C N—N P—P As—As

Bond energy 353.3 163.8 201.6 147.4
(kJ mol)

7. Allotropy. Except nitrogen and bismuth, all other elements of this

group show allotropy. For example,
phosphorus exists as white, black or red phosphorus
arsenic exists as yellow or grey arsenic
antimony exists as yellow or silvery grey allotropic forms.
C. Oxidation States
The elements of group 15 have five electrons in their valence shell.
p-BLOCK ELEMENTS

They exhibit various oxidation states from —3 to +5 as discussed below :

(1) Negative oxidation states. These elements have five electrons in the
valence shell (ns*np?) and therefore, require three more electrons to acquire
the nearest noble gas configuration. But, the gain of three electrons is not
energetically favourable because it requires very large amount of energy to
gain three electrons and form M* ions. However, nitrogen being the smallest
and most electronegative element of the group forms N* (nitride) ion and
shows an oxidation state of — 3 in nitrides of some highly electropositive metals
such as Mg,N,, Ca,N,, etc. The other elements of this group form covalent
compounds even with metals and show an oxidation state of -3 with metals. For
example, calcium phosphide (Ca,P,), sodium arsenide (Na,As), zinc antimonide
(Zn,Sb,), magnesium bismuthide (Mg,Bi,). As is evident from the decreasing
electronegativities and decreasing ionisation enthalpies, the tendency of
the elements to exhibit -3 oxidation state decreases on moving down
from P to Bi due to increase in size and metallic character. In fact, the last
member of the group, Bi hardly forms any compound in —3 oxidation state.
In addition to —3 oxidation state, N and P show oxidation states of —2 in
hydrazine (NH,NH,) and diphosphine (P,H,) respectively. Nitrogen also shows
an oxidation state of -1 in hydroxyl amine (NH,OH) but P does not.
(11) Positive oxidation states. All the elements of group 15 also exhibit In the last element of a group,
positive oxidation states of +3 and +5. However, on moving down the group, after the removal of electrons from
the stability of +5 oxidation state decreases while that of +3 oxidation p-orbitals, the remaining ns? (e.g. 6s")
state increases due to inert pair effect. electrons behave like stable noble
Because of energy considerations, these elements cannot lose all the five gas and donot take part in compound
valence electrons. Therefore, they do not form M** ions and all the compounds formation. This reluctance of the
of group 15 elements having +5 oxidation state (i.e., PF., PCl,, SbF., BiF., s-electron pair to take part in chemical
etc.) are essentially covalent compounds. combination 1s called inert pair effect.
Nitrogen does not form compounds in +5 oxidation state such as
NF-., NC1., etc., because it does not have vacant d-orbitals in its valence shell
which can enable it to extend its octet. The stability of the highest oxidation
state (+5) decreases down the group. For example, the +5 oxidation state of
REMEMBER
Bi is less stable than that of Sb. This is due to inert pair effect. The only well
characterised Bi(V) compound is BiF,. NCI, and NF, donot exist.
The elements of group 15 form both covalent (e.g., NCl,, PCl, AsCl,, Nitrogen does not form compounds
SbCl.) and ionic compounds (e.g., BiF,, SbF,, etc.) in +3 oxidation state. The in +5 oxidation state such as NCl,,
+3 oxidation state becomes more and more stable on moving down the group. NF. , etc. because of the absence of
Nitrogen and phosphorus also show oxidation state of +4 because of the d-orbitals in its valence shell.
ability of one lone pair on NH, and PH, to form dative bonds with Lewis
acids. However, nitrogen can exist in various oxidation states from —3 to +5
in its hydrides, oxides and oxoacids as shown below :
Compound NH, NL, NH,OH N, N,O NO N,O, N, O, N,O,
Ammonia Hydrazine Hydroxyl Nitrogen Nitrous Nitric Nitrogen Nitrogen Nitrogen
amine oxide oxide trioxide tetraoxide pentaoxide
Oxidation state -3 —2 —1 0 +1 +2 +3 +4 +5

Phosphorus also exhibits +1 and +4 oxidation states in some oxoacids.

(iit) Disproportionation : In case of nitrogen, all oxidation states from
+1 to +4 tend to disproportionate in acid solution. For example,
+3 +6 +)

Nitrous acid Nitric acid Nitric oxide

Similarly, in case of P nearly all the intermediate oxidation states
disproportionate into +5 and —3 both in acid and alkali solutions. For example,
+3 +5 -d
4H,PO, ————> 3H,PO, + PH,
Phosphorous Phosphoric Phosphine
acid acid
However, +3 oxidation state in As, Sb and Bi becomes increasingly stable
with respect to disproportionation because of inert pair effect. Therefore, their
tendency to undergo disproportionation decreases.
 MODERN'S abc + OF CHEMISTRY-XIl

(iv) Maximum covalency : The maximum covalency of nitrogen is

restricted to four because it does not have vacant d-orbitals in its outermost
valence shell (n = 2). Therefore, only four (one 2s and three 2p) orbitals are
available for bonding and it cannot extend its valency beyond four (e.g., (NH,,*,
CH,),N*, etc.). That is the reason why nitrogen does not form pentahalides such as
NF, or NCl.. On the other hand, phosphorus and all other elements have vacant
d-orbitals in their valence shells and can use all their valence orbitals to
exhibit covalency of five or six e.g., PF, PCl,, AsF., PF, [SbF], ete.
CHEMICAL PROPERTIES AND TRENDS IN CHEMICAL REACTIVITY
Like first member of other groups, nitrogen differs from rest of members
of the group due to its (1) smaller size, (ii) high electronegativity, (iii) high
ionisation enthalpy and (iv) non-availability of d-orbitals in the valence shell.
Nitrogen has unique tendency to form pzi-pr multiple bonds
with itself and with other elements having small size and high
electronegativity (e.g., C and O). However, the heavier elements of this
group do not form pr—pn bonds because their atomic orbitals are so large and
diffused that they cannot have effective overlapping. These differences between
nitrogen and other members of the group result into anomalous properties
of nitrogen as explained below :
e Nitrogen is a colourless gas and exists as a diatomic molecule. The two
nitrogen atoms are held together by a triple bond (one o and two 7) between
two atoms and have very high bond enthalpy (941.4 kJ mol").
>-N i: N: or > N==N:
Nitrogen molecule is inert and Due to the presence of triple bond, which has very high bond
has very low reactivity because it enthalpy, the nitrogen molecule is inert and has very low reactivity.
has triple bond and therefore, has However, the tendency to form multiple bonds (pm—p7) is limited only to nitrogen.
very high bond enthalpy (941.4 kJ On the other hand, phosphorus, arsenic and antimony exist in various forms
mol‘), containing single bonds as P—P, As—As and Sb—Sb. For example, phosphorus
exists as tetrahedral P, molecules as shown in Fig. 1. In this case, four P atoms
he at the corners of a regular tetrahedron. Each P is bonded to three P atoms
by single P—P bonds. However, the single N—N bond is weaker than the single
P—P bond because of high interelectronic repulsions of non bonding electrons due
to small bond length (109 pm). As a result, the catenation tendency is weaker in
nitrogen. Therefore, nitrogen exists as gas while phosphorus exists as solid.
@ Since P—P single bond is much weaker than N==N triple bond, therefore,
phosphorus is much more reactive than nitrogen. For example, white phosphorus
is more reactive than nitrogen. It catches fire when exposed to air and burns
to form the oxide, P,O,,. It is stored under water to prevent it from burning.
Red P is stable in air at room temperature but reacts on heating.
The reactivity of other elements decreases from As to Bi. Arsenic and
antimony both occur in two forms. The most reactive is yellow form which
contains M, tetrahedral units and resembles white phosphorus. Arsenic is
stable in dry air but tarnishes in moist air giving first a bronze and then a
black coating on its surface.
Antimony is less reactive and is stable towards water and air at room
Fig. 1. Structure of P, molecule. temperature. On heating in air, it forms Sb,O,, Sb,O, or Sb,O,,. Bismuth forms
Bi,0, on heating.

Another factor which affects the chemistry of nitrogen is the absence

of d-orbitals in its valence shell. Nitrogen cannot form pr—dx bonds
whereas phosphorus and other heavier members of this group readily
form pi—dr multiple bonds. For example, phosphorus forms compounds
containing pt—dr bonds such as R,P = O, R,P = CH, (R = alkyl group),
POX, (X=F, Cl, Br), etc. Phosphorus and arsenic can also form dt—dn bonds
with transition metals where their compounds like P(C,H.), and As(C,H-),
act as ligands. Recently, a few stable compounds of P, As and Sb containing
pit—pt bonds (e.g., P=C, P= N, P=P, As=As, etc.) have been synthesized.
p-BLOCK ELEMENTS

Let us discuss some trends in chemical reactivity of group 15 elements

and their compounds.
1. Reactivity towards hydrogen (formation of hydrides)
All the elements of group 15 form gaseous trihydrides of the formula EH,
(where E = N, P, As, Sb or Bi) such as : Nitrogen forms a special hydride:
NH, FH. AsH, SbH, BiH, HN, : hydrogen azide
Ammonia Phosphine Arsine Stibine Bismuthine or hydrazoic acid
The lighter elements also form hydrides of the formula M,H, such as N,H,
(hydrazine), P,H, (diphosphine) and As,H, (diarsine). Nitrogen also forms a
special hydride of the formula HN,, known as hydrogen azide or hydrazoic acid.
Preparation. (4) By hydrolysis of binary metal compounds. The
trihydrides can be easily obtained by the hydrolysis of their binary metal
compounds with water or dilute acids :
Mg.N, + 6H,O——> 3Mg(OH), + 2NH,
Magnesium nitride Ammonia
Ca,N, + 6H,O0 ———> 3Ca(OH), + 2NH,
Calcium nitride
Ca,P, + 6H,O ———> 3Ca(OH), + 2PH,
Calcium phosphide Phosphine
Zn,As, + 6HCl ———+ 3ZnCl,
+ 2AsH,
Zine arsenide Arsine
Mg,Bi, + 6HCl ——-> 3MgCl, + 2BiH,
Magnesium bismuthide Bismuthine
(77) By reduction of trichlorides. The trichlorides of these elements
except that of bismuth give the corresponding hydrides on reduction with Zn/
acid or LiAlH,.
ECl, + 3LiAIH, ——> EH, + 3LiCl + 3AlH, (E = N, P, As, Sb)
Structure. All thesehydrides are covalent in nature and have Lone pair
pyramidal structure. These involve sp? hybridization of the central atom
and one of the tetrahedral position is occupied by a lone pair. The structure /N
of NH, molecule is shown in Fig. 2. Due to the presence of lone pair, the fo
bond angle in NH, is less than the normal tetrahedral angle. It has
been found to be 107.8°. As we go down the group the bond angle H H
decreases as:
Fig. 2. Shape of NH, molecule.
NH, ele le AsH, SsbH, Bil,
107.8° 93.6° 91.8° Of 3° 90°
Explanation. In all these hydrides, the central atom is
surrounded by four electron pairs, three bond pairs and one
lone pair. Now, as we move down the group from N to Bi, the
size of the atom goes on increasing and its electronegativity
decreases. Consequently, the position of bond pair shifts more
and more away from the central atom in moving from NH,
to BiH,. For example, the bond pair in NH, is close to N in
N—H bond than the bond pair in P—H bond in PH.,. As a result,
the force of repulsion between the bonded pair of electrons in
NH, is more than in PH,. In general, the force of repulsion More repulsion Less repulsion
between bonded pairs of electrons decreases as we move from (bond angle is large) (bond angle is less.)
NH, to BiH, and therefore, the bond angle also decreases in Fig. 3. Repulsions between electron pairs in NH,
the same order. and PH,.
Characteristics of hydrides. The important characteristics
of these hydrides are :
(4) Basic strength. All these hydrides have one lone pair of electrons on
their central atom. Therefore, they act as Lewis bases. They can donate an
electron pair to electron deficient species (Lewis acids). As we go down the
group, the basic character of these hydrides decreases. For example,
NH, is distinctly basic; PH, is weakly basic; AsH,, SbH, and BiH, are very
weakly basic.
 MODERN'S abc + OF CHEMISTRY-XIl

Explanation. Nitrogen atom has the smallest size among the hydrides.
Therefore, the lone pair is concentrated on a small region and electron
density on it is the maximum. Consequently, its electron releasing tendency
is Maximum. As the size of the central atom increases down the family, the
electron density also decreases. As a result, the electron donor capacity or the
basic strength decreases down the group.
(iz) Thermal stability. Thermal stability of the hydrides of group 15
Hydrides of Group 15
elements decreases as we go down the group. Therefore, NH, is most stable
NH, $ $ 3 and BiH, is least stable. The stability of the hydrides of group 15 elements
o
decreases in the order :
PH, | 8 o S
ASH
3
g] |8] |;
EE
a
=
—
2
|
NH, > PH, > AsH, > SbH, > BiH,
Explanation. This is due to the fact that on going down the group, the
size of the central atom increases and therefore, its tendency to form stable
5 ‘Oo ©
| cc a ow
SbH, | 74 5 covalent bond with small hydrogen atom decreases. As a result the M—H bond
= e = strength decreases and therefore thermal stability decreases.
BiH, |@ 5 s (711) Reducing character. The reducing character of the hydrides of group
mo | Ee | & 15 elements increases from NH, to BiH,. Thus, increasing order of reducing
character is as follows :
NH, < PH, < AsH, < SbH, < BiH,
Explanation. The reducing character depends upon the stability of the
hydride. The lesser the stability of a hydride, the greater is its reducing
character. Since the stability of group 15 hydrides decreases from NH, to
BiH,, hence the reducing character increases. For example, NH, being most
stable among the group 15 hydrides is not a good reducing agent. The other
hydrides being unstable act as good reducing agents. However, it may be
noted that ammonia at high temperatures reduces copper oxide to copper :
3CuO + 2NH, beat, 3Cu + N, + 3H,O
(iv) Boiling and melting points. Ammonia has a higher boiling point
than phosphine and then the boiling point increases down the group because
of increase in size.(Fig. 4).

NH, (238.5) Molecule NH, PH, AsH, SbH, BiH,

&
Boiling point (K) 238.5 185.5 210.6 254.6 290
Melting point (K) 195.2 139.5 156.7 185.0 -
Similar behaviour is observed for melting points.
(K)
point
Boiling
Explanation. The abnormally high boiling point of ammonia is due to
PH, (185.5)
its tendency to form hydrogen bonds. The electronegativity of N (8.0) is much
higher than that of H (2.1). As a result N—H bonds are polar and therefore,
NH, undergoes intermolecular hydrogen bonding as shown below:
Molecular mass ——*

Fig. 4. Plot of boiling points of the

hydrides of group 15 elements.

In PH, and other hydrides, the intermolecular forces are van der Waals
forces. These van der Waals forces increase with increase in molecular size
and therefore, boiling points increase on moving from PH, to BiH,.
(v) Solubility. Ammonia forms hydrogen bonding with water molecules
while phosphine and other hydrides do not form hydrogen bonding with water.
Therefore, NH, is soluble in water while PH, and other hydrides are insoluble
in water.
p-BLOCK ELEMENTS

The trends in the properties of hydrides of group 15 are given in Table 3.

Table 8. Properties of hydrides of group 15 elements.

Melting point (K) 195.2

Boiling point (K) 238.5
(EK — H) distance (pm) 101.7
HEH angle (°) 107.8
AH? (kJ mol) — 46.1 There is an important difference
Aj,.<H°(E—-H) (kJ mol“) 389 between the oxides of nitrogen
and other group congeners in their
2. Reactivity towards oxygen (formation of oxides) structures. The nitrogen has
The elements of group 15 combine with oxygen directly or indirectly to ability to form pz-px multiple
form two types of oxides, E,O, (trioxides) and E,O, (pentaoxides). However, bonds and this is present in its
nitrogen forms a number of oxides with oxidation states ranging from +1 to structures.
+5 which have no analogues of P, As, Sb or Bi. This is mainly because of On the other hand, the reluctance
strong tendency of nitrogen to form pa—pn multiple bonds with oxygen. The of P, As, Sb and Bi to form pr—pt
important oxides of group 15 elements along with their oxidation states are multiple bonds leads to the cage
listed in Table 4. structures for their oxides.
Table 4, Oxides of group 15 elements in different oxidation states.

Element ——> N
Oxidation state

N,O
Nitrous oxide
NO
Nitric oxide
Sb,0,
Nace
Dinitrogen
P,Og
Phosphorus
Jee cle
Arsenic Antimony
Bi:
Bismuth
trioxide trioxide trioxide trioxide trioxide

mae
Dinitrogen
P,O5
Phosphorus
tetraoxide tetraoxide
Sb,0,
N2O5
Dinitrogen
P,O45
Phosphorus
As,05
Arsenic Antimony
Bi,0,
Bismuth
pentoxide pentoxide pentoxide pentoxide

The oxides in the higher oxidation state of the elements are more acidic than that Acidic character of oxides of
of the oxides in the lower oxidation state. The acidic character of the oxides of elements of group 15
group 15 elements decreases down the group. All the oxides of nitrogen except eho a See ee ee
N,O and NO and phosphorus are strongly acidic; oxides of arsenic are weakly (N,O & NO are neutral)
acidic; oxides of antimony are amphoteric while those of bismuth are weakly basic. See ee ee ane
The basic nature of oxides increases with increasing atomic number. For (As ,O, & Sb,O, are amphoteric
example, P (III) and As (III) oxides are acidic, Sb (III) oxide S amphoteric and while Bi,O, is basic.)
Bi (III) oxide is distinctly basic. It dissolves in acids to form salts. Cee 0 aC eo Oa
Bi,0,+ 6HNO, ———> 2Bi(NO,), + 3H,O
The oxides of nitrogen and phosphorus are discussed later.
3. Reactivity towards halogens (formation of halides)
Group 15 elements form two series of halides of the type EX, (trihalides)
and EX, (pentahalides). The trihalides are formed by all the elements while
 MODERN'S abc + OF CHEMISTRY-XIl

pentahalides are formed by all the elements except nitrogen. Nitrogen

eannot form pentahalides due to the absence of vacant d-orbitals
in its outermost shell. Similarly, the last element, Bi has little tendency
to form pentahalides because +5 oxidation state of Bi is less stable than +3
oxidation state due to inert pair effect.
(a) Trihalides.
All the elements of group 15 form trihalides of the general formula EX,,.
All these trihalides are known (X = F, Cl, Br or I and E =N, P, As, Sb, Bi).
Structure. The valence shell electronic configuration of these elements is
ns? np," np,” np,* and all these elements undergo sp’ hybridisation. The three
of the four sp? hybrid orbitals overlap with p orbital of halogen atom to form
three o bonds with halogen atoms. The fourth sp? hybrid orbital contains the
lone pair of electrons. Therefore, the geometry of trihalides may be regarded
as pyramidal.
The bond angles of the trihalides of an element increase as the
electronegativity of the halogen decreases, 1.e.,
sp” hybridisation PF, PCl, PBr, Fl,
96.3° 100.4° 101° 102°
- Lone pair Properties of trihalides (7) The trihalides of group 15 elements are
X = halogen atom predominantly covalent with the ionic character increasing down the group.

AS
For example, BiF, is ionic while other halides of Bi, z.e., BiCl,, BiBr,, etc. and
U~ SbF. are partly covalent and partly ionic.
(11) Out of all the trihalides, the trihalides of nitrogen are the least stable.
Though NF, is stable, NCI, is explosive. NBr, and NI, are known only
Fig. 5. Pyramidal shape of
as their unstable ammoniates i.e., NBr,.NH, and NI,.NH,. Pure NBr, also
a trihalide of group 15.
explodes even at 173K. The nitrogen triiodide ammoniate is stable only in the
moist state. In the dry state, it explodes with noise when struck liberating
REMEMBER vapours of iodine.
In contrast to trihalides of P, As
8NI,.NH, ———> 5N, + 91, + 6NH,]
and Sb, the trihalides of nitrogen NCl,, NBr, and NI, are unstable because N—xX bond ts weak due to large
behave as Lewis bases. This is difference in the size of N and X atoms. However, NF, is stable because of
due to the absence of d-orbitals small difference in size of N (75 pm) and F (72 pm) resulting strong N—F
in N and the presence of lone bond. As a result NF, is an exothermic compound. Because of stability of NF,
pair of electrons. NF, has a little it behaves quite differently from others. It is unreactive and does not hydrolyse
tendency to donate a pair of with water, dilute acids or alkalies. However, it does react only when sparked
electrons and hence behaves as with water vapour.
very weak Lewis base because of PF, is rather less reactive towards water and is more easily handled than
high electronegativity of fluorine. the other halides.
Fluorine is highly electronegative (111) The trihalides are easily hydrolysed by water. However, the products
and has strong tendency to are different in hydrolysis of different chlorides.
withdraw electrons from N. As NCL, + 3,0 ——\ NH, + 3HCI1O
a result, N-atom acquires partial Hypochlorous acid
positive charge and hence the PCl, + 3H,OQO ——\> H,PO, + 3HCl
tendency to donate electron pair Phosphorous acid
of electrons decreases. Therefore, 2AsCl, + 3H,O ——_> As,O, + 6HCl
the Lewis base strength of Antimony and bismuth trichlorides are only partially hydrolysed to form
trihalides of nitrogen increases oxychlorides.
as the electronegativity of halogen SbCl, + H,O =~ SbOCl (or SbO*Cl) + 2HCl
decreases, 1.e.,
Antimony oxychloride
Ni. = NCL =< NGr, = Ni.
BiCl, + H,O =—— BiOCl(or BiO*Cl) + 2HCl
p> The tendency of trihalides to
Bismuth oxychloride
act as Lewis base decreases
It may be noted that in accordance with Le Chatelier principle, the excess
from N to Bi for a given halide.
of HC] suppresses the hydrolysis by shifting the equilibrium to the left.
p-BLOCK ELEMENTS 7/11 »»

(tv) The trihalides of P, As and Sb (especially fluorides and chlorides) act

as Lewis acids and combine with Lewis bases :
PF, + Fr, — > £PF,
SbF; + 2F —— | [SbF,]?
SbCl, + 2Cl —— _ [SbCl,]?-
The Lewis acid strength however, decreases in the order :
PCl, > AsCl, > SbCl, ; PF, > PCL, > PEr, > PI,
(6) Pentahalides.
P, As and Sb form pentahalides of the general formula EX,; EF, (E = P,
As, Sb and Bi), ECl, (E = P, As and Sb) and PBr, and PI,. As already studied,
nitrogen does not form pentahalides because of the absence of d-orbitals in
its valence shell.
The pentahalides of group 15 elements are thermally less stable
than trihalides. This is due to the following reasons :
(i) As we go down the group, the stability of +5 oxidation state decreases
while that of +3 oxidation state increases due to inert pair effect. Therefore,
the pentahalides of Bi are not known except for BiF,.
(it) As the size of halogen atom increases from F to I, the strength of
E—X bond decreases and the steric hindrance increases. As a result,
pentabromides and pentaiodides are unstable.
Therefore, the pentahalides of group 15 elements are less in number
than trihalides. For example, pentafluorides of P, As, Sb and Bi are known,
pentachlorides of only P, As, and Sb are known while bromides and iodides
of only P are known.
Preparation. The pentahalides are prepared as :
3PCl, + 5AsF; ——> 3PF, +_ 5AsCl,
PCl, a) + Cl, (inCCl,)———> PCI rs)
2As,0, + 10F —> 4AsF.+ 380,
2Sb,0, + 10F, ——> 4SbF, +. 30,
2oBi + 5F, —— 4BiF,
Structure. The pentahalides of group 15 elements have trigonal
bipyramidal geometry in which the central atom is sp°d hybridised. The
three halogen atoms occupy equatorial positions while the other two occupy
axial positions. This is not a regular structure because all the bond angles
are not same. The axial bonds are at 90° while equatorial
bonds are at 120° each. The axial positions experience greater
repulsion than equatorial positions by bond pair of electrons.
As aresult, axial bonds are usually larger than the equatorial
bonds. The structure of PF, is shown in Fig.6 in which P—F
axial bond lengths are 158 pm while P—F equatorial bond ft)
tT tf
lengths are 153 pm.
sp’d hybridisation
Properties (i) Pentahalides are thermally less stable
than their corresponding trihalides. PF, is molecular in both x
the gaseous and solid states. PCl, exists as molecules in
the gas phase but exists as [PC1,]* [PCl,] in the crystalline
state. PBr. and PI, also exist in the ionic form as [PBr,]*
[PBr,]— and [PI,]*I respectively in the solid state.
(iz) All the pentahalides behave as Lewis acids because
of the presence of vacant d-orbitals. The central atom (except
N) can accept a pair of electrons thereby expanding its
coordination number to 6.
EX. +X ——> [EX]
During this the hybridisation of the central atom changes
from sp*d to sp°d7?. Fig. 6. Trigonal bipyramidal shape of EX, molecule.
 MODERN'S abc + OF CHEMISTRY-XIl

4. Reactivity towards metals

All the elements of group 15 combine with metals to form their binary
compounds in which the elements show —8 oxidation state. For example, nitrogen
forms nitrides (Mg.N, : magnesium nitride, Ca,P, : calcium nitride) arsenic
forms arsenides (Na : sodium arsenide), antimony forms antimonides
(Zn,Sb, : zine antimonide and bismuth forms bismuthides (Mg.B1, : magnesium
bismuthides).

ANOMALOUS BEHAVIOUR OF NITROGEN

Nitrogen, the first member of group 15, differs from its rest of family
members. This may be due to :
(z) its small size.
(it) its high ionisation enthalpy and electronegativity.
(iit) absence of d-orbitals in its valence shell.
Some of the characteristics in which nitrogen differs from other family
members are given below :
(1) Nitrogen is a gas at room temperature while the rest of the members
of the family are solids.
(it) Nitrogen does not exhibit pentavalency in its compounds while other
members show pentavalency.
(111) Nitrogen has a tendency to form pz-pz bonds and exists as N, molecule
while other elements do not have such tendency. Instead, they prefer
to form single bonds as P—P, As—As etc.
(iv) Due to the absence of d-orbitals in the valence shell, nitrogen cannot
form da-pz bonds and therefore, compounds of the type R,N = O and
R,N = CH, are not known. However, P and arsenic form compounds
such as R.P = O, R,P = CH, containing dz-pz bonds.
(v) The hydride of nitrogen (NH,) is more basic than the hydrides of the
other members of the family.
(vi) Nitrogen does not form any complex whereas the other members form
complexes.
(vit) Nitrogen can form hydrogen bonds in its compounds and rest of the
members do not form hydrogen bonds due to small electronegativities.
(viii) Nitrogen forms a variety of the oxides while the other members form
trioxides and pentoxides only.
(1x) Exeept NF,, the trihalides of nitrogen (NCI,, NBr, and NI,) are explosive.
The trihalides of other elements are, however, stable.

aor SOLVED EXAMPLES

_j] Example 1. valence shell and therefore, it cannot extend its octet. That is
why nitrogen does not form pentahalides.
Nitrogen exists as diatomic molecule and phosphorus
|] Example 3.
exists as tetraatomic molecule, P, Kxplain.
Why is N, less reactive at room temperature ?
(Pb. S.B. 2015, H.P.S.B. 2014, 2016)
(Pb.S.B. 2013, ALLS.B. 2015, H.P.S.B. 2015, 2016,
Solution: The size of nitrogen atom is quite small. As a
Meghalaya S.B. 2017)
result, two nitrogen atoms can be linked to each other by three
covalent bonds in order to complete the octets of both the
Solution: In molecular nitrogen, there is a triple bond
between two nitrogen atoms (N = N) and it is non-polar in
nitrogen atoms as : N == N :. However, phosphorus being large
character. Due to the presence of a triple bond, it has very high
in size has less tendency to form three bonds. Therefore, P atom
bond dissociation energy (941.4 kJ mol) and therefore, it does
completes its octet by sharing its valence electrons with three
not react with other elements under normal conditions and is
other P atoms. As a result, it exists as P, molecule.
very unreactive. However, it may react at higher temperatures.
_} Example 2. |} Example 4.
Though nitrogen exhibits + 5 oxidation state, it does Phosphine has lower boiling point than ammonta.
not form pentahalides. Give reason. Give reason.
N.C.E.R.T) (A.I.S.B. 2013, D.S.B. 2015, 2017) (A.L.S.B. 2008, D.S.B.2013,
Solution : Nitrogen belongs to second period (m = 2) and Mizoram S.B.2013, Uttarakhand S.B. 2014,
has only s and p-orbitals. It does not have d-orbitals in its AP_S.B. 2016, Ar. SB. 2017)
p-BLOCK ELEMENTS

Solution : Ammonia exists as associated molecule due to each other. On the other hand, phosphorus is comparatively
its tendency to form hydrogen bonding. Therefore, it has large in size so that lone pairs on P atoms donot repel to the
high boiling point. Unlike NH,, phosphine (PH,) molecules same extent. As a result P—P bond 1s stronger than N—N bond.
are not associated through hydrogen bonding in liquid state. Therefore, P has a tendency for catenation because of high bond
This is because of low electronegativity of P than N. As a enthalpy of P—P bond.
result, the boiling point of PH, is lower than that of NH,. _) Example 6.
L] Example 5. Out of Bi(V) and Sb(V) which may be a stronger
Unitke phosphorus, nitrogen shows little tendency for oxidising agent and why ? (D.S.B. 2008)
catenation. Solution : On moving down the group, the stability of
Solution : Nitrogen has little tendency for catenation +5 oxidation state decreases while the stability of +3 oxidation
because N—N single bond is weak. This is because nitrogen state increases due to inert pair effect. Therefore, +5 oxidation
has small size and the lone pairs on two nitrogen atoms repel state of Bi is less stable than +5 oxidation state of Sb. Thus,
Bi(V) is a stronger oxidising agent than Sb(V).

= Answers to Practice Problems =

1 . Which of the two : BH, or NE, is more basic ? 1, NH,

2 . Which hydride of group 15 elements has lowest boiling point ? mi
3. Red, black, white or yellow.
3. Name three allotropes of phosphorus. Which of these is most reactive ?
White P is most reactive.
A'- Which of the two : NH, or PH, is soluble in water ?
4. NH,
+]. Arrange BilH1,, PH, and NH, in the increasing order of their reducing character.
5. NH, < PH, < Bil,

CHEMISTRY OF NITROGEN AND ITS COMPOUNDS

DINITROGEN
Nitrogen was discovered by Daniel Rutherford in 1772. It is the first
member of group 15 of the periodic table. It has the electronic configuration 1s?
2s* 2p? and therefore, has five electrons in its valence shell. In the molecular
form, it exists as a diatomic molecule (N,) having triple bond between nitrogen
atoms (N== N). Therefore, it is also referred to as dinitrogen. It 1s a typical
non-metal with high electronegativity next only to fluorine and oxygen.
Preparation of Dinitrogen REMEMBER
In the laboratory, dinitrogen is prepared by heating an aqueous solution Thermal decomposition of sodium
containing an equivalent amount of ammonium chloride and sodium nitrite. azide 1s used to inflate the air bags
NH,Cl(ag) + NaNO, (ag) ==> N, (g) + 2H,OW) + NaCl(aq) used for safety devices in some
During the preparation, small amounts of NO and HNO, are also formed cars.
in the reaction. These impurities can be removed by bubbling the gas through
aqueous sulphuric acid containing a small amount of potassium dichromate.
It can also be prepared by
(1) Thermal decomposition of ammonium dichromate.
Heat
(NE) Qn Ome, —> CroO, +N, + 4H,0
(it) By the action of ammonia with cupric oxide or bleaching powder.

2NH, + Meat) SE , 3cu +N, + 38H,O

Heat
2NH, + 8CaOCl,——\ 38CaCl, +N, + 3H,O
Bleaching powder
(iit) Very pure nitrogen can be obtained by the thermal decomposition
of sodium or barium azide
2NaN, 573 K
——s 2Na + 3N,
Sodium azide
Ba(N,), —> Ba + 3N,
Barium azide
zis MODERN'S abc + OF CHEMISTRY-XIl

R U Curious ... Commercial Isolation of Dinitrogen from Air

Commercially dinitrogen is prepared by the liquefaction and fractional
J] How do airbags installed in
distillation of air. Air contains dinitrogen (0.p. 77.2 K) and dioxygen (b.p. 90
the dash board of your car
work? K). When the liquid air is allowed to boil, dinitrogen with lesser boiling point
gets distilled first leaving behind dioxygen. The dinitrogen obtained from air
An airbag is a vehicle safety
device. Its purpose is to provide contains traces of oxygen and some other gases as impurities.
protection to the occupants Properties of Dinitrogen
when they strike interior objects
Physical Properties
such as steering wheel, window,
dashboard, etc. during accidents. (z) Dinitrogen is a colourless, odourless and tasteless gas.
The airbagis made ofathinnylon (ii) It has two stable isotopes *N and °N.
fabric and contains sodium azide (iii) It is a non-toxic gas.
(NaN,). When accident occurs, (iv) It is slightly lighter than air and its vapour density is 14.
the impact sensors provided in
(v) It has very low solubility in water (about 23.2 cm? per litre of water
the car detect the collision. These
sensors send an electrical signal at 1 atmosphere pressure and 273 K).
which overheats and ignites (vi) Its melting and boiling points are low; 63.2 K and 77.2 K respectively.
sodium azide (NaN,) placed in Chemical Properties
the airbag. Sodium azideis a fast Dinitrogen is chemically unreactive at room temperature. It is neither
burning fuel and within about
combustible nor it supports combustion. The N—N bond in nitrogen molecule is
20-30 milliseconds of impact, it
decomposes to produce N, gas. a triple bond (N == N) with a bond distance of 109.8 pm and bond dissociation
enthalpy of 941.4 kJ mol!. The low reactivity of nitrogen is due to very small
2NaN, —>2Na+ 3N,
size of the molecule and high bond dissociation enthalpy of the molecule.
The N, gas produced passes However, reactivity increases rapidly with the rise in temperature. At higher
through filters and fills the nylon temperature dinitrogen combines with some metals to form predominantly
airbag and inflatesit. The airbag
lonic nitrides and with non-metals to form covalent nitrides.
then hits the car’s occupant and
protects him from injury. After 1. Action with litmus. Dinitrogen is neutral towards litmus because it
hitting, the airbag deflates has no action on blue or red litmus.
immediately and the gas escapes 2. Action with metals. It combines with a number of active metals on
through tiny holes in the fabric strong heating to form their respective nitrides. For example,
(or as it 1s sometimes called the Heat
6lLi + N, 2Li,N
cushion) and cools. Deployment
Lithium nitride
is accompanied by release of Heat
dust like particles usually 383Mg + N, —— Mg.N,
talcum powder or corn starch Magnesium nitride
which are used to lubricate the 8Ca + N, _Heat _, Ca,N,
airbag during deployment. The Calcium nitride
powder protects the bag from
sticking to itself, while it is
oA & WW. Meee
Heat
2AIN
folded inside the car. The N, gas Aluminium nitride
released is absolutely harmless. 3. Combination with non-metals. Dinitrogen combines with non-metals
The only precaution is to open like dioxygen and dihydrogen.
the door and windows for good (4) Combination with dihydrogen. Dinitrogen reacts with dihydrogen
ventillation to avoid the affect of at about 700 K under a pressure of 200 atm in the presence of iron as catalyst
dust particles. It may be noted
(Haber process). A small amount of molybdenum is also used as a promotor.
that some airbag manufacturers Fe, M
mix sodium azide with other N, + 8H, ——_— K, atm pressure pe
2NH, AH” =- 46.1 kJ mol
chemicals that will react with
sodium and form less toxic (74) Combination with dioxygen. Dinitrogen combines with dioxygen
compounds.
during lightning or at high temperature of about 2000 K and form nitric oxide.
N, +0, 220008, ono AH® = 135 kJ mol
Nitric oxide
Calclum cyanamide is used as a Nitric oxide is a colourless gas but is very unstable. It immediately reacts
fertilizer under the name nitrolim
with more of oxygen to form nitrogen dioxide.
(CaCN, + C).
2NO + O, ———> 2NO,
4, Combination with compounds. Dinitrogen also combines with certain
p-BLOCK ELEMENTS 7M5 —

compounds on strong heating. For example, Fixation of Nitrogen

With calcium carbide The process of conversion of
Cac, + N, ==>
1300 K CaCN, + Cc atmosp
t a dinit
heric lini he intoint usefit l
Calcium Calcium Carbon compounds is called nitrogen
sachs cyanamide fixation. Fixation of nitrogen is
brought about in the following ways :
With alumina in the presence of carbon
@ During lightning and thunder
Al,O,+ N, +3C123K, 2AIN + 8CO storms the energy in lightning
Aluminium Aluminium allows nitrogen and oxygen to
oxide nitride combine to form oxides of nitrogen
Both these compounds are hydrolysed on boiling
with water to give ammonia. which are washed into the soil
. and. are taken up by the plants as
a a te ae; abe nitrates. As Sadie live a plants,
AIN + 3H,O ——~+ AIKOH), + NH, they are transferred to the animal
Therefore, calctum cyanamide is used as a fertilizer under the name bodies where a series of metabolic
nitrolim (CaCN, + C). changes take place.
Uses of Dinitrogen The atmospheric nitrogen can be
converted into useful compounds
(z) Dinitrogen is used in the manufacture of compounds like ammonia, (which can be used by plants) by
nitric acid, calclum cyanamide, ete. _ . | raEge Cop aCe a age
(it) It is used in providing inert atmosphere in iron and steel industries. algae. All types of bacteria are not
(ii) Liquid nitrogenis used as refrigerant to preserve biological specimens, able to fix nitrogen. The symbiotic
in freezing food stuffs and also in cryosurgery. bacteria present in the root nodules of
(iv) It is used in gas-filled thermometers used for measuring high leguminous plants (e.g., peas, beans,
temperatures. erams, etc.) catch up the nitrogen
(v) Dinitrogen is used in filling electric bulbs to reduce the rate of Soriaay oman ea tom bodene
volatilisation of the tungsten filament. to the bacteria. The non-leguminous
AMMONTA plants like Alnus, Ginkgo also fix
ee
Ammonia .
is the most important | compound of nitrogen.
. It is present in atmospheric
Seen calone nitrogen.
HennilGa Certain blue-
ade nels
small quantities in air and soil where it is formed by the decay of nitrogenous HON EaE Wei penne does
organic matter e.g., urea. biochemical processes involve an
NH,CONH, + 2H,0 ———> (NH,),CO, = = 2NH, + CO, + H,O enzyme called nitrogenase in which
Urea the active sites contain molybdenum
Laboratory Preparation and iron atoms. |
Ammonia is prepared in the laboratory by heating ammonium salt; NH,Cl Dinitrogen can be made to take
or (NH,),SO, with a strong alkali like NaOH. Pee eee ee eo
under suitable conditions to prepare
NH,Cl + NaOH ———+ NH, + H,O + NaCl useful compounds. This is called
(NH,),SO, + 2NaOH ———» 2NH, + 2H,0 + Na,SO, artificial fixation.
It can also be prepared by heating ammonium chloride with slaked lime. _ The common examples of
Het industrial fixation of nitrogen is the
2NH,Cl + Ca(OH), ——— CaCl, + 2NH, + 2H,O manufacture of ammonia by Haber’s
Slaked lime process. In this process,
a large amount
It can also be prepared by the hydrolysis of magnesium nitride. of atmospheric nitrogen is fixed
in the
Mg.N, + 6H,O ——> 3Mg(OH), + 2NH, a LBL
Ammonia can be dried by passing over
quicklime (CaO). However, it cannot be dried
with dehydrating agents such as conc. H,SO,
P,O,and anhydrous CaCl, because ammonia
reacts with these compounds.
Manufacture of ammonia N.—— PRL igs
Ammonia can be manufactured by |(i, — N, 2H) = 1:3) 20 MPa
Haber’s process which involves the | Condensing
en Catalyst chamber pipes
N,(g) + 3H, (g) —— 2NH, (g); | a
AH°® =—_- 92.3 kJ mol! at 7OO K ps io O
or a | Ks

AH°(NH;) =— 46.1 kJ mo]

This is a reversible exothermic reaction. _ _
The favourable conditions for high yield of (N, +H, +'NH,) Liquid NH,
ammonia can be understood by applying
Fig. 7. Flow chart for Haber's process for the manufacture of ammonia.
Le Chatelier’s principle.
 MODERN'’S abc + OF CHEMISTRY-AXIl

(4) Low temperature. Since the forward reaction is exothermic,

therefore, low temperature will favour the formation of ammonia. However,
an optimum temperature of about 700 K ts necessary.
(ii) High pressure. High pressure of the order of 200 atmospheres or
200 x 10° Pa is required to favour the forward reaction.
(111) Presence of catalyst. The use of catalyst such as iron oxide containing
a small amounts of molybdenum or potassium oxide (K,O) and aluminium
oxide (Al,O,) as promoter, increases the rate of attainment of equilibrium of
ammonia.
Details of the process
The plant required for the manufacture of ammonia is shown in Fig. 7. In
this method, a mixture of N, and H, in the molar ratio of 1 : 3 is compressed
to about 200 atmosphere pressure. The compressed gases are then cooled and
passed through soda lime tower to free them from moisture and carbon dioxide.
Then these are fed into catalyst chamber packed with iron oxide with small
amount of K,O and A1,O, or molybdenum. The chamber is heated electrically
to a temperature of 700 K when the two gases combine to form ammonia. The
reaction being exothermic, the heat evolved maintains the desired temperature
and further electrical heating is not required.
The gases which escape from the chamber contain about 15-20% ammonia
and the remaining are unreacted N, and H,. These are passed through
condensing pipes where ammonia gets liquefied and is collected in the receiver.
The unreacted gases are pumped back to the compression pump where they
are mixed with fresh gaseous mixture.
Structure of ammonia. Ammonia is expected to have a tetrahedral
geometry because the central nitrogen atom involves sp? hybridisation as already
discussed. It has one position occupied by a lone pair. The lone pair distorts its
geometry and the molecule has pyramidal geometry with nitrogen atom at
the apex. The N—H bond length is 101.7 pm and HNH bond angle is 107.8°.
Properties of Ammonia
Physical properties (7) Ammonia is a colourless gas with a characteristic
pungent smell called ammoniacal smell.

YN 7,0
all
e
(ii) It is lighter than air (density = 0.68 g/cm?)
(iit) It is highly soluble in water; one volume of water can dissolve about
1000 volumes of the gas at 273 K. The high solubility of ammonia
in water is due to its tendency to form intermolecular hydrogen
Jaw bonding.
H
H H (zv) Ammonia can be easily liquefied under pressure. Liquid ammonia has
b.p. 239.7 K and f.p. 198.4 K. Like water, ammonia is also associated
Fig. 8. Structure of ammonia. in the solid and liquid states through hydrogen bonds. This accounts
for its higher melting and boiling points than expected on the basis
of its molecular mass.
Chemical properties
1. Basic nature. Ammonia gas is highly soluble in water. Its aqueous
solution turns red litmus blue indicating its weakly basic character. The basic
character of ammonia is due to the formation of OH- ions in aqueous solution.
NH, (aq) + H,O (aq) == NH,‘ (aq) + OH (aq)
Being basic ammonia forms salts with both weak and strong acids such
as NH,Cl, (NH,),S0O,, (NH,),CO,, ete.
NH, (ag) + HCl (ag) ———> NH,Cl (s)
2NH,(ag) + H,SO, ———> (NH,),SO, (s)
2. As a Lewis base: tendency to form complexes. Ammonia acts as a
Lewis base due to the presence of lone pair of electrons on the nitrogen atom.
Therefore, it can form coordinate bond with electron deficient molecules (such
as BF.) or a number of transition metal cations forming complex compounds.
p-BLOCK ELEMENTS

For example,
BF, + NH, ———> BF, «+ NH;
Ag* (aq) + 2NH, (ag) ——— [Ag(NH,),]* (aq)
Colourless
Cu”* (ag) + 4NH, (ag) ———> [Cu(NH,),]?* (aq)
Deep blue
Cd?* + 4NH, ——— [Cd(NH,),]** (aq)
Since ammonia forms complexes, the white precipitate of silver chloride
dissolves in excess of ammonium hydroxide to form a soluble complex.
AgCl + 2NH,OH [Ag(NH,),/Cl + 2H,O
White ppt. Diammunesilver (I)
chloride (colourless)
Similarly, copper sulphate dissolves in excess of ammonium hydroxide to
form deep blue coloured complex.
CuSO, + 4NH,0OH [Cu(NH,),JSO, + 4H,O
Tetraammuinecopper (II)
sulphate (Blue)
The formation of such complex compounds finds applications in detection
of metal ions (Ag*, Cu’, etc.)
3. Action with oe een (z) Chlorine reacts with ammonia in two ways
depending upon whether ammonia is in excess or chlorine is in excess.
Excess NH, :8NH,+ 3Cl, ——— 6NH,Cl+ N,
Excess Cl, : NH, + 3Cl,——— NCl, + 3HCl
Bromine also reacts in a similar way.
Excess of ammonia :
8NH, + Br, ———> 2NH,Br + 3N,
Excess of bromine :
NH, + 38Br, ——~+ NBr, + 3HBr
(it) Iodine reacts — guid ammonia i form a dark brown complex.
2NH, + 31, = ———> NH,NI, -- 3HI
Nitrogen tri-iodide
ammoniate (brown complex)
The complex is very explosive when dry. It explodes violently when rubbed Tests of ammonia
against a hard surface as follows: @ Ammonia can be tested by its
8NH,NI, —“> 5N, + 91, + 6NH,I reaction with Nessler's reagent.
4. Oxidation. Amini is oxidised S aiftfogen iti oxidising agents It gives brown precipitate with
Nessler's reagent (an alkaline
like CuO, NaClO, Ca(OCl), etc. For example, when ammonia is passed over
solution of K,HgI,) due to the
heated copper oxide, it gets oxidised to dinitrogen.
formation of iodide of Muillion's
8CuO + 2NH, ——> 38Cu + N, + 3H,O base.
Similarly, 4NH, + 3Ca(OCD, am 7 2N, + 3CaCl, + 6H, O 2K,Hgl,+NH,+3KOH—- Nessler's
When vapours ofNH, and O, are passed over red hot platinum gauze at reagent
1075 K, it 1s oxidised to niric oxide. H,N —-Hg-O-Hg—-1+7KI+2H,0
4NH, + 5O, ——_—- 4NO + 6H,O Iodide of Million's base
(brown ppt).
2 1075 K Nitric oxide
This reaction forms the basis of Ostwald's process for the @ With a drop of HCl, it produces
dense white fumes of ammonium
manufacture of nitric acid.
chloride.
5. Combustion. Ammonia is neither combustible nor supporter of @ It turns moist red litmus paper
combustion. However, it burns in the presence of oxygen to form dinitrogen blue and moist turmeric paper
and water. brown.
4NH, + 30, ——> 2N, + 6H,O @ It gives a yellow precipitate with
6. Formation of amides. When ammonia is passed over heated sodium chloro-platinic acid.
or potassium at 575 K, it forms amides with the liberation of dihydrogen. H,PtCl, + 2NH, —> (NH,),PtCl,
2Na + 2NH, —°2*8, 2NaNH, + H, Chloroplatinic Ammonium
Sodamide acid chloroplatinate
2K + 2NH, —22*, 2KNH, + H, (yellow ppt.)
Potassium amide
 MODERN'S abc + OF CHEMISTRY-XIl

7. Precipitation of heavy metal ions from the aqueous solution of

their salts. Heavy metal ions such as Fe**, Cr**, Al®**, etc. are precipitated
from their aqueous salt solutions as hydroxides with ammonia.
FeCl, (aq) + 3NH,OH (aq) ——_> Fe(OH), (s) + 83NH,CI (aq)
Brown ppt.
AICl, (aq) + 3NH,OH (ag) ———> Al(OH), (s) + 3NH,Cl (aq)
White ppt.
CrCl, (ag) + 3NH,OH (ag) ———> Cr(OH), (s) + 3NH,Cl (aq)
Green ppt.
ZnSO, (aq) + 2NH,OH (aq) ———> Zn(OH), (s) + (NH,),5O, (aq)
White ppt.
Nitrogen also forms other hydrides Uses of ammonia
such as (4) It is used in the manufacture of nitric acid and sodium carbonate.
N,H, : Hydrazine (it) Liquid ammonia is used as a refrigerant.
HN, : Hydrazoic acid (iit) It is used in the manufacture of rayon.
(tv) Itis commonly used for preparing various nitrogenous fertilizers such
as ammonium nitrate, ammonium sulphate, ammonium phosphate
and urea.
(v) Itis an important reagent and is used as a solvent in the laboratory.
OXIDES OF NITROGEN
Nitrogen combines with oxygen under different conditions to form a number
of binary oxides which differ with respect to the oxidation state of the nitrogen
atom. They range from N,O (oxidation state of N +1) through NO (+2), N,O, (+3),
N,O, (+4) to N,O, (5). The tendency to form pz—pz multiple bonds dictates the
structures of oxides. The important oxides are NO, N,O,, NO,, N,O, and N,O,.
The molecular formulae of various oxides of nitrogen are given in Table 5.
Table 5. Oxides of nitrogen.
Oxidation Physical appearance Properties
state of N acidic or neutral character

N,O Colourless gas Unreactive gas

Dinitrogen monoxide Neutral
Nitrous oxide or
Nitrogen (I) oxide
NO Colourless Paramagnetic, reactive and
Nitric oxide
or Nitrogen (II) oxide Neutral thermodynamically unstable

N,O, Pale blue solid Unstable in gaseous phase

Dinitrogen trioxide Acidic
or Nitrogen (III) oxide

N,O, Colourless solid Exists in equilibrium with NO,

Dinitrogen tetroxide or liquid both in gaseous and liquid state
or Nitrogen (IV) oxide Acidic
Lae Brown gas Reactive and paramagnetic
Nitrogen dioxide Acidic
or Nitrogen (IV) oxide

N,O; Colourless solid Unstable as gas, in solid state

Dinitrogen pentoxide or gas exists as [NO,]* [NO,]-
or Nitrogen (V) oxide Acidic

Nitrous oxide (N,O) is known as 1. Nitrous oxide (N,O). It is prepared by heating ammonium nitrate.
Heat
laughing gas because it causes NH,NO,——— N,O + 2H,O
hysterical laughter when inhaled in
It is a colourless unreactive gas having faint pleasant smell. It is also known
minor quantities.
as laughing gas because it causes hysterical laughter when inhaled in minor
quantities. It is a neutral oxide and reacts with sodamide to form sodium azide.
p-BLOCK ELEMENTS

N,O + 2NaNH, ———> NaN, + NH, + NaOH The largest use of N,O is as
Sodamide Sod. azide propellant for whipped ice-
In small amounts, it acts as an anaesthetic for minor operations. cream. Because it has no taste,
It decomposes into nitrogen and oxygen at 873 K. and is non-toxic and therefore, it
2N,0 ———> 2N, + O, meets the strict food and health
Therefore, it supports the combustion acting as a source of oxygen. regulations.
2. Nitric oxide (NO). It is prepared by the catalytic oxidation of ammonia
at 1100 K in the presence of platinum.

4NH, + 50, =>

1100K
4NO + 6H,O
It can also prepared by the reaction of nitric acid on copper as :
3Cu + 8HNO, ———> 3Cu(NO,), + 2NO + 4H,O
It can also be prepared by the reduction of sodium nitrite with ferrous
sulphate in the presence of sulphuric acid.
2NaNO, +2FeSO,+3H,SO,——> Fe,(SO,), + 2NaHSO, + 2H,O + 2NO
It is a neutral oxide.
It is a colourless gas. It has odd number of electrons (11 valence electrons)
and therefore, it is paramagnetic in the gaseous state. However, in the liquid
and solid states, it forms a loose dimer in such a way that the magnetic effects
of two unpaired electrons are cancelled out. The molecule is diamagnetic.
Nitric oxide due to the presence of an odd electron, is very reactive. It
readily reacts with oxygen to give brown fumes of nitrogen dioxide and with
halogens to give nitrosyl halides.
2NO (g) + O, (g) ——— 2NO, (g)
2NO + Cl, ——~+ 2NOCIl
Nitrosyl chloride
Nitric oxide readily forms complexes with transition metals. For example,
Fe** combines with NO to form the complex [Fe(H,O),NO]?* which is
responsible for the colour in brown ring test for nitrates.

It is thermodynamically unstable and decomposes into elements at high

temperatures (13873 K — 1473 K)
oNO (g) 13873-14783 K N, (g) A O, (g)

3. Dinitrogen trioxide (N,O,). It is prepared by cooling equimolar

quantities of nitric oxide and nitrogen dioxide to below 253 K.
NO(g) + NO,(g) —== N,0,
It can also be prepared by reacting nitric oxide and dinitrogen tetraoxide
at 250 K.
2NO + NO, —~*-, 2N,0,
It is a blue solid and is acidic in nature. It is anhydride of nitrous acid
(HNO,).
N,O, +/a,0 —— 2HNO,
It exists in the pure form only in the solid state at very low temperatures.
Above its melting point (273 K) it dissociates to NO and NO,,.
N, O, Above 173 K NO ‘ N O,

Blue Colourless Brown

4, Nitrogen dioxide (NO,). It is prepared by heating dried lead nitrate
in a steel reaction vessel.
2Pb(NO,), ——— > 2PbO + 4NO, + O,
It is also an odd electron molecule and in the gas phase, it exists in
equilibrium with N,O, as :
NO, 2NO,
Colourless Brown
Above 415 K, it contains mainly NO, and at 250 K, it consists of mainly
NO.
Cool
2NO, N,O,
 MODERN'S abc + OF CHEMISTRY-All

Oxides of nitrogen are emitted 5. Dinitrogen pentoxide (N,O,). It is prepared by dehydrating the
into the atmosphere during concentrated nitric acid with phosphorus pentoxide.
burning of coal and oil in power
4HNO, + P,O,,——>
410 2N,0.+ 4HPO,
Phosphorus Metaphosphoric
stations and automobile engines.
pentoxide acid
These are also present in the N,O, exists as colourless solid below 273K. As the temperature rises,
automobile exhausts. These cause the colour changes to yellow due to the partial decomposition of colourless
air pollution in major cities N,O, to brown NO,.
and near power stations. These 2N,0. ———> 4NO, + O,
oxides of nitrogen also cause At 303 K, the crystals melt giving a yellow liquid which decomposes at
acid rain and photochemical 313 K to give NO,,.
smog (discussed in class XI in N,O, acts as a strong oxidising agent and oxidises iodine to I,O,.
environmental chemistry).
The oxides of nitrogen N,O,, NO,, N,O. are acidic and react with water
to give oxoacids of nitrogen. For example, N,O, gives nitrous acid (HNO,)
while N,O, give nitric acid (HNO,).
'R U Curious ..@ NO, + H,O —/-aP 2,
Nitrous acid
O You will be surprised to note
that though nitric oxide
N,O, + HOA 2HNO,
Nitric acid
(NO) is very reactive and
Therefore, N,O, is regarded as anhydride of nitrous acid and N,O, is
harmful, yet it occurs in
regarded as anhydride of nitric acid. Nitrogen dioxide (NO,) reacts with
biological systems in traces.
water to give both nitrous acid and nitric acid.
> Itactsasaneuro-transmitter 2NO@r aa.) — HNO, + HNO,
and plays a significant role | Nitrous Nitric
in controlling blood pressure acid acid
by relaxing blood vessels. It Therefore, NO, is a mixed anhydride of nitric acid and nitrous acid.
also protects from bacterial
infections. Out of various oxides, NO and NO, are used in the manufacture of nitric
acid and nitrate fertilizers. Liquid N,O, is also used as an oxidiser for the rocket
fuels in missiles and space vehicles. However, NO causes a pollution problem
in atmosphere due to its poisonous nature. Its vapours are emitted in the
atmosphere during the burning of oil and coal.
The general methods of preparation of nitrogen oxides are summed up below:

SUM UP

Oxide of nitrogen Common method of preparation

(i) NH,NO, —*, N,O + 2H,O

Gi) HNO, + NH,OH (ag) ———> Jefe se paaL
i) 3Cu + 8HNO, ——__> 38Cu(NO,), + 2NO + 4H,O
s 1100K
(it) sin lleI - 50, aT 4NO + 6H,0
(itt) 2NaNO, + 2Fe5O, + 3H,50, t———_> Fe, (S0,), + 2NaHs0O, + +2NO + 2H,0
DE ee ee
2NO +N,O, ——“*> 2N,0,

(i) 2Pb(NO,), 673 K 2PbO + 4NO, + O,

(ii) Cu + 4HNO,(conc.) ————> Cu(NO,), + 2NO, + 2H,O
P,O,, + 4HNO, ———> 2N,0, + 4HPO,
The molecular and Lewis dot resonance structures of oxides of nitrogen are given ahead.
p-BLOCK ELEMENTS

N,O, Nitrous oxide :

NTispm Nopm
wen Lo:
Linear

NO, Nitric oxide :

N,O,, Dinitrogen trioxide :

N,O,, Dinitrogen tetraoxide :

— #8

N,O,, Dinitrogen pentoxide :

Planar

NITRIC ACID (HNO,)

Oxoacids of nitrogen
Nitrogen forms numerous oxoacids though several are unstable in the free OH
state and are known only in aqueous solution or as their salts. The common
N =N
oxoacids of nitrogen are given below :
/
Table 6. Oxoacids of nitrogen. HO
Hyponitrous acid
Formula Oxidation
HO—N =O
State of N
Nitrous acid
Hyponitrous acid HNO, weak acid known as its salts
Nitroxylic acid H,N,O, highly explosive difficult to get
in pure state HO — ‘a
Nitrous acid HNO, weak acid and unstable =o
Nitric acid HNO, weak acid and stable Nitric acid
Peroxonitric acid HNO, unstable and explosive p>

HO—O—N,
Out of the oxoacids of nitrogen, nitric acid is the most important. It is =O
very strong oxidising agent and is quite useful. Nitrogen shown an oxidation Peroxonitric acid
state of +5 in nitric acid.
 MODERN'’S abc + OF CHEMISTRY-AXIl

Laboratory preparation of nitric acid. In the laboratory, nitric acid

can be prepared by heating sodium or potassium nitrate with concentrated
sulphuric acid to about 423-475 K
NaNO, + H,SO, ———> NaHSO, + HNO,
Anhydrous nitric acid can be obtained by distillation of concentrated
aqueous nitric acid with P,O,,.
Manufacture of Nitric Acid
Nitric acid is commonly manufactured by Ostwald process in which it
is prepared by the catalytic oxidation of ammonia by atmospheric oxygen. The
reaction is carried out at about 500 K and 9 x 10° Pa (9 bar) pressure in the
presence of Pt or Rh gauge as catalyst.
4NH, (g) sont Sian 4NO (g)
+ 6H,O (g)AH=-90.2kJ
rom alr

Nitric oxide thus formed combines with oxygen to form nitrogen dioxide.
2NO (g) + O, (g) —~+ 2NO, (g)
Nitrogen dioxide so formed, dissolves in water to give nitric acid.
3NO, (g) + H,O (2) ——+ 2HNO, (aq) + NO @)
The NO thus formed is recycled and the aqueous HNO, can be concentrated
by distillation upto about 68% by mass.
Dilute nitric acid is further concentrated by dehydration with concentrated
sulphuric acid to get about 98% acid.
Properties of Nitric acid
Physical Properties
(i) Pure nitric acid is a colourless liquid.
(iz) It has boiling point 355.6 K and freezing point 231.4 K.
(zit) Laboratory grade nitric acid contains about 68% of HNO, by mass
and has a specific gravity of 1.504.
(iv) The impure acid is generally yellow due to the presence of nitrogen
dioxide as impurity. Nitric acid containing dissolved nitrogen dioxide is known
as fuming nitric acid.
(v) It has a corrosive action on skin and produces painful blisters.
Chemical Properties
1. Acidic character. It is one of the strongest acids because it is highly
lonised in aqueous solution giving hydronium and nitrate ions.
HNO,(aq) + H,O (2) ———> H,O° + NO, (aq)
It turns blue litmus red. It forms salts with metallic oxides, hydroxides,
carbonates and bicarbonates giving only one series of salts called nitrates.
NaOH + HNO, ——-> NaNO, + H,O
Na,CO, + 2HNO, ———-> 2NaNO, + H,O + CO,
NaHCO, + HNO, ——-> NaNO, + H,O + CO,
CaO + 2HNO, ——-> Ca(NO,),+ H,O
2. Decomposition. Nitric acid decomposes on heating giving nitrogen
dioxide, water and oxygen.
4HNO, (aq) ——Heat, 4NO, (g) + O, (g) + 2H,OW)
3. Action on metals. With the exception of gold and platinum (noble
metals), nitric acid attacks all metals forming a variety of products. The product
depends upon the nature of metal, the concentration of acid and temperature.
A. Metals that are more electropositive than hydrogen (Mg, Al,
Mn, Zn, Fe, Pb, etc.). In this case nascent hydrogen is liberated which further
reduces nitric acid.
M + 2HNO, ———> M(NO,), + 2H
(Metal)
HNO, + H — Reduction product + H,O
p-BLOCK ELEMENTS

In this case, the principal product is NO, with conc. HNO,, N,O with dil.
HNO, and ammonium nitrate with very dil. HNO,. For example, Zn reacts as:
Using concentrated nitric acid (forms nitrogen dioxide)
Zn + 2HNO, ——— Zn(NO,), + 2H
HNO, + H ——~+> NO, + H,O] x 2

Zn + 4HNO, ———> Zn(NO,), + 2NO, + 2H,O

Cone. Nitrogen
dioxide
Using dilute nitric acid (forms nitrous oxide)
Zn + 2HNO, ——— Zn(NO,), + 2H] x 4
2HNO, + 8H ———> 5H,O0+N,0
47n + 10HNO, ———> 4Zn(NO,), + N,O + 5H,O
Dilute Nitrous oxide
Using very dilute nitric acid (forms ammonium nitrate)
Zn + 2HNO, ———> Zn (NO,), + 2H] x 4
HNO, + 8H ———> NH, + 3H,O
NH, + HNO, ———> NH,NO,
47n + 10OHNO, ———> 4Zn (NO.,), + NH,NO, + 3H,O
V. dilute Ammonium
nitrate
B. Metals which are less electropositive than hydrogen (Cu, Bi, Hg,
Ag). In this case nascent hydrogen is not liberated.
HNO, ———> Reduction product + H,O + [O]
Metal + (O) + HNO, ———— Metal nitrate + H,O
The principal product is NO, with conc. HNO, and NO with dil. HNO,,.
For example, Cu reacts as
Using concentrated nitric acid
2HNO, ——— 2NO0, + H,0 + [O]
Cu+O+2HNO, ——+ Cu(NO,), + H,O
Cu + 4HNO, ——_-> Cu(NO,), + 2NO, + 2H,O
Cone. Nitrogen
dioxide
Using dilute nitric acid
2HNO, ——> 2NO + H,0O + 3[0]
Cu+O+2HNO, ——+> Cu(NO,), + H,O] x 3
3Cu + 8HNO, ——> 3Cu(NO,), + 2NO + 4H,O
Dilute Nitric oxide
Similarly,
Hg +/ 4NGae/— Hg (NO,), + 2NO, + 2H,O
(conc.) Mercuric nitrate
6Hg + 8HNO, ——— 3Hg, (NO,), + 2NO + 4H,O
(dil.) Mercurous nitrate
Ag + 2HNO, ———+ AgNO, + NO, + 2H,O
(conc.)
3Ag + 4HNO, ——> 3AgNO, +NO_ + 2H,0
C. Action on noble metals. Noble metals like gold and platinum are It may be noted that some metals
not attacked by nitric acid. However, these metals are attacked by aqua regia such a chromium and aluminium
(3 parts conc. HCl and 1 part conc. HNO,) forming their chlorides. donot dissolve in conc. ANG:
because of the formation of a
HNO, + 3HCl —— NOCI + 2H,0 + 2Cl passive film of oxide on their
wo ee Nitrosyl
Aqua regia chloride surfaces.
 MODERN'S abc + OF CHEMISTRY-XIl

The free chlorine attacks gold, platinum, etc.

Au + 3Cl ———+ AuCl,
Gold chloride
Pt + 4Cl —— > Pcl,
Platinum chloride
Chemical Reaction of Metal and HNO,
It may be noted that during chemical reactions of metals with HNOg, it not
only acts as acid but also as an oxidising agent. During its reaction, it gives a
variety of reduction products. The different stages of reduction of nitric acid are:
+o +e7 +? ees ee ie” 44e7 tf
HNO, ——> NOG NO ——— N,0 NEL
The product of the reduction of HNO, depends upon the
(4) nature of the metal
(it) concentration of nitric acid
(111) temperature.
In general, the more the dilution, the greater is the extent of reduction.
The mode of reactions of HNO, and metals can be divided into two main
categories.
(a) Metals lying above hydrogen in electrochemical series react with HNO,
as:
Metal +HNO, ———> Metal nitrate + H
HNO, + H ———> Reduction product + H,O
(6) Metals lying below hydrogen in electrochemical series react with HNO,
as:
HNO, ———> Reduction product + H,O + [O]
Metal + HNO, + OQ ——> Metal nitrate + EO
4, Oxidising nature — Oxidation of non-metals and compounds.
Nitric acid behaves as a strong oxidising agent. It has a tendency to give
nascent oxygen as :
2HNO, ———> 2NO, + H,O + O
(conc.)
2HNO, ———> 2NO + H,O- + 3(O)
(dilute)
Therefore, nitric acid oxidises many non-metals and compounds.
A. Oxidation of non-metals. Dilute nitric acid has no action on non-
metals like carbon, sulphur, phosphorus, etc. However, concentrated nitric
acid oxidises many non-metals. For example,
(4) Nitric acid oxidises sulphur to sulphuric acid
2HNO, ——-> 2NO, + H,O + O] x 3
~ S,+H,0+30 ——> H,SO,
~S, + 6HNO, ——> H,SO,+6NO, + 2H,O
or S,+48HNO, ——_> 8H,SO, + 48NO, + 12H,O
(it) Nitric acid oxidises carbon to carbonic acid
2HNO, ——-> 2NO, + H,O + O] x 2
C+H,O+20 ——_> H,CO,
C+4HNO, ——-> H,CO, + 4NO, + 2H,O
(tit) Nitric acid oxidises phosphorus to phosphoric acid
2HNO, ——~+ 2NO, + H,O + O] x5
2P + 3H,0 +50 ——>» 2H,PO,
2P + 10OHNO, ——_> 2H,PO, + 10NO, + 2H,O
or P+5HNO, ——> H,PO, + 5NO,+H,O
p-BLOCK ELEMENTS

or P, + 20 HNO, ——-> 4H,PO, + 20NO, + 4H,O

Phosphoric acid
(iv) It oxidises todine to iodic acid.
2HNO, ———+ 2NO, + H,0 + O] x 5
L,+ H,0O + 60 ——-+> 2HI0,

I, + 10HNO, ——-> 2HIO, + 10NO, + 4H,O

Todic acid
(v) Nitric acid oxidises arsenic to arsenic acid.
2HNO, ———+ 2NO, + H,0 + O] x 5
2As + 3H,O0 + 50 ——__> 2H.AsO,
2 As + 10HNO, ——— 10NO, + 2H.,AsO, + 2H,O
or As + 5HNO, ———> 5NO,+ H,AsO, + H,O
Arsenic acid

Similarly,
Sb + 5HNO, ——~+ H,SbO, + H,O + 5NO,
Antimoniec acid
B. Oxidation of compounds. Dilute as well as concentrated nitric acid Nitrous acid versus nitric acid
oxidises a number of compounds. Although nitric acid acts only as an
(vi) Nitric acid oxidises hydrogen sulphide to sulphur. oxidising agent, nitrous acid acts
dil HNO, : both as an oxidising agent as well
3H,5 + 2HNO, ——-> 2NO + 4H,0O,/4 35 as reducing agent.
conc. HNO, : e@ HNO, can be easily oxidised to
HNO,, therefore, it acts as a
HS + 2HNO, ——+> 2NO, + 20g 'S
reducing agent.
(vit) Nitric acid oxidises sulphur dioxide to sulphuric acid
eee 1als V0 eee oo debe
dil HNO, :
2HI + HNO,
350, + 2HNO, + 2H,O ——> 3H,SO, + 2NO e@ HNO, can be easily reduced to NO,
cone. HNO, : therefore, it acts as an oxidising
SO, + 2HNO, ——~+ H,s0, + 2NO, agent.
(viit) Nitric acid oxidises ferrous sulphate to ferric sulphate. eefgee |gVie oer a De,[0
dil HNO, :
2H,0 + 2NO +S
6FeSO, + 2HNO, + 3H,SO, ——~+ 3Fe,(SO,), + 2NO + 4H,O Zi >2
conc. HNO, :
2KOH + I, + 2NO
2FeSO, + 2HNO, + HsSO,——> Fe,(S5O,), + 2NO, + 2H,O
SO, + 2HNO, —> H,SO, + 2NO
5. Action on organic compounds. Nitric acid also reacts with organic
compounds. For example, sucrose (cane sugar) is oxidised to oxalic acid by nitric
acid.
COOH
Om = Fe A + 36HNO, —— > 6 ane = 36NO, + 23H,O
Sucrose Nedciat
Oxalic acid
In the presence of sulphuric acid, nitric acid reacts with aromatic compounds
forming nitro compounds. This process is called nitration. For example, it
reacts with benzene to form nitrobenzene.
C,H, + HNO, ~2“4, C,H,NO, + Ho
Benzene Nitrobenzene
Similarly, phenol reacts with nitric acid in the presence of H,SO, to give
2, 4, 6-trinitrophenol (known as picric acid).

Nitric acid attacks proteins giving a yellow nitro compound known as

xantho protein. Therefore, nitric acid stains skin and renders wool yellow.
 MODERN'S abc + OF CHEMISTRY-XIl

Structure. Spectroscopic studies have shown that gaseous nitric acid has
planar structure [Fig. 9 (a)]. Nitrate ion, NO, has also planar symmetrical
structure [Fig. 9 (b)].

(a) Nitric acid (6) Nitrate ion

The structure of NO, is resonance hybrid of the following structures :

0h O: 0: O
2. om

N ————e
I,
N ——s N
\, = N

Es 6aw QO: oy
a Os
hin’ :O7
70
|74N“O
y
Fig. 9. Structure of nitric acid and nitrate ion

Brown Ring test for NO,” ion

Nitrates give brown ring test with Fe** ions in the presence of conc. H,SO,.
The colour of the complex,
This is based upon the tendency of Fe** to reduce nitrates to nitric oxide which
[Fe(H,O).NO]** is due to charge
reacts with Fe* to form a brown coloured complex during the qualitative test
transfer i.e., an electron is for nitrates. The test is usually performed by adding dilute FeSO, solution to
transferred from NO to Fe** an aqueous solution containing NO, ion and then adding conc. H,SO, slowly
ion. As a result, this complex along the sides of the test tube. A brown ring at the interface between the
formally contains Fe (+1) and NO* solution and sulphuric acid indicates the presence of NO, ion.
(nitrosonium ion). The complex is 3Fe?* + NO, + 4H* ——~ NO + 3Fe* + 2H,O
named as pentaaquanitrosonium Fe** + NO + 5H,0 ——> [Fe(H,0), NO]?*
iron (I)(and not as pentaaquanitrosyl (Brown complex)
iron (II) ion. Uses of Nitric Acid
(1) Itis used in the manufacture of ammonium nitrate for fertilizers.
(it) It is used in the manufacture of sulphuric acid by lead chamber
process.
(iii) It is used in the manufacture of explosives such as trinitro toluene
(TNT), nitroglycerine, picric acid, etc.
(iv) It is used in the manufacture of dyes, perfumes and silk.
(v) It is used for the manufacture of nitrates for use in explosive and
pyrotechnics.
(vi) It is used in pickling (cleaning) of stainless steel and etching of metals.
(vit) It is also used as an oxidizer in rocket fuels.
(viit) It is used in the purification of gold and silver as aqua regia.

= — SOLVED EXAMPLES =
_} Example 7. _} Example 8.
Why does NO, dimerise ? Explain. Ammonia is a good complexing agent. Explain.
(Pb. S.B. 2013)
(D.S.B. 2010)(A.LS.B. 2014, Solution : Ammonia is a good complexing agent because of
Ar. S.B. 2015, Assam S.B. 2017) the presence of lone pair of electrons on nitrogen. This lone pair
Solution : NO, contains odd number of valence electrons. can easily be donated to electron deficient compounds forming
It behaves as a typical molecule. In the liquid and solid state, complexes. For example, it reacts with Cu** ion to form a deep
it dimerises to form stable N,O, molecule, with even number blue complex.
of electrons. Therefore, NO, is paramagnetic, while N,O, is Cu** (aq) + 4NH,(aq) ———> [Cu(NH,),]?*
diamagnetic in which two unpaired electrons get paired. Complex (deep blue)
p-BLOCK ELEMENTS

_} Example 9. the same direction as the N—H bond moments. Thus, it has
Why does ammonia act as a Lewis base? donor properties.
N(ASS.B. 2014 Kerala S.B. 2016, _L] Example 12.
Assam S.B, 2017)) Give one reaction in which ammonia acts as a reducing
agent.
Solution : Nitrogen atom in NH, has one lone pair of
electrons which is available for donation. Therefore, it acts as
Solution : When ammonia is passed over heated cupric
a Lewis base.
oxide, copper is formed as :
_L] Example 10. 3Cu0 +2NH, —“®%-,» 3Cu+N,+3H,O
Write the products of the following reactions (give L] Example 13.
balanced chemical equations) : Complete the reactions:
(i) Mg,N, +H,0 — (i) I,+ HNO, (cone.) —> (i) NEH,NO, (S$). —
Hee
(iit) Cu + HNO, (cone.) —> (iv) Li + N, —> (iw) N,O+ NaNH, »—>
Solution :
(1) Mg.N, + 6H, QO —> 3Mg(OH), + 2NH, (iii) Cu** (aq) + NH; (ag.) —>
SGanrania (iv) CuQf/+ NH, “Sf>
(iz) I, + 1OHNO, (conc.) —-+ 2HIO, + 10NO, + 4H,O Solution :
Todic Nitrogen Hea
(z) NH,NO, (s) a, N,O (g) + 2H,0 (2)
acid dioxide
(1zz) Cu + 4HNO, (cone.) —+ Cu(NO,), + 2NO, + 2H,O (it) N,O + 2NaNH, ——> NaN, + NH, + NaOH
Copper (iii) Cu**(ag) + 4NH, (ag) ————> [Cu(NH,),]** (aq)
nitrate (iv) 38CuO + 2NH, ——— 38Cu+N, + 3H,O
(iv) 6Li+N, —~+ 2Li,N
_}) Example 14.
Lithium nitride
_}) Example11. What is the covalence of nitrogen in N,O,
NF, does not have donor properties like ammonia. (D.S.B. 2013)
Explain. (Pb. S.B. 2015) Solution ; N,O, has the structure
Solution : NF, has a pyramidal shape with one lone pair
on N atom. @; gt

:0 No,
er an, In this structure, N atom has four shared pair of electrons,
two with an oxygen atom to form N =O bond, one with
The lone sae on N 2 in ascite dived on to the N-F oxygen atom to form N—O bond and one with another
bond moments and therefore, it has very low dipole moment oxygen atom to form N — O bond. Thus, the covalency of
(about 0.234 D). Thus, it does not show donor properties. But N in N,O, is four. It may be noted that for a coordinate
ammonia has high dipole moment because its lone pair is in bond, the covalency is also one.

— Answers to Practice Problems =

6. (i) NF, (ii) NH, (iii) N, (iv) N,O,
7. Trinitrotoluene
6. Give an example of compounds in which the oxidation state of nitrogen is
(4) +3 (i)-3 (iii) O (iv) +5 8. N,O. It is prepared by heating
7. What does the abbreviation T.N.T. stand for ? ammonium nitrate.
8. What is laughing gas ? How is it prepared ? 9. Leguminous plants
9. Which plants mostly help in nitrogen fixing ? 10. [Fe(H,0),NO]SO,.
0 . Write the formula of the compound formed during ring test of nitrate radical. pentaaquanitrosoniumiron(I)
Give its name. sulphate
11. Name the oxide of nitrogen ea ee (it) NO
(t) Which is blue solid ?
12. NO,
(11) Causes pollution problem.
12. Which oxide of nitrogen is produced by heating lead nitrate ?

_CHEMISTRY OF PHOSPHORUS AND ITS COMPOUNDS _

PHOSPHORUS
We have already learnt that phosphorus is widely distributed in nature.
It occurs mainly in the form of phosphate minerals in the crust of earth.
Phosphorus is produced by heating bone ash (containing about 58% of
calcium phosphate) or phosphate rock [Phosphorite, Ca,(PO,),] with silica
(S10,) and coke in an electric furnace at 1775 K.
| 7/28 MODERN'’S abc + OF CHEMISTRY-AXIl

The reactions taking place are :

2Ca,(PO,), + 6Si0, 472%, 6casio, + P,O,,
Calcium silicate
PO, + woe 225. wco PB,
The vapour of phosphorus thus produced upon condensation give white
phosphorus, which exists as P,.
ALLOTROPIC FORMS OF PHOSPHORUS
Phosphorus exists in many allotropic forms. Of these three main allotropic
forms are:
(1) White phosphorus
(it) Red phosphorus
(411) Black phosphorus
1. White phosphorus. It is the common variety of phosphorus and is
obtained from phosphorite rock with coke and sand in an electric furnace at
1775 K as explained above. It consists of P, units as shown in Fig. 10. In
this case, the four P-atoms lie at the corners of a regular tetrahedron with
ZPPP = 60°. Each phosphorus is bonded to each of the other three P-atoms
by covalent bonds, so that each P-atom completes its valence shell.
Properties :
The main characteristics of white phosphorus are :
(iz) It is soft, translucent white waxy solid with garlic smell.
(iz) It can be cut with a knife.
Fig. 10. Structure of (iii) It melts at 317 K and boils at 553 K.
white phosphorus (tv) It is insoluble in water but soluble in benzene, carbon disulphide,
liquid NH,.
(v) It is very poisonous. The vapours of phosphorus, if continuously
inhaled, may prove fatal.
(vi) It glows in dark (a property known as chemiluminescence).
(vii) White phosphorus, P, molecule are stable upto 1070 K even in the
vapour phase. When heated above 1070 K, P, molecules begin to dissociate
into P, molecules which have a bond enthalpy of 489.6 kJ mol’.
above 1070K
Pi 2P,
(viit) White phosphorus is less stable and therefore, more reactive than the
other solid phases under normal conditions. This is because of angular strain
in the P, molecules where the angles are only 60°. Its ignition temperature
is very low (303 K) and therefore, it catches fire in air to form dense white
fumes of P,O,,. Therefore, it cannot be kept in air to form dense white fumes
of P,O,,. It is generally stored under water.
P, + 50, —— > FO,
(ix) It combines with metals forming their phosphides such as Na,P,
Mg.P.,, Ca,P,, Ag,P, Cu,P,, etc.
12Na + P, —-+ 4Na,P
Sodium phosphide
12Ag + P, —W—> 4Ag,P
Silver phosphide
6Mg + P, ——> 2Mg.,P,
Magnesium phosphide
The reaction with sodium or potassium is very vigorous.
(x) It is a weak reducing agent and reduces sulphuric acid to sulphur
dioxide, nitric acid to nitrogen peroxide, etc.
P, + 10H,SO, —— > 10S0,+ 4H,PO, + 4H,O
Phosphoric acid
P, + 20HNO, ——~+ 4H,PO, + 20NO, + 4H,0O
p-BLOCK ELEMENTS

It also reduces solutions of copper, silver and gold salts to their corresponding
metals.
P, + 3CuSoO, + 6H,O ——»> Cu,P, + 2H,PO,+ 3H,SO,
Copper
sulphate
Cu,P, + 5CuSO, + 8H,O ———> 8Cu + 5H,SO, + 2H,PO,
or P, + 8CuSO, + 14H,O ———> 8Cu_ + 8H,SO, +2H,PO,+2H,PO,
Similarly,
P, + 20AgNO, + 16H,0———> 20Ag + 4H,PO,+ 20HNO,
(xi) It readily combines with halogens to form trihalides (PX,) and on
Strike anywhere matches
prolonged treatment forms pentahalides (PX,). For example, white phosphorus
The sulphide, P,S, is used in
catches fire in chlorine forming phosphorus trichloride (PCl,) and phosphorus
strike anywhere matches. The
pentachloride (PC1,).
matches contain P,S,, KClO,,
P 4 + 6Cl, ——— 4PCl, fillers and gelatin as a binder. The
P A + 10Cl, ——— 4PCl, frictional heat between the match
(excess) stick and the sand paper on the
(xii) White phosphorus combines with sulphur with explosive violence side of the match box initiates a
forming a number of sulphides such as P.S,, P,S., P,S3, P,S,, ete. violent reaction between P,S, and
BE, + 38,:—— > BPs, KCI1O,. This generates sufficient
Tetraphosphorus heat which makes match stick to
trisulphide burst into flames.
(xiii) On heating with caustic soda solution, it forms phosphine.
P, + 3NaOH + 3H,0 ——> PH, + £NaH,PO,
Phosphine Sodium
hypophosphite
This is an example of disproportionation reaction in which oxidation state
of phosphorus decreases from 0 in P, to —3 in PH,, while it increases from 0
in P, to +1 in NaH,PO,.
2. Red phosphorus. It is obtained by heating white

| IYpepe dpe
phosphorus in an inert atmosphere (out of contact of air) at
573 K for several days.

P,(s)
573 K
inert atmosphere P, (s) \IZ NI /
White phosphorus Red phosphorus
Like white phosphorus, red phosphorus also exists as
P, tetrahedra but have polymeric structure consisting of Fig. 11. Structure of red phosphorus.
P, tetrahedra linked together as shown in Fig 11.
In this structure, P, molecules are linked by covalent bonds. The important
characteristics of red phosphorus are :
(i) It is a hard crystalline solid without any smell. It posesses iron
orey lustre.
(ii) It is non-poisonous in nature.
(111) It is insoluble in water as well as carbon disulphide.
(iv) It is denser than white phosphorus.
(v) It does not glow in the dark.
(vi) Red phosphorus is quite stable and its ignition temperature is quite
high (5438 K). It, therefore, does not catch fire easily.
(vit) Chemically it is less reactive than white phosphorus.
(viii) It is a bad conductor of electricity.
(ix) It burns with oxygen at 565 K to form phosphorus pentoxide.
P,(s) +50,(g) —— P,O,,(s)
 MODERN'S abc + OF CHEMISTRY-iIl

REMEMBER (x) Being less reactive than white phosphorus, it reacts with halogens,
sulphur and alkali metals only when heated forming their
e@ White P is most reactive form corresponding salts.
while Heat ,
P, + 66), ss. 4PCI
e Black Pis the least reactive form. = os ‘i
P, € 20c,,. -——— > 4PECl.
Heat
4P, + 35, —— 8P,S,
P, + 12Na ~~, 4Na,P
(xi) Red phosphorus does not react with caustic alkalies. This property
is Made use in separating red phosphorus from white phosphorus.
(xii) Red phosphorus can be converted into white phosphorus by boiling
it in an inert atmosphere and then condensing the vapours of white
phosphorus formed under water.
3. Black phosphorus. Black phosphorus has two forms; c-black phosphorus
and B-black phosphorus, o-black phosphorus is formed by heating red
phosphorus in a sealed tube at 803 K.
803 K
Red phosphorus ms a o-Black phosphorus

p-~ Pas p—~ Pig p—~ Pr p— It can be sublimed in air and has opaque monoclinic or rhombohedral crystals.
99° | | | | B-Black phosphorus is obtained by heating white phosphorus at 473 K
aa gE nesgO ts si Ps |under very high pressure (4000-12000 atm) in an inert atmosphere.
| | 473K
pa PPN pe PPN p
PN p
PN White phosphorus 4000-1200 atm. pressure B-Black phosphorus

It has a double layered crystal lattice. Each layer is made up of zig-zag

gig pg gaggsrgO gg iy chains with P—P—P bond angles of 99° (Fig. 12) and P—P bond distance of
| | | | 218 pm . Since it is highly polymeric, therefore, it has high density.
Fig. 12. Structure of black phosphorus. The important characteristics of black phosphorus are :
(4) It has a black metallic lustre.
(it) It has sharp melting point of 860 K. Its specific gravity is 2.69.
(iii) It has a highly polymeric layered structure and exists in three
crystalline and one amorphous forms. Therefore, it has high density.
(tv) It is a moderate conductor of heat and electricity.
(v) It is thermodynamically the most stable and inactive form of
phosphorus. It does not burn in air upto 673 K.
Thus, the three allotropes of phosphorus differ in their chemical reactivity.
White phosphorus is the most reactive form while black phosphorus
is the least reactive form. Therefore, white phosphorus is stored under
water to protect it from air while red and black phosphorus are stable in air.
The main characteristics of three forms of phosphorus are summed up
in Table 7.
Table 7. Some physical properties of three forms of phosphorus.
Properties White Red
phosphorus phosphorus
Colour White but turns Dark red Black
yellow on exposure
State Waxy solid Brittle powder Crystalline
Density 1.84 g cm? 2.1g¢cem> 2.69 gem?
Ignition temperature 307 K 543 K 673 K
Stability Less stable at More stable at Most stable
ordinary ordinary
temperature temperature
Chemical reactivity Very reactive Less reactive Least reactive
p-BLOCK ELEMENTS

PHOSPHINE
Phosphatic Fertilizers
It is hydride of phophorus, PH,. To increase the fertility of soil
Preparation certain chemical compounds known
as fertilizers are used. These
(1) From phosphides. By the action of water or dilute mineral acid on
provide the essential nutrients,
metallic phosphides (Ca,P,, AIP, etc.) potassium, nitrogen and phosphorus.
Ca,P, + 6H,O0 ———> 3Ca(OH), + 2PH, The most important phosphatic
Calcium phosphide fertilizer is superphosphate of lime
Ca(H,PO,),. This is produced directly
Ca,P, + 6HCl ———+ 3CaCl, + 2PH, from phosphate rocks by treatment
Calcium phosphide with H,SO,. This makes insoluble
AIP + 3HCl ——-+ AICl, + PH, phosphate rock soluble in water to
iumprove the release of phosphorus to
Aluminium the soil for uptake by plants.
phosphide Ca,(PO,), + 2H,SO, —>
(ii) From phosphorous acid. Pure phosphine can be prepared by Ca(H,PO,), + 2CaSO,
heating phosphorous acid at 478 — 483 K. The phosphatic rock generally
contains fluorides which react with
4H,PO, ~~", 3H,PO,
478-483K
+ PH, H,SO, to give HF which in turn forms
Phosphorous acid Phosphoric acid other side products. The gaseous side
products are removed by washing
(iit) From phosphonium salts. Pure phosphine can also be obtained with water in a scrubber. About
by heating phosphonium iodide with caustic soda solution. 90% of phosphate rock mined is
PH,I + NaOH ——-—> Nal +H,0 + PH, used for the production of phosphatic
fertilizers and the remaining 10% is
Phosphonium iodide is obtained from phosphorus.
used for the production of elemental
P, + 21, + 8H,O ———> 2PH,I + 2HI + 2H,PO, phosphorus. Treatment of phosphate
(iv) Laboratory preparation. Phosphine is prepared in the laboratory rock with phosphoric acid gives triple
by heating white phosphorus with concentrated sodium hydroxide solution in super phosphate, Ca(H,PO,).H,O. It
is free from calcium sulphate and
an inert atmosphere of carbon dioxide or coal gas.
therefore, contains larger percentage
4P +3Na0OH + 3H,0 ——-> 3NaH,PO, + PH 3 of phosphorus :
Sodium Ca,(PO,),F + 7TH,PO, + 5H,O
hypophosphite —— 5Ca(H,PO,),.H,O + HF
It may be noted that pure phosphine is not inflammable but the gas may Phosphate Esters
catch fire in air. This may be due to the presence of impurity of P,H, which Phosphate esters are important
in life processes. The most important
is spontaneously inflammable. Therefore, a current of carbon dioxide, coal gas
of these biomolecules are DNA,
is passed through the flask to displace air. RNA, adenosine mono-, di- and fri-
To get pure phosphine, the gas is passed through a U-tube placed in a phosphates (AMP, ADP and ATP).
freezing mixture. The liquid P,H, gets condensed while PH, remains unaffected. These are discussed 1n Unit 14. These
contains P-O-P links, the hydrolysis
Impure gas may also be purified by treating it with hydrogen iodide followed
of these links releases energy which
by heating with KOH solution. can be put to useful work.
PH, + HI AQ, “4
Phosphonium iodide
PH, I + K@H —S=7f7H,
S + KI + 0
The impurity P,H, may also be controlled by using alcoholic solution of
potassium hydroxide in place of aqueous solution of caustic soda.
Structure
Like ammonia, phosphine has pyramidal structure. Phosphorus involves
sp® hybridisation. Three bonds are formed by the overlap of sp? hybrid orbitals
of phosphorus with 1s-orbital of hydrogen. One of the orbital is occupied by
a lone pair of electrons. The HPH bond angle in PH, is 93.6° and P—H bond
distance 142 pm.
Fig. 13. Structure of phosphine
PROPERTIES OF PHOSPHINE
Physical properties
(z) It is a colourless gas with unpleasant smell of rotten fish or garlic.
(it) It is highly poisonous in nature.
(iit) It is heavier than air (vapour density = 17) and is slightly soluble
in water.
 MODERN'S abc + OF CHEMISTRY-XIl

(iv) On cooling to 185.5 K, phosphine condenses to a liquid and on cooling

to 139.5 K_ it solidifies.
(v) Itis shghtly soluble in water. The solution of PH, in water decomposes
in presence of light giving red phosphorus and hydrogen.
Chemical properties
1. Action towards litmus. It is feebly basic and reacts with halogen
acids to form a phosphonium salt (basic nature).
PH, + HA«+— > BES (4 =Cl Br. DD
Phosphonium halide
e.g. PH, + HCl ——_> PH,g)
Phosphonium chloride
PH, + HBr ——~> JH,5r
Phosphonium bromide
PH, + HI ——¥+/#rna@
Phosphonium iodide
2. Combustibility. Pure phosphine is not combustible. But when
Summary of the chemical heated to 423 K in air or oxygen, it burns forming phosphoric acid.
properties of phosphine PH, 423 K
+ 2g > FPO,
3. Decomposition. By heating in the absence of air at 713 K
or by passing an electric spark through it, phosphine breaks into its
elements.

4PH 3
713 K
absence of air
P
4
+ 6H,
4, Action with chlorine. When heated in the atmosphere of
chlorine, phosphine burns forming phosphorus trichloride (PCl,) or
pentachloride (PC1,).
PH, + 3Cl,—— PCl, + 3HCl
PH, + 4ClL,—— PCl, + 3HCl
5. Action with nitrous oxide. When sparked with nitrous
oxide, it reduces the latter to nitrogen.
PH, 3 +4N,0——»> 4H,PO, + 4N,
6. Action with nitric oxide. Nitric oxide is reduced to nitrogen.
PH , + 4NO ——> H,PO, + 2N,
7. Precipitation reactions. When bubbled through certain metallic salt
solutions, phosphides of the metals get precipitated.
8CusO, + 2PH, ——~ Cu.P, + 3H,SO,
Copper sulphate Cupric phosphide
(Black ppt.)
38HgCl, + 2PH, ———+ Hg.P, + 6HCl
Mercuric chloride Mercuric phosphide
3AgNO, + PH, ——~> Ag.P + 3HNO,
Silver nitrate Silver phosphide
(Black ppt.)
Silver phosphide is converted to silver as follows :
Ag.P + 3AgNO, + 3H,O ——> 6Ag + 3HNO, + H,PO,
Uses of Phosphine
REMEMBER (4) It is used in preparing Holme’s signals for the ships to know about
the position of the rocks in the sea.
Holme's signals give signals to
A mixture of calcium carbide and calcium phosphide is taken in a vessel. A
ships in deep seas and oceans about hole is made in it and the vessel is immersed in the sea water near the rock. While
danger points. calcium phosphide liberates phosphine and calcium carbide liberates acetylene.
|
Ca.P, + 6H,O ——~+ 3Ca(OH), + 2PH,
CaC, + 2H,0 ——> Ca(OH), + C,H,
p-BLOCK ELEMENTS

Phosphine catches fire in air and lights up acetylene. This acts as a signal
for the approaching ship.
(it) It is used to prepare Smoke screens in warfare. Calcium phosphide
reacts with water to form phosphine which burns in air to form P,O,, which
acts as a smoke screen.
Comparision between Phosphine and Ammonia
Both ammonia and phosphine are the hydrides of the elements N and P
respectively which belong to the group 15 of the periodic table.
Thus, these hydrides are expected to have many common characteristics.
But they differ also in some of the properties. The comparison between the
properties of ammonia and phosphine is given below.

Points of resemblence
. Colour Colourless Colourless
. Decomposition by Decomposes into Decomposes into
electric spark elements elements
. Action with chlorine | Reacts violently to Reacts with chlorine to
form PCI, form nitrogen trichloride
. Actions with halogen | Forms phosphonium Forms ammonium salts
acids salts
. Combustibility Burns in air to form Burns in air to form
phosphoric acid nitrogen and water
Points of differences
1. Smell Unpleasant smell of Characteristic ammoniacal
rotten fish. smell.
. Density Heavier than air. Lighter than air.
. Solubility Sparingly soluble in Highly soluble in water.
water.
. Nature Highly poisonous. Non-poisonous.
. Action towards Neutral. Basic.
. Stability Less stable. More stable.
. Stability of salts Less stable. More stable.

HALIDES OF PHOSPHORUS
Phosphorus forms two types of halides .e., phosphorus trihalides (covalency
of P = 3) PX,(X = F, Cl, Br, I) and phosphorus pentahalides PX.(X = F, Cl,
Br) (covalency of P = 5). With chlorine it forms :
1. Phosphorus trichloride
2. Phosphorus pentachloride.
1. Phosphorus trichloride, PC],
Preparation. It is prepared in the laboratory by passing dry chlorine
gas over heated white phosphorus. The vapours of PCl, distil over and are
collected in a receiver cooled by water.
P,+ 6Cl, ———> 4PCl,
The receiver has a calcium chloride tube attached to it which protects it
from the reactions of outside moisture. It can be purified by distilling over
white phosphorus to remove the excess of chlorine.
It can also be obtained by the reaction of thionyl chloride with white Lone pair
phosphorus

[&
P, + 8SOCl, ——> 4PCl, + 4SO, + 2S,Cl,
Thionyl chloride
Structure
Phosphorus in PCl, undergoes sp’ hybridisation. Three of the sp* hybrid
orbitals overlap with p-orbitals of chlorine to form three P—Cl o bonds while
the fourth sp* hybrid orbital contains a lone pair of electrons. Therefore, like Fig. 14. Structure of phosphorus
PH,, PCl, has pyramidal structure as shown in Fig. 14. The C1—P—C] bond trichloride.
 MODERN'’S abc + OF CGHEMISTRY-KIl

angle in PCI, is 100.4° which is greater than HPH bond angle in PH,(93.6°).
This is due to stearic crowding of two large Cl atoms in comparison to H
atoms. As expected the P—Cl bond is much larger (240 pm) than P—H bond
(142 pm) because of larger size of Cl atom.
Properties of Phosphorus Trichloride
Physical Properties
(t) It is a colourless oily liquid fuming constantly is the moist air.
(it) Its specific gravity is 1.6.
(iit) Its boiling point and freezing point values are 347 K and 161 K
respectively.
(iv) It has a highly pungent smell.
Chemical properties
1. Action with water. It fumes in moist air and reacts with water
violently to form phosphorous acid.
PCl, + 3H,O ——-> H,PO, + 3HCl
Phosphorous acid
2. Action with atmospheric air or oxygen. It slowly combines with
dry oxygen to form phosphorus oxychloride.
2PCl, + ,_ “= 2POCIl,
Phosphorous oxychloride
3. Action with sulphur trioxide. It reacts with sulphur trioxide to
form phosphorus oxychloride.
PCl, + SO, ——> POCI, + SO 2
Phosphorus
oxychloride
4, Action with chlorine or sulphur. It combines with chlorine
or sulphur to form phosphorus pentachloride or thiophosphorus
oxychloride.
Wl.»¥Y Cl,— PCI,
BCle/ + Ss —— PSCl,
Thiophosphorus oxychloride
5. Action with sulphur monochloride, thionyl chloride and
sulphuryl chloride. It is readily oxidised to phosphorus (V)
derivatives, PCl., POC], and PSCl,.
3PCl, + §S,Cl,—— PCl, + 2PSCIl,
Sulphur
monochloride
3PCl, + SOCl,——> POC], + PSCl, + PCI,
Thionyl chloride
PCl 3 + SO,Cl,—— PCl 3 + SO 2
Sulphuryl] chloride
In these reactions, PCl, behaves as a reducing agent.
6. Action with organic compounds. It reacts with organic compounds
containing —OH group such as acetic acid, ethyl alcohol, ete.
(4) With organic acid, it forms acid chlorides.
3CH,COOH + PCl, ———> 3CH,COCl] + HPO,
Acetic acid Acetyl chloride Phosphorous acid
(it) With alcohols, it forms alkyl chlorides.
3C,H.OH + PCl, ———+> 3C,H-Cl + HPO,
Ethy alcohol Ethyl chloride Phosphorous acid
7. Action with finely divided metals. Finely divided metals react
on heating to form metal chlorides.

12Ag + 4PCl —““, 12AgCl + P,

6Na + PCI, Heat, 3NaCl + Na,P
8. PCl, undergoes many substitution reactions and is main source of
organophosphorus compounds.
p-BLOCK ELEMENTS

Uses It may be noted that in gaseous

It is mainly employed in the organic chemistry as an important reagent and liquid phases, PCl, has
to replace the hydroxyl group (-OH) by chlorine atom in organic reactions. trigonal bipyramidal structure.
2. Phosphorus pentachloride, PCl, However, inthesolid state, it exists
Preparation. Phosphorus pentachloride is prepared by the reaction of as an lonic solid [PC1,]* [PCl1,I-.
white phosphorus with excess of dry chlorine. In this, the cation [PCl,]* is
P, + 10Cl, ———> 4PCl, tetrahedral and the anion [PCl,]~
(Excess) is octahedral.
It can also be obtained by the reaction of dry chlorine on phosphorus In solution, it exists either
trichloride. molecular or ionically dissociated
PCl, + Cl, ———> PCl, depending on the nature of the
Phosphorus pentachloride can also be prepared by the action of SO,Cl, solvent.
on phosphorus.
P, + 10S0,Cl, ———> 4PCl, + 10SO,
Structure
In PCl., phosphorus undergoes sp*d hybridisation and has trigonal
bipyramidal structure as shown in Fig. 15. It has three equatorial
©
P—C] bonds and two axial P—C] bonds which are different. Therefore, all the l
five P—C] bonds are not equal. The axial bonds are larger than equatorial |
bonds as :
|
P—C] (axial) = 219 pm, P—Cl (equatorial) = 204 pm I
|
Properties of Phosphorus pentachloride, PC1,
Physical
(4) It is a yellowish white powder having pungent smell. Fig. 15. Structure of PCl..
(it) It fumes in moist air due to its strong affinity for water.
(iit) On heating, it sublimes at 483 K and can be melted (m.p. 318 K)
only by heating it under pressure.
Chemical properties
1. Stability. PCl, is thermally less stable than PCl,. On heating it sublimes REMEMBER
but decomposes on stronger heating into trichloride and chlorine.
Pentahalides are thermally less stable
PCl. == PCI, + Cl, than trihalides. For example, PCl,
2. Action with water. In moist air, it hydrolyses to POCI, and finally exists as molecules in the gaseous
gets converted to phosphoric acid. state but exists as [PC1,]* [PCl,]1n the
PCl.+ H,O ——_/ cl, + 2HCl crystalline state. PBr, and PI, also exist
Phosphorus oxychloride in the ionic forms as [PBr,]* Br and
POC], + 3H,O (~aoWHPYy + 3HCl [PI,]*I- respectively in the solid state.
Phosphoric acid
3. Action with compounds containing OH group. It reacts with
compounds containing hydroxyl groups (—OH) to give the corresponding
chloro compounds in which each —OH group is replaced by a chlorine
atom. For example,
(4) With organic acid
CH,COOH + PCl.——+ CH,COCl + POCI, + HCl
Acetic acid Acetyl chloride
(it) With ethyl alcohol
C,H,OH + PCl,——> C,H,Cl + POCI,+ HCl
Ethyl alcohol Ethyl chloride
(it) With sulphuric acid
HO—SO,—OH + 2PCl, ——>ClSO,Cl + 2POCI, + 2HCl
Sulphuric acid Sulphuryl chloride
4, Reaction with phosphorus pentoxide and sulphur dioxide. PCl,
reacts with P,O,, forming phosphorus oxychloride and with SO, forming
phosphorus oxychloride and thionyl chloride.
6PCl, + P,O,, ——— 10POCIl,
Phosphorus oxychloride
a 7/36 MODERN'S abc + OF CHEMISTRY-iIl

PCl. + SO, —— POC], + SOCI,

Phosphorus’ Thionyl
oxychloride chloride
5. Reaction with phosphorus pentasulphide. PCl, reacts with
phosphorus pentasulphide to form phosphorus thiochloride.
6PCL + B.8,,-——— 10PSel,
Phosphorus Phosphorus thiochloride
penta sulphide
6. Reaction with metals. PCl, reacts with finely divided metals on
heating to give corresponding chlorides.
2Ag + PCl. ——> 2AgCl + PCl,
Sn + 2PCl, ——~+ SnCl, + 2PCl,
7. Reaction with chloride ion acceptors. PCl. forms addition products
with chloride ion acceptors such as boron trichloride containing
tetrahedral [PCl1,]* species.
PCl. + BCL, {~SECHY? [BCLI-
PCl. + NbCl, ~—~ [PC1,]* [NbCl,]-
8. Reduction. Phosphorus pentachloride is reduced with hydrogen to
form PCl.,.
PCL. + 2H ———» PCl, + 2HCl
9. Reaction with potassium fluoride. With KF, PCl,. forms potassium
phosphorus hexafluoride, K*[PF,|-.
PCl. 3 + 6KF —~> K*[PF,]> + 5KCI
Potassium phosphorus
hexafluoride
Uses
Fiig. 16. S Structure of FPO It is extremely useful in organic reactions to replace a hydroxyl group
P,O,. (-OH) by chlorine atom such as for the synthesis of C,H,Cl, CH,COCI, ete.

OXIDES OF PHOSPHORUS
Phosphorus forms two common oxides namely (2) phosphorus trioxide (P,O,)
and (it) phosphorus pentaoxide (P,O,,)

Phosphorus also forms phosphorus 1. Phosphorus (IID) oxide (P,Og)

tetraoxide, P,O,. It is prepared from Preparation
P,O, as Phosphorus trioxide is formed when phosphorus is burnt in a limited
4P,0, “*S 3P,0, + P, supply of air.
Red phosphorus Fr; + 30, (limited) ——> P,O.
It is a colourless solid. Properties
Both P,O, and P,O,, are acidic oxides (i) Phosphorus (III) oxide is a crystalline solid with garlic odour.
and they react with water to form (it) It is soluble in carbon disulphide, ether and chloroform.
aqueous solutions of phosphorous acid side ae i oe |
and phosphoric acid, respectively: (111) Heating 1n air. On heating in air, it forms phosphorus pentaoxide.
P,O, (s) + 6H,O (2) —» H,PO, (aq) P,O, + 20, ——> P,0,, _
Phosphorous acid Phosphorus (V) oxide
P,O,, (s) + 6H,O (1) —+ H,PO, (aq) (iv) Action of water. It dissolves in cold water to give phosphorous acid.
Phosphoric acid P,O, + 6H,0 ———> 4H,PO,
It readily reacts with water to (cold) Orthophosphorous acid
give phosphorous acid (H,PO,) and It is, therefore, considered as anhydride of phosphorous acid.
phosphoric acid (H,PO,).
With hot water, it gives phosphoric acid and inflammable phosphine.
P,O, + 6H,0 —-> 2H,PO, + 2H,PO,
Phosphorous Phosphoric
P,O, + 6H,O (hot) ———> 3H,PO, + PH,
ca aba Phosphoric acid
Its structure is similar to P,O, but in (v) Action with chlorine. It reacts vigorously with chlorine to form a
addition, twoP atoms form coordinate mixture of phosphoryl chloride and metaphosphoryl chloride.
bonds with their lone pairs of electrons Ej, 41, 2POCIl, + 2PO,Cl
to two O atoms. In P,O,,, all the four Phosphoryl Metaphosphoryl
P atoms form coordinate bonds. chloride chloride
p-BLOCK ELEMENTS

Structure. Each atom of phosphorus in P,,O, is present at the corner of a

tetrahedron (just as P, units in elemental phosphorus). Each phosphorus atom
is covalently bonded to three oxygen atoms and each oxygen atom is bonded to
two phosphorus atoms. This is shown in Fig. 16. It is clear from the structure
that the six oxygen atoms he along the edges of the tetrahedron of P atoms.
2. Phosphorus (V) oxide (P,O,,)
Preparation
It is prepared by heating white phosphorus in excess of air.
P,+ 50, (excess) ———-> P,O,,
Properties
(4) It is snowy white solid.
(11) Action with water. It readily dissolves in cold water forming
metaphosphoric acid
P,O,, + 2H,O ——— 4HPO,
(cold) Metaphosphoric acid
With hot water it gives phosphoric acid.
P,O,, + 6H,0 ——~> 4H;,PO, |
(hot) Phosphoric acid
(iit) Dehydrating nature. Phosphorus pentaoxide has strong affinity
for water and therefore, acts as a powerful dehydrating agent. It
extracts water from many organic and inorganic compounds including
sulphuric acid and nitric acid.
Fig. 17. Structure of P,O,>.
P,O
H,SO, > SO;
P,O
2HNO, <0” N,O-

2HCIO, ee Cl,0,
Perchloric acid Chlorine (VII) oxide

| P,O19
CH,CONH, =H,0” CH,CN
Acetamide Methyl cyanide
Structure. Its structure is similar to that of P,O,. In addition, each
phosphorus atom forms a double bond with oxygen atom as shown in Fig. 17.
OXOACIDS OF PHOSPHORUS
Phosphorus forms a number of oxoacids as given in Table 8.
Table 8. Oxoacids of phosphorus
Formula Oxidation state of P
Phosphinic acid
(or Hypophosphorous acid)
Phosphonic acid REMEMBER
(or orthophosphorous acid or phosphorous acid) The P—OH group in oxoacids of
Pyrophosphorous acid phosphorus is ionisable and gives
Hypophosphoric acid proton. Therefore, number of P—OH
Orthophosphoric acid (or phosphoric acid) sroups determines the basicity of the
Diphosphoric acid oxoacid.
(Pyrophosphoric acid)
Metaphosphoric acid
Peroxophosphoric acid
Some important oxoacids of phosphorus are discussed below :
(i) Phosphinic acid or Hypophosphorous acid, H,PO,
Preparation. It is prepared by heating phosphorus with alkalies like
barium hydroxide when precipitate of barium phosphate is formed. The
precipitate is separated and heated with a calculated amount of sulphuric acid.
irae MODERN'S abc + OF CHEMISTRY-iIll

3Ba(OH), + 2P, + 6H,O 2, 2PH, + 3Ba(H,PO,),

O
ppt
Ba(H,PO,), + H,SO, ——— BaSO, + 2H,PO,

iw
P
Barium sulphate is separated by filtration and solution is concentrated
when hypophosphorous acid separates out.
H H It has one P==O, one P—OH and two P—H bonds. Since it has only one
Phosphinic acid P—OH bond, so it has only one ionizable hydrogen atom. Therefore, it behaves
as monobasic acid, lonising as :
or Hypophosphorous acid
Basicity = 1 HPO, == H+ ZN
The other two hydrogen atoms directly bonded to P are not ionizable. Due
to the presence of two P—H bonds, the acid as well as it salt behave as strong
reducing agents. Therefore, it is used in organic chemistry to reduce arene
diazonium salts to arenes.
On heating to 313 K it decompose to phosphine
8H,PO, 222 ROPH/ + 2H,PO,
Phosphine Phosphorous acid
However, on heating above 333K, it decomposes to phosphoric acid and
phosphine
2H,PO, 725, H.PO, + PH 3
Phosphoric acid Phosphine
(it) Orthophosphorous acid or Phosphonic acid, H,PO,.
Preparation. It is prepared by the hydrolysis of phosphorus trichloride
or trioxide.
PCl, + 3H,0 ———> H,PO, + 3HCl
Phosphonic acid or P,O, + 6H,0 ———> 4H,PO,
Orthophosphorous acid
Basicity = 2 It has one P=O, one P—H and two P—OH bonds. Since it has two P—OH
bonds, so it has two ionisable H atoms. Therefore, it behaves as dibasic or
diprotic :

HPO, =— H* +.H,Po0, K. =13 16"

1
H,PO; —— H* + HPO? K, =2x 10%
2
It gives two series of salts such as NaH,PO, and Na,HPO,, known as
sodium dihydrogen phosphite and disodium hydrogen phosphite respectively.
On heating it decomposes into phosphoric acid and phosphine :

4H,Po, *°7%, 3H.PO,+ PH,

It is readily oxidised by air in the presence of a catalyst iodine into
phosphoric acid.
2H.PO, + 0, “> 2H.PO,
It is a strong reducing agent.
O (iii) Orthophosphoric acid, H,PO,
Preparation. It is prepared by adding phosphorus pentaoxide to water
le and boiling the solution.
ee. P,O,, + 6H,0 ———> 4H,PO,
OH 4 \~ —
A small amount of metaphosphoric acid may also be formed but it changes
Orthophosphoric readily into phosphoric acid on boiling.
acid It can also be prepared by heating phosphorus with conc. HNO, or by
Basicity = 3 dissolving PCl, in water
P, + 20HNO, —“Heat
> 4H,PO, + 20NO, + 4H,O
PCl, + 4H,O —“5 H,PO, + 5HCl
Heat
p-BLOCK ELEMENTS 7/39 »»

It has one P=O and three P—OH bonds. Since it has three P—OH bonds,
so it has three ionisable H atoms. Therefore, it behaves as tribasic or triprotic
and lonises in three stages :
H,PO, —— H*+H,P0, K,, = 7.5 x 10°
H,PO, == H*+ HPO,” K,, = 6.2 x 10°
HPO,” =—— PO,” K,, = 1.0 x107
Therefore, it forms three series of salts such as NaH,PO, (eoduiai dihydrogen
phosphate), Na,HPO, (disodium hydrogen phosphate) and Na,PO, (sodium
phosphate).
(itv) Pyrophosphoric acid, H,P,0O,
It contains phosphorus in +5 oxidation state.
Preparation. It is prepared by heating orthophosphoric acid to 523K.

9H,PO, =, H,P,0, + H,O

Pyrophosphoric
acid
The acid is formed by the loss of a molecule of water from two molecules
of phosphoric acid and has the structure :
OH OH

P P
re \No \No
OH OH
It contains four P—OH bonds, two P=O bonds and one P—O—P bond.
Since it contains four OH groups, it is tetrabasic. It dissolves in water to
form orthophosphoric acid.
H,P,0, + H,o Het, 2H.PO,
Orthophosphoric acid
Upon strong heating, it decomposes to form meta phosphoric acid

H,P,o, 2", | 2HPO, + HO

Metaphosphoric acid
(v) Metaphosphoric acid, HPO,
It has one P—OH bond and therefore, exists as monobasic.
Preparation. It is prepared by heating orthophosphoric acid to 525 K.

p20 K
H.PO, a HPO, + H,O
Orthophosphoric Metaphosphoric
acid acid
However, it may be noted that metaphosphoric acid does not exist as simple
monomer, rather it exists as cyclometaphosphoric acid or polymetaphosphoric
acid.

ea x

he
N, Yo
gp tg
P p p
Pa \s \o/ Do No” bo”
Trimetaphosphoric acid Polymetaphosphoric acid
(HPO3)3 (HPO,),,
 MODERN'S abc + OF CHEMISTRY-XIl

The basie structural and characteristic features of these phosphorus

oxoacids are :
(t) All these acids contain phosphorus atom or atoms bonded tetrahedrally
to four other atoms or groups.
(it) These contain at least one P—=O unit and one P—OH group. The
P—OH group is ionizable giving proton. The number of P—OH groups
determines the basicity of the oxoacid.

| ~~P ay, + . Ht
O O

P=
oo. i.
(4it) Some oxoacids have one (or more) P—H groups and this bond is
non-ionisable.

|
Y~n
(iv) Some oxoacids have P—O—P or P—P bonds obtained by corner
sharing of tetrahedra.

O O
|
a Neate
(v) Peroxo acids have P—O—O—H or P—O—O—P linkages.
(vt) The oxoacids in which P has lower oxidation state (less than +5)
contain in addition to P—OH and P=O bonds, either P—P (e.g., in H,P,O,)
or P—H (e.g., in H,PO,) bonds but not both. These oxoacids in +3 oxidation
state of P tend to disproportionate to higher and lower oxidation states.
For example, ortho phosphorous acid (or phosphorous acid) on heating
disproportionates to give ortho phosphoric acid (P = +5) and phosphine, PH,
REMEMBER a) Sey
Peroxomonophosphoric acid (H.,,PO-) +3 +5 —3
and peroxodiphosphoric acid 4i1,PO, — SIabl SO; cel
(H,P,O,) contain -O—O— linkages.
Orthophosphorous acid Orthophosphoric acid Phosphine
(vit) Acids which contain P—H bonds have strong reducing properties.
For example, hypophosphorous acid is a good reducing agent because it
contains two P—H bonds and therefore, reduces AgNO, to metallic silver.
4AgNO, + 2H,0 + H,PO, ———> H,PO, + 4Ag + 4HNO,
It is used in organic chemistry to reduce arene diazonium salts to arenes.
C,H,.N,Cl + H,PO, + H,O ——> C,H, +H,PO,+ N, + HCl
Benzene Benzene
diazonium chloride
p-BLOCK ELEMENTS 7/41 —

The structures of different oxoacids of phosphorus are given below :

ee —
molecules

AO
Metaphosphoric
acid
Be
Orthophosphoric acid
HPO, (P = +5)
a acid
(or Pyrophosphoric acid)
HPO, (P = +5) (Tribasic) H,P,0, (P = +5)
(Monobasic) (Tetrabasic)

+{O] A{] |-[O]

UA.O—OH Ax oe —-
OH OH
eure) acid i oric acid Hypophosphoric acid

(Tribasic) (Tetrabasic) (Tetrabasic)

O O
| 2m/w , || |

ANG Nw Vj» AO\Wo7™s

Hypophosphorous acid siteaeaiaes a) Pyrophosphorous acid
or Phosphinic acid or Phosphonic acid H,P,O, (P = +3)
HgPO, (P = +1) HgPOs (P = +3) (Dibasic)
(Monobasic) (Dibasic)

The formulae of oxyacids of P can be remembered as :

The prefix
@ meta acid is used for the acid obtained by the loss of one water molecule.
® pyroacid is used for the acid obtained by heating two molecules with loss of one water molecule.
@ ‘iypo' is generally used for the acid having lower oxygen content than the parent acid.
The main oxoacids of phosphorus acid are summed up below :

SUM UP
Oxoacid Formula Characteristic bonds Method of preparation
W
Hypophosphorous P, + 40H + 4H,0O WaOH/Ga(Ow,” BWIA se BL
or Phosphinic

Orthophosphorus PO : | PO, + 6H,0

or Phosphonic | PCl, + 3H,O

Pyrophosphorus ! | Fe AL Fe a) 5 Uloe Oe 8
 MODERN'S abc + OF CHEMISTRY-XIl

Hypophosphoric Four P—OH 2P+ 2NaClO, + 8H,0 ——— Na,H,P,0,.6H,O + 2HCl

Two P=O Sod. salt of
One P—P hypophosphorie acid

Orthophosphoric P,O,, + 6H,O —_— 4H,PO,

P, + 20HNO, Heat
4H,PO, + 20NO, + 4H,O
PCl, + 4H,O Heat H,PO, + 5HCI

Pyrophosphoric Four P—OH

Two P=O
One P—O—P

Metaphosphoric Three P—OH 525K’,

525 K /HPO, + H,O
Three P=O
Three P—O—P
for (HPO,),

| SOLVED EXAMPLES
a=

_} Example 15 (e) POCL, +3H,0 M——-+ H,PO,+3HCl

In what way it can be proved that PH, is basic in () 3HgCl,+2PH, ——— > Hg,P,+6HCl
nature. (g) 2Ag+PCl.—-2AgCl+ PCl,
Solution : PH, reacts with acids like HI to form phosphonium LJ Example 18
iodide, PH,I.
Why does PCL, fume in moisture ?
PH, + HI ——> PH,lI
.C.E.R.T. (Hr.S.B. 2015, 2017, Kerala S.B. 2016)
Phosphonium iodide
This shows that PH, is basic in nature. This basic nature Solution: PCl, gets hydrolysed in the presence of moisture
of PH, is due to the presence of lone pair on phosphorus atom and gives fumes of HCl.
and therefore, it acts as a Lewis base. PC], +3H,O ——> H,PO,+3HCI
_}] Example 16 _} Example 19
Write the disproportionation reaction of H,PO . Calculate the volume of 0.1 M NaO8 solution required
(Assam S.B. 2013) to neutralize the solution produced by dissolving 1.1 g
Solution : On heating H,PO, disproportionates to give of P,O,in water.
phosphoric acid and phosphine.
Solution : P,O, reacts with water to form phosphorous
4H,PO, ——-> 3H,PO, + PH, acid (H,PO,) as :
_} Example 17
P,O, +6H,O ——> 4H,PO, z(t)
Write balanced equations for the following reactions:
HPO, is dibasic and it neutralizes with NaOH as :
(QQ) P,+NaOH+H,O -——> (D.S.B. 2009, H,PO, + 2NaOH ——-> Na,HPO, + 2H,O ...(1t)
Tripura S.B. 2016, Assam S.B. 2016)
(Assam S.B. 2013) Multiply eqn. (iz) by 4 and add to eqn. (z) :
(db) As, + Cl, (excess), ———> P,O, + 8NaOH ——-> 4Na,HPO, + 2H,O
4x31+6x16 8(23+16+1)
(c) PO, He Ce 7° = 220 ¢ = 320¢
(d) Ca,P, +H,O ———> D.S.B. 2008, 2014)
Now 220 g of P,O, require NaOH = 320 g
(e) POCI, +H,Q ——_> 1.1 g of P,O, will require NaOH for neutralization
(p) HgCl,+PH, ——> (A./.S.B. 2010) 320
= — x1.1=1.6
(g) Ag+PCl, ——,> (A. LSB. 2014) 220 6

Solution :
Wt. of NaOH present in 1000 mL of 0.1 M NaOH =4¢
(a) P,+3Na0H+3H,O0 ——> PH, + 3NaH, PO, ”. 4g of 0.1 M NaOH is present in = 1000 mL
Phosphine . 1.6 g of 0.1 M NaOH is present in
(db) As,+10Cl, ——> 4AsCl,
1000 x 1.6
(c) P,O,,+6H,O ——-> 4H,PO, = —— > = 400 mL
(d) Ca,P,+6H,O ——> 2PH,+3Ca(OH), Vol. of 0.1 M NaOH required = 400 mL.
p-BLOCK ELEMENTS

_} Example 20 _}] Example 25

All the five bonds in PCI, are not equivalent. Justify. What happens when
N.C.E.R.T)
(A.I.S.B. 2008, D.S.B. 2012, (i) (NH,),Cr,O, is heated?
Pb.S.B. 20138, 2015, 2017) (ii) PCl, is heated? (H.P.S.B. 2015)
Solution : PCl, has trigonal bipyramidal structure in (iit) HPO, is heated? Write the equations involved.
which there are three P—C] equatorial bonds and two P—Cl (ALS.B. 2015, DSB. 2008, 2013, 2017)
axial bonds. The two axial bonds are being repelled by three Solution :
bond pairs at 90° while the three equatorial bonds are being
(z) On heating (NH,),Cr,O,, nitrogen gas is evolved.
repelled by two bond pairs at 90°. Therefore, axial bonds are
repelled more by bond pairs than equatorial bonds and hence (NH,),Cr,0, —*“> Cr,O, + N, + 4H,O
are larger (219 pm) than equatorial bonds (204 pm). (zi) On heating, PCl, first sublimes and then decomposes
_}] Example 21 on strong heating :
HPO, is diprotic acid. Explain. Pcl, —=-¥ PCl, + Cl,
(Hr.S.B. 2005, H.P.8.B. 20165, Pb.S.B. 20138, 2017) (iit) On heating, H,PO, disproportionates to give
Solution : H,PO, has three H atoms and therefore, it is orthophosphoric acid and phosphine.
expected to be tribasic. However, in its structure, two hydrogen +3 +5 —3
atoms are joined through oxygen atoms and are ionisable. The 4H,PO, —— 3H,PO, + PH,

|
third H a is linked to P and is non-ionisable. Orthophosphoric Phosphine
acid
_}] Example 26
H,PO, es
—_—__ HPO,2 + 2H*

a,
(i) Draw the structure of phosphinic acid (H,PO,).
(it) Write a chemical reaction for its use as reducing
HO H
agent, (C.B.S.E. Sample Paper 2011)
_} Examp 22 Solution : (i) Phosphinic a HPO.
le
How do you account for the reducing behaviour of
HPO, on the basis of its structure.
|
a
(Assam S.B. 2016) ) OH
Solution : H,PO, has one P==O, one P—OH and two HW” Se
P—H bonds as. (1) H,PO, reduces Ag* ion to Ag which shows its reducing

|
nature.
H,PO, + 4AgNO, + 2H,O —> 4Ag + 4HNO, + H,PO ie
we _} Example 27

HO
/ Osi (a) Suggest a quantitative method for estimation of the
gas which protects us from U.V. rays of the sun.
Since two H atoms are bonded directlytoP atom which impart (b) Nitrogen oxides emitted from the exhaust system of
reducing character to the acid. supersonic jet aeroplanes slowly deplete the concentration
_} Example 238 of ozone layer in upper atmosphere. Comment.
What happens when white phosphorus ts heated with (C.B.S.E. Sample Paper 2011)
concentrated NaO8H solution in an inert atmosphere Solution : (a) The gas which protects us from U.V. rays
of CO, ? N.C.E.R.T. of the sun is ozone. It reacts with I ions to give iodine as :
Solution : Phosphine is formed. O, + 2l + H,O ——> O, + 1, + 20H
P, + 3NaOH + 3H,O —““> PH, + 3NaH,PO, I, liberated is titrated against sodium thiosulphate solution
and amount of O, can be estimated.
Phosphine Sodium
hypophosphite (6) The release of nitrogen oxides (NO,) into stratosphere
by the exhaust system of supersonic jet aeroplanes deplete the
_} Example 24
concentration of O, because NO reacts with O, to give O,.
What is the basicity of H,PO,? NO (g) + O, (g) ——=>
NO, (g) + O, (g)
IN.C.E.R.TA.L.S.B. 2014, H.P.S.B. 2017) Therefore, NO is slowly depleting the concentration of ozone.
Solution: H,PO, contains three P—OH bonds and therefore,
_L] Example 28
its basicity is three.
O NCI, is readily hydrolysed while NF, does not. Explain.
Solution: In NCl,, Cl has vacant d-orbitals to accept the
lone pair of electrons donated by oxygen atom of H,O molecules.
Pon But in NF,, F does not have vacant d-orbitals. Therefore, NC1,
of Nou undergoes hydrolysis but NF, does not.
 MODERN'S abc + OF CHEMISTRY-All

NCl,+ 3H,O ——-+ NH, + 3HOCl (c) highest bond angle?

NF, + HO —3 No reaction (d) maximum reducing character? (A.LLS.B. 2018)
Solution: (a) PH,
_] Example 29
Among the hydrides of Group 15 elements, which have the (6) NH,
(a) lowest boiling point? (c) NH,
(b) maximum basic character?
(d) BiH,

13. Give one example each of oxyacid of P having the oxidation state
(i) +4 (it) +3
14, What is the chemical formula of laughing gas ? How is it prepared ?
15. Among the hydrides of group 15, predict the hydride having
(¢) most basic character (it) highest thermal stability
(zit) lowest boiling point (iv) strongest reducing agent.
16. Name the oxide of nitrogen obtained in the following reactions :
— Answers to Practice Problems = Heat
(i) Pb(NO,), 673 K
13. (2) Hypophosphoric
(it) Phosphorus acid (ii) NH NG, SSA
ie as Lae
(iii) N,O,+NO —**
15. (:) NH, (12) NH, (zt:) PH,
(iv) Big. 17. What is the oxidation state of phosphorus in the following :
16. (1) Nitrogen dioxide (i) H,PO, (ii) PCI,
(it) Nitrous oxide
(ii?) Ca,P, (iv) Na,PO,
(zit) Dinitrogen trioxide.
(v) POF,
17. (i) +3 (it) +3 (tit) -3 (iv) +5
18. Which of the following has maximum P—OH bonds ?
(uv) +5.
18. (zit) (t) Orthophosphoric acid
19. (1) Metaphosphoric acid (tt) Pyrophorous acid
(11) Phosphonie acid (iit) Pyrophosphoric acid
20. orthophosphoric acid, 19. Name the oxoacid of P which
metaphosphoric acid, (z) exists as polymeric
pyrophosphoric acid (it) has basicity two
20. Name three oxoacids of P having oxidation state of P as +5.

Jues
Conceptual ons ham

Draw the structure of P i and identify the number of single and double P-O bonds.
See text. Double bonds = 4, single bonds = 12.
Nitric oxide becomes brown when released in air.
When nitric oxide, NO is released in air, it becomes brown due to the formation of NO, (nitrogen dioxide), which is
a brown gas.
2NO (g) + O, (g) —> 2NO, (g)
(Brown)
p-BLOCK ELEMENTS 7/45 —

Q.3. Solid PCI, is ionic in nature. (AL S.B. 2076)

Ans. PCI, is ionic in the solid state because it exists as [PC1,]* [PCl,]- in which the cation is tetrahedral and anion is
octahedral.
Q.4. Concentrated nitric acid turns yellow on exposure to sunlight. Why ?
Ans. On exposure to sunlight, nitric acid decomposes into NO,, O, and H,O. The presence of NO, in the partially
decomposed nitric acid gives it yellow colour.
4HNO, (1) —> 4NO,(g) + O, (g) + 2H,0 (2)
. Why does not nitrogen form pentahalides like phosphorus ?
. Nitrogen does not have vacant d-orbitals in its valence shell. Therefore, it cannot extend its valency beyond 3.
Therefore, 1t can form maximum of four bonds and cannot form pentahalides. On the other hand, phosphorus has
vacant 3d-orbitals in the valence shell and therefore, one electron can be easily promoted from valence 3s-orbital
to vacant 3d-orbital. Thus, it can exhibit pentavalency in its compounds.

2s 2p 3s 3p od

Q.6. Determine the oxidation number of nitrogen in (i) N,O (71) NO, (111) HNO, (tv) NH.

Ans. i) N,O:+1 (i) NO,:+4 (111) HNO,:+5 (wv) NH,:-3

Q.7. How is pyrophosphoric acid related to orthophosphoric acid?

Ans. Pyrophosphoric acid (H,P,O,) is the anhydride of orthophosphoric acid (H,PO,) and is obtained by the removal of
a molecule of water from two molecules of H,PO, as shown below:

2n.PO, S45 Po: + H,O

Orthophosphoric Pyrophosphoric
acid acid
Q.8. N,O supports combustion more vigorously than air. Explain.
Ans. N,O decomposes to give O, which is about 1/3 of the volume of gases produced (2N, + O,).

oNjO, —““t> 2N,+0,

On the other hand, air contains 1/5th part of O, of its volume. Due to larger content of O,, N,O supports combustion
more vigorously than air.
Q.9. On being slowly passed through water, PH, forms bubbles but NH, dissolves. Why?
Ans. N—H bond in ammonia is more polar than P—H bond in phosphine. Therefore, NH, forms hydrogen bonds with
water molecules and hence dissolves in it. On the other hand, PH, does not dissolve and hence forms bubbles.
Q.10. Write the reaction of thermal decomposition of sodium azide.
Ans. Thermal decomposition of sodium azide gives nitrogen gas.

2NaN, ———> 2Na+3N,

Sodium azide
Q.11. Phosphoric acid has high viscosity and high melting point. Why ?
Ans. Phosphoric acid has a tendency to form hydrogen bonding in concentrated solutions. Therefore, it has high viscosity
and is a syrupy liquid and has high boiling point.
Q.12. PCl, exists as [PCI,| [PC1,]* but PBr, exists as [PBr,]* [Brl. Explain.
Ans. Both PCl, and PBr, have trigonal bipyramidal geometry. This is not a regular structure and is not very stable.
Therefore, PCl, splits up into more stable octahedral and tetrahedral structures, which are stable than trigonal
bipyramidal.
PCl, == [PCI,]- [PCL,]*
On the other hand, PBr; splits up into stable tetrahedral structure as
[PBr,] —— [PBr,]* [Brl-
 MODERN'’S abc + OF CHEMISTRY-AXIl

This splitting is different from PCl, because Br atoms are large and six atoms of Br cannot be easily accommodated
around smaller P atom.
Q.13. PCI, is known but PI, is not known. Why ?
Ans. Due to small size of Cl atom, five C] atoms can be accommodated around P atom. But I 1s of large size and therefore,
five I atoms cannot be accommodated around P atom. As a result, P—I bonds are weak and prefer to form PI, rather
than PI,. Therefore, PI, is unstable.
Q.14. Write the structural difference between white P and red P. (D.S.B. 2014)
Ans. White P consists of P, units in which four P atoms lie at the corners of a regular tetrahedron with 7PPP = 60°.
Red P also consists of P, tetrahedra units but it has polymeric structure consisting of P, tetrahedra linked together
by covalent bonds.
Q.15. What is liquid nitrogen used for ?
Ans. Liquid nitrogen is used as a refrigerant to preserve biological specimens. It is also used to provide low temperature.
Q.16. Why does iron become passive when dipped in conc. HNO, ?
Ans. Iron becomes passive when dipped in cone. HNO, due to the formation of a thin protective layer of the metal
oxide on its surface. This protective layer corresponds to ferrosoferric oxide, FeO.Fe,O, and prevents further
action of the metal.
Q.17. What is calcium cyanamide ? Why is it used as a fertilizer ?
Ans. Calcium cyanamide is CaCN,. It reacts with water to form ammonia.
CaCN, + 3H,O -——> CaCO, + 2NH,
So, it can provide nitrogen nutrient to the soil and plants. Therefore, it is used as a fertilizer under the name
nitrolim (CaCN, + C).
Q.18. In the ring test of nitrates, what chemical compound is formed ?
Ans. [Fe(H,O), NOJSO, .
Q.19. What is azote ?
Ans. Azote is the name given to nitrogen by Lavoisier.
Q.20. What is the basicity of H,PO, acid and why ? (A.LS.B. 2012)
Ans. H,PO, has the structure :

It has only one ionisable hydrogen and therefore, its basicity is one.
Q.21. Write down the balanced chemical equation representing action of HNO, on sulphur and iodine.
Ans. (c) Action of HNO, on S$

1s.(s)+6HNO, ——> H,SO, + 6NO,+ 2H,O

8 Sulphuric acid
(ii) Action of HNO, on I
L,(s)+ 10HNO, ——> 2HIO, + 10NO,+4H,O
Iodic acid
Q.22. Give examples of oxide of nitrogen
(a) blue liquid below 253 K (6) Known as laughing gas
(c) brown gas (d) colourless gas having oxidation state of N equal to 5
(e) prepared by heating lead nitrate.
Ans. (a) N,O, (6) N,O (c) NO, (d) NO, (2) NQ,.
Q.23. How would you prepare a sample of deuterated ammonia, ND, ?
Ans. It is prepared by the action of heavy water on magnesium nitride.
Mg,N, 2 + 6D,0——> 3MgOD), + 2ND a
Deuterated ammonia
p-BLOCK ELEMENTS 7/47 —

Q.24. N,O supports combustion more vigorously than air. Explain.

Ans. N,O decomposes to give O, which is about 1/3 of the volume of gases produced (2N, + O,).

2N,O — > 2N,+0,

On the other hand, air contains 1/5th part of O, ofits volume. Due to larger content of O,, N,O supports combustion
more vigorously than air.
Q.25. Name the promoter used in Haber's process. (CLB.S.E. Sample Paper 2017-18)
Ans. Molybdenum.
Q.26. Which one of PCI{ and PCI; is not likely to exist and why ? (D.S.B. 2012)
Ans. PCI; is not likely to exist because lone pair on P in PCI, can be donated to Cl* and not to CI.
Q.27. Which is a stronger reducing agent, SbH, or BiH, and why ? (A.LS.B. 2012)
Ans. BiH, is a stronger reducing agent than SbH,. This is because BiH, is less stable than SbH, because of larger
size of Bi than Sb.
Q.28. NF, is an exothermic compound whereas NCI, is not. Explain. (A.LS.B. 2011, 2012)
Ans. NF, is an exothermic compound while NCI, is not because :
(z) The bond dissociation enthalpy of F, is lower than that of Cl.,.
(it) Size of F is small as compared to Cl and therefore F forms stronger bonds with nitrogen releasing large
amount of energy.
Therefore, overall energy is released during the formation of NF, and energy is absorbed during the formation
of NCl,.
Q.29. The bond angles (O—N—O) are not of the same value in NO, and NO,*. (D.S.B. 2012)
Ans. In NO, there is one electron on N. Therefore, in NO,*, there is no electron on N atom and there is a lone pair
of electrons on N atom in NO...

Ixy IN.
\ O=N=0 \

NO,* is linear and has bond angle of 180°. Because of repulsions by a lone air of electrons in NO, , the molecule has
angular shape and bond angle has been found to be 115°. Hence, the bond angles in NO,* and NO, are different.
Q.30. H,PO, is a stronger reducing agent than H,PO,,. (A.LS.B. 2014, 2016)
Ans. The reducing character of the acid is due to H atoms bonded directly to P atom. In H,PO,, there are two P—H
bonds whereas in H,PO,, there 1s one P—H bond. Therefore, H,PO, is a stronger reducing agent than H,PO,.
O O
| |
Pp P
/\ws / Ns
HO H HO OH
(H,PO,) (H,PO,)

Q.31. Bi(V) is a stronger oxidizing agent than Sb(V). (D.S.B. 2014)

Ans. On moving down the group, the stability of +5 oxidation state decreases while the stability of +3 oxidation state
increases due to inert pair effect. Therefore, +5 oxidation state of Bi is less stable than +5 oxidation state of Sb.
Thus, Bi(V) is a stronger oxidising agent than Sb(V).
Q.32. N—N single bond is weaker than P—P single bond. (D.S.B. 2014)
Ans. N—N single bond is weaker than P—P single bond because of high interelectronic repulsions of non-bonding
electrons due to small bond length.
Q.33. What happens when orthophosphorous acid is heated? (C.B.S.E Sample Paper 2017-18)
Ans. Phosphoric acid and phosphine are formed.
Heat
4H,PO, ee 3H,PO, + PH,
 MODERN'S abc + OF CHEMISTRY-XIl

GROUP 16 ELEMENTS
GROUP 16
O The elements oxygen (O), sulphur (S), selentum (Se), tellurium (Te) and
Oxygen polonium (Po) constitute group 16 elements of the periodic table. These are
‘) named as oxygen family after the name of the first member of the group.
Sulphur The first four elements of this group are collectively known as chalcogens
(meaning ore forming elements) because many metal ores occur as oxides and
se
sulphides. The name is derived from the Greek word for brass and indicates
Selenium the association of sulphur and its congeners with copper. Most copper minerals
Te contain either oxygen or sulphur and frequently the other members of the group.
Tellurium All these are non-metallic in character. The metallic character increases
Po down the group. The last element of the family, polonium has metallic character.
Polonium OCCURRENCE
Oxygen is the most abundant of all the elements. It occurs in free form
@ Oxygen is most abundant of all as O, and makes up 20.946% by volume of the atmosphere. Most of it has
elements. been produced by the photosynthesis, in which the green colouring matter of
@ Sulphur is 16th most abundant plants, chlorophyll, absorbs energy from the sun and converts carbon dioxide
element. and water of the atmosphere into glucose and dioxygen.
Chlorophyll
6CO, + 6H,O Sunlight? “6t4124%6 + 60,
Glucose
Oxygen makes up 46.6% by mass of the earth’s crust and is the major
constituent of silicate minerals. As water, it comprises 89% by mass of the
oceans. Oxygen occurs as ozone (O,), an allotrope of oxygen in the upper
atmosphere and is of great importance.
Sulphur is the sixteenth most abundant element and constitutes 0.03—-0.1%
by mass of the earth’s crust. It occurs in the combined form as sulphide ores
and sulphate ores. The common sulphide minerals are galena PbS, zine blende
ZnS, copper pyrites CuFeS, and sulphate minerals are gypsum CaSO,.2H,O,
epsom salt MgSO,.7H,O, baryte BaSO,, etc. Native sulphur can be obtained
from volcanic sources in many places. It can also be present as H,S in natural
gas and crude oil and organo sulphur compounds in tar sands, oil shales and
coal. Organic materials such as eggs, proteins, garlic, onion, mustard, hair
and wool also contain sulphur.
The other elements are comparatively rare. Selenium and tellurium occur
as metal selenides and tellurides in sulphide ores. Selenium and tellurium are
found in anode mud or the anode slime deposited during the electrolytic refining
of copper. Polonium is found only in traces (0.001 ppm) in the earth’s crust.
GENERAL CHARACTERISTICS OF GROUP 16 ELEMENTS
A. Electronic Configurations
The elements of this group have six electrons in the outermost shell and
have the general electronic configuration as ns“np*. The electronic configurations
of these elements are given in Table 9.
Table 9. Electronic configurations of group 16 elements.
Atomic No. Electronic configuration
Oxygen, O [He] 2s72p+
Sulphur, S [Ne] 3s" 3p*
Selenium, Se , [Ar] 3d1° 4s? 4p4
Tellurium, Te 3 [Kr] 4d?° 5s? 5p*
Polonium, Po [Xe] 4/14 5d1° 6s? 6p4

B. Atomie and Physical Properties

The important physical properties of the elements of group 16 are recorded
in Table 10. The general trends in characteristic properties are discussed ahead:
p-BLOCK ELEMENTS

Table 10. Some physical properties of the elements of group 16.

Sulphur Selenium Tellurium Polonium

Atomic number 8 16 a4
Atomic mass 16.0 32.06 78.96
Covalent radius (pm) 66 104 Lif
Ionic (E?-) radius, (pm) 140 180 198
Ionisation enthalpy (kJ mol!) I 1314 1000 941
Ionisation enthalpy (kJ mol?) IT 3388 2251 2045
Electronegativity 3.50 2.44 2.48
Electron gain enthalpy (kJ mol) -— 141.4 — 208.8 — 195.5
Melting point (K) 55 a9 490
Boiling point (K) 90 718 958
Oxidation state —?,-1,+1 —2,+ 2, —2,+ 2,
+2 +4,+6 +4,+6
Density 1.32 2.06 4.19
(in solid state (g em™) (at m.pt) (rhombic (hexagonal
sulphur) grey form)

1. Atomic and ionic radii. The atomic and ionic radii of the elements of
this group are smaller than those of the corresponding elements of group 15. Atomic Ionic radius
The atomic and tonic radii of elements of group 16, as expected, increase on radius (pm) (pm)
going down the group. O2-
Explanation. The comparatively smaller atomic and ionic radii of group 140
16 elements compared to group 15 elements are due to the increased effective
nuclear charge of group 16 elements. As a result, there is greater attraction see
of the electrons by the nucleus and hence radii are less. The increase in 180
the radii of group 16 elements down the group is due to the increase in the
number of electron shells.
2. Ionisation enthalpies. The ionisation enthalpies of the elements of
oxygen family are less than those of nitrogen family. As we move down the
group from oxygen to polonium, the ionisation enthalpy decreases.
Explanation. We expect that the ionisation enthalpy of oxygen should be
more than that of N (group 15 element) because of decrease in size. However,
oxygen has unexpectedly low ionisation enthalpy than N. This is due to the reason
that nitrogen has completely half filled orbitals and the configuration is stable
because half filled and completely filled configurations have extra stability. But
the configuration of O is less stable and therefore, has less ionisation enthalpy.
N(Z = 7) : 1s? 2s? 2p,* 2p,* 2p,* (half filled, stable) cal a
O(Z = 8) : 1s? 2s? 2p,” 2p," 2p,1 (less stable)
However, it may be noted that the second ionisation enthalpies (IE,) of the
members of group 16 are higher than those of group 15. This is because after the
removal of first electron, the second electron has to be removed from a more S
symmetrical half filled configuration (2s*2p_12p *2P,") which is more stable. —

IE,(kJ mol) 1314 IE,(O) < IE,(N) _

IE,—
3388 IE,(N) < IE,(O)
As we move down a group there is Increase in nuclear charge. But at the os
same time, the atomic size as well as the number of inner electrons which shield
the valence electrons from the nucleus increase. The overall effect of increase in
atomic size and the shielding effect is much more than the effect of increase in,
nuclear charge. Consequently, the outermost electron is less and less tightly held
by the nucleus as we move down the group and hence ionisation energy decreases.
3. Melting and boiling points. The melting and boiling points increase
with the increase in atomic number as we go down the group.
Explanation. When we move down the group, the molecular size increases.
As a result, the magnitude of the van der Waals forces also increases with
increase in atomic number and therefore melting point also increases. The
melting point of polonium is, however, lower.
 MODERN'S abc + OF CHEMISTRY-XIl

4, Electronegativity. The elements of group 16 have higher values of

Electronegativity
electronegativity than the corresponding elements of group 15 in the same
O periods. Oxygen is the second most electronegative element, the first
3.50 being fluorine. The electronegativity decreases on going down the group. The
decrease in electronegativity down the group is due to increase in size of the
S atoms.
2.44 5. Metallic and non-metallic character. The first four elements namely
oxygen, sulphur, selenium and tellurium are non-metals. The non-metallic
Se
character is stronger in O and 5 and weaker in Se and Te. On the other hand,
2.48 last element is markedly metallic. However, it is radioactive and is only short-lived.
6. Electron gain enthalpy. The elements of this family have high
negative electron gain enthalpies. The values decrease down the group from
sulphur to polonium. Oxygen, unexpectedly has low negative electron
gain enthalpy. This is attributed to the small size of oxygen atom so that
its electron cloud is distributed over a small region of space and therefore, it
repels the incoming electron. Thus, the electron gain enthalpy of oxygen is
unexpectedly less negative in the family.
Electron gain 7. Catenation. Catenation is the tendency of an atom to form bonds
enthalpy with identical atoms. In this group, only sulphur has a strong tendency for
Cow its) mo) catenation. Oxygen also shows this tendency to a limited extent.
The greater tendency of sulphur for catenation than oxygen is because
of stronger S—S bonds as compared to O—O bonds. Because of small
size, the lone pairs of electrons on the oxygen atom repel the bond pair of
O—O bond to a larger extent than the lone pairs of electrons on the sulphur
atom in S—S bond. Therefore, S—S bond is much stronger (213 kJ mol) than
O—O bond (138 kJ mol) and hence sulphur has a stronger tendency for catenation
than oxygen. For example, chains of sulphur are present in polysulphides
H—S,—H, polysulphuric acids, HO,S—S,—SO.,H and in different
allotropic forms of sulphur. Similarly, oxygen forms polyoxides such as H,O,,
H—O—O—H.
The catenation tendency decreases on moving down the group from 5 to
Po. This is because the size of the atom increases down the group from S to
Po, the strength of element-element bond decreases and therefore, tendency
for catenation decreases.
8. Elemental state. Oxygen exists as diatomic molecule. Under normal
conditions, oxygen exists as a gas. In oxygen molecule, there is pt—p7 overlap
between two oxygen atoms forming double bond, O = O. The intermolecular forces
The S—S bond is very important In oxygen are weak van der Waal's forces and therefore, oxygen exists as a gas.
in biological systems and occurs in On the other hand, the other elements of family do not form stable pn—pn bonds
and do not exist as M, molecules. The other atoms are linked by single bonds
many proteins and enzymes. and form polyatomic complex molecules. For example, sulphur and selenium
molecules have eight atoms per molecule (S, and Se,) and have puckered ring
structure. The puckered ring structure of sulphur is shown in Fig. 18.
9. Allotropy. All the elements of the group exhibit allotropy. For example,
e Oxygen exists as O, and O, (ozone).
e Sulphur exists in a number of allotropic forms of which yellow ortho-
rhombic, o- and B-monoclinic forms are the most important. All these
allotropic forms of sulphur are non-metallic.
e Selenium exists in eight allotropic forms, of which three are red monoclinic
forms containing Se, rings. The thermodynamically stable form is grey-
hexagonal ‘metallic’ selenium which consists of polymeric helical chains.
The element exists as common amorphous black selenium. The grey
selenium is the only allotrope of selenium which conducts electricity.
e Tellurium has only one crystalline form having chain structure similar
to that of grey selenium.
e Polonium has two forms namely o-form and B-form, both are metallic
in nature.
Fig. 18. Puckered ring structure of C. Oxidation States
5, molecule.
All the elements of this group have ns“np* configuration in their outermost
shell. The atoms of these elements try to gain or share two electrons to
achieve noble gas configuration. Therefore, these elements show two types of
oxidation states.
p-BLOCK ELEMENTS

(4) Negative oxidation states. Oxygen has a very high value of

Exceptional oxidation
electronegativity, it tends to achieve noble gas configuration preferably by
states of oxygen
gaining electrons. Thus, oxygen exhibits oxidation state of —2 in its compounds.
However, there are a few exceptions in which the oxidation state of oxygen is
not —2. For example, the oxidation state of oxygen in OF, is +2, and in O,F,
it is +1 while in H,O, it is —1 and zero in O, and O,.
Since the electronegativites of these elements decrease as we move down
the group, the tendency of these elements to show —2 oxidation state decreases
down the group from S to Po. The least electronegative element, polonium
hardly shows —2 oxidation state.
(it) Positive oxidation states. Oxygen does not show positive oxidation
states except in OF, and O,F,.
Unlike oxygen, other elements also show oxidation state of +2, +4 and +6
due to the promotion of electrons to vacant d-orbitals.
For example, in the ground state, sulphur has only two unpaired electrons
and can form two bonds. This accounts for +2 oxidation state of S. If one of the
paired electron of p-orbital is promoted to d-orbital, there are four unpaired
electrons available for bonding. Therefore, S can show +4 oxidation state. On
further excitation, one of the 3s electron is promoted to vacant d-orbital and
this makes available 6 unpaired electrons. This accounts for oxidation state
of +6. These are illustrated below :

Oxygen atom in = — There are no d-orbitals

ground state Excitation not possible.
3s 3p 3d

erudite | LT RT|
Two unpaired electrons account
for an oxidation state of + 2.

ce pertaret FL)L. Four unpaired electrons account

for an oxidation state of + 4.

Six unpaired electrons account

iseaepert state AAT Pf for an oxidation state of + 6.

Fig. 19. Various oxidation states shown by sulphur.

Compounds of 8, Se and Te with O are typically tetravalent (+4 oxidation

state). These +4 compounds show both oxidizing and reducing properties.
Fluorine brings about the maximum oxidation state of +6 in its compounds.
Compounds in +6 oxidation state show only oxidising properties. The higher
oxidation state becomes less stable in going down the group. These compounds
are covalent and hence are typically volatile.

CHEMICAL PROPERTIES: TRENDS IN CHEMICAL REACTIVITY

Like other members of p-block elements present in the second period,
oxygen shows anomalous behaviour. This is due to its small size, high
electronegativity, high ionisation enthalpy and absence of d-orbitals in its
valence shell. The typical effect of small size and high electronegativity is
the presence of strong hydrogen bonding in water (H,O) which is not present
in H,S and other hydrides of group 16 elements.
Due to the absence of d-orbitals in oxygen, its covalency is limited to four
and in practice, rarely exceeds two. However, in case of other elements, the
valence shell can be expanded using vacant d-orbitals and hence covalence
exceeds four.
Both oxygen and sulphur are very reactive and the reactivity decreases
as O > S > Se > Te. Oxygen is very reactive and reacts with almost all the
elements. Its reactivity is only slightly less than the most reactive elements,
halogens. Inspite of high bond dissociation enthalpy of O, (493.4 kJ mol),
the reactions of oxygen are highly exothermic. Once initiated, these reactions
continue spontaneously (combustion) or even explosively.
 MODERN'S abc + OF CHEMISTRY-AXIll

Let us discuss some chemical trends in the reativity of elements.

1. Reactivity with hydrogen (formation of hydrides)
All the elements of group 16 form hydrides of the type HE (where E = O,
5S, Se, Te, Po). For example, H,O, HS, H,Se, H,Te and H,Po.
The hydrides of S, Se and Te are prepared by the action of acids on metal
sulphides, selenides and tellurides respectively. H,S is prepared in the laboratory

QL/
with the Kipps apparatus by the action of dilute sulphuric acid on Fes.
FeS (s) + 2H,O* (ag) ———> Fe” (ag) + H,S(g) + 2H,O (2)
Water is a colourless, odourless liquid while hydrides of the other elements
O of this group are colourless, bad smelling, poisonous gases.
Structure. All these hydrides have angular structure which involves
sp® hybridisation of the central atom. For example, the structure of water is
shown in Fig. 20 in which there are two bond pairs and two lone pairs. Due
H
H to the presence of lone pairs, the bond angle in H,O is less than the normal
tetrahderal angle. It has been found to be 104.5°. As we go down the group,
Fig. 20. Structure of water. the bond angle in the hydrides decreases as
H,O HS H,Se HTe
104.5° 92.1° a1 90°
Explanation. As we move down the group from O to Te, the size of the
central atom goes on increasing and its electronegativity goes on decreasing.
Consequently, the position of bond pairs of electrons shifts more and more away
from the central atom in moving from H,O to H,Te. For example, the bond
H,0(373)
pair in O— H bond is closer to oxygen than the bond pair in S— H bond. As
a result, the force of repulsion between the bonded pairs of electrons in H,O
high b.p. is due is more than in H,S. In general, the force of repulsion between the bonded
to hydrogen pairs of electrons decreases as we move from H,O to H,Te and therefore, the
bonding bond angle decreases in the same order as :
H,Te(269) H,O > HS > H,Se > H,Te
(K)
point
Boiling Trends in characteristics :
H,Se(232)
H.S(213) (t) Volatility : All the hydrides are volatile. The volatility increases from H,O
to H,S and then decreases. This is clear from their boiling points as given below:
34 81
Molecular mass ———-* Eine. lees H,Se H,Te
Fig. 21. Plot of boiling points of the af3 K 213 K 232 K 269 K
hydrides of group 16 elements. Thus, the trend of volatility is
H,O < H,S > H,Se > H,Te
Explanation. The high boiling point and therefore low volatility of water
is due to the association of HO molecules through hydrogen bonding. However,
hydrogen bonding is not present in other hydrides. The intermolecular forces
between the hydrides (except H,O) are van der Waal's forces. These forces
increase with increase in molecular size and therefore, boiling points increase
on moving from H,S to H,Se.
Hydrides of group 16 (it) Acidic character. The hydrides of this group are weakly acidic in
n character. For example, H,S behaves as weak diprotic acid ionising as :
o
te]

so HS
HS- =
Ht +
Ht +
HS
S*
£
—
The acidic character increases from H,O to H,Te as:
2
s) H,O < HS < H,Se < HiTe
4B
2o Explanation. The increasing acidic strength of the hydride is evident
D from their dissociation constant (K_) values.
£
=
at Hydrides H,0 lal H,Se Hote
a)©
K ie ie eee les Eee me BERS ee VIlie
Thermal
~ strengthdecreases
stabilityOo
increases
Acidic a

The increase in acidic character from H,S to H,Te can be explained on the
basis of size of the central atom. As the size of the central atom increases in
the order O <5 < Se < Te, the distance between the central atom and hydrogen
p-BLOCK ELEMENTS

also increases. As a result of increase in bond length, the bond dissociation

enthalpy decreases and bond cleavage becomes more and more easy. Therefore,
the acidic strength of the hydrides increases down the group.
(zit) Thermal stability. The thermal stability of the hydrides decreases
from H,O to H,Te as:
H,O > HS > H,5Se > HTe.
Explanation. On going down the group, the size of the central atom increases
and therefore, its tendency to form stable covalent bond with hydrogen decreases. As
a result, the M—H bond becomes weak and therefore, thermal stability decreases.
(jv) Reducing character. All the hydrides except water are reducing
agents. The reducing power of these hydrides increases from H,O to H,Te.
H,O < H,S < H,Se < H,Te.
This is due to the decrease in thermal stability of the hydrides. Greater
the unstability of the hydride, the greater is its reducing character.
The important physical properties of hydrides of group 16 are summed
up in Table 11.
Table 11. Some physical properties of hydrides of Group 16 elements.

m.p. (K) 273 188 208 enn

b.p. (K) 373 213 232 269
M-H distance (pm) 96 134 146 169
HMH angle 104.5° oa le 91° 90°
AH* (kJ mol) —286 20 73 100
E(M—H) (kJ mol) 4638 OAT 276 206
Dissociation constant
H,E = (H +HE)(K,)| 1.0x 1074 | 1.3 x 107 13x10+ | 23x10
HE- = (H'* + E*) (K,) _ fle ie mo x ies ee le

Other hydrides
Oxygen and, to a greater extent, sulphur differ from the remaining elements
in their tendency to form polyoxides and polysulphides, which are less stable
than normal salts. The two common examples are H,O, and H,5,. However,
these two differ considerably from each other. H,O, is fairly stable whereas
H,S, is unstable and decomposes readily to give sulphur and hydrogen sulphide.
The decomposition is accelerated by the presence of hydroxy] ions.
HS, —/~@ailm +/5
H,O, is a strong oxidising agent but H,S, is not. H,O, forms highly
Fig. 22. Structure of hydrogen
associated molecules because of hydrogen bonding while H,S, forms discrete
peroxide.
molecules. Both H,O, and H,S, have similar skew structure. The structure
of H,O, in gaseous phase is shown in Fig. 22.
Sulphur forms a few hydrogen polysulphides called sulphanes. Some of
these are :
HS Hydrogen disulphide H—S—S—H
HS. Hydrogen trisulphide H—S—S—S—H
HS. Hydrogen pentasulphide H—S—3—_5S—_5—_5S—H
2. Reactivity with oxygen (formation of oxides).
All the elements of group 16 form two main oxides EO, and EO, (E = §,
Se, Te or Po). In addition, they form other oxides as given in Table 12.
Table 12. Oxides of group 16 elements

Monoxides SO
Dioxides
Trioxides
Heptoxides BOT
Other oxides 5,0, 5,0,, SO,
a 7/54 MODERN'’S abc + OF CHEMISTRY-AXIl

Oxides of sulphur are more stable than the corresponding oxides of other
elements. For example, SO, and SO, are more stable than the corresponding
dioxides and trioxides of other elements. Heptoxide is only formed by sulphur.
(1) Monoxides. All elements except selenium form monoxides. Sulphur
monoxide is formed by heating a mixture of sulphur dioxide and sulphur under
reduced pressure at 425-475 K.

So, +5 2255; 280

It can also be prepared by the action of silver on thionyl chloride
SOC], + 2Ag——> SO + 2AgCl
Thionyl chloride
Tellurium monoxide and polonium monoxides are formed by heating their
corresponding trioxides. Monoxides are assigned the structure E=O (E = §,
Te, Po).
(iz) Dioxides. All the members of oxygen family (S, Se, Te and Po) form
dioxides of the formula EO, (e.g., SO,, SeO,, TeO,, PoO,). The dioxides are
obtained by direct union of elements :
E(s) + O,(@) ——> EO, (g)
C2 S.(s) +80,(g) ———> 8SO, ig)
The dioxides of these elements differ considerably in their properties and
structure. SO, is a gas at room temperature (b.p. = 263 K). In SO,, S atom
c\ yr 2p orbital | undergoes sp* hybridisation. Two of the three sp? hybrid orbitals form two
3d orbital ¢ O o-bonds with oxygen atoms. The remaining two unhybridised orbitals (8p and
CJ V6) 3d) form pi—pt and pr—dn double bonds with O atom. Thus, SO, has bent
or angular structure.

pr—adar bonding in S—O bond 3s ap 3d

Aakers Ft tt ()

(excited state)
excite Fhe AL | ff YN
yx ‘<_"
a %,
sp ryriisaton //“ : O O
Forms px—pr Forms px—an
bond with O atom bond with O atom

The third sp? hybrid orbital is occupied by a lone pair of electrons.

Since one of the orbital is occupied by a lone pair of electrons and the
repulsion between lone pair—bond pair is more than between bond pair-
bond pair, the bond angle of OSO is slightly reduced from 120° to 119.5°.
As is clear, the two m bonds are different because one is formed by pn—pt
overlap and the other is formed by pa—dr overlap. But actually both the
S—O bonds have exactly same bond length (143 pm). This is because of
resonance between two structures. The SO, molecule is resonance hybrid
6 or
of two structures (a) and (b) as shown in Fig. 23.
—_~—so=—s_, Si, S
a /, i <A The multiple bonding in S—O bond in SO, is due to pn—pn bonding
/ \ 119.5° , (as indicated in resonance structures). In addition, it has been suggested
O O Oo that there is possibility of pmt—drn bonding due to overlap of filled px
Resonance hybrid
Angular orbitals of oxygen with vacant 3d-orbitals of sulphur as shown.
Like sulphur, other elements also form dioxides. SeO, is a white
Fig. 23. Structure of 5O, molecule. crystalline solid. In the gaseous state, it exists as discrete molecules
p-BLOCK ELEMENTS

having structure similar to SO, (a). In solid state, it has a polymeric structure
consisting of infinite chains (0) as shown below :

125° :
O O 173 salt ‘I 90
, : O O
(a) SeO, in gaseous
state
(6) SeO, in solid state
Fig. 24. Structure of SeO,,.

TeO, and PoO, are also non-volatile crystalline ionic solids and occur in
two avstalline fore each. The dioxides of elements of group 16 have different
structures because the tendency of these elements to form px—pnt multiple
bonds decreases as the atomic size increases down the group.
Properties
The dioxides differ from one another in their reaction with water. SO,
dissolves giving H,SO,, which exists only in solution and cannot be isolated.
sO, + H,O ——— H,SO,
The gas is, therefore, known as sulphurous anhydride. Therefore, the
aqueous solution is acidic turning blue litmus to red. If the solution is boiled,
all the sulphur dioxide may be removed.

1,S0,—"> H,0 +50, 7

SeO, dissolves in water giving selenious acid, H,SeO, which can be
isolated in a crystalline state. TeO, is almost insoluble in water. However,
TeO, dissolves in alkalies to form tellurites and in acids to form basic salts
showing that it is amphoteric. PoO, also behaves similarly.
The +6 oxidation state of S is more stable than +4 oxidation state and
therefore, SO, acts as a reducing agent. Since the stability of +6 oxidation
state decreases from 5S to Te, therefore, the reducing property of dioxides
decreases from SO, to TeO,. For example, SO, is a reducing agent while TeO,
1s an oxidising agent.
(iit) Trioxides. All the elements of this group form trioxides of the
formula KO,. Amongst trioxides SO, is most important, while SeO, and TeO,
are also known.
Sulphur trioxide is prepared by direct combination of sulphur dioxide and
oxygen in the presence of finely divided platinum or divanadium pentoxide at
2, atmospheric pressure and 450°C.

280, (g) + O,(g) %295_,

— 1450°C os80, (g)
The vapours of sulphur trioxide formed are collected in a receiver and
cooled by freezing mixture.
It can also be prepared by the dehydration of sulphuric acid with phosphorus
pentoxide.
H,SO, Heat / P,O1
SO,
-H,0
Sulphur trioxide can also be prepared by heating ferric sulphate, which
decomposes to give sulphur trioxide.
Fe,(SO,), —> Fe,O,+ 380,
SO, has trigonal planar structure in the gaseous state in which S atom is
sp* hybridised. The three sp? hybrid orbitals of S overlap with p-orbitals of O
to form three S—O sigma bonds. The sulphur atom in the excited state is now
left with one p and two d-orbitals which overlap with p-orbitals of O to form
three m-bonds. In this, one p-orbital of O forms pr—pr bond with p-orbital of
 MODERN'’S abc + OF CHEMISTRY-AXIl

5S while other two O atoms overlap with d-orbitals of S atom forming pn—dt1
bonds as shown below :

3s 3p 3d O
forone ia) | | | | [|
es

awe |, eee |__

er
_
We f \

hdl rar
co bonds Forms one Form two
5 0
px—pn bond pn—aor bond

Therefore, SO, molecule has a trigonal planar structure. The bond angles
in SO, are exactly 120° each and S=O bond lengths are 142 pm.
Although, the three S—O ma bonds are different (one pa—pn and two
pi—dn) yet they are equal because of resonance as shown below :

O
ian <—_>
H

mo YIN
SS
SN” O
é aN
f 120°
O
Fig. 25. Structure of SO, molecule.

The molecules of 5O, are held together by weak van der Waals forces of
attraction. Therefore, it exists as a gas at room temperature. However, in
solid state, it exists as linear polymeric chain structure or cyclic trimer as
shown below :
fF

a \,
A SA
i)
Oo
erO
vw
NA NY |
\
O

O O O yi,\ 7 NY
Linear chain of SO,
Cyclic trimer of SO,
SeO, is prepared by the direct oxidation of Se or SeO,,. It is white hygroscopic
solid having melting point 118°C. It exists as monomer in the vapour state
(a) and as a cyclic tetramer (Se,O,,) in the crystalline state (0).

Se

4
SeO, monomer in vapour state Cyclic tetramer of solid SeO,
Fig. 26. Structure of SeO, and Se,O,,
p-BLOCK ELEMENTS

TeO, also exists and is unattacked by water. It acts as a powerful oxidising

agent at higher temperatures.
However, PoO, has not been well characterized, it has been detected in
traces only.
In addition to monoxides and dioxides, sulphur also forms other oxides
as given in Table 13.
Table 138. Oxides of Sulphur.
Oxidation state ofS Physical states

Sulphur suboxide Colourless gas

Sulphur monoxide Colourless gas
Sulphur sesquioxide Bluish green crystalline solid
Sulphur dioxide Colourless gas
Sulphur trioxide Volatile liquid
Sulphur heptoxide Viscous liquid
Sulphur tetroxide White solid.

3. Reactivity with halogens (formation of halides)

The elements of group 16 form a large number of halides of the type EX,
EX, and EX, (X = halogen). These are given in Table 14. The stability of the
halides decrease in the order
F->Clr>Bre>T

Table 14. Halides of group 16 elements.

Monohalides O,F, S.F,, S,Cl,,S,Br, Se,Cl,, Se, Br, =

Dihalides Ob CLG, beet eec le = TeCl,, TeBr, LoGh oir.

Tetrahalides — SF, SCL, olde rel peeliges Ueelre Theilodbelaeteinsite ec le Tiruliteas |cul

Hexahalides — SF, SeF, TeF

In addition to above compounds, some other halides of group 16 are

S.F>, TesFi9, Cl,O,, 1,0, 1,0, ete.
The highest oxidation state is realised only in the fluorides. With iodine,
only a tetra iodide, Tel, is known.

Since fluorine is more electronegative than oxygen, its compounds with

oxygen are called fluorides. For example, F,O should be written as OF,
and is named as oxygen difluoride. But since oxygen is more electronegative
than Cl, Br and I, the compounds of these halogens are called oxides. For
example Cl,O, is called chlorine hexaoxide. The compounds of oxygen with
halogens are discussed in detail in the next part.
Cl
(1) Monohalides
+] +4 0 205 pm / 99pm
25e,Cl, ————— seCl, + 3Se
é— Le
104°
Sulphur forms monohalides such as sulphur monofluoride (S,F,), sulphur
monochloride (S,Cl,) and sulphur monobromide (S,Br,). The electron diffraction Cl
studies have shown that the structure of S,Cl, is similar to H,O, as shown
Fig. 27. Structure of S,Cl.,.
in Fig. 27.
 MODERN'’S abc + OF CHEMISTRY-AiIl

(iz) Dihalides
All the elements except selenium form stable dichlorides and dibromides.
Diiodides are not readily formed while dihalides of selenium are not stable.
Amongst the dihalides, SCl, is best known and is discussed below :
SCl, is angular in shape. In this case, S atom undergoes sp® hybridisation,
in which two positions are occupied by lone pairs of electrons. Two sp® hybrid
orbitals of sulphur overlap with 3p—orbitals of chlorine atoms to form two
S—C]l bonds. The geometry is distorted due to the presence of lone pairs and
the bond angle is about 108° instead of normal tetrahedral angle of 109.5°.
(111) Tetrahalides
Amongst tetrahalides, tetrafluorides are the most stable.
Amongst tetrafluorides, SF, is a gas, SeF, liquid and TeF, solid. SF, is
highly reactive.
These tetrafluorides (e.g., SF,) involve sp°d hybridisation and have trigonal
bipyramidal structure in which one of the equatorial positions is occupied by a
lone pair of electrons. This geometry is regarded as see-saw geometry. Due to
larger lone pair-bond pair repulsion than bond pair-bond pair repulsion, the bond
angle decreases from 180° to 173”.
(111) Pentahalides
Fig. 29. See saw structure of SF,. Only sulphur forms one pentahalide, S,F,,,. It has the structure as shown
(Fig. 30) in which two SF. units are linked through sulphur atoms having
octahedral geometry.
(jv) Hexahalides
Among hexahalides, only hexafluorides are stable compounds.
F F F F These are all gaseous in nature. SF, is extremely stable and
N\ fe ss “i chemically inert for steric reasons. In SF, the six F atoms protect
ar aan
-

the sulphur atom from attack by reagents to such an extent that

F F F F even thermodynamically most favourable reactions like hydrolysis
do not occur. In contrast, the less sterically hindered SF, undergoes
Fig. 30. Structure of 5,F,,,
hydrolysis readily.
SF, + 2H,O ——~ 4HF + SO,
SF, + H,O ———~ No reaction
As the size of the central atom increases, reactivity increases. SeF, is
slightly more reactive and TeF, is still more reactive. TeF, is rapidly hydrolysed
with water.
TeF, + 6H,O ——~ H,TeO,+ 6HF
SF, has an octahedral structure (Fig. 31) in which sulphur undergoes
sp*d* hybridisation.
Hexahalides are not formed by chlorine, bromine and iodine. As the size
of the halogen atom increases, the coordination number of the elements of this
group decreases. As a result, hexachlorides, hexabromides and hexaiodides
are unknown. For the same reason, the number of tetrabromides is only
Fig. 31. Structure of SF... three, all of which are unstable and the number of tetraiodides is only two.

ANOMALOUS BEHAVIOUR OF OXYGEN

Like all other first elements of the groups, oxygen also differs from its
family members. The anomalous behaviour of oxygen is due to its
(i) small size
(iz) high value of ionization enthalpy and electronegativity
(iit) absence of d-orbitals in the valence shell.
Some of the important differences between oxygen and other
family members are :
(1) Oxygen is a gas at ordinary temperature while other elements exist
as solids at room temperature.
p-BLOCK ELEMENTS

(it) Oxygen molecule is diatomic (O,) while the molecules of other

elements are more complex, e.g., sulphur and selenium exist as octaatomic
molecules (i.e., S, or Se,) with puckered ring structures.
(111) Molecular oxygen is paramagnetic whereas the molecules of other
members are diamagnetic in nature.
(iv) Oxygen shows only —2 oxidation state compounds but other members
of the family also show positive oxidation states such as +2, +4, +6 in addition
to —2 oxidation state.
(v) The hydride of oxygen (i.e., H,O) is a liquid at room temperature
while the hydrides of other members (H,S, H,Se, H,Te etc.) are gases.
(vi) Oxygen forms px—pz double bonds with the elements having similar
size such as carbon, nitrogen etc. The tendency to form multiple bonds is
not shown by other elements.

CHEMISTRY OF OXYGEN AND ITS COMPOUNDS

DIOXYGEN
Preparation of Dioxygen
1. By the decomposition of oxygen rich compounds. Certain compounds
containing large amounts of oxygen such as chlorates, nitrates, permanganates,
etc. give dioxygen on strong heating.
The thermal decomposition of KC1O, requires a temperature of 670-720 K.
It can be carried out at a lower temperature of about 420 K by the use of
MnO, as a catalyst.
2KMnO, Heat, K,MnO, + Mn0O, +O,
Pot. permanganate Pot. manganate
Heat
2KC1O, \no, 2KCl +30,
Pot. chlorate . y

2KNO, _Heat 2KNO, + O,

Pot. nitrate
These methods can be used for the laboratory preparation of dioxygen.
2. By heating dioxides, peroxides and higher oxides. Dioxygen can
be prepared by heating oxides of certain metals low in electrochemical series
and higher oxides of certain metals.
2HgO (s) Heat _, 2Hg(s) + O, (g)
Mercuric oxide
2Ag,O (s) Heat, 4Ag(s) + O, (g)
Silver oxide ;
3 MnO, (s) Heat_, Mn.0,(s) + O, @)
Manganese dioxide
2Pb,0, (s) H@*s 6PbO(s) + O, (g)
Lead tetraoxide

2PbO, (s) 845 2PbO(s) + O, (g)

Lead dioxide
2BaO, HS, 2BaO + O,(g)
Barium peroxide Barium oxide
3. From hydrogen peroxide. Hydrogen peroxide is readily decomposed
into water and dioxygen by catalysts such as finely divided metals and
magnanese dioxide.
2H,O, (ag) ———> 2H,0 (J) + O, @)
 MODERN'’S abc + OF CHEMISTRY-AXIl

4. Laboratory method of preparation of dioxygen. In laboratory

dioxygen is prepared by the following methods:
(a) Thermal decomposition of potassium chlorate. In laboratory,
dioxygen is prepared by heating a mixture of potassium chlorate (4 parts) and
manganese dioxide (1 part) in a hard glass tube to about 420 K. The manganese
dioxide acts as a catalyst.
420K
2KCIO, Mn0, 2KCl + 30,
The gas is collected by the downward displacement of water.
Note. In the absence of MnO, catalyst, the decomposition takes place
at 670-720 K. Therefore, MnO, acts as a catalyst and also lowers the
temperature for the decomposition of KCI1O,,.

(6) By the action of water on sodium peroxide. Dioxygen can be

prepared by the action of water on sodium peroxide.
2Na,O, (s) + 2H,O (1) ——_> 4NaOH (aq) + O, (g)
Dioxygen can also be prepared by the action of acidified potassium
permanganate on sodium peroxide.
2KMnO, + 3H,SO, ———> K,SO, + 2MnSO, + 3H,O + 5(O)
Na,O, + H,SO, ———> Na,SO, + H,0,] x 5
H,0, +O ——> H,0+0,] x 5
2KMnO, + 5Na,O, + 8H,SO, ——> K,SO,+5Na,SO,+2MnSO, + 8H,O +50,
In this case, acidified KMnO, solution is added from the thistle funnel.
5. Pure dioxygen from barium hydroxide. Pure dioxygen can be
prepared by the electrolysis of a solution of Ba(OH), using nickel or platinum
electrodes.
6. Industrial preparation. The main sources for the industrial preparation
of dioxygen are air and water.
(i) Isolation from air. Oxygen is prepared from air by first removing carbon
dioxide and water vapour and then by the fractional distillation of air. During
this process, dinitrogen with less boiling point (78 K) distils as vapour while
dioxygen with higher boiling point (90 K) remains in the liquid state and can
be separated.
(ii) From water. Dioxygen can also be obtained by the electrolysis of water
containing a small amount of acid or alkali.
2H,0 __Electrolysis _, 2H, (g) + O, (g)

Dioxygen is collected at the anode while dihydrogen is liberated at cathode.

Properties of Dioxygen
Physical properties
(4) Dioxygen is a colourless, tasteless and odourless gas.
(ii) It is slightly soluble in water and its solubility is about 3.08 cm? in
100 cm? of water at 293 K. This solubility is just sufficient for the vital
support of marine and aquatic life.
(iit) It can be liquefied to a pale liquid under pressure.
(iv) It liiquefies at 90 K and freezes at 55 K.
(v) Its boiling point is 90.2 K.
(vi) It has three stable isotopes 1°O, 10, 180.
(iv) Molecular oxygen is paramagnetic inspite of having even number of
electrons.
Chemical Properties
The dioxygen is quite stable in nature and its bond dissociation enthalpy
is very high. Therefore, it is not very reactive as such
O, ——> 0+0
Bond dissociation enthalpy = 493.4 kJ mol"!
p-BLOCK ELEMENTS

Therefore, dioxygen reacts at higher temperatures. However, once the

reaction starts, it proceeds of its own. This is because the chemical reactions
of dioxygen are exothermic and the heat produced during the reactions is
sufficient to sustain the reactions.
Some of its chemical properties are :
1. Action with litmus. Like dihydrogen, it is also neutral and has no
action on blue or red litmus.
2. Supporter of combustion. Dioxygen is a supporter of combustion
but itself is not combustible.
3. Reaction with metals. Dioxygen directly reacts with almost all metals
(except Au and Pt.)
(1) Active metals like Na, Ca react at room temperature to form their
respective oxides.
4Na + O, ——-> 2Na,0
2Ca + O, —— > 2CaO
However, sodium also reacts with dioxygen at 575 K to form sodium peroxide.
2Na + O, Q24, Na,O,
Sod. peroxide
(it) Magnesium burns in dioxygen to form magnesium oxide.
2Mg + O, —— > 2MgO
(it) Metals like Fe, Al, react only on heating.
4Al1 + 30, —— > 2Al,0,
aveo+: gO, <—-> 2he,0,
(iv) Less active metals like gold and platinum (noble metals) do not combine
with dioxygen.
4. Action with non-metals. Dioxygen reacts with a number of non-metals
to form their respective oxides. For example,
1073K
Hydrogen
1
» 2H, + OO, Electric dischares
" ; ee
2H,O0 é

Nitrogen > N, + O, Heat, 2NO

Nitric oxide
Sulphur (se © =e SO,
Sulphur dioxide

Carbon 7 2C + O, Heat 2CO

(Limited) Carbon monoxide
C + O, pHeat, CO,
(Excess) Carbon dioxide

Phosphorus : P, + 650, SS, P,O19

(Solid)
Phosphorus pentoxide
5. Reaction with compounds. Dioxygen is an oxidising agent and it
oxidises many compounds under specific conditions. For example,
(i) With hydrogen chloride. Dioxygen combines with vapours
of hydrogen chloride in the presence of cupric chloride catalyst at 700 K to
evolve chlorine.
FOO K
4HCl + O, “Cul,” 2Cl, + 2H,O
(iz) With ammonia. Dioxygen oxidises ammonia to nitric oxide
in the presence of platinum gauze catalyst at 1073 K.
4NH, +50, “2*, 4NO + 6H,O
Nitric oxide
 MODERN'’S abc + OF CHEMISTRY-AXIl

This reaction forms the basis of the Ostwald process for the manufacture
of nitric acid.
(iii) With sulphur dioxide. Dioxygen combines with sulphur dioxide
at 723 K in the presence of finely divided platinum or vanadium pentoxide
(V,O-) to form sulphur trioxide.
723 K
250, + O, “rorvecs 250,

This reaction forms the basis of Contact process for the manufacture
of sulphuric acid.
(jv) With carbon disulphide. Carbon disulphide burns in dioxygen to
form carbon dioxide and sulphur dioxide.
CS, + 30, Heat, CO, + 280,
(v) With metal sulphides. Many metal sulphides such as ZnS, HgS, etc.
react with dioxygen at high temperatures to form metal oxides and sulphur
dioxide.
27nS + 30, +, 27n0 + 280,
2HgS + 30, Heat, 2HgO + 280,
(vi) With hydrocarbons. Saturated as well as unsaturated hydrocarbons
burn in excess of air or oxygen to form carbon dioxide and water. These
reactions are called combustion reactions and are highly exothermic in
nature. Therefore, the hydrocarbons are used as fuels.
CH, +,20, ———} CO, + 2H,0; AH =— 890 kJ mol!
Methane
CH, + £0,——> 2C0,+3H,O; AH=-1580kJ mol
Ethane
2C,H, + 50, ——+ 4CO,+2H,0; AH=-1304kJ mol
Acetylene
Uses of Dioxygen
(4) Dioxygen is used in the oxy-hydrogen or oxy-acetylene torches which
are used for welding and cutting of metals.
(ii) It is used in metallurgical processes to remove the impurities of
metals and non-metals by oxidation. It is also used in making steel and in
metal fabrication where it functions as an aid to combustion.
(111) It is essential for life support systems in hospitals and in underwater
during diving and also by mountaineers and pilots at high altitudes. Oxygen
cylinders are widely used in hospitals, high altitude flying and in mountaineering.
It is also used for artificial respiration in case of surgery and heart ailments.
(tv) Liquid oxygen is used as a rocket fuel. For example, hydrazine in
liquid oxygen provides the tremendous thrust in rockets.
(v) It is used in the manufacture of large number of oxygen containing
organic compounds such as phenol, ethylene oxide, sulphur dioxide, sulphuric
acid, etc.
(vi) It is used as an oxidising agent and as a bleaching agent.
(vit) A mixture of carbon dust and liquid oxygen is used as an explosive
for coal mining.
(viii) Oxygen-18 isotope is used as a tracer in the study of reaction
mechanisms.
(1x) It is used on a large scale for the production of TiO, and synthesis
gas (CO + H,).
p-BLOCK ELEMENTS

OXIDES
The binary compounds of oxygen with other elements are called oxides.
We have studied that oxygen combines with metals and non-metals to form
their respective binary oxides. In these oxides, the oxidation state of oxygen
is always —2.
Classification of oxides
Oxides can be simple (e.g., MgO, Al,O, etc.) or mixed (Mn,O,, Fe,O,,
Pb,O,,, etc.) as discussed below :
A. Simple oxides.
The simple oxides behave as acids or bases according to their dissolution
in water. On the basis of acid-base characteristics, the oxides may be classified
into the following four types :
1. Acidie oxides. The oxides which combine with water to give acids are
called acidic oxides. These are generally the oxides of non-metals such
as carbon, sulphur, phosphorus, etc. For example,
SO, + HAY 2——> > 0,
Sulphurous acid
SO,(g) + H,O(/) ——~+ H,SO, (aq)
Sulphuric acid
CO, + Ae — > a),
Carbonic acid
Pin 6H,O ———+ 4H,PO,
Phosphoric acid
N,O.7) + H,O() ——+ 2HNO, (aq)
Nitric acid
ClLOMg) + H,O(/) ———+ 2HCIO, (aq)
Perchloric acid
These acidic oxides neutralise hydroxides to form salt and water.
SO, + 2NaOH ———> Na,SO, + H,O
P,O,,(s) + 12Na0OH (ag) ——-> 4Na,PO,(aq) + 6H,O (2)
It may be noted that oxides of some metals in high oxidation state such
as Mn,O,, CrO,, V,O., etc. also have acidic character.
Mn,O, + H,O ———+} 2HMnO,
Permanganic acid
CrO, + H,0 (EL Cry,
Chromic acid
2. Basic oxides. The oxides which combine with water to give basic solution
are called basic oxides. These are mostly the oxides of metals. For example,
Na,O + H,O ——+ 2Na0H
MgO +H,0 ——— Mg(OH),
BaO + H,O ——-+ Ba(OH),
REMEMBER
Fe,O, (s) + 3H,O (1) ———> 2Fe(OH), (aq)
@ Pb,O,1s amixed oxide of PbO and
The basic oxides react with acids to form salt and water.
PbO, and is given the formula
Na,O + 2HCl ——-> 2NaCl+H,O
PbO,.2PbO.
Fe,O, (s) + 3H,SO, (ag) ——— Fe,(SO,), (aq) + 3H,O (7)
@ Fe,0, 1s amixed oxide of FeO and
Some other examples are K,O, CaO, BaO, etc. Fe,O, and is given the formula
3. Amphoteric oxides. The oxides which show acidic as well as basic Fe,O, FeO.
character are called amphoteric oxides. These are the oxides formed by @ Mn,0O, is a mixed oxide of MnO
elements like aluminium, zinc, tin and lead, etc. which are present on the border and MnO, and is given the
line between metals and non-metals. For example, aluminium oxide (Al,Q,) formula 2MnO.Mn0O,,.
reacts with both acids (hydrochloric acid) and alkalies (sodium hydroxide).
a 7/64 MODERN'S abc + OF CHEMISTRY-XIl

Al,O, (s) + GHC] (aq) +9H,O ——+ 2[AI(H,0),] 3+(aq) + 6CIT (aq)
(Basic)
Al,O, (s) + 6NaOH (aq) + 3H,0 ——-~ 2Na,[Al(OH),] (aq)
(Acidic)
Some other examples of amphoteric oxides are Si0,, ZnO, ete.
4. Neutral oxides. The oxides which neither react with acids nor with
bases are called neutral oxides. These are neutral to litmus solution. For
example, N,O, CO, NO, etc.
B. Mixed oxides.
Metal oxides which consist of two simple oxides with the metal in different
oxidation states are called mixed oxides. These mixed oxides show the
properties of both the metal oxides simultaneously. For example, red lead
Pb,O, is a mixture of lead oxide (PbO) and lead dioxide (PbO,) as PbO,.2PbO.
Therefore, it gives a mixture of lead oxide and lead dioxide on treatment
with acids.

Mixed oxides Pb,O, + 4HNO, ———> PbO, + 2Pb(NO,), + 2H,O.

Pb,O, : PbO,. 2PbO Similarly, magnetic oxide of iron, Fe,O, (ferrosoferric oxide) is a mixture
ibe) pee pee of ferric oxide (Fe,O,) and ferrous oxide (FeO). It has the formula Fe,O,-FeO.
a4 ee ie -
Mn,O, : 2MnO. MnO, Therefore, it gives a mixture of ferric and ferrous salts on treatment with
acids.
Fe,0, + 8HCl ——> 2FeCl, + FeCl, + 4H,O
Mixed oxide of manganese, Mn,O, (trimanganese tetroxide) is considered
to be a mixed oxide of manganese oxide (MnO) and manganese dioxide (MnO,)
having the formula 2MnO-Mn0O,,.
Trends of Oxides in the Periodic Table
On moving from left to the right in a given period in the periodic table,
the nature of the oxides changes from basic to amphoteric and then to acidic.
For example, the oxides of third period has the following behaviour :

MgO AL S10, Poe so, CLO:

basic amphoteric weakly acidic strongly very
acidic acidic strongly
acidic
Basic to acidic character increases -

However, on moving down a group, acidic character of the oxides decreases.

For example, in the third group, the acidic character of oxides decreases as :

Al,O, Ga,O, bio P AGE

Amphoteric Weakly basic Basic

Acidic character decreases ee

DIFFERENT TYPES OF OXIDES

A binary compound of oxygen with another element is called oxide.
These may be classified on the basis of oxygen content as :
1. Normal oxides. These contain oxygen atoms according to the normal
oxidation number i.e., -2. For example, MgO, H,O, CaO, Li,O, Al,O,g, ete.
2. Polyoxides. These contain oxygen atoms more than permitted by the
normal valency. Therefore, these contain oxygen atoms in oxidation state
different than —2.
p-BLOCK ELEMENTS

(1) Peroxides. These contain OF" ion (:6-6=) having oxidation number
of oxygen as —1. For example, H,O,, Na,O,, BaO, ete.
(ii) Superoxides. These contain O,~ ion (:0-65) having oxidation number
of oxygen as —1/2. For example, KO,, RbO,, CsQ, ete.
3. Suboxides. These oxides contain less oxygen than expected from the
normal valency. For example, N,O (nitrous oxide), C,O, (carbon suboxide) etc.
4, Mixed oxides. These oxides are made up of two simple oxides. For
example, red lead Pb,O, (2PbO, + PbO,), magnetic oxide of iron, Fe,O,
(FeO + Fe,O,) and mixed oxide of manganese, Mn,O, (MnO, + 2Mn0O).

OZONE
Ozone is an allotropic form of oxygen. It is present in the upper atmosphere
(about 20 km above the surface of the earth). It is believed to be formed in
the upper atmosphere by the action of ultraviolet rays on oxygen as
30, + Ultraviolet rays ———> 20, AH... = 142.7 kJ mol
Therefore, ultraviolet rays, which are harmful to human beings, are absorbed
by oxygen to form ozone. The layer of ozone thus formed also prevents the
remaining ultraviolet rays to reach the earth’s surface. It may be noted that
during the above process, 10% conversion of oxygen to ozone occurs.
However, small traces of ozone are also found in the air of lower atmosphere.
Preparation of ozone
Ozone is prepared by passing silent electric discharge through pure, cold and
dry oxygen in a specially designed apparatus called ozoniser. The formation
of ozone from oxygen is an endothermic reaction.
gO, Bentelectric. 90 ” AH = 142.7 kJ mol!
~ discharge
Therefore, 142.7 kJ of energy is absorbed for the formation of one mole of
ozone. Since the formation of ozone is an endothermic process, therefore, it is
necessary to use a silent electric discharge (a sparkless electric discharge).
© Silent electric discharge is
If concentration of ozone greater than 10% is required, a battery of ozonisers
used during the preparation
can be used and the pure ozone (b.p. 385 K) can be condensed in a vessel
of ozone !
surrounded by liquid oxygen.
The formation of ozone is
Ozone is prepared in laboratory by the following two types of ozonisers: an endothermic process.
(4) Siemen’s ozoniser (iz) Brodie’s ozoniser. Therefore, it is necessary to
Preparation of pure ozone. In order to get pure ozone, the ozonised use a silent electric discharge.
oxygen is cooled by liquid air when ozone (b.p. = 385 K) condenses in preference The purpose of silent electric
to oxygen (b.p. = 90 K). The liquid thus formed still contains some dissolved discharge (a sparkless electric
oxygen which can be removed by carrying out fractional distillation. discharge) 1s to produce less
Properties of Ozone heat. This would prevent local
rise in temperature which
Physical Properties
otherwise might decompose
(4) Itis pale blue gas having pungent odour.
ozone back into oxygen.
(it) Itis heavier than air. Its vapour density is 24 while that of air is 14.4.
Therefore, it is about 1.5 times heavier than air.
(iit) Its boiling point is 385 K and melting point is 24 K.
(iv) Itis sightly soluble in water but more soluble in organic solvents like
turpentine oil, carbon tetrachloride, etc.
(v) It iquefies to a deep blue liquid at 161.2 K which can be solidified to a
black violet solid at about 80.6 K.
(vi) In contrast to dioxygen which is paramagnetic, ozone is diamagnetic.
(vit) The small concentrations of ozone are harmless. However, if the
concentration rises above about 100 ppm, breathing becomes
uncomfortable resulting in headache and nausea.
a 7/66 MODERN'S abc + OF CHEMISTRY-iIl

Chemical Properties
The important chemical properties of ozone are discussed below :
1. Action with litmus. Ozone is neutral towards litmus because it does
not give any colour change with blue or red litmus.
2. Decomposition. Ozone is thermodynamically unstable with respect to
oxygen because it results in liberation of heat (AH is negative) and increase
in entropy (AS is positive). These two factors reinforce each other resulting
in large negative Gibb’s free energy change (AG is negative) for its conversion
into oxygen. Therefore, the high concentrations of ozone can be dangerously
explosive.
Pure ozone decomposes even at room temperature though very slowly.
However, on heating above 475 K, it decomposes readily to form oxygen gas :
475 K
20, —— 20, AH = — 285.4 kJ
The reaction is catalysed by substances like platinum black, manganese
dioxide, copper oxide, etc.
3. Oxidising agent. Ozone is one of the most powerful oxidising agent
with the liberation of dioxygen. In fact, ozone is a stronger oxidising agent than
molecular oxygen because ozone has higher energy content and decomposes to
give atomic oxygen as :
O3 ° O» + O
Atomic oxygen
Therefore, ozone oxidises a number of non-metals and other reducing
agents. For example,
(a) Oxidation of compounds
(4) Ozone oxidises black lead sulphide to white lead sulphate :
O, —— > 0,+ 0] x4
PbS + 40 ——_> PbsO,
PbS + 40, ——_> PbSO, + 40,
Similarly, ozone oxidises sulphides of copper, zinc, cadmium, etc. to their
corresponding sulphates.
ZnS + 40, ———> ZnSO, + 40,
CuS + 40, ———> CuSO, + 40,
CdS + 40, ——-> CdSO, + 40,
(11) Ozone oxidises halogen acids to corresponding halogens.
0, ——> 0,40
ns +) >. BO,
2HCl +O, ——~+ H,0O+C1,+0,
(tit) Ozone oxidises nitrites to nitrates.
OO, -——- ere
REMEMBER Pes Bi os
KNO, + O, ——~+ KNO, + O,
The oxidation of potassium iodide
by ozone can be conveniently used (2v) Ozone oxidises potassium todide to 1odine.

for quantitative estimation of ozone. i, —— > 0,40

When ozone reacts with excess of 2KI + H,0 +O ——> 2KOH +I,
potassium iodide solution buffered i ae a a
with a borate buffer (pH = 9.2) eh Oe pe ae os
iodine is liberated which can be titrated (v) Ozone oxidises acidified ferrous salts to ferric salts.
against a standard solution of sodium o> 0.40
thiosulphate. This is a quantitative 2FeSO, + H,SO, + O > Fe,(SO,), + H,O
method for the estimation of ozone gas.
2FeSO, + H,SO, +0, ——> Fe,(SO,), + H,O + O,
Ferrous sulphate Ferric sulphate
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(vt) Ozone oxidises potassium ferrocyanide to potassium ferricyanide.

2 ——-- oF
2K, [Fe(CN),] + H,O +O — 2K,[Fe(CN),] + 2KOH
2K, [Fe(CN),] + H,O +O, + 2K,[Fe(CN),] + 2KOH + O,
Potassium Potassium
ferrocyanide ferricyanide
(vit) Ozone oxidises potassium manganate to potassium permanganate.
<= (Fe
2K,MnO, + H,O + O ——> 2KMn0O, + 2KOH
2K,MnO, + O, + H,O ——-> 2KMn0O, + 2KOH +O,
Pot. manganate Pot. permanganate
(6) Oxidation of non-metals. Ozone oxidises non-metals such as sulphur,
phosphorus or moist iodine to their oxyacids. For example,
(vit) Ozone oxidises moist todine to todic acid.
O. —— > 0,+0] x5
Le ee
1,0, + H,O0 ——-+> 2HIO,
I, +50, +H,O ——> 2HIO, + 50,
Todic acid
(ix) Ozone oxidises sulphur to sulphuric acid.
O. —— > 0,+0)] x3
oo c= BU,
nO), HO -——> Hest),
oa, + BLO :<—> Boe, +30,
(x) Ozone oxidises moist phosphorus to phosphoric acid.
O, ——~+ O, +O] x 10
Rao AO: s
P,O,,+
4™"10 6H,O ———+ 4H,P@¢
P, +100, + 6H,O ———+ 4H 4@@®, i” A0 O,
Phosphoric acid
(c) Oxidation of metalloids. Ozone oxidises certain metalloids such as
arsenic, antimony, etc. to their respective oxyacids. For example,
(1) Oxidation of moist arsenic :
0. San @ TH! x5
2As + 50 —-> As,O-,
As,O, + 3H,0 ——> 2H,AsO,

Arsenic acid
(it) Oxidation of moist antimony :
ees 0,+0
2Sb + 50 ———> Sb,0O,
Sb,0O, +3H,O0 ———> 2H,SbO,
2Sb + 50, + 3H,0 ———> 2H,SbO, + 50,
Antimonic acid
(d) Oxidation of metals. Ozone oxidises certain metals such as silver,
mercury, etc. to their respective oxides. For example,
(4) Silver is oxidised to silver oxide.
O, ——— O0,+0
2Ag +O ——-» Ag,O
“Bags 0, ——> Ag,O + 0,
Silver oxide
a 7/68 MODERN'S abc + OF CHEMISTRY-XIl

(it) Mercury is oxidised to mercurous oxide.

0, ==> Bere
2Hg +O ——+ Hg,0
2He-bO, ——> He,0 = GD,
Mercurous oxide
During this reaction, mercury loses its meniscus and starts sticking to the
sides of the glass. This is known as tailing of mereury. Mercury does not stick
to glass and is, therefore, used in thermometers. But mercurous oxide formed
in the reaction dissolves in mercury and starts sticking to the glass surface.
4. Bleaching agent. Due to the oxidising action of ozone, it acts as a mild
bleaching agent as well as a sterilizing agent. It acts as a bleaching agent for
vegetable colouring matter.
Vegetable colouring matter + O, ——» Oxidised coloured matter + O,
(colourless)
For example, ozone bleaches indigo, ivory, litmus, delicate fabrics, etc.
5. Formation of ozonides. Ozone reacts with alkenes in the presence
of carbon tetrachloride (CC1,) to form an ozonide. For example,

HC
YN
CH, =CH, +0, SC, |
Ethylene Q— 0
Ethylene ozonide

Sci CH,— CH,

4 \ CH,
CH, —CH = CH, + O, hy
Propylene QO
Propylene ozonide
6. Action with peroxides. Ozone reacts with peroxides such as hydrogen
peroxides and barium peroxide and liberates oxygen.
Heo, + O,-—— > H,0 + 20,
BaO, + O, ——> BaO + 20,
Structure of ozone. The structure of ozone molecule is angular as
shown in Fig. 32. The O—O—O bond angle is 116.8° and O—O bond length is
O 127.8 pm.

The bond length in ozone molecule is intermediate between single

Fig. 32. Structure of ozone molecule. and double bonds in oxygen atoms (single O—O bond = 148 pm, double O=O
bond = 122 pm). Ozone molecule thus, is considered to be a resonance hybrid
of the following two resonating structures (a) and (0).

Q@ @6 ¢
Tests of Ozone / \ ‘ \ oa he : :
@ InIn the
the presence
pre fO.,O,, mercury 1loses
of 6: 6: 6 NS: 6~
its meniscus and starts sticking to
glass (tailing of mercury). (a) (b)
@ It turns moist start iodide paper Resonating structures
blue. Uses of Ozone
@ It turns
a alcoholic solution of 1. Ozone is used for disinfecting and sterilising water because ozone has
benzidine brown. germicidal properties.
2. It is used for bleaching, flour delicate fabrics, oils, flour, starch, ivory, etc.
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3. Itis used for purifying air of crowded places such as cinemas, underground
railways, auditoriums, tunnels, mines, etc. and for destroying objectionable
odours in slaughter houses.
4. It is used in industry for the manufacture of potassium permanganate,
artificial silk, synthetic camphor, etc.
5. It is used in the laboratory for the ozonolysis of organic compounds.
Depletion of Ozone Layer
Ozone is formed in the upper atmosphere by a photochemical reaction
involving oxygen. Ozone absorbs radiations strongly in the ultraviolet region
of the spectrum between 220-290 nm and this protects the earth and its
inhabitants from the harmful effects of ultra-violet radiations. Therefore,
the thick layer of ozone is called ozone blanket- Without this protective
ozone layer, more ultraviolet radiations will reach the surface of the earth
and cause damage to plant and animal life. The increased exposure to
ultraviolet radiations may cause skin cancer, damage to immune system
leading to increased viral infections, damage to land’s plants and crops and
damage to marine plants and marine animals.
Recently in 1980, scientists have observed a hole in the ozone blanket
covering the upper atmosphere around Antarctica. This depletion of ozone
layer in the stratosphere has become a worldwide concern of all scientists.
It has been observed that the hole in ozone layer is because of its reaction
with chlorofluorocarbons (CFC’s). These volatile compounds have been used
for some years as aerosol propellants and as refrigerants. Chlorofluorocarbons
are long lived molecules and diffuse into the stratosphere where they are
decomposed by ultra violet radiations to produce chlorine. These chlorine
atoms react with ozone causing a decrease in its concentration at a faster
rate than its formation from O,.
CIACKS. = hv —> Cl + CICF,
Cl + oo - — Clos
ClO + ei + Jf,
So the effect of CFC’s on the ozone layer is a single greatest threat
to the global atmosphere: The depletion of ozone layer is a serious threat
to mankind. Scientists believe that every 1% decrease in ozone leads to 2%
increase in skin cancer due to exposure to sun’s ultra-violet rays.
There is another cause of ozone depletion. It is because of release
of nitrogen oxides (NO,) into the stratosphere by the exhaust system of
supersonic jet aeroplanes. NO molecule can react with ozone to give O,.
NO) +0,@) — ~<a, Ned. Bt O, &)
Three scientists, P.J. Crutzen, M.J. Molina and F.S. Rowland got 1995
Noble Prize in Chemistry for their pioneering work in this area. As a result,
there is a great awareness all over the world to find alternatives for CFC’s
and control the emission of oxides of nitrogen into stratosphere.

CHEMISTRY OF SULPHUR AND ITS COMPOUNDS

ALLOTROPES OF SULPHUR
Sulphur exists in numerous allotropic forms of which three forms are the
most important. These three main allotropic forms are : The mineral of sulphur, pyrite, FeS,
(4) Rhombic sulphur (it) Monoclinic sulphur is often called fool's gold because of
(iit) Plastic sulphur its golden yellow colour. It contains
the disulphide ion (52>), the sulphur
(4) Rhombic sulphur or c-Sulphur
analogue of the peroxide ion, (O;-)-
It is the common form of sulphur and is formed by slowly evaporating the
solution of roll sulphur in CS,, when octahedral crystals of sulphur appear.
Properties
(4) It is bright yellow in colour.
(ii) Its specific gravity is 2.06 g cm.
(iii) Its melting point is 385.8 K.
 MODERN'’S abc + OF CHEMISTRY-AXIl

(iv) This is the most stable form of sulphur at room temperature and
all other varieties of sulphur change into this form on standing.
(v) It is insoluble in water but dissolves to some extent in benzene,
alcohol and ether. However, it is readily soluble in CS,.
(vi) It has low thermal and electrical conductivity.
Structure
Rhombic sulphur exists as S, molecules. The sulphur atoms are arranged
in a puckered ring as shown in Fig. 33.
(4) Monoclinic sulphur or $-Sulphur
This form of sulphur is prepared by melting rhombic sulphur in a dish
and cooling till a crust is formed. Two holes are made in the crust and the
Fig. 33. Puckered ring structure of remaining liquid poured out. On removing the crust, colourless needle shaped
sulphur. crystals of B-sulphur are formed.
Properties
(4) It is dull yellow in colour and like rhombic sulphur, it is also soluble
in carbon disulphide.
(ii) It has specific gravity of 1.98 g cm™.
(iit) Its melting point is 393 K.
(1v) Monoclinic sulphur also exists as S, molecules with puckered ring
structures like rhombic sulphur. However, the two forms differ in the symmetry
of their crystals.
(v) It is stable above 369 K and transforms into o-sulphur below this
temperature. Conversely, o-sulphur is stable below 369 K and transforms into
>369 K
Rhombic Monoclinic B-sulphur above this temperature. Thus, at 369 K both the forms are stable
<369 K
sulphur sulphur and coexist. This temperature is called the transition temperature-
Structure
Both rhombic and monoclinic sulphur have S, molecules. These S, molecules
are packed to give different crystal structures. The S, ring in both the forms
is puckered and has a crown shape.
(711) Plastic sulphur or 6-sulphur
Plastic sulphur is obtained by pouring molten sulphur into cold water
205.7 pm when a soft rubber like mass called plastic sulphur is formed.
Properties
(i) It is an amorphous form of sulphur.
(iz) It is soft and elastic in the beginning but hardens on standing and
eradually changes to rhombic sulphur.
(iit) It has no sharp melting point.
(iv) It has specific gravity of 1.95 g cm.
(v) It is insoluble in carbon disulphide. Plastic sulphur is regarded as
Fig. 34. Structure of cyclo-5, super cooled liquid 1.e.,a liquid which due to rapid cooling below its freezing
allotropic form of sulphur. point had no time to settle in a crystalline form.
Several other modifications of sulphur containing 6—20 sulphur atoms per
ring have been synthesised in the last two decades. Among these, another
S, species predominate at about important form is cyclo-S, (Engel's sulphur or ¢-sulphur) in which the six
1000 K. Like O,, 5, is paramagnetic membered ring adopts the chair form as shown in Fig. 34.
and blue coloured. At high temperatures (about 1000 K), S, is the dominant species and
is paramagnetic (like O,) and blue coloured.
SULPHUR DIOXIDE
It contains sulphur in + 4 oxidation state.
Preparation
Sulphur dioxide is formed together with a little (6-—8%) sulphur trioxide
when sulphur is burnt in air or oxygen.
S (s) + O, (¢) ——— SO, ig)
In the laboratory, sulphur dioxide is prepared by treating a sulphite
with dilute sulphuric acid.
Na,SO, (s) + H,SO, (ag) ———> SO, (g) + Na,SO, (aq) + H,O (J)
Sodium sulphite
or SOz (aq) + 2H* (aq) ———> SO, (g) + H,O (J)
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>369K |
Rhombic sulphur Monoclinic sulphur
< 369K
It may also be prepared in the laboratory by heating copper turnings with
concentrated sulphuric acid.
Cu + 2H,SO, ———> CuSO, + SO, + H,O
Industrially, it is produced as a by-product of roasting of sulphide ores
such as iron pyrites or zinc blende.
4FeS, + 110, ———> 2Fe,O0, + 8SO,
Iron pyrites
27nS + 30, ———+> 2Zn0 + 2SO,
Zine blende
The gas is dried, liquefied under pressure and stored in steel cylinders.
Properties
It has the following properties :
Physical properties.
(z) It is a colourless, toxic gas with a pungent and suffocating odour.
(ii) It is heavier than air.
(iii) It is readily soluble in water. At 0°C, 1 volume of water can dissolve
about 8 volumes of the gas.
(iv) It can be easily liquefied at room temperature under a pressure of
2 atmosphere. The liquid is colourless, boils at 263 K and freezes at
197.5 K, giving a white snow-like mass.
Chemical Properties.
(¢) Acidic character. Sulphur dioxide dissolves in water giving sulphurous
acid.
SO, (g) + H,O (1) ——— H,SO, (aq)
Therefore, SO, is regarded as anhydride of sulphurous acid. Its aqueous
solution is acidic turning blue litmus red.
Because of its acidic character :
(a) It reacts readily with sodium hydroxide solution forming sodium sulphite,
which then reacts with more sulphur dioxide to form sodium hydrogen sulphite.
2NaOH + SO, ———> Na,SO, + H,O
Sod. sulphite
Na,SO, + H,0 + SO, ——> 2NaHSO,
Sod. hydrogen sulphite
(6) When the gas is bubbled through lime water, it becomes milky. On
passing the excess of the gas, the milkiness disappears due to formation of
calcium bisulphite.
Ca(OH), + SO, ——-> CaSO, + H,O
Milkiness
CaSO, + SO, +H,0 —— + Ca(HSO,),
Cal. bisulphite
(Milkiness disappears)
In its reaction with water and alkalies, its behaviour ts very similar to
that of carbon dioxide.
(74) Combustibility. The gas is non-combustible and does not support
combustion. However, certain substances such as carbon, magnesium, etc.
extract oxygen from the gas and burn in it when ignited.
sO, + Cc —~ CO, +85
SO, + 2Mg ——-—> 2Mg0+S
(zit) Combination with oxygen. Sulphur dioxide reacts with oxygen
when heated forming sulphur trioxide.
205
250, + O, 250,
The above reaction is reversible and slow. Therefore, the reaction is carried
out in the presence of some catalyst such as platinised asbestos, vanadium
pentoxide, etc. This reaction is used in the manufacture of sulphuric acid by
Contact process.
 MODERN'’S abc + OF CHEMISTRY-AXIl

(jv) Combination with halogens. Sulphur dioxide combines directly with

the halogens (fluorine, chlorine and bromine) forming sulphury] fluoride, chloride
and bromide respectively. For example, SO, combines with chlorine in the presence
of charcoal (which acts as a catalyst) to give sulphuryl chloride (SO,Cl,).

SO, @) + Cl, ¢g) ==» so,cL. ©

Sulphuryl chloride
(v) Combination with hydrogen sulphide. Sulphur dioxide reacts with
hydrogen sulphide when the two gases are brought into contact with each
other. Therefore, it acts as a mild oxidising agent.
SO, + 2H,S ——— 2H,0+35S
(vi) As a reducing agent. Sulphur dioxide acts as a fairly strong reducing
agent in the presence of moisture.
It reduces
(a) potassium dichromate to chromium sulphate.
K,Cr,0, + H,SO, + 350, A@— @Bs0, + Cr,(S0,), + H,O
or Cr,0,7+ 350, + 20 '*/g—Ge 50" + 2Cre + HAO
(b) potassium permanganate to manganese sulphate.
2KMnO,+ 5SO, + 2H,0 ——~+ K,SO, + MnSO, + 2H,SO,
or2MnO,+ 580, + 2H,O ——> 280,77 + 2Mn** + 4H*
Therefore, it decolourises pink violet colour of acidified potassium
permanganate solution. The reaction serves as a convenient test for the gas.
(c) potassium todate to todine.
2KIO, + 550, + 4H,0 -——-+> 2KHSO,+ 3H,SO, + Ia
(ad) halogens to halide ions.
SO, Yai g/ Cl, —— H,S0, + 2HCl
or SO, + 2H,O + Cl, —— S502? + 2C1 + 4H
SO, + H,O + Br, —— H,SO, + 2HBr
or SO, + 2H,O + Br, 2 —— SO,~ + 2Br— + 4H*
e SO, acts as a bleaching agent. (e) ferric sulphate to ferrous sulphate,
Bleaching action of SO, is a Fe,(SO,, + SO, + 2H,O0 ——>2FeSO,+ 2H,SO,
temporary process.
or 2Fe** + SO, + 2H,O ———> 2Fe** +S0O? + 4H*
(f) lead dioxide to lead sulphate.
PbO, + SO, ——» PbSO,
(g) sodium peroxide to sodium sulphate.
Na,O, + SO,——> Na,SO,
(vit) Bleaching action. In the presence of moisture, sulphur dioxide acts
as a bleaching agent.
SO, + 2H,O ——— H,SO, + 2H
The nascent hydrogen bleaches vegetable colouring matter to colourless
matter.
Colouring matter + [H] ———> Colourless matter
On exposing the bleached article to air, the reverse process takes place,
i.e., colour is restored due to the atmospheric oxygen.
Colourless matter + [0] ———> Coloured matter.
Thus, bleaching by sulphur dioxide is a temporary process.
Structure
The structure of SO, has already been discussed (Fig. 23).
Uses
(z) Sulphur dioxide is used for the manufacture of important chemicals such
as sulphuric acid, sodium hydrogen sulphite, calcium hydrogen sulphite, etc.
These bisulphites are used as presrvatives for jams, pickels, jellies and squashes.
(iz) It is used for refining of petroleum and sugar.
(iit) It is used for bleaching delicate articles such as wool, silk, straw, etc.
p-BLOCK ELEMENTS

(tv) It is used as a disinfectant and a germicide.

(v) Itis used as an antichlori.e., for removing excess chlorine from bleached
articles.
(vi) Liquid SO, is used as a solvent to dissolve a number of organic and
inorganic chemicals.
(vit) Liquid SO, is used as a preservative.
(viit) Liquid SO, is used as a refrigerant because it can be liquified and
re-evaporated easily.
OXOACIDS
Sulphur, selenium and tellurium form a variety of oxoacids. Of these, the
oxoacids of sulphur are more numerous and more important than those of
selenium and tellurium. Let us first discuss the oxoacids of sulphur.
Oxoacids of sulphur
Sulphur forms a number of oxoacids. Only a few of these have been isolated
as free acids while a number of these have been found only as their aqueous
solutions or salts. Some of these are listed in Table 15.

Table 15. Some Oxoacids of sulphur.

Oxidation state of S Structural formula

Sulphurous acid
OH
0
l
Sulphuric acid
OHL
S
I
O =S—OH
Thiosulphuric acid |
OH
0 O
ll
Dithionous acid HO—s—s—(
O O
I I
0= SS),8=0
Polythionic acid

Disulphuriec acid
Pyrosulphuric acid

Peroxomonosulphuric acid

Peroxodisulphuric acid
 MODERN'S abc + OF CHEMISTRY-XIl

The structures of some important oxoacids of sulphur with the oxidation state of sulphur in brackets are given
below :

@
J | I
Oo

Ss

we Te uo . wo Te w le €
Sulphurous acid Sulphuric acid Thiosulphuric acid Peroxomonosulphuric acid
H,SO,(+ 4) H,S0,(+ 6) H,S,0, (+ 2) (or Caro's acid)
H,SO,(+ 6)

oO oO ~ ~/ ©
|
~JF J eS
5 5 5

OH :
Cc eo
. 07
oe\\@
eH a
xy \e
Dithionie acid Peroxodisulphuric acid Disulphuric acid
H,5,0,(+ 6) (or Marshall's acid) (or Pyrosulphuric acid)
H,8,0.(+ 6) (Oleum)
H,8,0, (+ 6)

REMEMBER SULPHURIC ACID

Peroxomonosulphuric acid, H,SO- Sulphuric acid is one of the most important industrial chemicals world
(also called Caro's acid) and wide. Because of its industrial applications, it is called king of chemicals.
peroxodisulphuric acid, H,S,O, Manufacture of Sulphuric Acid
(also called Marshall's acid) Sulphuric acid can be manufactured by Contact process. The process
contain —O—O- linkage. involves the following steps :
() Preparation of sulphur dioxide. Sulphur dioxide is prepared by
burning sulphur or iron pyrites in excess of air.
5+0, —— 580,
4FeS, + 110, ———> 2Fe,0, + 8SO,
Iron pyrites
(it) Oxidation of sulphur dioxide into sulphur trioxide. Sulphur
dioxide is catalytically oxidised to sulphur trioxide with atmospheric oxygen.
The reaction is reversible as well as exothermic in nature. This is the key
reaction for the process. The high yield of SO, will lead to more production of
the acid.
280, (g) + 0, (g) 2-5 280, (g) A H*=-196.6 kJ
(it) Absorption of sulphur trioxide into 98% sulphuric acid to
form oleum. Sulphur trioxide is absorbed in about 98% H,SO, to form oleum
or fuming sulphuric acid.
pu), + HO, ——> 45,0;
Oleum
(iv) Dilution of oleum with water. Oleum is then diluted with required
quantity of water to get sulphuric acid of any desired concentration.
H,5,0_4+ 50 —>. 2050,
Conditions favouring the maximum yield of sulphur trioxide.
The key step in the manufacture of sulphuric acid is the catalytic oxidation
of SO, with O, to give SO,. This is a reversible and exothermic process. It is
the key reaction for the process:
250, +0, ——> 2S0, AH® = -196.6 kJ
p-BLOCK ELEMENTS

The conditions for the maximum yield of sulphur trioxide are derived by
using Le Chatelier’s principle as follows :
(1) Low temperature. The forward reaction is exothermic and therefore,
low temperature favours the oxidation of sulphur dioxide. However, it is essential
to have minimum temperature of 720 K, called optimum temperature, to
get the maximum yield of the product.
(11) High pressure. Since the volume of the gaseous products is less
than that of the gaseous reactants, high pressure should favour the oxidation
of sulphur dioxide. But a very high pressure may cause the corrosion of the
vessel in which oxidation is carried. Therefore, a pressure of 2 to 3 bar is
sufficient for the oxidation.
(111) Use of catalyst. A catalyst increases the speed of reaction. Platinised
asbestos was used as catalyst. But it is easily poisoned by the impurities present
in the gases and, therefore, has now been replaced by vanadium pentoxide
(V,O-). It is comparatively cheap and is not poisoned by the impurities.
(iv) Purity of gases. The gases must be purified before subjecting them
to oxidation in the presence of catalyst.
Conc. H,SO,
Water spray spray Conc. H,SO
Impure | -——
| Dry SO, +O,
AIM. - HN _

Preheater ;
Sulphur

Air —>— —__— [UZ

Sulphur burner Testing box converter
_ walpr t poig Arsenic purifier
Dust precipitator sl containing gelatinous
Washing and = Drying tower —_—_hydrated ferric oxide
cooling tower

Fig. 35. Contact process for the manufacture of H,SO, acid

Description of the plant. The plant employed for the Contact process
has been shown in Fig. 35.
1. Sulphur burners. Sulphur or iron pyrites are burnt in excess of air
to form sulphur dioxide.
5/ ure, f— 5o,
4FeS, + 110, ——— 2Fe,0, + 850,
2. Purification Unit. The gaseous mixture coming out of sulphur burners
is generally impure. The gases are purified as follows :
(i) Dust chamber. Steam is introduced to remove dust particles.
(it) Coolers. The hot gases are cooled to about 373 K by passing them
though cooling pipes.
(iit) Scrubber. Gases are introduced into a washing tower (packed with quartz)
also known as scrubber which dissolves mist and any other soluble impurities.
(iv) Drying tower. A spray of conc. H,SO, is used for drying of gases.
(v) Arsenic purifier. This is a small chamber fitted with shelves containing
gelatinous ferric hydroxide Fe(OH). The impurities of arsenic oxide present
in the gases are absorbed by ferric hydroxide.
line MODERN'S abc + OF CHEMISTRY-XIl

3. Testing box. The gases coming out of purification unit are tested in this
box with the help of a strong beam of light. If some impurities are present,
they will scatter light and the path will become visible. In case the gases are
impure, they are passed through the purifying unit again.
4, Contact chamber or converter. The pure gases are then, heated to
about 723-823 K in a pre-heater. These are then introduced in the contact
chamber. It is a cylindrical iron chamber fitted with iron pipes. Each pipe is
packed with the catalyst consisting of either platinized asbestos or V,O.. In
this chamber sulphur dioxide is oxidised to sulphur trioxide.
250, +0; ——* 250,; AH = —196.6 kJ
As the forward reaction is exothermic, the pre-heating of the incoming
gases is stopped once the oxidation reaction has started. The heat produced
in the reaction is sufficient to maintain the temperature of the reaction.
5. Absorption tower. It is a cylindrical tower packed with acid proof
flint. Sulphur trioxide escaping from the converter is led to the bottom of
the tower while concentrated sulphuric acid (98%) is sparyed from the top.
It may be noted that sulphur
Sulphur trioxide gets absorbed by sulphuric acid to form oleum or fuming
trioxide is not directly absorbed
sulphuric acid.
in water to form sulphuric acid
because the process is accompanied H,SO, + SO, ———> H,S,0,
Oleum
by formation of dense fog of the
acid particles. Therefore, it becomes Oleum is then diluted with calculated amount of water to get acid of
quite inconvenient for the workers. desired concentration.
H,S,0,+ H,O ———> 2H,SO,
A flow sheet diagram of Contact process is given below :

[If impurities are present, passed Impure SO,

through purifying unit again]

EeEE ]-Cen : Arsenic esting

Conc. H,SO
ae
|
iil
50
Pure

oetion ee
ea Vain. an ——— Pre heater
[Abszrrtin | ¢§_o ee
| << you

Properties
Sulphuric acid has the following properties:
Physical properties : (2) Pure sulphuric acid is a colourless, dense,
viscous liquid (specific gravity of 1.84 at 298 K). It is known as oil of vitriol.
(it) It freezes at 283 K and boils at 611 K.
The high boiling point and viscosity of sulphuric acid suggest that it is an
associated molecule. The different molecules are held together by hydrogen
bonding as shown below:

"\\ Zou a SL ro bonds

ao So. “a Ne === me” Mapas

(iit) The concentrated acid has strong affinity for water and the dissolution
process is highly exothermic and a large quantity of heat is evolved. Concentrated
p-BLOCK ELEMENTS

sulphuric acid is diluted by adding acid to water and not water to acid. In
the latter case, so much heat is produced that acid will spurt out of the
container. Sulphuric acid forms hydrates such as H,SO,.H,O (m.p. 8.5°C) and
H,SO,.2H,O (m.p. 38°C).
(iv) It is highly corrosive and produces burns on the skin.
Chemical Properties
1. Dissociation. Sulphuric acid is quite stable but on strong heating, it
dissociates into SO, and H,0.
H,SO, =~ H,O + SO,
2. Acidic character. It is a strong dibasic acid and ionises in aqueous
solution as :
H,SO, (aq) == H*(aq)+HSO, (aq) K_ =Very large
H,SO, (aq) == 2H* (ag) +S0,* (aq) Ka, = 1.2 x 107
The larger value of K_, (K,, > 10) means that H,SO, is largely dissociated
into H* and HSO, ions. Greater the value of dissociation constant (K,), the
stronger is the acid.
Therefore, it forms two series of salts : normal sulphates such as sodium
sulphate (Na,SO,), copper sulphate (CuSO,), etc. and acid sulphates or
hydrogen sulphates or bisulphates such as sodium hydrogen sulphate
(NaHSO,).
Thus, it reacts with alkalies, metal carbonates, metal bicarbonates, metal
oxides, ammonia, etc. which are the characteristic reactions of an acid.
(a) Action with metal hydroxides. Being a dibasic acid, it forms two series
of salts.
NaOH +H,SO, ——-> NaHSO, + H,O
Sodium bisulphate
2NaOH + H,SO, ——~ Na,SO, + 2H,0
Sodium sulphate
(6) Action with metal carbonates and bicarbonates.
Na,CO, + H,SO, ———> Na,SO, + H,O + CO,
2NaHCO, + H,SO, ———> Na,SO, + CO, + 2H,O
(c) Action with metal oxides.
CaO +H,SO, ———> CaSO, + H,O
(d) Action with ammonia. Dense white fumes of ammonium sulphate are
formed.
2NH, + H,SO, ——— (NH,),SO,
(e) Being an acid dilute H,SO, liberates hydrogen with metals like zine,
magnesium, tron, tin, ete.
H,SO, (dil.) + Zn ——> ZnSO, +H,T
H,SO, (dil.) +Mg ———> Mgso, +H,T
However, metals like copper and silver which are less electropositive than
hydrogen, fail to react with the dilute acid.
3. Dehydrating agent. Due to strong affinity for water, concentrated acid
acts as a powerful dehydrating agent. Its corrosive action on skin is due to this
property. Its strong affinity for water is illustrated by the following properties:
(a) Drying of gases : Many wet gases like carbon dioxide, sulphur dioxide,
chlorine, hydrogen chloride, etc. which have no action with acid, are dried by
bubbling into the concentrated sulphuric acid.
(6) Charring. When concentrated acid is dropped on paper, wood or sugar,
it absorbs moisture and brings about charring.
C Ho. —— > 11H,O 4 10
(absorbed by acid) Charring
 MODERN'S abc + OF CHEMISTRY-iIl

(c) Action with formic acid.

Oxoacids of Selenium and Tellurium
HCOOH ~—s0,~” CO + H,0
Conc.
Selenium forms two oxoacids :
Selenious acid H,SeO, ; Selenic Formic acid (absorbed by acid)
acid H,SeO, (d) Action with oxalic acid.
Selenious acid is white solid and
can be dehydrated to selenium dioxide coon "41, co + co, + HO
in a stream of dry air. On refluxing with (absorbed by acid)
H,O,, it gets converted to selenic acid. COOH
With alkalies, it forms two types of salts (e) Action with ethyl alcohol. At 170°C, ethyl alcohol gets dehydrated to
MHSeO, and M,SeO, (where M = alkali ethylene.
metal). Cone. H,SO, |
Anhydrous selenic acid is viscous C 9H,OH 170°C C,H , H,O
liquid and crystallizes to a white solid Ethyl alcohol Ethylene
(m.p. 62°C). It resembles H,SO, in its
(f) Action with hydrated salts. It removes water of crystallisation from
chemical properties and is strong acid
hydrated salts. For example,
like H,SO, having close dissociation
constant. However, it differs from Cone. H,S0, —
CuSO,.5H,O , CuSO, + 5H,O
H,5O, in being strong oxidizing agent. Hydrated copper Anhydrous
It can dissolve Au, Pd and even Pt in
sulphate (blue) copper sulphate (white)
the presence of chloride ion. It oxidises
halides ion (except F-) to free halogen. 4, Oxidising agent. Hot concentrated sulphuric acid is a moderately
Like H,,SO,, it forms many hydrates as strong oxidising agent. In this respect, it is intermediate between phosphoric
H,Se0,.H,0, H,Se0,.4H,0, etc. It also and nitric acids. The oxidising character of H,SO, is due to the fact that it
forms selenates like sulphates. decomposes to give nascent oxygen.
Tellurium forms oxoacids : H,SO, ——— H,0+S0, + (O)
Tellurous acid H,TeO,, Nascent
Telluric acid H,TeO, The nascent oxygen brings about a number of oxidation reactions. Both
Tellurous acid was not known
metals and non-metals are oxidised by concentrated sulphuric acid which is
earlier because it could not be prepared reduced to SQ,.
by dissolving TeO, in water as TeO, is (a) It oxidises carbon to carbon dioxide.
almost insoluble in water. These days, 29H,SO, + C ——> 2S0,+ CO, + 2H,O
it has been prepared by the hydrolysis
of tetrahalide of tellurium. Its structure (6) [t oxidises sulphur to sulphur dioxide.
has not been well established. Like 2H,5O, + 85 ——> 350, + 2H,O
selenious acid, it forms two series
of salts, MHTeQ, and M,TeO,. The (c) It oxidises phosphorus to phosphoric acid.
dissociation constants of H,TeO, and 10H,S50, + P, ——— 4H,PO, + 1050, + 4H,O
H,SeO, are close : (d) lt oxidises hydrogen sulphide to sulphur.
Ee ae A cles H,SO, + H,S ——— 2H,O+50,+5
K, =2x 10% (e) It oxidises halogen acids (HBr and HI) fo halogens.
H,SeQ, : K,=3.5x 197" Hoe, + 2hbe ———»* 20.0 + be, + 50,
K, =5 x 10 (f) If oxtdises metals such as Cu, Pb, Hg, Ag etc. to their corresponding
Telluric acid, H,TeO, is quite stable sulphates liberating SO,.
and is well known. Cu + 2H,SO, ——~+ CuSO, + 50, + 2H,O
It is white solid (m.p. 136°C). It is With zinc, which is a stronger reducing agent than copper, the reduction
quite different from H,SO, and H,SeO, of concentrated sulphuric acid goes further to give sulphur or H,S.
and exists as octahedral Te(OH),
molecules. It is fairly strong oxidising 5. Action with salts. It is a strong non-volatile acid and decomposes the
agent but unlike H,SO, and H,SeO, it salts of volatic acids forming its own salts.
is weak dibasic acid. It also forms two °oMX + H,SO, ——> 2HX + M,SO,
series of salts e.g., NaTeO(OH), and (M = metal, X = F, Cl, NO,)
Li,TeO,(OH),. Na,CO, + H,SO, ——> Na,SO, + H,O+CO,
The anhydrous telluric acid is stable
in air upto 100°C but above 120°C it
KNO, + H,SO, ——> KHSO, + HNO,
loses water to form polymetatelluric NaCl + H,SO, ——> NaHSO, + HCl
acid. In case of bromides and iodides, the halogen acid formed is oxidised to
free halogen as it is a strong reducing agent. For example,
p-BLOCK ELEMENTS

[Nal + H,SO, ——> NaHSO, + HI] x2

H,SO, ——> H,O +=+S0, +0
2HI + Oo—>H,O #1,
2Nal + 3H,SO, ———> 2NaHSO,+S0, + I,+2H,O
Therefore, because ofits low volatility sulphuric acid is used to manufacture
more volatile acids from their corresponding salts.
6. Precipitation reactions. Sulphuric acid gives white precipitate when
treated with solution of lead and barium salts.
BaCl, + H,SO, ——— BaSO, + 2HCl
white ppt.
Pb(NO,), + H,SO, ———+ PbSO, + 2HNO,
white ppt.
(CH,COO),Pb + H,SO, ——+> PbSO, + 2CH,COOH
white ppt.
7. Action with sulphur trioxide. Sulphur trioxide is absorbed by conc.
sulphuric acid to form pyrosulphuric acid known as oleuwm or fuming sulphuric
acid.
Ho, + SO, ——— H,S,O i
Oleum

STRUCTURE OF SULPHURIC ACID AND SULPHATE LON

Both sulphuric acid and sulphate ion have tetrahedral structure in which
S atom is sp? hybridised as shown below:

Po. to
In sulphate ion, all the S—O bond lengths are equal (149 pm) and therefore,
it is a resonance hybrid of the following resonating structures:

sx
\_ +—> Sem See. "OY

Uses of sulphuric acid. Sulphuric acid is one of the most important

industrial chemicals and is known as king of chemicals. The industrial
strength of a nation can be judged by the quantity of sulphuric acid it procduces
and consumes. The important uses of sulphuric acid are :
(i) In fertilizer industry. It is used in the preparation of fertilizers such
as ammonium phosphate, ammonium sulphate, super phosphate of lime, etc.
The bulk of sulphuric acid produced is used in the manufacture of fertilizers.
(it) In petroleum refining. It is used for the refining of crude petroleum.
The crude petroleum is treated with sulphuric acid to remove unwanted sulphur
and other tarry compounds.
(iit) In dyes, drugs, paints and pigments. It 1s used directly or indirectly
in the manufacture of chemicals such as dyes, drugs, paints, pigments, etc.
(iv) In chemical industry. It is used for the manufacture of hundreds
of other compounds such as hydrochloric acid, nitric acid, phosphoric acid,
sulphates, bisulphates, diethyl ether, etc.
 MODERN'’S abc + OF CHEMISTRY-AKIl

(v) In metallurgy. Sulphuric acid is used for metallurgical processes such

as electrolytic refining, electroplating, galvanising, etc. A number of metals
like copper, silver, etc. are extracted from their ores using sulphuric acid.
(vi) It is used for cleaning the surfaces of metals (picking) before
electroplaing.
(vit) It is used in the manufacture of explosive such as dynamite, T.N.T.
nitro cellulose products (gum, cotton), etc.
(viit) It is also used as a drying and dehydrating agent.
(ix) It is used for storage batteries.
(x) As a laboratory reagent. It is widely used in laboratory as a drying
and dehydrating agent and in many other chemical reactions. It is very
important chemical reagent.
Currently, our country is producing more than 2.5 million tonnes of
sulphuric acid per annum compared to over 40 million tonnes produced in
U.S.A. and 120 million tonnes produced worldwide.

SOLVED EXAMPLES

_L] Example 30 (d) Te (s) + Cl, (g) —___-5

Sulphur in vapour state shows paramagnetic () C+H,SO,(conc.) ———>
character. Why? (A.J.S.B. 2008; D.S.B. 2008, 2012)
Solution :
Solution: Inthe vapour state sulphur exists as 5, molecules. (a) Cu+cone. 2H,SO, ——> CuS0,+50,+2H,0
S, molecule like O, molecule has two unpaired electrons in the
(b) SF,+2H,O ——— 50,+4HF
antibonding molecular orbitals ( 7,* and t,*) and hence shows
(c) 2H,S+SO, _ Catalyst, 35+2H,0
paramagnetism.
(d) Te(s) + 2Cl,(g) ————>__ TeCl,.
L] Example 31
Why is H,S less acidic than H,Te ? (e) C+2H,50O,(conc.) ——+ CO,+2S0,+2H,O
(Pb.S.B. 2017, Kerala S.B. 2018) L] Example 34
What happens when
Solution : In H,Te the size of central Te is more than that
of S in H,5 and therefore, the distance between the central atom
(a) Concentrated H,SO, 1s added to calcium fluoride.
(b) SO, 1s passed through water ? E
and hydrogen, Te—H is more than that of S—H. As a result of
large bond length, the bond dissociation enthalpy of, Te—H is Solution:
(a) It forms hydrogen fluoride.
less than that of S—H and bond cleavage of Te—H bond is easy.
CaF, +H,SO, ———— CaSO, + 2HF
Therefore, H,Te is more acidic than H,S.
(b) Sulphuric acid 1s formed
_}] Example 32 SO,+H,O ——— H,SO,
Dioxygen is a gas while sulphur is a solid at room
_}] Example 35
temperature. Why? (ALLSB, 2013, 2018)
Write the order of thermal stability of the hydrides of
Solution : Oxygen exists as a stable diatomic molecule and
group 16 elements. N.C.E.R.T. (D.S.B. 2017)
is, therefore, a gas. On the other hand, sulphur exists in solid
Solution : The thermal stability of the hydrides of group 16
state as S, molecules and have puckered ring structure. The main
elements decreases from H,O to H, Te as:
reason for this different behaviour is that oxygen atom has strong
H,O > H,S > H,Se > H,Te
tendency to form multiple bonds with itself and forms strong
O = O bonds rather than O—O bonds. On the other hand, _}] Example 36
sulphur-sulphur double bonds (S=S) are not very strong. As a What happens when sulphur dioxide ts passed into
result, catenated —O—O—O— chains are less stable as compared aqueous solution of Fe (LID) salt? N.C.E.R.T.
to O=0 molecule while catenated —S—S—S— chains are more Solution : Fe(III) salt 1s reduced to Fe(II) salt.
stable as compared to S=S molecule. Therefore, oxygen exists 2Fe?* + SO, + 2H,O ——-> 2Fe** + SO? + 4H"
as a diatomic gas and sulphur exists as S, solid.
_}] Example 37
_] Example 33
Why is K,, << Ka for H,SO,in water ?
Write balanced equations for the following reactions:
Solution : H,SO, is a very strong acid in water because of
(a) Cu+tconce. H,SO, ———_-4 its first ionisation to H,O+t and HSO,.
(Db) SH,+H,Q ——> H,SO, + H,O ~~
== H,O° + HSO,
(o) H,S+SO, —Lxalys,
©
p-BLOCK ELEMENTS

It is almost completely ionised so that its K_, is very large Solution : Oxygen cannot show an oxidation state of +6
(K_, > 10). However, dissociation of HSO™, in water to due to the absence of d-orbitals in its valence shell. Therefore,
oxygen does not form OF. In contrast, S contains d-orbitals in the
H,O* and SO? is very small (K,, = 1.2 x 10). That is valence shell and hence can show a maximum oxidation state of
why its K,, << K,. +6. Since F, is a very strong oxidising agent, it oxidises sulphur
H,SO, + H,O ==> _H,0* + SO? to its maximum oxidation state of +6 and hence forms SF,.
_}] Example 41.
_}] Example 38
SOCI, can act as a weak Lewis acid as well as a weak Lewis
SH, 1s easily hydrolysed whereas SF, is not easily
base. Explain.
hydrolysed. Why ? (A.IS.B. 2009, Mizoram S.B. 2015)
Solution: The basic character of SOCL, is due to the presence
Solution : In SF, molecule, sulphur atom is coordinately of a lone pair of electrons on S atom. Like ammonia, it has a
saturated and is stearically protected by six F atoms and hence pyramidal structure involving sp? hybridisation with a lone pair
does not allow H,O molecules to attack the S atom. Therefore, SF, of electrons as:
does not undergo hydrolysis. On the other hand, in SF,, sulphur

ia
atom is not stearically protected because it is surrounded by only
four F atoms. As a result, attack of H,O molecules on 5 atom can
take place easily and hence hydrolysis can occur. Therefore, SF,
easily undergoes hydrolysis.
_}] Example 39 So, Lewis basic character is due to the presence of a
lone pair of electrons. In addition, SOCI, has also empty d-
SF,is known but SCl,is not known. Give reason.
orbitals which can be used to accept electron pairs and hence
(D.S.B. 2005, Pb. S.B. 2016)
it behaves as a Lewis acid.
Solution: Due to small size of S, six large Cl atoms cannot be
accommodated around 5S atom. But small six F atoms can be easily _}] Example 42.
accommodated around 5S atom to form SF,. Moreover, because of Sulphur disappears when boiled with an aqueous alkaline
low electronegativity of Cl, it cannot easily cause promotion of solution of sodium sulphite.
electrons in 5 to form $ (VI). Solution : When sulphur 1s boiled with an aqueous alkaline
_}] Example 40 sodium sulphite solution, it forms sodium thiosulphate, which is
soluble in water. So, sulphur disappears.
Why does OF ,not exist but SF, exists?
(A.P.S.B. 2011, 2018)

21. Name the element of group 16 which has

(t) highest electronegativity (it) highest metallic character
(iit) highest melting point (iv) Maximum ionisation energy.
22. Among the hydrides of the members of oxygen family, which has
(¢) lowest boiling point
(it) maximum thermal stability
(iii) weakest acidic character
23. What is the oxidation state of S in the following oxyacids of sulphur ?
(t) Peroxy monosulphuric acid
(it) Thiosulphuric aicd - Answers to Practice Problems =
(iit) Dithionic acid
21. (1) Oxygen (i1) Polonium
(tv) Sulphuric acid (iit) Tellurium (iv) Oxygen
24. Why is sulphuric acid highly viscous ? 22. (1)H,S (i) H,O (zz) H,O
25. Name the acid formed when sulphur heptoxide dissolves in water. 23. (2) +8 (11) +2 (111) + 5 (iv) +6
24. Due to hydrogen bonding.
26. What is the oxidation state of S in 5,0, and SO, ?
25. Persulphuric acid, H,S,O,.
27. What happens when conc. H,SO, is dropped on sugar ? 26. +7:4+6
28. What is the formula of peroxodisulphuric acid ? What 1s its basicity ? 27. Charring occurs (because of C).
28. H,5,O0,, two.
29. Arrange H,O, H,S and H,Se in decreasing acidic strength. 29. H,O < HS < H,Se.
30. What is the structure of SCl, ? 30. Angular.
 MODERN'’S abc + OF CHEMISTRY-AXIl

Conceptual ake uestions | 2 SSS

. The two O—O bond lengths in ozone molecule are equal. Why? (A.LS.B. 2013, DSB. 2014)
. Ozone is a resonance hybrid of two structures and therefore, the two O—O bond lengths are equal.

CS\ekL
NO /O.

Q.2. SF, 1s known but SH, is not known. Explain. (Pb. S.B. 2005, Pb. S.B. 2016)
Ans. Fluorine is the strongest oxidising agent and oxidises sulphur to its maximum oxidation state of +6 and hence forms
SF,. Therefore, fluorine can easily cause the promotion of electrons from the filled to the vacant 3d-orbitals.

5 @ OO COOCO
e) APOOO
However, hydrogen is a very weak oxidising agent and cannot oxidise S to its maximum oxidation state of +6.
Therefore, it cannot cause the promotion of electrons. Thus, SF, is known but SH, is not known.
. SO, has zero dipole moment. Why ? (Pb. S.B. 2016)
. Inthe gaseous state, SO, has planar triangular structure with O—S—O bond angles of 120° each. Therefore, individual
S—O dipole moments cancel each other and resultant dipole moment is zero.

k, ‘i
20°

ON.
» Which oxide of sulphur acts as a as 7 as reducing agent ?
. Sulphur dioxide (SO,) acts as oxidising as well as reducing agent.
. Ozone is used for purifying air in crowded places such as cinema halls, tunnels, etc. Explain.
. Ozone is an endothermic compound and easily decomposes to produce O, as :
20, —> 30,
Therefore, it purifies crowded places.
Q.6. Why is O—O bond length in ozone molecule (127 pm) more than in O, (121 pm) ?
Ans. Ozone molecule is a resonance hybrid of two structures:

4 \ oe a \
The molecular structure of O, is bent with bond angle of about 117°. The actual bond is intermediate between a
single and a double bond between oxygen atoms (single O—O bond = 148 pm, double O=O bond =122 pm) and bond
length is about 127 pm. This is larger than double bond in O, molecule (121 pm).
. Sulphur hexafluoride is used as a gaseous electrical insulator. Explain. (D.S.B. 2005)
. SF, is inert, nontoxic gas at non temperature. The inertness of SF, is due to be it the presence of 5 atom which
does not allow thermodynamically favorable reaction like hydrolysis. Because of its inertness and good dielectric
properties, SF, is used or a gaseous insulator in high voltage generator.
» Which hydride has greater bond angle ?
H,0, H,S, H,Se and H,Te (Hr. S.B. 2005)
. H,O.
p-BLOCK ELEMENTS 7/83 —

Q.9. SF, is not easily hydrolysed. (D.S.B. 2005)

Or
SF, is kinetically inert substance. Explain. (A.LS.B. 2011, DSB. 2011)
Ans. SF, is chemically inert and therefore, does not get hydrolysed. Its inert nature is due to the presence of stearically
protected sulphur atom which does not allow thermodynamically favourable hydrolysis reaction.
Q.10. Why oxide ion is called hard ion ? Explain.
Ans. Oxide ion is very small in size and therefore, it cannot be easily polarized. Hence, it is called hard ion.
Q. 11. Which of the following compounds has a lone pair of electrons at the central atom ?
(C.B.S.E. Sample Paper 2011)
H,S,0,, H,S,0,, H,SO,, H,SO,,.
« B,50.2
. Ozone is thermodynamically unstable. Explain. (C_.B.S.E. Sample Paper 2011)
. Ozone is thermodynamically unstable with respect to oxygen because it results in liberation of heat (AH is —ve) and
increase 1n entropy (AS is +ve). These two factors reinforce each other resulting negative AG (AG = AH — TAS) for
its conversion to oxygen.
20, ——=—» 30,
. Sulphuric acid has low volatility. Give chemical reactions in support of this.
(CLB.S.E. Sample Paper 2011)
. Sulphuric acid has low volatility and decomposes the salts of volatic acids forming its own salts :
2MX+H,SO, —-> 2HX + M,SO,
(M = metal, X = F, Cl, NO,)
e.£., NaCl+H,SO, —~> NaHSO,-+ HCl
KNO, + H,SO, — /@RRaD, + NHO,.
. When SO, is bubbled through a solution of H,SO,, a compound X is formed which further reacts with
water to give H,SO,. Explain the reaction.
. H,SO, absorbs SO, forming oleum (X) which reacts with water to give H,SO,.
H,SO, + SO, —> H,S,0, Ho, 2H,SO,
oleum
Q. 15. Out of PH, and H,8, which is more acidic and why?
Ans. The strength of an acid depends upon the stability of anion (i.e. conjugate base) formed after giving its proton.
PH, ———>
Wi
PH, (aq) + Ht (aq)
Wate
H,S —— ~ HS-(ag) + Ht (aq)
SinceS tence = 2.5)1s more electronegative than P (electronegatity = 2.1), the Sin HS can accommodate
the negative charge more easily than P in PH,. Therefore, HS” is more stable than PH,-. In other words, H,S can
release a proton more easily than PH, and hence H,5 is a stronger acid than PH,. Their dissociation constants
are :
K, (HS) = Aad x“io ' K/(PH.) = 1.6 x 10.
Q. 16. What is oleum? (Assam S.B. 2018)
Ans. H,S,O, (H,SO, + SO,)

“GROUP 17 ELEMENTS» GROUP 17

Group 17 of the periodic table contains five elements : fluorine (F), chlorine F
(Cl), bromine (Br), iodine (1) and astatine (At). These are named as halogens. —
The name halogens is derived from two Greek words halo meaning sea salt
and gens meaning born 1.e., sea salt produce because the first three members
occur as salts (chlorides, bromides and iodides) in sea water. The name was cls
introduced by Schweigger in 1811. These are among the most reactive non-
metallic elements. The last member of the family, astatine is a radioactive
element.
Like groups 1 and 2, the elements of group 17 show great similarity
amongst themselves, which is not found in the elements of other groups of a
the periodic table. They also show a regular gradation in their physical and .
chemical properties. However, like other elements of second period, fluorine At
(the first element of the group) differes in several ways from the rest of the Astatine
croup members.
 MODERN'S abc + OF CHEMISTRY-XIl

OCCURRENCE
The halogens are very reactive and therefore, do not occur in the free state.
However, all except astatine are abundant in the earth’s crust as halide ions,
X-. Fluorine and chlorine are fairly abundant while bromine and iodine are
comparatively less abundant.
Fluorine is the thirteenth element in order of abundance in crustal
rocks of the earth. It is present mainly as insoluble fluorides. The three most
important minerals are
(t) fluorite : CaF,;
(it) eryolite : Na,AlF, and
(111) fluoroapatite : 3Ca,(PO,),-CaF, or Ca.(PO,),F.
Small quantities of fluorine are also present in soil, river water, plants
and bones and teeth of animals.
Chlorine is twentieth most abundant element in crustal rocks. The major
deposits are of NaCl. Sea water contains chlorides, bromides and iodides of
sodium, potassium, magnesium and clacium, but is mainly sodium chloride
solution (2.5% by mass). The dried beds of inland lakes and seas contain large
deposits of sodium chloride (NaCl), carnallite (KC]l.MgCl,.6H,O) and calcium
chloride (CaCl.,).
Bromine is relatively less abundant in crustal rocks than either fluorine
and chlorine. Bromides occur in sea water and salt lakes as bromides of alkali
and alkaline earth metals 7.e., NaBr, KBr, MgBr,, etc.
Iodide occurs in certain forms of marine life in their systems. For example,
lodine occurs 1n various sea weeds (upto 0.5% by mass) as alkali metal iodides
and in chile saltpetre (upto 0.2%) as sodium iodate (NalO,). Crude chile salt
petre is mainly sodium nitrate which contains impurities of iodine as sodium
iodate (NalO.,) and sodium periodate (NalIO,). Iodides occur only in low
concentration in sea water but these are absorbed and concentrated by sea
weeds.
GENERAL CHARACTERISTICS OF GROUP 17 ELEMENTS
A. Eleetronie Configurations
The elements of this group have seven electrons in the outermost shell
and have the general electronic configuration ns?np° (Table 16).
Table 16. Electronic configurations of elements of group 17.
Elements Atomic number Electronic
configurations
Fluorine, F , [He] 2s* 2p°
Chlorine, Cl [Ne] 3s7 3p?
Bromine, Br [Ar] 3d? 4s? 4p°
Iodine, I | [Kr] 4d! 5s? 5p°
Astatine, At [Xe] 471+ 5d?" 6s? Gp?
B. Atomic and Physical Properties
The important atomic and molecular properties of group 17 elements are
siven in Table 17. These are discussed below :
Table 17. Atomic and Molecular Properties of Halogens
Atomic Properties
Property F Cl Br I At
Atomic number 9 17 35 53 85
Atomic mass 19.00 30.45 79.90 126.90 210
Covalent radius (pm) 64 99 114 133 —
Ionic radius X- (pm) 133 184 196 220 —
Ionization enthalpy (kJ mol) 1680 1256 1142 1008 —
Electron gain enthalpy (kJ mol!) -333 —349 —325 —296 —
Electronegativity 4 a2 3.0 Ba ae
Anya) (kJ mol) 615 381 347 305 —
p-BLOCK ELEMENTS 7is5)

Molecular Properties Atomic Ionic

radius (pm) radius (pm)
Property |tee Cl, |a i;
Melting point (K) 54.4 172.0 265.8 386.6 F
Boiling point (K) 84.9 239.0 332.5 458.2
Distance X—X (pm) 143 ees 228 266
Enthalpy of dissociation (kJ mol) 158.8 242.6 192.8 161.1
Density (g cm-*) 1.51 1.66 3.19 4.94
E/V (at 85 K) (at 203 K) (at 273 K) (at 273 K)
X,(g) + Ze~- —> 2X (aq) Pett | 1.36 1.09 0.54

1. Atomic and ionic radii. The halogens have the smallest atomic radii
in their respective periods due to maximum effective nuclear charge. Among
themselves, the atomic and ionic radii increase with increase 1n atomic number.
This is due to increase in the number of electron shells.
The radius of the halide ion is always greater than the corresponding (kJ mol”)
halogen atom. This is because the halide ion is formed by the gain of one F
electron by the atom. As a result, the number of electrons increases while the 1680
magnitude of nuclear charge remains the same. Therefore, the same nuclear
|
charge acts on large number of electrons than are present<¢ in s the neutral Cl
Lo:
atom. In other words, effective nuclear charge per electron is reduced and the ——
electron cloud is held less tightly by the nucleus. This causes increase in size. Br
2. lonisation enthalpies. The ionisation enthalpies of halogens are very high. 1142
This indicates that they have very little tendency to lose electrons. However, I
on going down the group from fluorine to astatine, the ionisation enthalpy
decreases. This is due to gradual increase in atomic size which is maximum
for iodine. Consequently, it has the least ionisation enthalpy in family.
3. Melting and boiling points. The melting and boiling points of halogens Electron gain
increase with increase in atomic number as we go down the group. enthalpy (kJ mol")
Explanation. The forces existing between these molecules are weak van F
der Waal's forces which increase down the group. This is also clear from the — 333
change of state from fluorine to iodine. At room temperature, fluorine and
chlorine are gases, bromine is a liquid while iodine and astatine are solids.
4. Electron gain enthalpies. (i) All these have maximum negative eee
electron gain enthalpies in their respective periods. This is due to the fact that Br
the atoms of these elements have only one electron less than the stable noble — 325
gas (ns*np®) configurations. Therefore, they have maximum tendency to accept I
an additional electron.
(it) In general, electron gain enthalpy becomes less negative from top to
bottom in a group. This is due to the fact that the effect of increase in atomic
size is much more than the effect of increase in nuclear charge and thus, Chlorine has the highest negative
the additional electron feels less attraction by the large atom. Consequently, ?le¢ttongain enthalpy inthe periodic
electron gain enthalpy decreases. ltt
(iit) Fluorine has unexpectedly less negative electron gain enthalpy than
chlorine. Therefore, chlorine has the highest negative electron gain
Electronegativity
enthalpy in this group. The less negative electron gain enthalpy of fluorine
as compared to chlorine is due to very small size of the fluorine atom. As F
a result, there are strong interelectronic repulsions in the relatively small 4.0
2p subshell of fluorine and thus, the tncoming electron does not feel much Cl
attraction. Therefore, its electron gain affinity is small.
Thus, negative electron gain enthalpy among halogens varies as : :
F < Cl > Br > I Br
5. Electronegativity. Halogens have large electronegativity values. The 3.0
values decrease down the group from fluorine to iodine because the atomic I
size increases and the effective nuclear charge decreases. Fluorine is the 27
most electronegative element in the periodic table.
 MODERN'S abc + OF CHEMISTRY-XIl

6. Metallic or non-metallic character. Because of very high ionisation

REMEMBER energy values, all halogens are non-metallic in character. The non-metallic
Fluorine is the most character decreases as we go down the group. Therefore, the last element,
electronegative element in iodine is a solid with a metallic lustre and forms positive ions such as I*
the periodic table. and J**.
(}) Chlorine has the highest 7. Colour. All the halogens are coloured. The colour of different halogens
negative electron gain enthalpy are given below :
among halogens. Halogen Fluorine Chlorine Bromine lodine
1) Iodine is most metallic among Colour Light Greenish Reddish Dark
halogens. yellow yellow brown violet

Explanation. The colour of halogens is due to the fact that their molecules
absorb radiations from visible light and the outer electrons are easily excited
to higher energy levels. The amount of energy required for excitation depends
upon the size of the atom. Fluorine atom is the smallest and the force of
attraction between the nucleus and the outer electrons is very large. As a
result, it requires large excitation energy and absorbs violet light (high energy)
and therefore, appears pale yellow. On the other hand, iodine needs very less
excitation energy and absorbs yellow light of low energy. Thus it appears dark
violet. Similarly, we can explain the greenish yellow colour of chlorine and
reddish brown colour of bromine.
C. Oxidation States
Halogens have only one electron less than the next noble gas. Therefore,
they can get the noble gas configuration either by gaining one electron to form
uninegative ion, X-, or by sharing electrons with other atoms. Thus, they show
an oxidation of state of —1 or + 1. Since fluorine is the most electronegative
element, it always shows an oxidation state of —1. It does not show any
positive oxidation state.
The other elements also show positive oxidation states of +1, +38, +5 and
+ 7. The higher oxidation states of chlorine, bromine and iodine are due to the
presence of vacant d—orbitals in their valency shells. As a result the outer
s— or p—electrons can easily be promoted to the vacant d—orbitals as shown below:
Ground state s 5p
(Oxidation state = —1, +1)

Fit |
stn tte CEL
First excited state
Fluorine shows only—1 oxidation
state.
Second excited state

(Oxidation state
=+5) titt| yf
Pidatian sts ALtTty|
Third excited state

These higher oxidation states are realised mainly when the halogens are
in combination with the small and highly electronegative fluorine and oxygen
atoms, e.g., In oxides, oxoacids and interhalogen compounds. The oxidation
states of +4 and +6 occur in oxides and oxoacids of chlorine and bromine and
+7 oxidation state occurs in interhalogen compounds such as IF..
Thus,
a the exhibit the “es oxidation states :

Bile —1, +1, +3 —1, +1, +3 —1, +1, +3

states +5, +7 +5,+7 +5,+7

TRENDS IN CHEMICAL REACTIVITY

The halogens are the most reactive elements as a family. They react readily
with metals and non-metals to form halides. Fluorine is the most reactive
of all the halogens. The reactivity of the halogens decreases down the group.
p-BLOCK ELEMENTS

The high reactivity of halogens is due to the following reasons :

(4) Low dissociation enthalpies. All the halogens have very low
dissociation enthalpies. As a result, they can readily dissociate into atoms
and react with other substances. As shown below, the dissociation enthalpies
of halogens are quite low in comparison to common molecules such as H,, O,
and N.,.2

Dissociation 158.8 242.6 192.8 151.1 458

enthalpy
X, —— 2X (kJ mol")
(ii) High negative electron gain enthalpy. Halogens have very
high negative electron gain enthalpy values (Table 17) and therefore, have
very strong tendency to gain an electron. Thus, halogens are very reactive
elements due to their low dissociation enthalpies and high negative electron
gain enthalpies. As clear from the values of bond dissociation enthalpies,
fluorine has the lowest bond dissociation enthalpy. This is due to weak F—F
bond because of the repulsion between the non-bonding electrons in the small
molecule. Therefore, it is most reactive among the halogens.
Reactivity and Oxidising Power of Halogens
The reactivity of halogens can also be understood in terms of their oxidising
power. Halogens have high electron acceptance property and therefore they
have strong tendency to take up the electron :
1 =
— X, te ——> X
As a result, they act as powerful oxidising agents. Fluorine is the
strongest oxidising agent and oxidises other halide ions in solution or even
in the solid phase. In general, a halogen of lower atomic number will oxidize
halide ion of higher atomic number and therefore, will liberate them from
their salt solutions as given below :
F, + 2X ——> 2F JG, (X= Cl Br, D
Cl, + 2X ——> 2Cl/o4 X, (X
= Br, DD
Br, + 27 ———> 2Br + h,
The decreasing oxidising power of the halogen as we go down the group is
shown by their decreasing reduction potentials.
KF, + 2e ——/@mars B® = +2.87V REMEMBER
Cl, + 2 /~_@Sr K° = +1.36V
e F, is the strongest oxidising
Br, + 2 ~@, —=—ey K° = +1.09 V
agent while I, is the weakest
lL, + 2g 2V BK° = +0.54V
oxidising agent.
e I ion is the strongest reducing
E° (volts) 2.87 agent while F ion is the weakest
The electrode potential of F, is maximum while that of I, is the minimum. reducing agent.
This means that F,, can be 7) most easily and I, is acd least readily.
This means that F, is the strongest oxidising ‘agent while I, is the
weakest oxidinng agent.
As we know, chlorine has the highest negative electron gain enthalpy, so
gaseous Cl] atoms have maximum tendency to accept electrons and therefore,
chlorine is expected to be strongest oxidising agent. However, chlorine is not
strongest oxidising agent, but fluorine is the strongest oxidising agent. This
can be explained with the help of Born Haber cycle. As we have learnt, electron
gain enthalpy is the property of the isolated atoms in the gaseous state as
X(g) + e ———> X (g) A.gtt” Electron gain enthalpy
However, oxidising power of halogen is a property in solutions as :

5% (s, 2 org) +e + nH,O —> xX (aq)

 MODERN'S abc + OF CHEMISTRY-iIl

For gaseous F’, and Cl,, the process may be thought to proceed as :
, 1 — a.
(z) an. (g) ——> X(g) = A,..,41° : Dissociation process
2
(iz) X (g) + e@ —— X (g) A,,H° : Electron gain enthalpy

(tit) XxX (g) + nH,O ——_> X (aq) Awyall” : Enthalpy of hydration

This process may be expressed as :

Daicn oe Anya
qi”
=X (g) —_(i) > X (g) st (it) .S (g) ptep (ziz) Be. (aq)

| AH |
The overall tendency for the change (oxidising power) depends upon the
net effect of the three steps. As we know that energy is needed to dissociate
or convert molecular halogen into atomic halogen. The enthalpy change for
this step is positive. On the other hand, energy is released in step (ii) as well
as step (iii) therefore, enthalpy for these steps is negative. Now, although
flourine has less negative electron gain enthalpy, yet it is strongest oxidising
agent because of the following reasons :
(1) F, has low enthalpy of dissociation because of weak F—F bond.
(11) F, has very high enthalpy of hydration because of smaller size of
the F- ion.
Therefore, the larger amount of energy released in step (iii) and lesser
amount of energy required in step (z) overweighs the smaller energy released in
step (ii) for fluorine. As a result, AH overall is more negative for fluorine than
for chlorine. Thus, fluorine is very strong oxidising agent. The values of enthalpy
changes of different steps are given below :

REMEMBER
It may be noted that since bromine occurs as liquid at room temperature, it
Fluorine is the strongest oxidising involves enthalpy of fusion also, while iodine which is solid at room temperature,
agent because of its smaller size, involves enthalpy of sublimation as well as enthalpy of fusion. The overall
low bond dissociation enthalpy of energy released for these are less than those of F, and Cl.,,.
F, and high exothermic hydration The relative oxidising power of halogens can be further illustrated by their
enthalpy of the small F ion. reactions with water. Fluorine is so strong oxidising agent that it oxidises
water to dioxygen. The reaction is spontaneous and strongly exothermic.
The ability of fluorine to stabilize
2F, (g) + 6H,O (1) ———> 4H,O* (aq) + 4F- (aq) + O, g)
the highest oxidation state of other
The reaction with chlorine and bromine are thermodynamically possible but
elements is next to oxygen e.g., in
they react very slowly forming corresponding hydrohalic and hypohalous acids.
the compounds such as IF-., 5SF,,
X, (g) + H,O (1) ——-> HOX(aq) + HX (aq) (X=Cl or Br)
BiF.., PtF,, etc.
The reaction of iodine with water is non-spontaneous. In fact, iodide can
be oxidised by oxygen in acidic medium.
AT (ag) + O, (g) + 4H* (ag) ——~> 2I,(s) + 2H,O @
This reaction is just reverse of the reaction observed with fluorine.
Let us discuss some general trends in reactivity of halogens :
1. Reactivity with hydrogen
All halogens react with hydrogen to give hydrogen halides.
H, +X, ——> 2HX
p-BLOCK ELEMENTS 7/89 =

The reactivity of halogen towards hydrogen decreases down the group from
fluorine to iodine. For example, fluorine combines with hydrogen violently
even in the dark, chlorine reacts in diffused sunlight, bromine reacts with
hydrogen only on heating while iodine reacts with hydrogen heating in the
presence of platinum as catalyst.

H, + F, lent, onF
H, + Cl, gain? 2HCl
H, + Br, —Het, HBr
H, a + I2 ee" _, OI
Ft, catalyst

Hydrogen fluoride and hydrogen chloride are manufactured by heating a mixture of calcium fluoride (fluorite
or fluorospar) and sodium chloride with concentrated H,SO, respectively.
CaF, (s) + H,SO, (aq) ——> CasdO, (s) + 2HF (g)
2NaCl (s) + H,SO, (aq) ——> Na,SO, (s) + 2HCI (g)
HBr is manufactured by direct reaction of H, and Br, at about 570 K in the presence of platinum catalyst.
H, (g) + Br, (g) Pt/asbestos, orp
HI is manufactured by the reaction of HI with H,S or hydrazine.

21, (s) + NH, (ag) SS 4H (ag) +N, )

HBr and HI cannot be prepared satisfactorily by the treatment of metal bromides or iodides with conc. H,SO,
because HBr and HI formed are moderately strong reducing agents. They reduce sulphuric acid to SO, and are
themselves oxidised to Br, and I, respectively.
For example, 2NaBbr+HjsO, —/@ ,Nagey, + 2HEr
ILSO, eae Het 50,140
2HBr+O {a —*@e@yo + Br,

2ZNaBr + 2H.SQOq “Sew/ Naso, + SO, + Br, + 2H,0

Sunilarly, 2ZNal + 2030, “yf Naso, + SO, + 1, + 20,0
The difficulty can be solved by using a non-oxidising acid like H,PO,.

Properties of hydrogen halides

Some important characteristics of hydrogen halides are discussed below :
(7) Physical state. Hydrogen fluoride is a low boiling liquid (b.p. 292 K)
while HCl, HBr and HI are gases. The anomalous property of HF is due to
presence of hydrogen bonding in the molecules. Due to hydrogen bonding in
HF molecules it exists as associated molecule (HF).
..H—F ......... H—F H—F ......... H—F ..........

In the solid state (HF), has the zig-zag structure :

(iz) Melting and boiling points. Amongst the hydrogen halides,
the boiling point of HF is highest (b.p. 293 K) due to extensive
intermolecular hydrogen bonding. The other halides show negligible
hydrogen bonding because of the lower electronegativity of the halogen
atom in them. Therefore, the boiling points of HCl, HBr and HI are
much lower than that of HF. As we move from HCl to HI, the boiling
points regularly increase down the group. They are held together by
weak van der Waals’ forces which increase with increasing size of Seisi cen head
halogen atom.
a 7/90 MODERN'S abc + OF CHEMISTRY-XIl

Similarly, like boiling point, the melting point of HF is higher than that
of HCl. The melting points of other halides increase gradually from HCl to
HI as the size of halogen atom increases.
(iit) Nature of bonds. All the halides are covalent compounds with some
ionic character. This is indicated by low melting and boiling points of the
hydrogen halides and also by the fact that the compounds in pure state are poor
conductors of electricity. The degree of ionic character decreases in the order :
HF > HCl > HBr > HI
This order is expected from the order of decreasing electronegativity of
the halogens.
(jv) Bond length and bond dissociation enthalpy. As the size of
halogen atom increases, the bond length (H—X) increases in the same order.
The bond length of HX molecule increases as :
Hydrides of Group 17 HF (91.7 pm) < HCl (127.4 pm) < HBr (141.4 pm) < HI (160.9 pm)
Now, bond dissociation enthalpy is inversely proportional to bond length
HF : i.e., shorter the bond length, greater is the bond strength or bond dissociation

HCl
8
o
enthalpy. Therefore, bond dissociation enthalpy decreases in the order :
HF > HCl > HBr > HI
£
==] (v) Thermal stability. The thermal stability of the hydrides decreases
HBr
=)
= from HF to HI. HF is most stable whereas HI is least stable. For example,
o
=
fa
HF and HC] are stable up to 1500 K while HBr dissociates to the extent of
Hl
2 10% and HI is dissociated to the extent of 20% at 700 K.
=
<
The decrease in stability of the hydrides its due to decrease tn bond strength
which decreases when we go down the group.
decreases Reducing
~ Thermal
stability increases
character
(vi) Reducing character. The decreasing thermal stability of hydrogen
halides from HF to HI indicates that the reducing character increases down
the group as
HF < HCl < HBr < HI
Thus, HF is not a reducing agent at all. HCl is a weak reducing agent,
HBr is a stronger reducing agent while HI is the strongest reducing agent
among all the hydrides.
(vit) Acidic strength. In gaseous state, hydrogen halides are covalent. But
in aqueous solutions, they ionise and behave as acids. The acidic strength
of these acids decreases in the order :
HI > HBr > HCl > HF
Thus, HF is the weakest acid and HI is the strongest acid among
these hydrogen halides.
Explanation. The above order of acidic strength is reverse of that expected
on the basis of electronegativity. Fluorine is the most electronegative halogen,
therefore, the electronegativity difference will be maximum in HF and should
decrease gradually as we move towards iodine through chlorine and bromine.
Thus, HF should be more tonic in nature and consequently it should be strongest
acid. Although many factors contribute towards the relative acidic strengths,
the major factor is the bond dissociation energy. The bond dissociation energy
decreases from HF to HI so that HF has maximum bond dissociation energy
and HI has the lowest value.
Hydrogen halide
Bond dissociation
energy (kJ mol')
Since H—I bond is weakest, it can be easily dissociated into H* and I- ions
while HF can be dissociated with maximum difficulty. Thus, H/ is the strongest
acid while HF ts the weakest acid among the hydrogen halides.
The properties of hydrogen halides are summed up in Table 18.
Table 18. Properties of hydrogen halides
Property
Melting point (K)
Boiling point (K)
Bond length (H—X) (pm)
Dipole moment wD)
Ages HJ mol)
Dissociation constant (pK,)
p-BLOCK ELEMENTS

2. Reactivity towards oxygen : formation of oxides

Structure of OF, is similar to H,O
Halogens form many binary compounds with oxygen but most of these while that of O,F, is similar to that
are unstable. Fluorine forms two oxides OF, and O,F,. However, only OF, is of H,0,,.
thermally stable at 298 K while O,F, is highly unstable and decomposes into
Ss.
elements even at 113 K. These Geides are called oxygen fluorides because
fluorine is more electronegative than oxygen.
rw 103°.
F
Oxygen difluoride (OF,) is prepared by passing F, through dilute (2%)
aqueous solution of NaOH while dioxygen difluoride (O,F,) is prepared by
passing electric discharge through a mixture of O, and F, under low pressure
and at liquid air temperature.
2F,+ 2NaOH ——> 2NaF+H,0 + OF,
(2% solution) >». pm O-

O>
4 F,
-
Electric discharge
low pressure
OF, &,dy
liq. air temperature O.F, F

OF, dissolves in water and gives a neutral solution and therefore, it 1s not Fig. 36. Structures of OF, and O,F,.
an acid anhydride. It dissolves in NaOH to give sodium fluoride and dioxygen.
2NaOH + OF, ———> 2NaF + H,O + O,
Being a strong oxidising agent, OF, has been used as a rocket fuel.
Both these fluorides are strong fluorinating agents. O,F, oxidises plutonium
to PuF, and this reaction is used in removing Pu as PuF, from spent nuclear
fuel. O,F, also combines with H.S to give oxygen.
H,S + 40,F, ——— SF, + 2HF + O,
On the other hand, the oxides of eilorine: bromine antl lodine are called
oxides. They form oxides from +1 to +7 oxidation states. Chlorine forms
the largest number of oxides while iodine forms the least number of oxides.
In these binary compounds, the bonds are mainly covalent because of small
difference in electronegativity between the halogens and oxygen. However,
the bond polarity increases as we move from chlorine to iodine because of
increasing difference in electronegativity.
The stability of oxides formed by halogens decreases as :
[Sb > Er
The oxides of iodine are more stable than those of chlorine which are more
stable than those of bromine. Thus, bromine oxides are least stable. Iodine—
oxygen bond is stable because of greater polarizability of I while the stability
of chlorine—oxygen bond is due to multiple bond formation involving d-orbitals
of Cl atom. However, bromine being in between lacks both the characteristics.
The higher oxides of halogens tend to be more stable than the lower ones.
These are listed in Table 19.
Table 19. Oxides of halogens in different oxidation states

Oxidation Fluorine Chlorine Bromine

state

Among these chlorine dioxide is the only one prepared on a large scale by
the reduction of ClO,- with SO, in strongly acidic medium :
Fig. 37. Structures of oxides of
2NaClO, (ag) + SO, (g) -8%4_, 2C10, (g) + Na,SO, (aq). chlorine.

All these oxides of chlorine are powerful oxidising agents and decompose
explosively when subjected to mechanical shock or heat. ClO, and Cl,O are
used as bleaching agents for paper, pulp, textiles and water treatment. The
structures of some common oxides of chlorine are given in Fig. 37.
 MODERN'S abc + OF CHEMISTRY-XIl

The oxides of bromine, Br,O, BrO,, BrO,, etc. are the least stable halogen
oxides and exist only at lower temperatures. They are very powerful oxidising
agents.
The oxides of iodine, I,0,, 1,0, and 1,0, are insoluble and decompose on
heating. For example, 1,0, decomposes on heating above 673 K
1,0, Hes: ST +50,
It is strong oxidising agent. It oxidises H,S to sulphur and HCl to chlorine.
It oxidises CO to CO, quantitatively liberating iodine which can be titrated
against sodium thiosulphate.
0.4 5CO ——» I, + FO.
This reaction is used for the detection and estimation of carbon monoxide
and is the basis of the analytical method for determining CO in atmosphere
or in other gaseous mixtures.
3. Reactivity towards metals
Halogens react with metals to form metal halides. For example, bromine
reacts with magnesium to give magnesium bromide.
Mg (s) + Br, (1) ——~+ MgBr, (s)
Fluorine is most reactive and the reactivity decreases as we move down
the group. The ionic character of the metal halides decreases in the order :
MF > MCI > MBr > MI (where M is a monovalent metal).
If a metal exhibits more than one oxidation states, the halides in higher
oxidation state will be more covalent than the one in the lower oxidation state.
For example, SnCl,, PbCl,, SbF., and UF, are more covalent than SnCl,,
PbCl,, SbCl, and UF, respectively.
4. Reactivity of halogens towards halogens
Halogens combine amongst themselves to form a number of compounds
known as interhalogen compounds. Each halogen has a tendency to combine
with each other halogen. These interhalogen compounds are of the type AX,
AX,, AX. and AX. where X is large size halogen atom showing negative
oxidation state. These are discussed later.
Anomalous Behaviour of Fluorine
Like other elements of the second period, fluorine also differs from
the rest of the members of the halogen family in many characteristics.
This behaviour may be attributed to its.
(i) very small size,
(it) high electronegativity,
(iii) absence of vacant d-orbitals in the valence shell.
Due to above reasons, fluorine exhibits many properties which are different from
other halogens. For example,
1. Oxidation state. Fluorine shows oxidation state of -1 only while other halogens
show oxidation states such as +1, +3, +5 and +7 also.
2. Bond dissociation enthalpy. The bond dissociation enthalpy of fluorine molecule
is less than that of other halogen molecules. This is due to the fact that the repulsion
between non-bonding electrons in small fluorine molecules are very strong. As a result
F—F bond is weak and can be easily broken.
3. Anomalous behaviour of hydrofluoric acid. Due to high electronegativity of
fluorine, the bonding pair in H—F molecule is largely attracted towards fluorine and
therefore, 1t forms hydrogen bonds. On the other hand, HCl, HBr and HI are gases
at room temperature. Due to association in HF molecules, its boiling point is high in
comparison to other halogen acids. In aqueous solution, HF is much weaker acid than
other hydrogen halides.
4, Ionic character of fluorides. Only fluorine can form ionic fluorides. For example,
AIF, SnF,, etc. are ionic in nature while the corresponding chlorides are covalent.
5. Solubility. Fluorides have abnormal solubilities than other halides. For example,
AgF is soluble in water whereas AgC] is insoluble; CaF, is insoluble in water while
CaCl, is soluble.
p-BLOCK ELEMENTS

6. Formation of polyhalide ions. Fluorine does not form polyhalide ions such
as F, while other halogens form polyhalide ions such as I,, Br, , I, ete.
7. Oxidising power. Fluorine acts as strongest oxidising agent among the halogens.
Therefore, it brings about highest oxidation state of other elements with which it combines.
But other elements do not bring about the highest oxidation state of the element.
8. Formation of oxoacids. Fluorine forms only one oxoacid HOF, whereas other
elements form a number of oxoacids.

HALOGENS AND THEIR COMPOUNDS

CHLORINE
Chlorine was first prepared by C.W. Scheele in 1774 by the action of HCl
on MnO.. In 1810, Davy established its elementary nature and suggested the
name chlorine on account of its colour (Greek : Chioros meaning yellowish
ereen). The bleaching action of chlorine was discovered by Scheele in the early
work (1774) and was put to technical use by Berthollet in 1785.
Occurrence
Chlorine is very reactive and does not occur in nature in free state. It
constitutes about 0.19% of lithosphere. It occurs mostly as chlorides of sodium and
other alkali and alkaline earth metals. The most abundant compound of chlorine
is sodium chloride (rock salt) and occurs in extensive evaporite deposits, saline
lakes and brines and in the ocean. All the chlorine is virtually produced from
it. Other sources of chlorine are sylvine (KCl), carnallite (KCL. MgCl,.6H,O), etc.
Preparation
Chlorine can be prepared by any one of the following methods :
(1) By heating manganese dioxide with concentrated hydrochloric
acid. Chlorine is prepared easily by heating manganese dioxide with cone.HCl.
MnO, + 4HC] —“—> MnCl, + Cl, + 2H,O
However, a mixture of common salt and concentrated H,SO, is used in
place of HCl.
4NaCl + MnO, + 4H,SO, ——> MnCl, + 4NaHSO, + 2H,0 + Cl,
In the laboratory, equal amounts of sodium chloride and manganese
dioxide are finely ground and taken in a round bottomed flask. Concentrated
sulphuric acid is poured from tap funnel and reaction mixture is heated
gently. Greenish yellow vapours of chlorine gas rise up and are collected by
the upward displacement of air.
(it) By the action of HC] on potassium permanganate or potassium
dichromate.
2KMnO, + 16HCl ———> 2KCl + 2MnCl, + 8H,O + 5Cl,
K,Cr,O, + 14HCl ———> 2KCl] + 2CrCl, + 7H,O + 3Cl,
It is amore convenient though a little expensive method for the preparation
of chlorine in the laboratory.
(iit) By the action of HCI on lead oxides or bleaching powder.
PbO, + 4HCl ——-> PbCl, + 4H,O + Cl,
Pb,O, + 8HC]l ——~+ 38PbCl, + 4H,O + Cl,
CaOCl, + 2HCl ——~+ CaCl, + H,O + Cl,
Manufacture of Chlorine
Chlorine is manufactured by the following methods :
(4) Deacon’s process. Hydrochloric acid is oxidized by atmospheric air
in the presence of CuCl, (catalyst) at 723 K.
 MODERN'’S abc + OF CHEMISTRY-AXIl

CuCl,
4HC1+0, ea Goa waK? 2ClL + 2H,0
The reaction is reversible and results in about 65% conversion. Nowadays,
this method is modified by using improved catalyst (CuCl, with didymium
oxide as promoter; didymium is old name meaning twin and it consists of two
lanthanide elements praseodymium and neodymium). This process works at
a slightly lower temperature than the original process.
(iz) Electrolytic process
Chlorine is obtained by the electrolysis of brine solution (concentrated
sodium chloride solution). Chlorine is liberated at the anode. The sodium metal
liberated at the cathode reacts with water to form NaOH and H..
At anode :
Cr —~ > ecl +) e
Cl + Cl —+ 3e—Cl2
At cathode:
Nat + ef => Na
2Na + 200°" “/-NaOH + H,
It is also obtained as a by product during the manufacture of sodium by
the electrolysis of fused NaCl in Down's process.
Properties of Chlorine
Physical properties
(4) It is greenish yellow gas.
(iz) It has strong pungent and suffocating odour.
(iit) It is a poisonous gas which causes headache.
(iv) It is about 25 times heavier than air.
(v) It is soluble in water and its aqueous solution is called chlorine
water. It is also soluble in organic solvents like carbon tetrachloride. It can
be liquefied easily into greenish yellow liquid which boils at 239 K.
(vi) Its b.p. is 239 K and m_p. is 171 K.
Chemical properties
Due to its high electronegativity, chlorine is a very reactive element although,
not as much as fluorine. Some of its important reactions are discussed below.
1. Combination with metals non-metals and metalloids : Chlorine
reacts with a number of metals, non-metals and metalloids to form their
corresponding chlorides.
(4) Combination with metals:
2Na + Cl, ——> 2NaCl

Ca + Cl, ——> CaCl,

2Fe + 3Cl,—i*", 2FeCl,
2A1 + SCl,—2", 2AlCl,
(44) Combination with non-metals :
5, + 4CL, ——— 48,Cl,
Sulphur monochloride
P, + 10Cl, ——+ 4PCl,
Phosphorus pentachloride
p-BLOCK ELEMENTS

2B + 3Cl, ——> 2BCl,

Boron trichloride

(411) Combination with metalloids :

2As + 3Cl, ——> 2AsCl,

Arsenic trichloride

2Sb + 3Cl, ——> 2SbCl,

Antimony trichloride
2. Affinity for hydrogen: Chlorine has great affinity for hydrogen.
Therefore, it reacts with compounds containing hydrogen to form HCl.
sr ee —— 2 HCl
H,S + Cl, — > 2HCl + &
Canttge. oF BOL, +> 16 BG! + 10G
Turpentine oil
3. Action with water : Since chlorine has great affinity for hydrogen,
it decomposes water in the presence of sunlight to produce hydrochloric acid.

2H,O + 2Ccl,— 2s", 4HCl + ~~ OO,

4. Action with halides : Chlorine displaces the less electronegative
halogens (bromine and iodine) from their metallic halides. During the reactions of Cl, with
dilute or concentrated alkalies,
2KBr + Cl, ——» 2KCl + Br, chlorine (O.S.=0),issimultaneously
2KI + Cl, —— > 2KCl +1, reduced to Cl ion (O.S. =—1) and is
Since chlorine is less electronegative than fluorine, it has no effect on oxidised to either hypochlorite ion
fluorides. (OCT; O.S. = + 1) or to chlorate ion
(ClO; ;O.S. = + 5). Such reactions
5. Action with alkalies : (1) The reaction of chlorine with strong alkalies which involve simultaneous
such as sodium hydroxide or potassium hydroxide depends upon the temperature oxidation and reduction are called
of the reaction mixture. disproportionation reactions.
In cold, chlorine reacts with dilute alkalies to form chlorides and Like chlorine, bromine and iodine
hypochlorites as : also undergo disproportionation
reactions with cold and hot alkalies.
2NaOH (dil.) + Cl,———
Cold
NaCl | + Naclo. + H,
H,O
Br, + 2NaOH (dil.) —““>
Sodium
hypochlorite NaBr + NaOBr + Bl. O

Similarly, the reaction of chlorine with cold solution of KOH is 3Br, +6NaQOH (conc.) —“*_, 5NaBr

2KOH (dil.) + Cl, —“*> KCl + KCIO + H,O + NaBrO, + 3H,O

Potassium Fluorine reacts with water at very
hypochlorite low temperature to form HOF.
However, chlorine reacts with hot and concentrated alkalies hke NaOH F, + H,O(ice) —==—= HF + HOF
or KOH to form chlorides and chlorates as : However, HOF is very unstable
and therefore, it is said that F,
6NaQOH (conc.) + 3Cl, _
#5 §Nall 4 NaClo, - 3H,O does not undergo disproportionation
Sodium chlorate reaction.
Moreover, fluorine does not show
Similarly, the reaction of chlorine with Aot KOH solution is
higher positive oxidation states such
6KOH (conc.) + 3Cl, it, 5KCI + KC1O, + 3H,O as +3, + 5 or + 7, therefore F,, does
Potassium chlorate not react with NaOH to form NaFO,,.
(it) Reaction of chlorine with calcium hydroxide depends upon the nature 3F, + 6NaOH >
of calcium hydroxide. When chlorine gas is passed through hot milk of lime,
5NaF + NaFO, + H,O
calcium chloride and calcium chlorate are produced as :
 MODERN'S abc + OF CHEMISTRY-XIl

6Ca(OH), + 6C]
; Heat
5CaCl, + Ca(ClO,), + 6H,O
Milk of lime Calcium chlorate
However, if chlorine is passed through dry slaked lime, bleaching powder
is produced.
2Ca(OH), + 2Cl, ——+ Ca(OCl, + CaCl, + 2H,O
Slaked lime Calcium hypochlorite
(Bleaching powder)
The actual composition of bleaching powder is
Ca(OC]),.CaCl,.Ca(OH),.2H,O
6. Action with ammonia: The reaction of chlorine with ammonia depends
upon the proportion of the reactants as :
(z) If ammonia is In excess, nitrogen is formed
8NH, + 3Cl, ———> 6NH,Cl +N,
(excess)
(it) If chlorine is in excess, nitrogen trichloride (explosive) is formed.
REMEMBER
NH, + 3€ly53=>——,,_ NC, + 8HCl
Bleaching action of Cl, is due to
(excess) (explosive)
oxidation of coloured substances to
colourless substances by nascent 7. AS an oxidising agent : Since chlorine reacts with water and produces
oxygen. Since the bleaching action hydrochloric acid alongwith nascant oxygen, it acts as an oxidising agent.
of Cl, is due to oxidation while Cl, + H,O. ——> HCl + HCIO
that of SO, is due to reduction,
therefore, bleaching action of
HClO ——>+HCl+0
Cl, is permanent and that of Cl, + H,O ——> 2HCl1+0
SO, is temporary.
Therefore, in the presence of moisture or in aqueous solution, Cl, acts as
In SO,, on exposure of the bleached
a powerful oxidising agent. Some of its important oxidising reactions are :
article to air, the reverse process
takes place i.e., colour is restored (¢) It oxidises sulphur dioxide to sulphuric acid.
due to oxidation by atmospheric Cl, + SO, + 2H,O0 ——— 2HCl + H,SO,
oxygen. This cannot occur in case
of Cl, (tz) It oxidises sulphites to sulphates.
Cl, + H,O + Na,SO, ———> 2HCl + Na,SO,
(iii) It oxidises thiosulphates to sulphates.
Cl, + H,O + Na,S,0, ———> 2HCl + Na,SO,+S
(iv) It oxidises hydrogen sulphide to sulphur.
Cl, + H,S ——~> 2HC1+S
(v) It oxidises nitrites to nitrates.
Cl, + H,O + NaNO, ———> 2HCl + NaNO,
(vi) It oxidises acidified ferrous salts to ferric salts.
2FeSO, + Cl, + H,SO, ——->Fe,(SO,), + 2HCl
(vit) It oxidises sodium arsenite (Na,AsO.,) to sodium arsenate (Na,AsO,,).
Na,AsO, + Cl, + H,Q ———> Na,AsO, + 2HCl
(viii) It oxidises iodine to iodic acid.
I, + 6H,O + 5Cl, ——> 2HIO, + 10 HCl
Iodie acid
p-BLOCK ELEMENTS

8. Addition reactions : Chlorine reacts with many substances like

carbon monoxide, nitric oxide and sulphur dioxide in presence of sunlight to
form addition products :
CO + CL, Sunbeht, COCL,
Carbonyl chloride (phosgene)
2NO + Cl, 2", eNOCI
Nitrosyl chloride
SO, + Cl, Ss", So,Cl,
Sulphuryl] chloride
9. Reaction with other halogens : Chlorine can reacts with other
halogens like F,, Br, or L, to form interhalogen compounds. For example,
Cl, + F, Ht, 2ciF
CL tah, 2 SC.
Br, + Cl, 8", 2BrCl .
Bromine monochloride
Lec, == 5 acl
Iodine monochloride
10. Action with organic compounds: Reaction of chlorine with organic
compounds depends upon the nature of the organic compound.
(4) With saturated compounds like methane, chlorine produces substituted
products.

CH, + Cl, =“ CH,Cl + HCl

Chloromethane
(it) With unsaturated compounds like ethene, ethyne, chlorine forms
addition products :
C,H, + Cl, ——> C,H,Cl,
Ethene 1,2-Dichloroethane
C,H, + 2Cl, ae C,H,CI,
Ethyne 1,1,2,2-Tetrachloroethane

(zit) Organic compounds like turpentine oil (C,,H,,) when introduced in

the atmosphere of chlorine gas catches fire.
C,H, + 8Cl, ———+ 16HCI + 10C
Turpentine oil
This reaction reveals that chlorine has a great affinity for hydrogen.
11. Bleaching agent : Chlorine bleaches natural colouring matter of green
leaves, flowers, indigo, litmus in the presence of water. Its bleaching action is
due its ability to oxidise the colouring matter to colourless matter as :
Cl,+H,Q ——> 2HCl1+0O Chlorine is a powerful bleaching agent.
Colouring matter +O ——-~> Colourless matter Its bleaching action is due to oxidation
and is permanent.
Colourless matter + Cl, - H,O—> Colourless matter + 2HCl

Some noteworthy points regarding its bleaching action are :

(4) Chlorine bleaches only in the presence of water. Thus, dry chlorine
does not act as a bleaching agent because in absence of water, it cannot
produce nascent oxygen needed for oxidation. Tests of Chlorine
(1) Since chlorine bleaches by oxidation, the bleaching action of chlorine (a) It is a greenish yellow gas with
is permanent. pungent smell.
(iit) Since during bleaching by chlorine, hydrochloric acid is produced, (6) It turns starch iodide paper blue.
delicate articles are likely to be destroyed by hydrochloric acid. Therefore, (c) It bleaches moist flowers, indigo
and litmus paper.
chlorine is used only for bleaching paper pulp, wood pulp and cloth.
 MODERN'’S abc + OF CHEMISTRY-AKIl

Summary of chemical properties of chlorine :

NaClO, NCI,
| Hot or N,

Coloured
Bleaches
substances

cei
ory2
o\e" Oy ~
On AS
© Ay fe
San
Lt
oy

Uses of Chlorine
(i) Large quantities of chlorine are used industrially for bleaching wood
pulp (required for manufacture of paper and rayon), bleaching of
cotton, paper, wood, textiles, etc.
(it) It is used for the manufacture of dyes, drugs, refrigerants, etc.
(111) In the manufacture of chlorinated organic solvents such as chloroform
(CHCl,), carbon tetrachloride (CC1,), etc. which are used for dry-
cleaning and degreasing machinery.
(tv) Inthe manufacture of chlorates which are used in flash light powders,
matches and explosives.
Mustard gas was used by (v) In the manufacture of bleaching powder, aluminium chloride and
Germany in World War I. sodium hypochlorite which are important industrial compounds.
(vi) In the manufacture of vinyl chloride which is a starting material
CH,
Cl Cl for polyvinyl chloride plastics.
2) +! | —> (vit) In sterilisation of drinking water.
CH, Ss—S
Ethene Sulphur (viit) In the manufacture of D.D.T. which is an important insecticide.
monochloride (1x) In the manufacture of poisonous gases like phosgene (COCI,), tear
CHCl CHCl gas (CCl,.NO,) and mustard gas (CICH,CH,SCH,CH,Cl)
| S (x) In the extraction of metals like platinum and gold.
cH,_s—cHf % HYDROGEN CHLORIDE
Mustard gas
Hydrogen chloride is a major industrial chemical and is very familiar
laboratory reagent. Glauber prepared this compound in 1648 by heating
common salt with concentrated sulphuric acid. In 1810, Davy showed that it
is a compound of hydrogen and chlorine.
Preparation
In the laboratory, hydrogen chloride is prepared by heating sodium chloride
with concentrated sulphuric acid.
NaCl + H,So, #2°*, NaHSO, + HCl
NaCl + NaHSO, ©°*5 Na,SO, + HCl
HC] gas is dried by passing through concentrated sulphuric acid.
p-BLOCK ELEMENTS

On an industrial scale, hydrochloric acid is manufactured by heating a

mixture of concentrated sulphuric acid and sodium chloride in a Muffie furnace.
Properties of Hydrogen chloride
Physical properties
(i) It is a colourless gas.
(it) It has pungent suffocating smell. Drying of hydrogen chloride
(iit) It is highly soluble in water and its aqueous solution is known as gas : Since the gas is acidic in nature,
hydrochloric acid. it can be dried only over acidic
dehydrating agent like concentrated
(iv) The gas fumes in moist air.
sulphuric aeid.
(v) It is heavier than air (vapour density is 18.25). It is easily liquefied
However, the gas cannot be
to a colourless liquid (b.p. 189 K) and freezes to a white crystalline solid
dried either over quick lime (CaQ) or
(fp. 159 K). phosphorus pentaoxide because it reacts
(vi) Its b.p. is 189 K and mp. is 159 K. with these dehydrating agents as :
Chemical properties CaO + 2HCl —- + CaCl, + H,O
1. Action with litmus : Dry HC] gas has no action on litmus. However, Quick lime
its aqueous solution turns blue litmus red indicating its acidic character. 2P,0, + 3HC1—> 3HPO, + POCI,
2. Acidic properties : Its aqueous solution behaves as a strong acid
because it is almost fully ionised in water.
H,O + HCl —— H,0* + Cr K, = 1x10’
Its aqueous solution is called hydrochloric acid. The high value of
dissociation constant (K,) indicates that it is a strong acid in water. It reacts
with ammonia to form white dense fumes of ammonium chloride, NH,Cl.
NH, + HCl ——+> NH,Cl
It shows all the typical properties of the acids.
3. Reaction with metals : Active metals like Na, Zn, Mg, Fe, Al, etc.
react with the liberation of hydrogen gas.
2Na + 2HCl —— 2NaCl =
H
Jn + 2HCl———> ZnCl, 4+ H,
Mg + 2HCl ——> MgCl, + H,
Fe + 2HCl > FeCl, + H,
2Al + 6HC]l ——> 2AICl, + 3H,
4. Oxidation : It is oxidised by atmospheric oxygen in the presence of
cupric chloride, CuCl, as catalyst at 723 K to produce chlorine gas.
CuCl,, 723K
4HCl + O, 2H,O + 2Cl,
5. As a reducing agent : It acts as reducing agent because it can be
oxidised to chlorine by strong oxidising agents like manganese dioxide (MnQO,),
potassium permanganate (KMnO,) and potassium dichromate (K,Cr,O,) as :
MnO, + 4HCl—> MnCl, + 2H,O + Cl,
2KMnO, +16HC]l ——-> 2KCl + 2MnCl, + 8H,O+5Cl,
K,Cr,O, +14HCl ——-> 2KCl + 2CrCl, + 7H,O+3Cl,
6. Action with fluorine: Fluorine can displace chlorine from hydrogen
chloride.
2HCl + F, —— 2HF + Cl,
However, bromine and iodine have no action on hydrogen chloride.
7. Action with salts of weak acids : Hydrochloric acid decomposes salts
of weak acids like carbonates, bicarbonates, sulphides, sulphites, thiosulphates
or nitrites. During these reactions, characteristic gases are evolved which are
used to identify the acid radicals as :
K,CO, + 2HCl ——> 2KCl] + H,O + o,T
NaHCO, + HCl ——+ NaCl + H,O + o,T
Na,S + 2HCl ——> 2NaCl + H,ST
Na,SO, + 2HCl ——> 2NaCl + H,O + SO,T
 MODERN'’S abc + OF GHEMISTRY-AKIl

Na,S,O, + 2HCl > 2NaCl + S + H,O + SO,T

2NaNO, + 2HCl ——-> 2NaCl + H,O + NO,T +NOT
8. Action with some metal salts
(4) With lead acetate solution : Hydrochloric acid reacts with lead acetate
solution to form a white precipitate of lead chloride which is soluble in hot
water.
Pb(CH,COO), + 2HCl ——> PbCl, + 2CH,COOH
Lead acetate (white ppt.)
(it) With silver nitrate solution. Hydrochloric acid reacts with
Summary of the chemical properties of
silver nitrate solution to form a white precipitate of silver chloride
hydrogen chloride
which is soluble in ammonium hydroxide due to the formation of
a complex, [Ag(NH,),]Cl.
HCl] + AgNO.——> _ AgCl + HNO,
(white ppt.)
AgCl + 2NH,OH =e SAgINH,),] Cl + 2H,O
Diamminesilver (I) chloride
(iit) With mercurous nitrate solution. Hydrochloric acid reacts
with mercurous nitrate solution to form a white precipitate of
mercurous chloride, Hg,Cl, which is neither soluble in hot water
nor in ammonia.
Hg,(NO,), + 2HCl——-> Hg,Cl, + 2HNO,
(White ppt)
9. Formation of aqua regia. A mixture of three parts of
concentrated hydrochloric acid and one part of concentrated nitric
acid is known as aqua regia. In aqua regia, hydrochloric acid
(which is a reducing agent) is oxidised, by nitric acid (which is an
oxidising agent) to form nascent chlorine.
3HCl + HNO, ———> NOC] + 2H,O + 2Cl
Nitrosyl Nascent
Tests of Hydrogen chloride
chloride chlorine
() Itisacolourless gas having pungent Aqua regia can dissolve even noble metals like gold and platinum which
smell. are not otherwise dissolved by any single acid as :
(it) It gives white dense fumes with Au + 3C] ——-> AuCl,
ammonia Auric chloride
(iii) It turns blue litmus red. (soluble)
(tv) It gives white precipitate with silver Au + 4Ht + NO, + 4Cl ———> AuCl, + NO + 2H,0O
nitrate solution. The precipitate is
soluble in ammonium hydroxide but 3Pt + 16 H*+ 4NO,- + 18Cl———. 3[PtCl,]*", + 4NO + 8 H,O
is insoluble in dilute nitric acid. Uses of Hydrogen Chloride
(4) In dyeing calicoprinting and tanning industries.
(it) In pickling (cleaning metallic surfaces) before tinning, galvanising
Sodium chlorate, NaClO, is and electroplating.
produced on a large scale by the (iit) In the manufacture of chlorides and chlorine.
electrolysis of brine in a cell in which
(iv) In the manufacture of glucose by the hydrolysis of starch.
efficient mixing of chlorine produced at
the anode with OH- produced at the (v) In the preparation of aqua regia which is used to dissolve noble
cathode takes place. Sodium chlorate is metals like gold.
used as a precursor for the production (vi) As an important reagent in the laboratory.
of ClO, used for bleaching paper pulp.
(vit) It is used in medicines.
The dazzling fireworks and flares
used during Diwali and other festival OXOACIDS OF HALOGENS
times contain potassium chlorate, KC1O, Among the halogens, fluorine has very little tendency to form oxoacids
as the oxidiser. The different colours due to its high electronegativity and small size. However, it forms one oxoacid
are obtained by adding small quantities
HOF known as fluoric (I) acid or hypofluorous acid. The rest of the halogens
of strontium (red), barium (green) or
copper (blue) salts. form four series of oxoacids, HOX, HXO,, HXO, and HXO,,. These are given
KCl1O, is also used in the head of in Table 20. Most of these cannot be isolated in pure state. They are stable
safety matches. only in aqueous solution or in the form of their salts.
p-BLOCK ELEMENTS remit —

Table 20. Oxoacids of halogens.

(OxidationState[|
+1 Halic (I) acid
_‘Flworine | Chlorine [Bromine [Todo
HFO HClO HBr O HIO
|
Hypohalous acid |Hypofluorous acid Hypochlorous acid | Hypobromous acid | Hypoiodous acid
+rs| Halie (IIT) acid HClO,
Halous acid Chlorous acid
+5 Halic (V) acid Hclo, HBrO, HIO,
Halie acid Chloriec acid Bromic acid Iodic acid
+7
of Halie (VII) acid Hclo, HBrO, HIO,
Perhalic acid Perchloric acid Perbromic acid Periodic acid

The structures of oxoacids of chlorine are given below :

J
O

T
O O cl
~~ ae a Ne of _:
Hypochlorous acid Chlorous acid O, O
(HOCI) (HOCIO) Y Ww
Chloric acid Perchloric acid
(HOCIO,) (HOCIO,)
Fig. 38. Structure of oxoacids of chlorine.

Acidic character of Oxoacids of Halogens

The following two important generalisations can be made regarding the
acidic character of oxoacids of halogens :
(1) The acidic strength of oxoacids having the same oxidation number of the
halogen atom decreases with increase in atomic number t.e., with decreasing
electronegativity of the atom. For example, HCIO is the strongest while HIO
is the weakest of all the acids in which oxidation state of halogen atom is +1.
This 1s evident from their dissociation constant (K_) values.

Explanation. This can be explained on the basis of the electronegativity

of the halogen atom. The electronegativity of the halogen atom attached to
oxygen decreases in the order C] > Br > I. Therefore, the tendency to withdraw
electrons from oxygen atom towards itself decreases from Cl to Br to I. As
a result, the tendency to pull the electrons from the hydrogen decreases.
Consequently, the release of Ht ion from HClO will be easier than HBrO.
Similarly, the release of H* ion from HBrO will be easier than from HIO.
Thus, the acidic strength decreases in the order :
HC1O > HBrO > HIO
H—0>>—Cl H——O—>—I eee
Greater tendency Lesser tendency Acidic character :
to withdraw electrons from O to withdraw electrons from O e HClO > HBrO > HIO
(it) With the increase in oxidation number of a particular halogen atom, e HClO, > HCIO, > HC1O, > HC1O
TA 02 MODERN'’S abc + OF CHEMISTRY-AiIl

Structures of conjugate the acidic character of corresponding oxoacid increases. For example, the acidic
lasses of oxoamdaourCl strength of oxoacids of chlorine increases in the order :
- HClO < HCIO, < HCIO, < HCIO,
O
Explanation. This can be explained on the basis of Lowry Bronsted
concept. According to this concept, a strong acid has a weak conjugate base
and a weak acid has a strong conjugate base.
The conjugate bases of the oxoacids of chlorine are shown below :

o—Ccli:os

Let us consider the stabilities of the conjugate bases, ClO”, ClO,”, ClO,” and
ClO, formed from these acids, HClO, HClO,, HClO, and HClO, respectively.
These anions are stabilized by the delocalisation of the charge between oxygen
atoms. If the ion is stabilized to greater extent, it has lesser attraction for
the proton and therefore, will behave as weaker base (lesser tendency for the
reaction to go in backward direction). Consequently, the corresponding acid will
be strong because weak conjugate base has strong acid and strong conjugate
base has weak acid and vice versa. Now, the charge stabilization is minimum
Db «= 10; in ClO” and maximum in ClO,-. The charge stabilization increases in the order:
In all these ions, Cl is sp? ClO7 < ClO, < ClO, < ClO,
hybridized. This means that ClO~ will have minimum stability and therefore, will
have maximum attraction for the H*. In other words, ClO~ will be strongest
base and so its conjugate acid HCI1O will be the weakest acid.
Similarly, in this series, CIO, is the weakest base (maximum stabilized)
and its conjugate acid HCI1O, is the strongest acid. Thus, the acidic strength
increases in the order.
HClO < HClO, < HClO, < HClO,

Oxidising power of perhalates

Perhalates are powerful oxidising agents. Their oxidising power decreases in the order :
BrO, > IO, > ClO;
This order can be explained on the basis of their electrode potentials for the following reactions :
BrO; = + 2H* + 2e- — BrO,; + 4H,0; E°=+1.74V
104 + 2H* - 2e- ae lo, + HA, E°=+1.64V
ClO; + 2H* - 2e- —— ClO, + H,O; E°=+1.23 V
Thus, BrO, is the strongest oxidising agent among perhalates because of its very high electrode potential.
Therefore, only strongest oxidising agents such as F, |H,O (E° = 2.87V) or XeF, |H,O (E° = 2.64 V) are effective
for its preparation from bromates. It is because of this reason that perbromates and perbromic acid can be
obtained by oxidation of bromates (BrO,-) by fluorine in alkaline solution :
BrO3; + F: + 20H- — > BrOg; + 2F +H,0
INTERHALOGEN COMPOUNDS
The compounds containing two or more halogen atoms are called
interhalogen compounds. They may be represented by the general formula
XX’, where X is a halogen of larger size and X’ of smaller size and X’ is more
electronegative than X (or X is more electropositive than X’). As the ratio between
radii of X and X’ increases, the number of atoms per molecule also increases.
Thus, iodine (VII) fluoride should have maximum number of atoms because the
ratio of radii between I and F is maximum. Each halogen combines with every
p-BLOCK ELEMENTS

other halogen to form interhalogen compounds. For example, CIF, IC1,, BrF.,etc.
These are of two types :
(1) Neutral interhalogens. These are neutral molecules containing
two or more halogen atoms. For example, ICI, BrF., IF ., IF., etc.
(11) Interhalogen anions and cations. These are negatively charged
interhalogen polyhalide anions XX’, (n = 1, 2, 3, 4) and polyhalonium cations
(XX’,*). The most important of these compounds iis the linear triatomic iodide
10n, sie, which is formed when iodine dissolves in an aqueous solution of
notasciaii iodide.
I,(s) + (ag) ——+ I,(aq)
From KI
Some other polyhalide anions are ICI,” ICl, and polyhalonium cations are
CIF,*, CLE*, BrF,*, I,*, ICL,*, ICL,*, ete.
Nomenclature
The interhalogen compounds are named as halogen halides. The halogen
with the positive oxidation state (i.e., A) is named as such and the halogen
with negative oxidation state (i.e., X) is named as halide. For example,
CIF BrF, IF,
Chlorine fluoride Bromine trifluoride lodine heptafluoride
The different types of interhalogens of the type XX’ (diatomic), XX’,
(tri atomic), XX’, (hexa atomic) and XX’, (hepta atomic) are given in Table 21.
The different interhalogen ions are given below :
Table 21. Type of Interhalogen compounds and their physical state and colour.

ee: See
CIF : Chlorine fluoride
ae eee AL fee
CIF, : Chlorine trifluoride | ClF.: Chlorine pentafiuoride
ee
(colourles gas) (colourles gas) (colourles gas)
BrF : Bromine fluoride BrF, : Bromine trifluoride | BrF : Bromine pentafluoride
(pale brown gas) (yellow green liquid) (colourless liquid)
IF* : Iodine fluoride IF,* : Iodine trifluoride IF, : Iodine heptafluoride
(very unstable detected (yellow powder) (colourless gas)
spectroscopically)
BrCl :Bromine chloride
(gas)
IC] : Iodine chloride IC1, :Iodine trichloride : Iodine pentafluoride
(rubby red solid, o form pane solid) ee gas but solid
brown red solid, B form) at 77 K)
IBr : Iodine bromide
(black solid)
* are unstable
Interhalogen ions

ICI,-, IBr,-, BrCl,-, CIF,-, ICI,*, BrF,*, CIF,*

ICL, BrF,,IF,,*, CIF,*, BrF,*
IF, BrF, IF,*, BrF,*, CIF,*
Preparation
All interhalogen compounds are prepared by direct combination or by the
reactions of halogen with other interhalogen compounds. For example,
cl + F, —%., ecr
equal volumes
cloo+ 3F, —8*= ear,
(excess)
CIF + F, ———>» CIF,
CIF, F, —“~— ar,
 MODERN'’S abc + OF CHEMISTRY-AXIl

I, » e, —— > 216i
(equimolar)
L * 8c, ——3 2ICi,
(excess)
Br, + F,2 ——> 2BrF
Br, + 38F, ———> 2BrF,
(diluted with water)
Br, ~ oF, <—— > @BErk.
(excess)
I, + 5F, 25K, /2iK
clooo+ oF, —*> ear.
I, + Ww, ~~ Rar
Lower interhalogens combine to form higher interhalogens.

ce + F, —=*s
475-573 K
cr,
CIF, + F, JAA” wf/crr,
IF. - re {eee «CS,
Some interhalogen compounds are prepared from some halides,
KBr + 3F, FP, KF + BrF,
KI + 4F, —“PS , kF + IF,
General Properties of Interhalogen Compounds
Some of the important general properties of interhalogen compounds are:
(1) Polar nature. All the interhalogen compounds are essentially
covalent and are diamagnetic. They have some polarity. The polarity is due to
the difference in electronegativity between the two halogen atoms. The more
electronegative halogen atom acquires a negative charge.
(it) Physical state. Interhalogen compounds exist as gases, liquids and
solids. They are volatile solids or liquids except CIF which is a gas at 298 K.
Their physical properties are intermediate between those of constituent halogens
except that their melting and boiling points are a little higher than expected.
(iit) Reactivity. The interhalogen compounds have almost similar
reactions to those of component halogens. However, these are generally more
reactive than the component halogens (except F,). This is because covalent
bond between dissimilar atoms (X—xX’) in interhalogen compounds is weaker
than that between similar atoms (X—X or X’—X’) in halogens except F—F bond.
This is due to the fact that the overlapping of orbitals of two dissimilar atoms
is less effective than the overlapping of orbitals of similar atoms. For example,
the bond dissociation enthalpy of X—X’ bond is less than the bond dissociation
enthalpy of X, and X’,. Thus, they readily convert metals into mixed halides.
2M + XX’ ——> MX + MX’
e.g, 2Na + IC] ——> Nal + NaCl
(iv) Fluorinating agents. Most of the interhalogens containing fluorine
act as powerful fluorinating agents. They convert several metal oxides and
metal halides to fluorides.
W + 6CIF ——~ WF, + 3Cl,
Se + 4CIF ———> SeF, + 2Cl,
6MgO + 4CIF, ———> 6MgF, + 2Cl, + 30,
3U0, + 4BrF, ———> 3UF, + 2Br, + 30,
2AgCl + CIF, ——> 2AgF+ Cl, +CIF
CIF, or BrF, are used for the production of UF, in the enrichment of
uranium (2°°U).
U + 3ciF, =="; ur, + 3ClF
p-BLOCK ELEMENTS

(v) Hydrolysis. All the interhalogen compounds undergo hydrolysis giving

halide ion (derived from the smaller halogen atom) and a hypohalite (for XX’), Reactivity of interhalogen
halite (for XX’,), halate (for XX’) and perhalate (for XX’,) anion derived from compounds.
the larger halogen. Interhalogen compounds are more
XX’ + H,O ———> HX’ + HOX reactive than the halogens (except
e.8., IC1+H,O ———+ HCl + HOI F’,) because covalent bond between
dissimilar electronegative atoms
Hypoiodous acid
(X —X') in interhalogen compounds
BrF. + H,O ———> 5HF + HBrO, is weaker than the bond between
Bromic acid two similar atoms (X — X or
(vi) Ionisation. Interhalogen compounds are partially ionised in the X'-X')in halogens. This is because
solution or in the liquid state. For example, fused IC] and IC], have specific the overlapping of orbitals of two
conductance of the order of 10-? ohm! cm. This suggests appreciable self- dissimilar atoms is less effective
ionisation of these compounds. than the overlapping of orbitals
of similar atoms.
2Ic1 —— + ICly
21ICl, —— ICl,* + ICL
They also give conducting solutions in various solvents.
(vit) Reaction with alkali metal halides. Interhalogens react with alkali
metal halides to form polyhalides. For example,
ICl + KCl ——> K*[ICL]-
ICl, + KCl ——> K*[ICl,-
IF, + CsF ——> Cs* [IF,]-
IF, + CsF ——> Cs? [IF,]-
(viit) Oxidising agents. The interhalogen compounds act as strong
oxidising agents.
(ix) Thermal stability. The thermal stability of the interhalogen compounds
depends upon the electronegativity difference between the two component
halogen atoms. In general, the thermal stability of AX type interhalogens
decreases as the electronegativity difference between them decreases. For
example, thermal stability decreases as :
IF > BrF > CIF > IC] > IBr > BrCl
Electronegativity difference 1.5 1.2 1.0 0.5 0.3 0.2
Structures of some common interhalogen compounds
(a) Neutral interhalogens. The structures of some common interhalogen
compounds such as XX’,, XX’, and XX’, are given below. These are easily
understood on the basis of VSEPR theory. For example,
(i) XX’, involves sp*d hybridisation of the central halogen atom and the
molecule has trigonal bipyramidal geometry with two positions occupied
by lone pairs. Its structure is termed as T-shaped. For example, CIF, has
T-shaped structure as shown below:

c To 4
3s 3p 3d FO

(Ground state) a af
=... Cl :

a
(Excited state)
TTT “WR
sp*d hybridisation F
[Three bonds with F and two positions occupied by lone pairs] as a
Fig. 39. Structure of CIF,.
(ii) XX’, involves sp*d* hybridisation of the central halogen atom and
the molecule has octahedral geometry with one position occupied by a lone
pair of electrons. Its structure is termed as square pyramidal.
 MODERN'S abc + OF CHEMISTRY-XIl

For example, IF. has — a structure as described below:

(Gro and Stat Mam oooo Rt

Lk;
TInt ANIME Et <—B F
(Excited)
sp*d* hybridisation
[Five bonds with F and one position occupied by a lone pair] Square
Fig. 40. Structure of IF. pyramidal
(iii) XX, involves sp*d*? hybridisation of iodine atom and the molecule
has pentagonal bipyramidal structure. For example, IF, has ————
bipyramidal — as — below:
F |
(roundstate)
WE Ce AlSS

erne} state)
IN]CNTNTN] NTA]TO j
aa
sp*d* hybridisation
[Seven bonds with F] Pesecoaet
Fig. 41. Structure of IF,. bipyramidal
(6) Interhalogen ions
Triatomic (XX’,)” ions
(i) XX’, ions involved sp*d hybridisation having trigonal bipyramidal
geometry with three positions occupied by lone pairs. The structure is linear.
For example ICl,~ is linear as desivbed below:
It may be noted that ICl,~ (Cl-I«<—Cl) has one covalent and one coordinate
bond. For a covalent bond a half filled orbital is needed and for a coordinate
bond, an empty orbital is needed. Therefore, in IC1,- ion, one half filled orbital
and one empty CZ —_ lone pairs ve hybridised as shown below:
Hypervalent Compounds
The molecular species like SF,,
PF, XeF,, I, in which the central Ground
fl ALL ooo al
eis hae
electrons are
more than octet of
called hypervalent TT NTN] (NT TT e
compounds. These have expanded
(ee state) os
octet.
sp® hybridisation 13
[One covalent bond is formed with Cl and one coordinate
Cl
bond using its hybrid empty orbital
ICl,-
Fig. 42. Sturucture of IC]. Linear
(ii) XX’, involve sp*d? hybridisation having octahedral
geometry with two positions occupied by lone pairs. The two lone pairs are
present on positions above and below the square plane and the structure is
regarded as square planar. For example, ICI, has square planar geometry
as described below:
In IC], the central atom iodine forms three covalent bonds and one
coordinate bond. Therefore, in the excited state of I, three half filled orbitals
and one empty x _ lone pairs hybridised as shown below:

if ae Foro m. 2 ']
)--0
aeasa state)
J NIN; Tp “~
(Excited state)
sp® d* hybridisation
[Three covalent bonds are formed with Cl]IN|
ft vi Ici,
one coordinate bond using empty hybrid orbital | Sadl acl
Fig. 43. Sturucture of IC1,~
p-BLOCK ELEMENTS

Polyhalide Ions
In addition to neutral interhalogens, interhalogen cations or anions,
some polyhalide ions, X, are also known. The common examples are Cl,
leteege eed ee verre
The most common example of polyhalide anion is I,-. It is formed during
the dissolution of iodine in KI solution.
Les) Eee —<—$=$== Ei rotey
(from KI solution)
We know that I, is virtually insoluble in water. However, it readily
dissolves in KI solution due to the formation of I, (KI,).
Tribromide (Br,)is much less stable than I~. A few compounds containing
Cl, ion are known but fluorine cannot form F,- ion.
Structure of Polyhalides
Structure of I, ion. In I, (I—I< I ), there is one covalent bond and
one coordinate bond between iodine atoms. For covalent bond, one half filled
orbital is needed while for a coordinate bond, an empty orbital is needed.
The structure is similar to I, ion is as described below:
5s 5p 5d

I
(Ground state)
MATH CTT TT
I
(Hybridisation
state) sp*d hybridisation
I~ 10n
[One covalent bond and one coordinate bond between Linear

Fig. 44. Structure of I~

Structure of I ion. In this polyhalide ion, there are three covalent

bonds (I—I) and one coordinate bond (I <— I). Therefore, in the excited state
of iodine, three half filled orbitals and one empty orbital including lone pairs
get hybridised as shown below:

. Oo HEED | Os |
— RL / 4S
— stat

(Hybridisation
mo eel (os i
state) sp*d? hybridisation te
[Three covalent bond (I—I) and one coordinate
ae d<wrH Ee aieaae

Fig. 45. Structure of I~

Evidence of Cationic Iodine

All halogens are non-metallic due to high electronegativities and ionisation
energies. However, the last element iodine exhibits some properties showing
the presence of positive ions. The positive iodine is found in unipositive (I*)
and tripositive (I?*) states.
(t) Iodine monochloride (IC1]) conducts electricity in the molten state. On
electrolysis, iodine is liberated at the cathode while both iodine and chlorine
are liberated at the anode. The liberation of iodine at the cathode indicates
the presence of cationic iodine. The ionisation of IC] may be represented as :
acl — |i + ICl-
(at cathode)
 MODERN'S abc + OF CHEMISTRY-XIl

(zz) ICl, conducts electricity and on electrolysis, iodine and chlorine are
liberated at both the electrodes. Therefore, the ionization may be represented as
2ICl, tt
x. ICL* + ICL
The ions IC1,* and IC1, contain I** ions.
(iit) A large number of compounds containing iodine as I** have been
isolated which are ionic. For example, iodine triacetate, I(CH,COO),, iodine
phosphate, IPO,, iodine triperchlorate I(C1O,),. On electrolysis, these compounds
in aqueous solution liberate iodine at the cathode as:
IPO, —— I*+P0;>
Uses of interhalogen compounds
(i) The interhalogen compounds can be used as non-aqueous solvents.
(ii) Interhalogen compounds of fluorine are very useful fluorinating
agents. For example, CIF, and BrF, are used for the production of UF, in
the enrichment of 7°°U.
U (s) + 38ClF, (2) ——~+ UF, ) + 3ClF (g)

Pseudo halogens
There are certain uninegative ions made up of two electronegative atoms
which have properties similar to the halide ions. These are called pseudo
halides. Like the halides, the pseudo halides have the corresponding pseudo
halogens which behave lke halogens in their chemistry. Some examples are:
Pseudo halides Pseudo halogens
Cyanide CN- Cyanogen (CN),
Thiocyanate SCN- Thiocyanogen (SCN),
Cyanate OCN- Oxycyanogen (OCN),

| SOLVED EXAMPLES
_}] Example 43 Solution : Oxidation state of the halogen.
Hlectron gain enthalpies of halogens are largely negative. (i) C1,0 +2
Why? (A.L.S.B. 2017) (ii) ClO, +4
Solution : The halogens have the smallest size in their (iii) KBrO, +5
respective periods and therefore, high effective nuclear charge. (iv) NaClO, ae
Moreover, they have only one electron less than the stable noble _] Example 46
gas configuration (ns?np*).
Why does fluorine not play the role of central atom in
Therefore, they have strong tendency to accept one electron to
interhalogen compounds? (A.LS.B. 2011)
acquire noble gas electronic configurations and hence have largely
Solution : Fluorine does not play the role of a central atom
negative electron gain enthalpies. in interhalogen compounds because it is highly electronegative.
_] Example 44 Moreover, it has only one electron less than the octet and does
Fluorine exhibits only —1 oxidation state where as other halo- not have vacant d-orbitals in its valence shell. Therefore, it can
gens exhibit positive oxidation states also such as +1,+3,+5 form only one bond with other halogen atoms and cannot act as
and+7. Why? \N.C.E.R.T, (Hr. S.B. 2015, H.P. S.B. 2016, central atom in interhalogen compounds.
Meghalaya 8.6. 2016, Mizoram S.B. 2018, _}] Example 47
Assam S.B. 2018) Bond enthalpy of fluorine ts lower than that of chlorine.
Solution : Fluorine is most electronegative element and Why? (A.L.S.B. 2018, Hr. S.B. 2018)
cannot exhibit any positive oxidation states. On the other
Solution: Fluorine atoms are small and internuclear distance
hand, the other halogens are less electronegative and therefore,
between two F atoms in F, moleculeis alsosmall (1.43A). Asaresult,
can exhibit positive oxidation states. They also have vacant
electron-electron repulsions among the lone pairs on two fluorine
d-orbitals and hence can expand their octets and show +1, +3, +5
atoms in F, molecule are large. These large electron-electron
and +7 oxidation states also.
repulsions weaken the F—-F bond. However, the electron-electron
_} Example 45
repulsions among lone pairs in Cl, molecule are less because of
Calculate the oxidation state of the halogen in the following:
larger Cl atoms and larger Cl-Cl distance (1.99A). Therefore, the
(i) CLO (ti) CLO, (it) KBrO,
bond enthalpy of fluorine is lower than that of chlorine.
(tv) NaClo,
p-BLOCK ELEMENTS

_j] Example 48. (it) NH, +38Cl, (excess) —+ NCI, + 3HCl1

Write balanced equations for the following : (iii) 2NaNO, + 2HCL—-> 2NaCl+H,0+NO,+NO
(a) NaCl is heated with sulphuric acid in the presence of (iv) 2F,(g) + 2H,O(1)—> 4H*(aq) + 4F
(aq) + O,(g)
MnO, (v) K,CO, + 2HCl —-+ 2KCl+CO, +H,O
(6) Chlorine gas is passed into a solution of Nal in water. (vt) 2Cl, +2H,O —-> 4HCl +0,
(c) S1O, is treated with HF. (vit) F, + 2Cl —+2F+Cl,
(d) NaClO, ts treated with SO,. _} Example 538
(e) lodine ts treated with conc. HNO,. Write two uses of C1O,.
Solution:
Solution : ClO, is used as:
(t) a bleaching agent for paper pulp and textiles.
(a) 4NaCl + MnO, + 4H,S0, (cone) ———>
(it) In water treatment.
MnCl, + 4NaHSO, + 2H,O + Cl,
_] Example 54
(6) 2Nal (aq) + Cl, (g) ———> 2NaCl (aq) + LI, (g)
Explain why fluorine forms only one BEGtEEnE HOF?
(c) SiO, + 6HF ———> H,SiF, + 2H,O
(d) 2NaClO, + SO, (g) ———> 2Cl0, + Na,SO,
Solution : Due to small size and high oie neetette
(e) I, + 10HNO,——-> 2HIO, + 10 NO, + 4H,O
fluorine cannot act as central atom in higher oxoacids.
_}] Example 49.
_}] Example 55
Write the balanced chemical equation for the reaction of Write the reactions of F, and Cl, with water.|N.C.E.R.
Cl, with hot and concentrated NaOH. Is this reaction a Solution : Fluorine reacts eels with water giving
dic opeporionaion reaction ? Justify. oxygen and ozone.
Solution: 2K, + 2H,O ———> 4HF + O,
3Cl, + 6NaOQH ——> 5NaCl + NaClO, +3H,O 3F, + 3H,0 ——— 6HF + O,
hot and conc. Chlorine reacts slowly with water giving oxygen.
This is a disproportionation reaction because the oxidation 2Cl, + 2H,O ——> 4HC] + O,
state of Cl is changed from zero (in Cl,) to —1 (in NaCl) and _}) Example 56.
+5 (in NaClQ,). Which neutral molecule would be isoelectronic with
_}] Example 50. ClO? Is that molecule a Lewis base?
HCl when reacts with finely divided tron forms ferrous N.C.E.R.T, (D.S.B. 2008, Pb.S.B. 2013)
Solution: C1O-iis isoelectronic with CIF. Yes, it is a Lewis
chloride and not ferric chloride. Why ? |
base.
Solution : HC] reacts with finely divided iron and Poducee
L] Example 57
H, gas
Complete the following chemical reaction equations:
2Fe + 6HC]l ———> 2FeCl, + 3H,
(i) F,(g) + H,0 (1) —— (tt) Ca,P,(s) + H,O(l) ——>
Liberation of hydrogen prevents the formation of ferric
chloride. (iit) P, + NaOH + H,O——_> (Assam S.B. 2018, 2015)
_}) Example 51. Solution: (7) 2F,(¢)+2H,O (2) —— 4H" (aq) + 4F (aq) + O, (g)
(it) Ca,P,(s) + 6H,O (/) —-+ 3Ca (OH), + 2PH,
Explain why inspite of nearly same electronegativity,
(ii) P, + 3NaOH + 3H,0 —-> PH, + 3NaH,PO,
oxygen forms hydrogen bonding while chlorine does not.
_] Example 58
Solution : Oxygen has smaller size than chlorine. The
IF’, exists but BrF,does not exist. Why ?
smaller size of oxygen favours hydrogen bonding. In other words,
though electronegativity of Cl] is same as that of O, it does not Solution: The atomic size of iodine (133 pm) is much bigger
form hydrogen bonding because of its larger size. than bromine (114 pm). Therefore, seven small sized F atoms can
be accommodated around big I atom but not around small sized
_} Example 52
Br atom.
Complete the following reactions _} Example 59
(t) NaOH + Cl,— Molten ICL, has high electrical conductivity. Why?
hot and cone. Solution: The high electrical conductivity of molten IC], is
(ti) NH, + Cl, (excess) ——> (D.S.B. 2017) because of its ionisation to ICL,* and ICI, ions as
(tit) NaNO, + HCl—+ 2ICl,
== ICL,* + ICL-
(tv) F,(g) + H,OW —> (D.S.B. 2008) _] Example 60
(v) K,CO,+HCl—+ [is known but F, 1s not known. Why?
(vi) Cl,+H,O —> (D.S.B. 2017)
Solution: F, is not known because fluorine has no vacant
(vit) Fo+2Cl-—> (D.S.B. 2017)
d-orbitals available and therefore, cannot expand its octet. On the
Solution:
other hand, iodine has vacant d-orbitals and hence can expand its
(1) 6NaOH + 38ClL,—— 5NaCl + NaClO, + 3H,O
octet and can form I,.
hot and cone.
 MODERN'S abc + OF CHEMISTRY-XIl

= Answers to Practice Problems

ol. C10,
OZ. (@)Cl (az) F (atz) I 31. Give an example of oxide of chlorine having +6 oxidation state of Cl.
oo. (4) HCl (i) HF 32. Name the element of group 17, which has the following properties :
(ait) HI (iv) HF (:) highest electron affinity
34. (1) sp°d (11) strongest oxidising agent
(iit) highest melting point
(it) sp*d?
33. Among hydrides of halogens predict the hydride having
(iii) sp*d?
(t) lowest boiling point (it) highest boiling point
oo. CN ,CNS—
(iit) most acidic (tv) most stable
of. (a) HCl 34. Which type of hybridisation occurs in
(6) HBrO (z) BrF, (ii) BrF,
(c) HClO, (uz) IF,
(d) HI 35. Give two examples of pseudohalides.
(e) HClO, 36. Complete the reactions
38. Cl>F>Br>I1
(3) IO + TD +.H*——+ Gi) NaClO, + 1,——>
(iii) I, + S,0,7 ——~>
37. Which among the following pairs is stronger acid ?
(a) HF or HCl (6) HIO or HBrO
(c) HClO, or HC1O, (qd) HI or HCl
(e) HClO, or HBrO,
38. Arrange the following im the decreasing order of negative electron gain enthalpy.
F, Cl, I, Br

GROUP 18 ELEMENTS

GROUP 18 The group 18 consists of elements helium (He), neon (Ne), argon (Ar),
krypton (Kr), xenon (Xe) and radon (Rn). It constitutes zero group of the
He
periodic table. These gases at ordinary temperature do not have chemical reactivity
Helium
and therefore, these were called inert gases. However, nowadays, a number of
Ne compounds of these gases, particularly of xenon and krypton have been prepared.
Neon This shows that these gases are not completely inert. Consequently, these gases
Ar are called noble gases instead of inert gases which signifies that these gases have
some reactivity. This name is analogous to noble metals like gold and platinum
which show very low reactivity rather than complete inertness. Because of the
low abundance of these gases on earth, they have also been called rare gases.
Krypton
OCCURRENCE OF NOBLE GASES
Xe
Due to the inert nature of noble gases, they always occur in the free state. Except
radon, all these gases are present In atmosphere in the atomic state. Their total
Rn percentage in dry air is about 1% by volume, of which argon (0.93%) is the major
Radon component. It originates in the air mostly from electron capture (f* decay) of potassium
40
ip i ¥ 4 1°”
@ Lord Rayleigh and William Ramsay
made the first discovery of the noble The amount of noble gases present in atmosphere (in percent by volume)
gas argon in 1894. is given below :
e@ J.N. Lockyer first discovered helium
in the solar spectrum during a Element Abundance (Volume “)
total solar eclipse on 18th August 5.24 x 10+
1868. Later on, in 1895, helium was
1.82 x 10%
discovered on the earth by Wilham
Ramsay. 0.934
@ Xenon is called stranger gas. Its 1.14 x 10°
name was derived from the Greek Sr soles
word “xenos” which means stranger.
Traces
p-BLOCK ELEMENTS 7/111 >

Helium is also present in natural gas to the extent of 2 to 7%. Helium

and sometimes neon are found in small quantities in minerals of radioactive
elements such as monazite, clevite, pitch blende, etc. Helium, neon and argon
are found in the water of certain springs. Radon is radioactive and does not
occur in the free state because it decays very rapidly.
ISOLATION OF NOBLE GASES AND USES
1. From air
All non-radioactive noble gases except helium are commercially isolated
from air. Their total abundance in dry air is about 1% by volume of which
argon is the major component. Neon, argon, krypton and xenon are obtained
as by products of liquefaction of air and separation of its constituents by
fractional distillation.
This method is based on the difference in the boiling points of noble gases.
The gases are separated from one another and also from oxygen and nitrogen
(which are other major constituents of air) by fractional distillation.
Helium is commercially obtained from natural gas. The natural gas contains
hydrocarbon (methane, etc.), carbon dioxide, nitrogen, hydrogen sulphide and
helium as the main constituents. The natural gas is compressed to about 100
atm and cooled to 73K. Under these conditions, helium does not liquefy while
other gases get liquefied.
At this stage, helium contains about 2% nitrogen as impurity. To remove
the last traces of nitrogen, it is kept in contact with activated charcoal
maintained at 83K, when nitrogen gets adsorbed and unadsorbed helium of
99.9% purity is obtained.
Radon is obtained as a decay product of 77°Ra.
“eka —— >*.Rn + ~He
GENERAL CHARACTERISTICS OF GROUP 18 ELEMENTS
A. Electronic Configurations
Except helium, the atoms of all noble gases have eight electrons in the
valence shell. The general electronic configuration of noble gases (except He)
may be expressed as ns?np®. On the other hand, helium has 1s? electronic
configuration shown (Table 22) below.
These configurations being stable, the noble gases neither have any tendency
to gain nor lose electrons, and, therefore, they do not enter into chemical
combinations. It is, therefore, reasonable to assume that inert nature of the
noble gases is due to their stable electronic configurations.
B. Atomic and Physical Properties
Some of the important physical constants (Table 23) of noble gases are
discussed below:
1. Existence. All the noble gases are monoatomic, colourless and odourless
gases. The monoatomic state of these gases is due to stable electronic
configuration (ns*np*) of their atoms. As a result, they are not capable of
combining even amongst themselves.
Table 22. Electronic configuration of noble gases
Element Atomic no. Electronic configurations
1s?
1522s22p8
Lege cay ahe
1872572 p83s*3p sd 4e*4z59
1572 572p835*3p sd 4574 84d eb
1572572p%3s*3p*sd 4574p 9404 f*55*5p hd 6e*6p*
 MODERN’S abc + OF CHEMISTRY-XIl

Table 23. Atomic and Physical Properties of Group 18 Elements (Noble Gases)

Atomic number 2 10
Atomic mass (g mol?) 4.00 20.18
Atomic radius (pm) 120 160
Ionisation enthalpy (kJ mol?) 2372 2080
Electron gain enthalpy
(kJ mol) 48 116 96 96 cit 68
Melting point/K — 24.6 83.8 115.9 161.3 202
Boiling point/K 4.2 27.1 87.2 eer 165.0 211
Density (at STP) g em™®? aoc ie: 9.0 x 10+ 1.8x 10° a7 40 5.9 x 10° 9.7x 10°
LJ 1 .
radioactive 2. Atomic radii. In the case of noble gases, the atomic radii correspond
to van der Waal's radii. As we go down the group, the van der Waal's radius
increases due to the addition of new electronic shells.
Ionisation enthalpy 3. Lonisation enthalpies. The ionisation enthalpies of noble gases are
(kJ mol") very high. This is attributed to the stable completely filled configurations of
noble gases. However, the ionisation enthalpies decrease with increase in
He atomic number from He to Rn due to increasing atomic size.
mia pes 4. Electron gain enthalpies. Due to the stable ns?np® electronic
Ne configurations, noble gas atoms have no tendency to accept additional electron.
2080 Therefore, their electron gain enthalpies are zero or have large positive values.
5. Melting and boiling points. The melting and boiling points of noble
Ar gases are very low in comparison to those of other substances of comparable
1520 atomic and molecular masses. This indicates that only weak van der Waal's
Kr forces are present between the atoms of the noble gases in the liquid or the
1351 solid state. These van der Waal's forces increase with the increase in atomic
size of the atom, and therefore, the boiling points and melting points increase
Xe from He to Rn. Helium has the lowest boiling point (4.2 K) of any known
1170- substance. It has an unusual property of diffusing through most commonly
Rn used laboratory materials such as rubber, glass or plastics.
Ey 6. Ease of liquefication. The noble gases are not easily liquefied. This
is due to the fact that there are only weak van der Waal's forces which hold
atoms together. This is also clear from low values of heats of vaporisation of
these gases. Due to increase in atomic size and, therefore, increase in van der
Waals forces, the ease of liquefication increases down the group from He to Rn.
7. Solubility in water. The noble gases are only slightly soluble in water.
The solubility, in general, increases from He to Rn.
The solubility of noble gases in water is due to dipole-induced dipole
interactions. Water is a polar molecule. When it comes near a noble gas
atom, it induces dipole in the noble gas atom by distorting or polarizing the
symmetrical electron cloud of noble gas atom. As a result, an induced dipole
appears on the noble gas atom, leading to interaction with the dipole of polar
water molecule. Therefore, because of dipole-induced dipole interactions between
water molecules and noble gas atoms, the noble gas dissolves in water. As
the size of noble gas atom increases, the extent of polarization also increases.
Consequently, the magnitude of the dipole-induced dipole interactions increases
and hence the solubility of the noble gas in water increases from He to Rn.

H
By a
Nyt * re

Polar water Distorted Symmetrical

molecule electron cloud electron cloud of
noble gas
Fig. 46. Distortion of noble gas by polar water molecule
p-BLOCK ELEMENTS

PROPERTIES OF NOBLE GASES

Physical Properties
(t) All the noble gases are colourless, odourless and tasteless,
(it) All the noble gases are monoatomic.
(iit) They are sparingly soluble in water.
Chemical Properties
In general, noble gases are not very reactive. Their inertness to chemical
reactivity 1s attributed to the following reasons :
(i) The noble gases have completely filled ns*np® electronic configurations
in their valence shells.
(it) The noble gases have very high ionisation energies.
(iit) The electron affinities of noble gases are almost zero or large and positive.
Therefore, they have neither tendency to gain nor to lose any electron and
do not enter into chemical combinations. Before 1962, it was believed that noble
gases do not combine at all and no compounds of noble gases were formed.
In March 1962, Neil Bartlett noticed that platinum hexafluoride, PtF, is
a powerful oxidising agent which combines with molecular oxygen to form red
ionic compound, dioxygenyl hexafluoroplatinate (V), O,* [PtF,]-.
O, (g) + PtF, (@) ——— O,? [PtF,]-
This indicates that PtF,, has oxidised O, to O,*. Now, oxygen and xenon
have some similarities :
(i) The first ionisation energy of xenon gas (1170 kJ mol) is fairly
close to that of oxygen (1175 kJ mol).
(11) The molecular diameter of oxygen and atomic radius of xenon are
similar (4A). Xe* [PtF,]” was the first compound
On this assumption, Bartlett reacted xenon and platinum hexafluoride in of noble gas. It was synthesized by
gas phase and an orange yellow solid of the composition XePtF, was obtained. N. Bartlett in 1962.
Xe (g) + PtF, (g¢) ——— Xe* [PtF,] (s)
Orange yellow
The formation of this compound has shown that xenon is not totally inert
and after this a number of compounds of xenon were prepared.
Recent studies have shown that this compound is formulated as :
XeF]* [Pt,F,,]-.
A number of xenon compounds have been synthesised. The compounds of
krypton are fewer. Only the difluoride of krypton (KrF) has been studied in detail.
Compounds of randon have not isolated but only identified (e.g., RnF,) by radio tracer
technique. However, no true compounds of helium, neon or argon are yet known.
Some important stable compounds of xenon in different oxidation states
are listed in Table 24.
Table 24. Some important stable compounds of Xenon.

Ae, XeF, petal re XeO,

Xenon Xenon Xenon xenon
difluoride tetrafluoride hexafluoride tetraoxide
XeOF XeOF,
Xenon oxydifluoride Xenon
oxytetrafluoride
XeO
Xenon trioxide

Compounds of Xenon
A. Xenon fluorides
The three common fluorides are XeF,, XeF, and XeF,.
1. Xenon difluoride, XeF,
It is prepared by heating a mixture of xenon and fluorine in the molecular
ratio of 2: 1 at 673 K in a sealed nickel vessel at 1 bar pressure. On cooling
Fig. 47. Structure of XeF,.
quickly a colourless solid XeF, is formed. (Linear)
Xe+ F, __NivVessel_. XeF,
(2: lratio) 673 K,1 bar
 MODERN'S abc + OF CHEMISTRY-XIl

Structure. XeF, has linear structure as shown in Fig 47. It involves

sp*d hybridisation of xenon which adopts trigonal bipyramidal geometry in
which three positions are occupied by lone pairs. Because of the symmetrical
arrangement of three lone pairs (each at an angle of 120°C), the net repulsions
on the Xe—F bond pairs is zero. Thus XeF, has linear geometry.
Reaction with water. XeF., hydrolyses slowly but completely in acidic,
neutral or alkaline solutions.
2XeF,, + 2H,0 ——> 2Xe+4HF +0,
2XeF’, + 4NaOH — 2Xe+4NaF + 0, + 2H,O
2. Xenon tetraftuoride: XeF’,
It is prepared in good yield by —— a mixture of xenon and fluorine, in the
Fig. 48. Structure of XeF’,.
molar ratio of 1: 5, in nickel vessel, at 873 K under a pressure of 6 —7 bar pressure.
(Square planar)
Xe + 2aF, EK, yer
(1: 5 ratio) 6-7 bar
Structure. XeF, has square planar structure as shown in Fig. 48. It
involves sp°d? hybridisation of xenon which adopts octahedral geometry in which
two positions are occupied by lone pairs.
Reaction with water. XeF, undergoes slow hydrolysis with moisture
and forms XeO, which is highly explosive.
6XeF, + 12H,O ——+ 4Xe + 24HF + 2XeO,(s) + 30,
Explosive
But, if the reaction is controlled at — 80° C, it forms xenon oxyfluoride;
XeF, + H,O uc80 , XeOF, - 2HF
Xenon oxyfiuoride
3. Xenon hexafluoride, XeF,
It is prepared by heating xenon with excess of fluorine (in the molar ratio
of 20) in a nickel vessel at 573 K under pressure of 60—70 bar pressure.
Xe +/3F, eae XeF,
(1 : 20 h atic)
Structure. XeF, has distorted octahedral structure in which all the six
positions are occupied by fluorine atoms and the lone pair is present at the centre
of one of the triangular faces (Fig. 49). It involves sp*d? hybridisation of xenon.
Reaction with water. It undergoes slow hydrolysis with atmospheric
moisture and forms XeO, which is highly explosive.
XeF,, +3H,O ——~+ XeO, + G6HF
Fig. 49. Structure of XeF,. Careful hydrolysis in nickel vessel gives colourless stable liquid, XeOF,,.
(Distorted octahedral) XeF, + H,O ——_> XeOF, + 2HF
Xenon fluorides react with fluoride ion acceptors to form cationic species
and fluoride ion donors to form fluoroanions.
xek bE. eer Webel
The structure of XeF, is best
XeF, + SbF, ——— [XeF,]* [SbF,]-
described as distorted octahedral
cel i oi xe (M = Na, K, Rb, Cs)
with lone pair at the centre of one of
the faces or in the middle ofan edge. B. Xenon oxides
The important oxides of xenon are XeO, and XeO,.
1. Xenon trioxide, XeO,. Xenon trioxide is prepared by the hydrolysis
of XeF’, or XeF’,.
6XeF, +12H,O ——-> 2XeO, + 4Xe + 24HF +30,
XeF, + 3H,O ———> XeO, + 6HF
However, the last reaction proceeds through the following stages :
XeF, + H,O ———> XeOF, + 2HF
XeOF, + H,O ——> XeO,F,+ 2HF
XeO,F, + H,O ——> XeO, + 2HF
Great care should be taken during its preparation because it is highly
explosive.
Structure. It has pyramidal structure as shown in Fig. 50 ahead. It
involves sp® hybridisation of xenon.
Reaction with water. It is soluble in water and quite stable in aqueous
solution. However, it explodes violently when dry.
p-BLOCK ELEMENTS

XeO, reacts with aqueous alkali to form the hydrogen xenate ion HXeO >
which slowly disproportionates to give xenon and perxenate ion, XeO,* in
which xenon has oxidation state +8.

vane
XeO, + OH- ——> HXeO,
2HXeO, + 20H- ——> XeO,4+ Xe +0, +2H,O
Perxenate solutions are yellow and are powerful oxidizing agents.
2. Xenon tetraoxide, XeO,. It is prepared by the action of conc. H,SO,
on sodium or barium xenate (Na,XeO, or Ba,XeO,) at room temperature. It
may be purified by vacuum sublimation at —78°C. Fig. 50. Structure of XeO,,.
Structure. XeO, molecule has tetrahedral structure as shown in Fig. 51.
C. Xenon oxyfluorides
The common oxyfluorides of xenon are : XeOF,, XeOF, and XeO,F,,.
1. Xenon oxydifluoride, XeOF,. It is prepared by the slow and partial
hydrolysis of XeF, at low temperature.
XeF, + H,O—-%°, XeOF, + 2HF
Structure. It has T-shaped structure as shown in Fig. 52. Xenon involves
sp*d hybridisation giving trigonal bipyramidal geometry in which two positions
are occupied by lone pairs.
2. Xenon oxytetrafluoride, XeOF,,. It is prepared by the partial hydrolysis
of xenon hexafluoride : Fig. 51 Structure of XeQO,.
XeF, + H,O ———> XeOF, + 2HF (Tetrahedral)
It can also be prepared by the action of XeF, on silicon dioxide.
2XeF, + SiO, —““, 2XeOF,+SiF,
The contents are immediately quenched with solid CO, as soon as the
yellow colour of XeF,, disappears. It is done to avoid the formation of XeO,
(explosive) as:
XeOF, + S10, ——— XeO, + SIF,
Structure. It has square pyramidal structure as shown in Fig. 53. It
involves sp°d? hybridisation of xenon and one position is occupied by a lone pair.
Reaction with water. It reacts with water giving xenon dioxyfluoride
XeO,F, which further reacts with water to give explosive compound XeO, as:
XeOF, + H,O ——-> XeO,F,+ 2HF
XeO,F, + H,O ——> XeO, + 2HF Fig. 52. Structure of XeOF,,.
(vit) Xenon dioxydifluoride, XeO,F,. It is prepared by mixing XeO, and (T-shaped)
XeOF, at low temperature of —78°C.
XeO, +XeOF, —8C, 2Xe0.F,
The compound is purified by fractional distillation.
It is also formed when XeOF, is hydrolysed or reacts with silica.
2XeOF, + SiO, ——— 2XeO.F, + SIF,
XeOF, + H,O ——> XeO,F, + 2HF
Structure. XeO,F, has distorted trigonal bipyramidal geometry as shown
in Fig. 54. In it xenon involves sp*d hybridisation in which one position is
occupied by a lone pair.
Reaction with water. It is easily hydrolysed to give xenon trioxide.
XeO0.F, AA Qa sy— Xed, + 2HF Fig. 53. Structure of XeOF,,.
(Square pyramidal)
USES OF NOBLE GASES
Some of the important uses of noble gases are discussed below :
1. Helium
(4) Itis non-inflammable and light gas and therefore, it is used for filling
balloons for meteorological observations. Although lifting power of helium is
about 92.0% of that of hydrogen, yet it is preferred because it is non-flammable.
(11) Helium-oxygen mixture is also used to assist breathing in asthma
because helium is less soluble in blood than nitrogen.
(iit) Helium-oxygen mixture is used by deep sea divers in preference to
nitrogen-oxygen mixture because of its very low solubility in blood.
(iv) Liquid helium (b.p. 4.2 K) is used as cryogenic fluid to attain low
temperatures. Fig. 54. Structure of XeO,F,.
(v) Helium gas is used as heat transfer agent in gas cooled nuclear (Distorted trigonal bypyramidal)
reactors because of its high thermal conductivity and inert nature.
 MODERN'’S abc + OF CHEMISTRY-AXIl

(vi) Itis used to produce and sustain powerful super conducting magnets
which form an essential part of modern NMR spectrometers and Magnetic
Resonance Imaging (MRI) systems for clinical diagnosis.
(vit) Helium is used for creating inert atmosphere during welding of
magnesium and aluminium which are easily oxidisable.
2. Neon. (z) It is used for filling discharge tubes for optical decorations and
advertisements. When neon is mixed with other gases and used in discharge
tubes, glows of different colours known as neon signs are produced. These are
widely used for advertising purposes. Neon bulbs are used in botanical gardens
and green houses.
(it) It is used in safety devices for protecting electrical instruments like
voltmeters, relays, rectifiers, etc. This is due to remarkable property of neon
for carrying extremely high currents even under high voltage.
(iit) Neon is used for filling sodium vapour lamps.
(iv) It is used in becon light as safety signal for air navigators because
its ight has fog penetration power.
3. Argon. (1) It is used for filling electric bulbs because of its inert nature.
(it) It is used to provide an inert atmosphere in high temperature
metallurgical processes (arc welding of metals or alloys).
(iit) It is used in laboratory for handling substances that are air sensitive.
(iv) Pure argon is used in gas chromatography.
(v) Itis used to protect metal surfaces from oxidation during the welding
of steel.
4. Krypton and Xenon. (i) These gases are used for filling incandescent
metal filaments of electric bulbs.
(it) Kr—Xe mixture is used in some flash bulbs for high speed photography.
(iit) Xenon 1s used in research laboratories for detecting mesons.
5. Radon. (i) Radon has been used in the treatment of cancer.
(it) It is also gaining importance in radioactive research.
(iit) Radon is also used in X-ray photography for the detection of flows
in metals and other solids.

SOLVED EXAMPLES
_}] Example 61. Solution: The hydrolysis reaction of XeF, is
Give the formula of the noble gas species which is
XeF,+H,O + XeOF, + 2HF
isostructural with
and XeF,+2H,O0 ——-+ XeO,F,+2HF
(2) IBr,~ ()ICL- (zt) Bro, The oxidation states of all the elements in the products
Solution: Isostructural noble gas molecules : remain the same as it was in the reacting state. Hence, it 1s not
(.) IBro : XeF, a redox reaction.
(ar) ICL : KeF, |] Example 665.
(1tt) BrO,- : XeO, Out ofnoble gases, only xenon ts known to form chemical
_}] Example 62. compounds.
Noble gas have low boiling points. Explain Solution: Except randon, which is radioactive, xenon has
(Kerala S.B. 2016) lowest ionisation enthalpy among noble gases and hence itreadily
Solution : Noble gases are monoatomic gases and are forms chemical compounds particularly, with O, and F,.
held together by weak van der Waal's forces (dispersion forces). _}] Example 66.
Therefore, they are liquefied at very low temperatures. Hence Complete the following reactions :
they have low boiling points.
(i) XeF',+ SbF,——_> (D.S.B. 2012)
_}] Example 63. Gi) XeF,+O0,F, ~S4,
Why are the elements ofgroup 18 known as noble gases? (D.S.B. 2012, ALS.B. 2012, 2014)
Solution: The elements present in group 18 have completely (iii) Xek, +H,O ——>
filled valence shell (except He 1s). Therefore, they have neither
(iv) Xeh’, + H,O ——_>
any tendency to lose nor to gain electrons. However, they react
with a few elements only under certain conditions. Therefore, (v) XeF,+H,O——> (D.S.B. 2012)
they are known as noble gases. (vi) XeF,+2H,0O——> (D.S.B. 2017)
_}] Example 64. (vii) XeF,+3H,0O——> (D.S.B. 2017)
Does the hydrolysis of XeF ,lead to a redox reaction ? Solution:
(:) XeF, + SbF, ——> [XeF,]* [SbF,]”
p-BLOCK ELEMENTS

Gi) Ker, + OF, SER, xer 4 6;

(tit) oXeF, + oH,O ——-+ 2Xe + 4HF+O, (111)
(iv) XeF, +H,O 2%, XeOF,+2HF
(v) XeF, + H,O ——> XeOF,+2HF
(vi) XeF, + 2H,O ——> XeO,F,+4HF
(vii) XeF, + 3H,O ——> XeO, + 6HF
L] Example 67.
Why is heltum used in diving apparatus?
.C.E.R.T, (.P.S.B. 2016)
Solution: Helium is used as a diluent for oxygen in diving
apparatus because of its low solubility in blood.
LL] Example 68. (iv)
How are xenon fluorides XeF’,, XeF',and XeF’ obtained ?
Solution: x J+ Fy) XeF,(s)
(excess

(ii) Xe(g) + 2F(g) GE, XeF,(s)

(1 : 5 ratio)
(iii) Xe(g) + 8F (2) aang? XeF ((s)
(1 : 20 ratio)
MeF a4
_}] Example 69.
Which one of the following does not exist? (v) F
(a) XeOF, (b) NeF, (c) XeF,, (d) XeF,
Solution: (6) NeF,.
_}] Example 70.
Why has it been difficult to study the gas of
radon ? C.E.R.
Solution: Radon is radioactive and has very
period. Therefore, it is difficult to study the chemistry of ane
_}) Example 71.
Which compound of xenon has distorted octahedral
shape ? (C.B.S.E. Sample Paper 2012)
Solution: XeF, has distorted octahedral shape.
(vt)
_}] Example 72.
Draw the molecular structures of the following :
(1) XeOF, (A.LS.B. 2006, 2012, D.S.B. 2017)
(11) XeF, (D.S.B. 2012, 2017)
(uit) XeF, (D.S.B. 2011)
(tv) XeF, (A.S.B. 2008, 2010)
(v) XeOF, (A.S.B. 2006, 2009)
(vi) XeO, (C_B.S.E. Sample Paper 2011)
Solution:
(z)
_}] Example 73.
What inspired N. Bartlett for carrying out reaction
EF between Xe and Pt’, ? (D.S.B. 2013)
Solution : In 1962, N. Bartlett noticed that platinum
hexafluoride, PtF, is a powerful oxidising agent which combines
XeOF 4 with molecular oxygen to form ionic compound, dioxygenyl
Square pyramidal hexafiuoroplatinate (V), OF [PtF,]-.
F
O,(g) + PtF,(g¢) —> O; [PtF,]-
(it)
F--- ae This indicates that PtF, has oxidised O, to O,*. Now, oxygen
a ee and xenon have some similarities :
/ Xe Z
fe
FE
IY (i) The first ionisation enthalpy of xenon gas (1170 kJ mol)
is fairly close to that of oxygen (1166 kJ mol").
F (11) The molecular diameter of oxygen and atomic radius of
XeFs xenon are similar (4A). These prompted Bartlett to carry out the
reaction between Xe and PtF,.
Distorted octahedral
 MODERN'S abc + OF CHEMISTRY-XIl

39. Name the noble gas which

() is most abundant in atmosphere
(iz) 1s radioactive
— Answers to Practice Problems = (is) as Jedet boils pout:
39. (i) Ar (ii)Rn (iii) Xe 40. Which was the first noble gas compound synthesised? Who prepared it ?
40. XePtF,, N. Bartlett. 41. What is the state of hybridisation of Xe in
41. (i) sp3d (ii) sp3d2 (1) XeF, (12) XeOF,

(iii) sp? (tv) sp3d? (zit) XeO, (wv) XeF,.

- Iodine is liberated when KI is added to CuSO, solution but Cl, is not liberated when KCl is added to
CuSO, solution. Why ?
. TheT isa strong reducing agent and therefore, it reduces Cu** to Cut and itself gets oxidised to I,.
2Cu2* +4KI ——> Cu], + I, +4K*
But Cl does not act as a reducing agent and therefore, it cannot reduce Cu** to Cu* and hence Cl, is not liberated.
. Why does chlorine water lose its yellow colour on standing ?
. Chlorine water is yellow due to the presence of hypochlorous acid (HCIO) in it. HC1O is unstable and decomposes
to form HC] on standing. Therefore, yellow colour disappears.
Cl, + H,O —— > HCl + HCIO
Yellow

HCIO ——-> HCl + O

Colourless

Most of the reactions of fluorine are exothermic. Justify.

» Due to low bond dissociation enthalpy of F, (lesser energy required) and strong bonds formed between fluorine and
most of the elements (large energy released) most of the reactions occur with liberation of energy. Thus, most of the
reactions of fluorine are exothermic.
. ICI, does not exist while IF, exists. Why? (Pb. S.B. 20165)
. ICL, does not exist because of steric factors. Although iodine can accommodate seven F atoms to form pentagonal
bipyramidal IF, but it cannot accommodate seven large sized Cl atoms. Therefore, it does not form ICL..
Q.5. Indicate whether the following statements are TRUE or FALSE. Justify your answer in not more than
three lines :
(1) The decreasing order of negative electron enthalpy of F, Cl, Bris F > Cl > Br.
(it) BrF,, has trigonal planar geometry.
(zit) Ammonia reacts with excess Cl, to form explosive NH,.
(tv) F, is better oxidising agent than Cl.,,.
(v) HBr is stronger acid than HI because of hydrogen bonding.
(vit) Fluorine forms only one oxoacid, HOF.
Ans. (i) False : Correct order is F < Cl > Br
(11) False : BrF, has T shaped geometry.
(iit) False : It forms explosive NCIl,.
p-BLOCK ELEMENTS

(zu) True

(v) False : HI is stronger acid than HBr because HI has lower bond dissociation energy due to larger I atom.
(vt) True

Q.6. Arrange the following in the decreasing order of property mentioned :

(¢) H,O, H,S, H,Se, H,Te : Boiling point

(it) NH,, PH,, AsH,, SbH, : Basic strength
Ans. (1) H,Te > H,Se > H,O > H,5
(iz) NH, > PH, > AsH, > SbH,
Q.7. Bleaching of flowers by Cl, is permanent while by SO, it is temporary.
Ans. Bleaching by Cl, is by oxidation while SO, bleaches by reduction. Hence, product bleached by SO, is reoxidised by
air to its original form.
. Write balanced equations for the following:
(a) Phosphorus is treated with concentrated nitric acid
(Db) Manufacture of phosphoric acid from phosphorus.
Ans. (a) P, + 20HNO, —— 4H,PO, + 20NO, + 4H,O
(b) P, +50, — > P,O0,
P,O,,+6H,O —— 4H,PO,
Q.9. Why do noble gases form compounds with fluorine and oxygen ? (Pb. S.B. 2005)
Ans. Both oxygen and fluorine being highly electronegative atom can easily cause promotion of electrons from filled
orbitals of noble gases to vacant d-orbitals.
Q.10. What is the hybridisation of xenon in XeF, and XeF’,?
Ans. XeF, : sp*d
XeF, : sp?d?.
Q.11. Which reaction prompted Bartlett to prepare first noble gas compound ? Which was the compound ?
Ans. The following reaction prompted Bartlett to prepare the first noble gas compound :
O, (g) + PtF.(¢) ——— O,* [PtF,] (s)
The first I.E. of Xe and O, and their size are comparable. XePtF, was the first noble gas compound prepared.
Q.12. Complete the following equations:
(7) XeF, + H,O a (D.S.B. 2005)
(iz) Ca(OCl), + HCl Fr, (D.S.B. 2005)
(iit) XeF’, + H,O ~ f> (D.S.B. 2005)
(iv) NaClO, (aq) + SO,(g) (A.I.S.B. 2005)
(v) Ca, (PO,), + $10, + C —> (A.I.S.B. 2005)
(vt) XeF’, + SbF, —> (A.I.S.B. 2018)
Ans. (1) XeF, + 3H,O —— XeO,+6HF
(iz) Ca(OC), + 4HCl — > CaCl, + 2H,O + 2Cl,
(ti2) 6XeF’, + 12H,O —— > 4Xe+ 2XeO, + 24HF + 30,
(tv) 2NaClO, (aq) + SO,(g) — > 2Cl0,(g) + Na,SO, (aq)
(v) 2Ca,(PO,), + 6510,+ 10C ——> P,+6CaSi0, + 10CO
(ut) XeF, + SbF, —— > [XeF,]* [SbF]
Q.13. Write chemical equations for the following processes :
(1) Chlorine reacts with a hot concentrated solution of sodium hydroxide.
(iz) Orthophosphorous acid is heated.
 MODERN'S abc + OF CHEMISTRY-KIl

(417) PtF,, and xenon are mixed together. (D.S.B. 2008)

Ans. (z) 6 NaOH + 3Cl, —— 5 NaCl+NaClO, + 3H,O
(iz) 4 H,PO, —Heat, 3H,PO,+ PH,
(iit) Pt F, + Xe —— Xet [PtF,|-
Q.14. Complete the following chemical equations :
Ca,P,(s)+H,O() —>
(i) Cu?*(aq) + NH,(aq) a
EXCESS

Ew2+HO® —> arene (D.S.B. 2008, A.I.S.B. 2008)

XeF,(g)+H,O ——>
. Gi) Ca,P,(s)+6H,O(@) —> 3Ca(OH),(ag) + 2 PH, ()
Cu** (aq) + 4NH, (aq) —— [Cu(NH,),]** (aq)
excess Deep blue colour
2F, (g) + 2H,O (2) —— 4H*(aq)+4F (aq) + O, (g)
6XeF’, (g) + 12H,O ——> 4Xe +2XeO, + 24 HF +30,
. lodide ions can be oxidised by oxygen in acidic medium. Give chemical equation to support this.
(CBSE Sample Paper 2011)
. Iodide can be oxidised by oxygen in acidic medium :
AT- (aq) + O, (g) + 4H* (ag) —> 21,(s) + 2H,O().
. Fluorine atom is more electronegative than iodine atom, yet HF is weaker acid than HI. Justify.
. Fluorine atom is smaller in size than iodine atom and therefore, bond dissociation enthalpy of H—F is very high
as compared to that of H—I bond. Consequently, H—I bond breaks more easily than H—F bond and hence HI is a
stronger acid than HF.
Q.17. Why is neon generally used for warning signals ?
Ans. Neon lights are visible from long distances even in fog and mist and therefore, neon is generally used for warning
signals.
Q.18. What happens when iodine reacts with sodium thiosulphate ? (West Bengal S.B. 2012)
Ans. Iodine oxidises sodium thiosulphate to sodium tetrathionate.
2Na,8,0, + I, ——> Na,5,0, + 2Nal
Sodium Sodium
thiosulphate tetrathionate
.» Name the halogen which forms only one oxoacid and also write the formula of the oxoacid.
(Kerala S.B. 2012)
. F, and oxoacid : HOF (hydrofluorous acid)
. What happens when XeF,, undergoes complete hydrolysis? (CBSE Sample Paper 2017-18)
. XeO, is formed.

@ Catenation. It is the tendency of the atoms of an element to form bonds with itself (self linking of atoms).
@ Inert pair effect. The reluctance of the s-electron pair to take part in chemical combination in heavier elements.
@ Pseudohalides. The uninegative ions made up of two electronegative atoms which have properties similar to the halide ions.
p-BLOCK ELEMENTS

QUICK CHAPTER ROUND UP

GROUP 15 ELEMENTS GROUP 16 ELEMENTS

Nitrogen differs from other elements of the group due to Group 16 elements are called chaleogens. These consists
small size, of O, 5, Se, Te and Po.
high electronegativity, General electronic configuration: ns*np*.
. Sulphur exists as S, and has puckered ring structure.
absence of d — orbitals in the valence shell Allotropic form of oxygen is O,, which is highly oxidising
tendency to form px—pt bonds with itself and with highly agent.
electronegative atoms (O or C). O shows oxidation state —2, +2(OF,), -1(H,O,), 0(0,, O,). Other
Elements of group 15 exhibit two oxidation states +3 and elements also show +2, +4 and +6 oxidation states.
+5 but +3 oxidation state is formed because of inert pair In hydrides :
effect. Bond angle : H,O > H,5 > H,Se > H,Te
In hydrides : Acidic character : H,O < H,5 < H,Se
Volatility : H,O < H,5 > H,Se > H,Te.
Bond angle : NH, > PH, > AsH, > SbH,
SO, is a gas while 510, is a network solid.
Basic character : NH, > PH, > AsH,
Halides have shapes SCl, (angular), SF, (see saw), SF,
Boiling point : NH, > PH, < AsH, < SbH, (octahedral).
Stability : NH, > PH, > AsH,> SbH, Ozone is obtained as:
Reducing character : NH, < PH, < AsHg. 300) 20,(g)
N,O (colourless, neutral), NO (colourless, neutral), N,O, Ozone acts as an oxidising agent
(pale blue solid, acidic), NO, (colourless solid, acidic) NO, 0,(g) ——> O,(g) + O(g)
(Brown gas, acidic), N,O, (colourless solid or gas, acidic) PbS + 40, ———> PbSO, + 40,
N,O is called laughing gas and is obtained by heating 2HCl + O, ——> Cl, + H,O + O,
Juels Bele:LSEP I, + 50, + H,O ——> 2HIO, + 50,
Black P is most stable and least reactive allotropic form feet ge |) as fe oe I
of P. White P is least stable and most reactive. In the presence of O,, mercury loses its meniscus and starts
sticking to glass (called tailing of mercury).
P, + 30, (limited) ——-> P,O,
eet oe
os ee
SO, acts as acidic, reducing agent, oxidising agent and
P,O, + 6H,O (cold) ——> 4H,PO, bleaching agent
P,O, + 6H,O (hot) ——> 37iEER, SIRT 4 Sulphur forms a number of oxyacids:

P,O,, + 2H,O (cold) ——-+ 4H,PO, Sulphurous acid, Sulphuric acid, Thiosulphuric acid
H,SO,(+4), H,SO (+6) H,S,0,(+2)
P,O,, + 6H,O (hot) ——> 4H,PO,
Peroxo monosulphuric acid Peroxodisulphuric acid
Phosphorus forms a number of oxoacids. Depending upon
H,SO.(+6), H,5,0,(+6)
the number of P—OH bonds, they have different basicity.
Disulphurie acid,
Hypophosphorous acid, HPO, (Basicity = 1),
H,S,0,(+6),
Phosphonic acid, H,PO, (Basicity = 2),
The key step in the manufacture of H,SO, by Contact
Orthophosphoric acid, H,PO, (Basicity = 3), process 1s:
Pyrophosphoric acid, H,P,O0, (Basicity = 4). 250, + O, —— 250,; AH = -196.6 kJ
The oxoacids having P—H bonds are good reducing Favourable conditions for maximum yield of SOQ, are:
agents. high pressure (2 bar), low temperature (720 K), catalyst
(Pi or ¥ ott).
Absorption of SO, by 98% H,SO, give oleum
SO, + H,S0, ——> H,5,0,
¢ Dilution of oleum gives H,SO, of desired concentration.
H,S,0, + H,O ——> 2H,SO,
e Sulphuric acid is dehydrating agent and oxidising agent.
 MODERN'S abc + OF CHEMISTRY-Aill

GROUP 17 ELEMENTS GROUP 18 ELEMENTS

e Group 17 elements are called halogens. These consist of Group 18 elements are called noble gases. These consist
F, Cl, Br, I, At. of He, Ne, Ar, Kr, Xe, Rn.
e General electronic configuration: ns*np*
General electronic configuration: ns*np®
e Halogens are extremely reactive and as such they are found
in combined state. Noble gases have high IE and almost zero EA values and,
therefore, they neither have tendency to lose nor to gain
e Fluorine shows only —1 oxidation state while other halogens
an electron.
show variable oxidation states from + 1 to + 7.
F Cl Br I Bartlett (1962) prepared the first noble gas compound :
—l —1,+1,+3 —1,+1,+3, —1,+1,+3, Xe* [PtF I.
+5,+7 +5,+7 +5 +7
Noble gases (especially Xe and Kr) form compounds with
e Chlorine has the highest negative electron gain enthalpy: oxygen and fluorine.
Pete = be
Some important compounds of xenon in different oxidation
e Oxidising power : F, > Cl, > Br, > L.
states are:
e Reducing power: | > Br > CIl>F.
XeF, (+2), XeF) (+4), XeOF, (+4), XeF, (+6), XeOF, (+6),
e In hydrides
XeO, (+6) ete.
Acidic character : HI > HBr > HCl >
Reducing character : HF < HCl < HBr < HI Xo/+ F, =" XeF,
(3:1 ratio)
Thermal stability : > HCl > HBr > HI
Bleaching action of Cl, is due to oxidation and is permanent
Xe + 2F, 2", XeF,
(1:5 ratio)

¢ In cold, Cl, reacts with alkalies to form chlorides,

Xe + 3F, 2", XeF,
2NaOH + Cl,(dil) “> NaCl + NaClO + H,O (1:20 ratio)

with hot and conc. e These are easily hydrolysed:

6NaOH + 3Cl,(conc.) —2%-» 5NaCl + NaClO, + 3H,O 2XeF, + 2H,O ——> 2Xe + 4HF + O,
e Acidic character : HClO, > HClO, > HClO, > HCIO
6XeF, + 12H,O ——-> 4Xe + 2XeO, + 24HF + 30,
HClO > HBrO > HIO.
e Partial hydrolysis gives different products
e Oxidising power : HCIO, > HClO, > HClO, > HClO
ee ss JEL) ——— sani ss al
Bro, = 10,°> Clo,
e Halogens form interhalogen compounds and ions.
Kel + 20,0 ——-> XeO.¥, + 2HF

e Interhalogen compounds are more reactive than the XeF, + HO 82> XeOF, + 2HF
constituent halogens because X—Y bond is weaker than
ohio oo 81DN eal en] Ili
X—X or Y—Y.
e J, is soluble in KI solution due to the formation of KI, (or I, ).
Molecule Hybridisation Shape
e Pseudo halides (CN-, SCN-, OCN-) possess properties
similar to halide ions and pseudo halogens [(CN),, (OCN),, XeF, sp*d Linear
(SCN),] resemble halogens.
sp*d* Square planar
Molecule/ion Hybridisation Shape
sre Distorted octahedral
sp*d T-shaped
sp*d* Square pyramidal Oi
p Pyr amidal
sped Pentagonal bipyramidal
spd T-Shape
sr Linear
spd Square planar ieetinl Square pyramidal
sp°d Linear Distorted trigonal
3
sp*d* Square planar se bipyramidal
p-BLOCK ELEMENTS

\ NCERT F a Solved
In-text Questions //

. Why are pentahalides more covalent than o +

trihalides?
. In pentahalides, the oxidation state is more (+5) than in |
trihalides (+3). As a result of higher positive oxidation Py
state of central atom, they have larger polarizing power
and can polarise the halide ion(X) to a greater extent
11099 \q we a
H H
than in the corresponding trihalide. Since larger the
polarisation, larger is the covalent character, therefore,
Q.8. What happens when white phosphorus is heated
with concentrated NaOH solution in an inert
pentahalides are more convalent than trihalides.
atmosphere of CO,?
Q.2. Why is BiH, the strongest reducing agent amongst
all the hydrides of group 15? . Refer Solved Example 25 (Page 43).

Ans. Among the hydrides of group 16, BiH, is least stable Q.9. What happens when PCI, is heated?
because Bi has largest size in the group and has least . Refer Solved Example 25 (Page 43).
tendency to form covalent bond with small hydrogen atom.
Therefore, 1t can readily lost H atom and has strongest
Q.10. Write a balanced equation for the hydrolytic
tendency to act as reducing agent. reaction of PCl, with heavy water.

Q.3. Why is N, less reactive at room temperature? . PCl, + D,O ——> POCI, + 2DCI
Ans. Refer Solved Example 3 (Page 12) Q.11. What is the basicity of H,PO,?

Q.4. Mention the conditions required to maximise the Ans. Refer Solved Example 24 (Page 43)
yield of ammonia. Q.12. What happens when H,PO, is heated?
Ans. Ammonia is formed according to the reaction: Ans. Refer Solved Example 25 (Page 43)
N,@) + 3H, (2) —— 2NH,(g) AH° =—46.1kJ mol* Q.13. List the important sources of sulphur.
The conditions for maximum yield of ammonia are: » Sulphur occurs 1n the combined form as sulphide ores and
(1) Low temperature of the order of about 700 K sulphate ores. The common sulphide ores in which sulphur
occurs are galena (PbS), zinc blends (ZnS), copper pyrites
(iz) High pressure of 200 x 10° Pa (about 200 atm).
(CuFeS,) and sulphate ores are gypsum (CaSO,.2H,0),
(111) Presence of catalyst such as iron oxide with small epsom salt (MgSO,.7H,O) and baryte (BaSO,). Traces of
amount of K,O and Al,O,
sulphur occurs as hydrogen sulphide in voleano. Organic
Q.5. How does ammonia react with a solution of Cu**? materials such as eggs, proteins, onion, garlic, mustard,
Ans. Ammonia reacts with a solution of Cu** to form deep hair and wool also contain sulphur.
blue coloured complex, tetraammunecopper (II) ion: Q.14. Write the order of thermal stability of the hydrides
Cu” (ag) + 4NH,(aq) —=——— [Cu( NH, ),]?*(aq) of group 16 elements.
Tetraamminecopper (IT) ion . Refer Solved Example 35 (Page 80)
(deep blue)
Q.15. Why is H,O a liquid and H,S a gas?
. Due to high electronegativity of oxygen and its small
Q.6. What is the covalence of nitrogen in N,O,? size, there are strong hydrogen bonding in water. As a
Ans. Refer Solved Example 14 (Page 27). result, the molecules exists as associated and is liquid
Q.7. Bond angle in PH; is higher than that in PH,. Why? at room temperature. But there is negligible hydrogen
bonding in H,8 because of low electronegativity of 5.
Ans. Both PH; and PH, involve sp* hybridisation of
Q.16. Which of the following does not react with oxygen
P atom. In PH : all the four orbitals are bonded, whereas
directly?
in PH, there is a lone pair of electrons on P. In PH _
fn, Ti, Pt, Fe
the HPH bond angle is tetrahedral angle of 109.5°. But
in PH,, lone pair-bond pair repulsion is more than bond Ans. Pt ; because it is a noble metal.
pair-bond pair repulsion so that bond angles become less Q.17. Complete the following reactions:
than normal tetrahedral angle of 109.5°. The bond angle (zt) C,H, + O, ———>
in PH, has been found to be about 93.6”. (it) 4Al + 30, ———~
a 71124 MODERN'S abe + OF CHEMISTRY
-AXII

Ans. (t) C,H, + 830, ——-> 2CO, + 2H,O Q.23. Mention three areas in which sulphuric acid plays
(iz) 4Al + 830, ——-> 2Al,0, an important role.
Q.18. Why does O, act as a powerful oxidising agent? (1) manufacture of fertilizers (e.g., ammonium sulphate,
superphosphate).
Ans. Ozone acts as a powerful oxidising agent because it has
higher energy content and decomposes readily to give (11) petroleum refining
atomic oxygen as: (111) metallurgical applications (¢.g., cleansing metals
O, ———> 0, + O before enamelling, electroplating, galvanising, etc.).
Therefore, ozone can oxidise a number of non-metals and Q.24. Write the conditions to maximize the yield of H,SO,
other compounds. For example, by Contact process.
PbS (s) + 40,(¢) ———> PbSO,(s) + 40,(@) Ans. (1) Low temperature (optimum temperature 720 K)
2I (ag) + H,OW) + O,(¢) ———> 20H (aq) + I,(s) + O,(g)
(11) High pressure (optimum pressure 2 bar)
Q.19. How is ozone estimated quantitatively?
(iit) Presence of catalyst (V,O, catalyst).
Ans. Ozone oxidises potassium iodide to iodine as :
Q.25. Why is Ka, << Ky Li for H,SO, in water?
2KI + O, + H,O ——> 2KOH
+ 0, +I,
Ans. Refer Solved Example 37 (Page 80)
The liberated iodine may be titrated against a standard
solution of sodium thiosulphate. Q.26. Considering the parameters such as bond
dissociation enthalpy, electron gain enthalpy and
I, + 2Na,5,0, ———> Na,5,O0, + 2Nal
hydration enthalpy, compare the oxidising power
Thus, to estimate O, quantitatively, ozone is allowed of yy, and CI,
to react with known amount of excess potassium iodide
. F,, is stronger oxidising agent than Cl,. This can be
solution buffered with a borate buffer (pH = 9.2). The
explained on the basis of bond dissociation enthalpy,
liberated I, is titrated against Na,5,O, solution using
electron gain enthalpy and hydration enthalpy. The
starch as an indicator. From this amount of ozone can
process of oxidising behaviour may be expressed as:
be calculated.
Q.20. What happens when sulphur dioxide is passed into
aqueous solution of Fe (III) salt? =X@) taal, x Xig) AA x X@)
Ahyd H

Ans. Refer Solved Example 36 (Page 80) separ629)

~
Q.21. Comment on the nature of two S—O bonds formed
in SO, molecule. Are the two S—O bonds in this The overall tendency for the change (1.¢., oxidising
molecule equal? behaviour) depends upon the net effect of three steps.
As energy is required to dissociate or convert molecular
Ans. Sulphur in SO, involves sp* hybridisation. Two of these
halogen into atomic halogen, the enthalpy change for this
sp* orbitals form two o bonds with oxygen atom by
step is positive. On the other hand, energy is released in
overlap of sp” of S with 2p of O atoms. The remaining
steps (II) and (III), therefore, enthalpy change for these
two unhybridised orbitals of S form pi-pmt and pr-dt
steps is negative. Now although fluorine has less negative
double bonds with O atoms. So, SO, has the two S—O
electron gain enthalpy, yet it is stronger oxidising agent
bonds as:
because of low enthalpy of dissociation and very high
enthalpy of hydration. In other words, large amount of
energy released in step (IIT) and lesser amount of energy
required in step (I) overweigh the smaller energy released
AP r
S NeO
O
in step (II) for fluorine. As a result, the AH overall is
more negative for F,, than for Cl,. Hence, F, is stronger
oxidising agent than Cl,.
Though the two S—O bonds appear to be different because
one is formed by p1-pt overlap and the other is formed by Q.27. Give two examples to show the anomalous behaviour
pt-dr overlap. However, both the S—O bonds are equal of fluorine.
(bond length 143 pm) because of resonance between two » (2) Since fluorine is most electronegative element, it
structures. shows only a negative oxidation state of —1. It does
S S Sz not show any positive oxidation state. On the other
hand, the other halogens show positive oxidation
Sf x,O 4O
70 *
-
XeOo--™—COCOO
WY Se,O states also such as +1, +3, +5, +6 and +7.
(iz) Maximum covalency of fluorine is one because it
Q.22. How is the presence of SO, detected? cannot expand its valency shell beyond octet because
Ans. Sulphur dioxide can be detected by the following tests: there are no d-orbitals in the valence shell. On the
(t) It has a pungent characteristic smell. other hand, other elements can exercise covalencies
upto 7 because of availability of vacant d-orbitals.
(it) It decolourises acidified potassium permanganate
solution. Q.28. Sea is the greatest source of some halogens.
Comment.
(zit) It turns acidified potassium dichromate solution green.
Ans. Sea is an important source of some halogens. Sea
(iv) It turns blue litmus red.
water contains chlorides, bromides and iodides of
p-BLOCK ELEMENTS

sodium, potassium, magnesium and calcium. But it is Q.30 Name two poisonous gases which can be prepared
mainly sodium chloride (2.5% by mass). The deposits of from chlorine gas.
dried up sea contains sodium chloride, carnallite (KCI. Ans (1) phosgene (COCI,)
MgCl,.6H,O). Certain forms of marine life also contain (12) tear gas (CC1,.NO,)
iodine in their systems. For example, various sea weeds Q.31 Why is ICI more reactive than I,?
contain upto 0.5% of iodine and chile salt petre contains Ans Interhalogens are more reactive compounds than their
upto 0.2% of sodium iodate. constituting halogens because of weaker X—Y bonding
Q.29. Give the reason for bleaching action of chlorine. than X—X and Y—Y bonds. I—Cl bond is weaker than —Cl
Ans. Bleaching action of chlorine is due to its oxidation. In bonds and therefore, more reactive than I,.
the presence of moisture, chlorine gives nascent oxygen Q.32 Why is helium used in diving apparatus?
CL, + H,O ——> 2HCI1 + O Ans Refer Solved Example 67 (Page 742)
Because of nascent oxygen, it bleaches colouring substance Q.33 Balance the following equation
as: XeF f+ HQ —/> XeO,F, + HF
Colouring substance + QO t——-> Colourless substance Xe, + 2H,O ———> XeO,F, + 4HF
It bleaches vegetables or organic matter. The bleaching Q.34 Why has it been difficult to study the chemistry
action of chlorine is permanent. of radon?
Ans Refer Solved Example 70 (Page 117)

Textbook Exercises I)
Discuss the general characteristics of group Q.6. How is ammonia manufactured industrially?
15 elements with reference to their electronic Ans. Ammonia 1s manufactured industrially by Haber’s process.
configuration, oxidation state, atomic size,
ionization enthalpy and electronegativity.
N,(g) + 3H,(g) ———= 2NH,(g)
Ans. Refer Text (Pages 2 — 4).
AFH? = — 46.1 kJ mol
The optimum conditions for the production of ammonia
Q.2. Why does the reactivity of nitrogen differ from
are a pressure of 200 x 10° Pa (about 200 atm), at
phosphorus? temperature of about 700 K and a catalyst iron oxide
Ans. Nitrogen has a unique ability to form px—pt multiple with small amounts of K,O and Al,O,.
bonds with itself and with other elements having small For detail refer Text (Page 15).
size and high electronegativity (e.g., C, O). Therefore, it Q.7. Illustrate how copper metal can give different
has triple bond between two nitrogen atoms (N = N) products on reaction with HNO,,.
and is non-polar. Due to triple bond it has very high
Ans. Concentrated nitric acid is a strong oxidising agent and
bond enthalpy (941.4k.J) and therefore, 1t does not react reacts with metals. The products of oxidation depend
with other elements under normal conditions and is very upon the concentration of the acid, temperature and the
unreactive. On the other hand, phosphorus forms single nature of the material undergoing oxidation. For example,
bond (P—P) and is reactive in comparison to nitrogen. copper reacts with HNO, giving different products as:
Q.3. Discuss the trends in chemical reactivity of group Cone. HNO, gives copper nitrate and nitrogen dioxide.
15 elements.
Cu + 4HNO, ——>Cu(NOQ,), + 2NO, + 2H,O
Ans. Refer Text Page 6. CcOrLc.

Q.4. Why does NH, forms hydrogen bonds but PH, does Dilute HNO, gives copper nitrate and nitric oxide.
not?
3Cu + 8HNO, ——-> 3Cu (NO,), + 2NO + 2H,O
Ans. Because of high electronegativity and small size of
nitrogen, ammonia forms hydrogen bonds. On the other
Q.8. Give the resonating structures of NO, and N,O,.

hand, P has low electronegativity and large size and

hence cannot form hydrogen bonds.
Q.5. How is nitrogen prepared in the laboratory? Write
the chemical equation of the reactions involved.
Ans. In the laboratory, nitrogen is prepared by treating an
aqueous solution of ammonium chloride with sodium
nitrite.
NH,Cl(aq) + NaNO,(aqg)———-N,(g) + NaCl(aq) + 2H, OW)
It may be noted that small amounts of NO and HNO,
are also formed in this reaction as impurities. These are
removed by passing the gas through aqueous sulphuric
acid containing potassium dichromate.
a 7/126 MODERN'’S abe + OF CHEMISTRY
-AXII

Q.9. The HNH angle value is higher than HPH, HAsH Q.14. Why does nitrogen shows catenation properties
and HSbH angles. Why? less than phosphorus?
Ans. All the hydrides of group (NH,, PH,, AsH, and SbH,) Ans. Refer Solved Example 5 (Page 13).
involve sp® hybridisation of the central atom in which Q.15. Give the disproportionation reaction of H,PO,.
one of the position 1s occupied by a lone pair of electrons.
Ans. H,PO, disproportionate on heating as :
4H,.PO, ———> 3H,PO, + PH,
Q.16. Can PCI, act as an oxidising as well as a reducing
M (M = N, P, As, Sb) agent? Justify.
Lo SS H . Phosphorus can show maximum oxidation state of +5 in
H H its compounds. In PCl,, its oxidation state is +6. Since it
Now, as we move down the group from N to P to As to cannot increase its oxidation state beyond +5, it cannot act
Sb, the size of the atom goes on increasing and its
as a reducing agent. However, it can act as an oxidising
electronegativity decreases. Consequently, the position of
agent by undergoing decrease in its oxidation state from
bond pair shifts more and more away from the central atom
+6 to +3. For example, it oxidises silver to AgCl, Sn to
in moving form NH, to SbH,. For example, the bond pair
SnCl, ete.
in NH, 1s close to N in N—H bond than the bond pair in
+5 +1 +9
P—H bond in PH.,. Asa result, the force of repulsion between
2Ag + PCl, ———> 2AgCl + PCI,
the bonded pair of electrons in NH, is more than in PH.
In general, the force of repulsion between bonded pairs Q.17. Justify the placement of O, S, Se, Te and Po in
of electrons decreases as we move from NH, to BiH, and the same group of the periodic table in terms
therefore, the bond angle also decreases in the same order. of electronic configuration, oxidation state and
Q.10. Why does R,P = O exists but R,N = O does not hydride formation.
(R = alkyl group). (A.LS.B. 2014) . Refer Text (Page 48 — 51).
Ans. R,N = O does not exist because nitrogen cannot have Q.18. Why is dioxygen a gas but sulphur a solid?
covalency more than four. Moreover, R,P = O exists » Duetosmall size and high electronegativity, oxygen atom
because phosphorus can extend its covalency more than forms pt-pt double bond, O = O. Theintermolecular forces
4 as well as it can form di-pn bond whereas nitrogen in oxygen are weak van der Waals forces and therefore,
cannot form d1-pm bond. oxygen exists as a gas. On the other hand, sulphur does
Q.11. Explain why NH, is basic while BiH, is only feebly not form stable pa-pn bonds and do not exists as 5,. It
basic. is linked by single bonds and form polyatomic complex
Ans. Both N and Bi have a lone pair of electrons in NH, and molecules having eight atoms per molecule (S,) and have
BiH, respectively. They can donate the electron pair and puckered ring structure. Therefore, 5 atoms are strongly
therefore behave as Lewis base. In NH,, N has small size held together and it exists as a solid.
and the lone pair is concentrated on a small region and Q.19. Knowing the electron gain enthalpy values for
electron density on it is maximum. Consequently, it has O —> O and O —-> O* as -141 and 702 kJ mol"!
greater electron releasing tendency. But the size of Bi is respectively, how can you account for the formation
large and the electron density of the lone pair is less. As of a large number of oxides having O* species
a result, it has lesser tendency to donate electron pair. and not O-?
Hence, NH, 1s basic while BiH, is only feebly basic.
Ans. The second electron enthalpy of oxygen for the formation of
Q.12. Nitrogen exists as diatomic molecule and
O*- is positive while first electron gain enthalpy of oxygen
phosphorus as P,. Why ?
for the formation of O- is negative. This means that if
Ans. Refer Solved Example 1 (Page 12) electron gain enthalpy is the only factor involved for the
Q.13. Write main differences between the properties of formation of divalent ions, we would except that oxygen
white phosphorus and red phosphorus. would prefer to form O- ions rather than O*- ions. Actually,
Ans. The main differences between white phosphorus and red a large number of oxides have O7 species and not O-.
phosphorus are: This is because (1) divalent O?- has the stable noble gas
configuration. (iz) In the solid state, large amount of energy
known as lattice enthalpy is released to form divalent
Colour White but turns Dark red O7- ions than monovalent O- ions. It is the greater lattice
yellow on exposure enthalpy of O*- ion which compensates for the high energy
State Waxy solid Brittle powder required to remove the second electron. This is responsible
Density 1.84 g em? 2.1¢cm™? for greater stability of O7 ion as compared to O- ion.
Ignition 307 K 543 K
Q.20. Which aerosols deplete ozone?
temperature
stability Less stable at More stable at Ans. Freons (Chlorofluorocarbon).
ordinary ordinary Q.21. Describe the manufacture of sulphuric acid by
temperature temperature Contact process.
Chemical Very reactive Less reactive Ans. Refer Text (Pages 74 — 75)
reactivity
p-BLOCK ELEMENTS

Q.22. How is SO, an air pollutant? This prompted Bartlett to carry out the reaction between
Ans. SO, dissolves in rain water and produces acid rain. The Xe and PtF,.
acid rain contains sulphuric acid. Q.31. What are the oxidation states of phosphorus in the

SO, + ca Soot following :

50,+H,O —Sia
Particles H,SO, (a) H,PO, (6b) PCI, (c) Ca,P,
In addition to H,SQO,, acid rain also contains HNO,. (d) Na,PO, (e) POF, 7
Q.23. Why are halogens strong oxidising agents? Ans. (a) H,PO, : +3
Ans. Halogens have strong tendency to accept electrons and (6) PCI, > +93
therefore, act as strong oxidising agents. Their oxidising (c) Ca,P, 7 38
power decreases from F, to I,.
(d) Na,PO, : +6
Q.24. Explain why fluorine forms only one oxoacid HOF?
(e) POF, > +6
Ans. Refer Solved Example 54 (Page 109).
Q.32. Write balanced equations for the following:
Q.25. Explain why inspite of nearly the same
(a) NaCl is heated with sulphuric acid in the
electronegativity, oxygen forms hydrogen bonding
presence of MnQ,,.
while chlorine does not.
(6) Chlorine gas is passed into a solution of Nal in
Ans. Oxygen has smaller size than chlorine, smaller size of
water.
oxygen favours hydrogen bonding.
Ans. (a) 4NaCl + MnO, + 4H,SO, ———>
Q.26. Write two uses of C1Q,,.
MnCl, + 4NaHSO, + 2H,O + Cl,
Ans. Refer Solved Example 55 (Page 109).
(6) 2Nal (aq) + CL,(¢) ———> 2NaCl(aq) + Ls)
Q.27. Why are halogens coloured? (H.P.S.B. 2016)
Q.33. How are xenon fluorides XeF,, XeF, and XeF,
Ans. All the halogens are coloured. This is due to absorption
obtained?
of radiations in the visible region which results in the
. Refer Solved Example 68 (Page 117).
excitation of outer electrons to higher energy levels. By
absorbing different quanta of radiations, they display Q.34. With what neutral molecule is ClO- isoelectronic?
Is that molecule a Lewis base?
different colours. Fluorine atom is the smallest and the
force of attraction between the nucleus and the outer . Refer Solved Example 56 (Page 109).
electrons is very large. As a result, it requires large Q.35. How are XeO, and XeOF, prepared?
excitation energy and absorbs violet light (high energy) Ans. XeF, + 3H,0 ——-> XeO, + 6HF
and therefore, appears pale yellow. On the other hand, XeF, + H,Q ———> XeOF, + 2HF
iodine needs very less excitation energy and absorbs
Q.36. Arrange the following in the order of property
yellow light of low energy. Thus, it appears dark violet. indicated for each set:
Similarly, we can explain the greenish yellow colour of
(a) F,, Cl,, Br,, I, . increasing bond dissociation
chlorine and reddish brown colour of bromine. enthalpy.
Q.28. Write the reactions of F, and Cl, with water. (6) HF, HCl, HBr, HI. increasing acid strength.
Ans. Refer Solved Example 55 (Page 109). (c) NH,, PH,, AsH,, SbH,, BiH, . increasing base
Q.29. How can you prepare Cl, from HCl and HCl from strength.
Cl,. Write reactions only. Ans. (oy 1 =i, = ty = Ol,
Ans. () Oxidation of hydrogen chloride gas by atmospheric (6) HF < HCl < HBr < Hl
oxygen in the presence of CuCl, catalyst at 723 K (c) BiH, < SbH, < AsH, < PH, < NH,
(Deacon’s process). Q.37. Which one of the following does not exist?
4HC1 + 0, “> 2C1, + 2H,0 (a) XeOF, (6) NeF, (c) XeF, (d) XeF,
Ans. (6) NeF,,.
(ii) H,+Cl, ——> 2HCI
Q.38. Give the formula and describe the structure of a
Q.30. What inspired N. Barilett for carrying out reaction noble gas species which is isostructural with:
between Xe and PtF,? (a) ICL (6b) IBr,- (c) BrO,-
Ans. In 1962, N. Bartlett noticed that platinum hexafluoride,
Ans. (a) XeF, square planar
PtF, is a powerful oxidising agent which combines with
molecular oxygen to form ionic compound, dioxygenyl (b) XeF, linear structure
hexafluoroplatinate (V), O,* [PtF,]-. (c) XeO, pyramidal structure
O,(g) + PtF,(g¢) ——— O,* [PtF,]- For detail of structures refer Text Pages 114 — 115.
This indicates that PtF, has oxidised O, to O,*. Now, Q.39. Why do noble gases have comparatively large
oxygen and xenon have some similarities: atomic sizes?
(:) The first ionisation enthalpy of xenon gas Ans. In case of noble gases, the atomic radii correspond to
(1170kJ mol") is fairly close to that of oxygen (1166 kJ
van der Waals radi, which are always large.
mol).
Q.40 . List the uses of neon and argon gases.
(zt) The molecular diameter of oxygen and atomic radius
of xenon are similar (4A). Ans . Refer Text (Page 116).
 MODERN'S abe + OF CHEMISTRY
-AXII

Exemplar Problems TI
Subjective Questions
can be easily accommodated around 5 atom to form
SF. Moreover, because of low electronegativity of Cl, it
. In the preparation of H,SO, by Contact Process, cannot easily cause promotion of electrons in 5 to form
why is SO, not absorbed directly in water to form 5 (VD.
H,SO,? 10. On reaction with Cl,, phosphorus forms two types
- When SO, is absorbed directly in H,SO,, acid fog is of halides ‘A’ and ‘B’. Halide A is yellowish-white
formed which is difficult to condense. powder but halide ‘B’ is colourless oily liquid.
. Write a balanced chemical equation for the Identify A and B and write the formulas of their
reaction showing catalytic oxidation of NH, by hydrolysis products.
atmospheric oxygen. Ans. A is PCl, (it is yellowish white powder)
P, + 10Cl, —~ 4PCl,
Ans. 4NH, + 50,
Pt/Rh gauge catalyst
500 K,9 bar 4NO + 6H,O
B is PCI, (It is a colourless oily liquid)
. Write the structure of pyrophosphoric acid. P, + 6Cl, —~ 4PCl,

Ans.
ro
HO—P— O—P—OH Pyrophosphoric acid
The products of hydrolysis of PC], and PCI, are :
PCl, + 3H,O ——~ H,PO, + 3HCl
| |
OH OH Bel, + 4H,0 —+> H,PO, + 6HC1

. PH, forms bubbles when passed slowly in water 11. In the ring test of NO; ion, Fe** ion reduces nitrate
ion to nitric oxide, which combines with Fe** (aq)
but NH, dissolves. Explain why?
ion to form brown complex. Write the reactions
Ans. NH, forms hydrogen bonds with water and therefore involved in the formation of brown ring.
soluble in water but PH, cannot form hydrogen bonds
» NO, + 3Fe*t + 4H*+ —> NO+ 3Fe** + 2H,O
with water and therefore, is not soluble in water. It
eSCAPes AS GAS. [Fe(H,O),]?* + NO ——> [Fe(H,0),(NO)]** + H,O
- In PC1,, phosphorus is in sp*d hybridised state but (brown complex)
all its five bonds are not equivalent. Justify your
12. Explain why the stability of oxoacids of chlorine
answer with reason.
increases in the order given below:
Ans. It has trigonal bipyramidal geometry in which all the
four bonds are not equal.
HC1O <HCIO, < HCO, < HCIO,
» Oxygen is more electronegative than chlorine, therefore
. Why is nitric oxide paramagnetic in gaseous state dispersal of negative charge present on chlorine increases
but the solid obtained on cooling it is diamagnetic? from C1O- to ClO," 10n because number of oxygen atoms
Ans. In gaseous state NO, exists as monomer which has attached to chlorine is increasing. Therefore, stability
one unpaired electron. In the solid state it dimerises to of ions will increase in the order given below :
N,O, so no unpaired electron is left hence solid form is ClO- < ClO,- < ClO,” < C1O,-
diamagnetic.
Thus due to increase in stability of conjugate base,
. Give reason to explain why CIF, exists but FCI, acidic strength of corresponding acid increases in the
does not exist. following order
. Because fluorine is more electronegative than Cl and
forms CIF,.But F cannot exhibits more than one valency
HCIO < HCIO, < HCIO, < HCIO,
because of the absence ofd-orbitals and therefore, cannot 135. Explain why ozone is thermodynamically less
form FCI,. stable than oxygen.

- Out of H,O and H,S, which one has higher bond » Ozone is thermodynamically unstable with respect to
angle and why? oxygen because it results in liberation of heat (AH =—ve)
and increase in entropy (AS = +ve).
Ans. Oxygen is more electronegative than sulphur therefore
bond pair of electrons of O—H bond will be closer to 20 a 30 2
oxygen. As a result, there will be more bond pair-bond These two factors reinforce each other resulting in large
pair repulsion between bond pairs of two O—H bonds. negative Gibbs free energy change (AG = —ve) for its
. SF, is known but SCI, is not. Why? conversion into oxygen. Therefore, the high concentration
Ans. Due to small size of 5, six large Cl atoms cannot be of ozone can result into dangerous explosion.
accommodated around 5 atom. But small six F atoms
p-BLOCK ELEMENTS

14, P,O, reacts with water according to equation: Ans. Reaction of nitric acid and P,O,,.
P,O, + 6H,0 — 4H,PO, AHINO, + P,O,, —> 4HPO, + 2N,0,
Calculate the volume of 0.1 M NaOH solution Resonating structures of N,O, :
required to neutralise the acid formed by
dissolving 1.1 g of P,O, in H,O.
:Q LP 7 AX
Ans. P,O, + 6H,O ——> 4H,PO, A
7 Ni
H,PO, can be neutralised with NaOH as:
18. Phosphorus has three allotropic forms — (1) white
4H.PO, + 8NaQH —> 4Na,HPO, + 8H,O
phosphorus (i1) red phosphorus and (ii1) black
phosphorus. Write the difference between white
P4Og + 8NaOH ——> 4Na,HPO, + 2H,O
1 mol 8 mol and red phosphorus on the basis of their structure
and reactivity.
Moles of P,O, = <2 = 0.005 mol . For structures of three allotropes of P, refer chapter in
Acid formed by 1 mol of P,O, require NaOH = 8 mol Brief.

Acid formed by 0.005 mol of P,O, require NaOH Differences between white P and red P
= § x 0.005 = 0.04 mol White phosphorus has discrete P, units. The four P
0.1 M NaOH means 0.1 mol of NaOH is present in 1000 atoms lie at the corners of a regular tetrahedron with
mL solution £PPP = 60°. Each P is bonded to each of the other three
P atoms by covalent bonds so that each P completes its
0.04 M of NaQH is present in solution = au x 0.04 valence shell.
Red phosphorus also consists of P, units but have
= 400 mL polymeric structure consisting of P, tetrahedra linked
together through P—P bonds to form the chain.
15. White phosphorus reacts with chlorine and the
product hydrolyses in the presence of water. Reactivity. White phosphorus is much more reactive
Calculate the mass of HCl obtained by the than red phosphorus. This is because in white
hydrolysis of the product formed by the reaction phosphorus, there is angular strain in P, molecules
of 62 g of white phosphorus with chlorine in the because the bond angles are only 60°.
presence of water. 19. Give an example to show the effect of concentration
Ans. Phosphorus react with Cl, as : of nitric acid on the formation of oxidation
product.
P, + 6CL, —-> 4PCl,
. Dilute and concentrated nitric acid give different
PCI, is hydrolysed as : oxidation products on reaction with metals. For example,
PCl, + 83H,O —~> 3H,PO, + 3HC1] x 4 copper reacts with dilute and conc. HNO, as:
P+ OCLs 1510 > TILPO, +DanC 3Cu + 8HNO, (dil.) —> 8Cu(NO,), + 2NO + 4H,O
3Cu + 4HNO, (Conc.) —> 38Cu(NO,), + 2NO, +
Moles of white P = 62 = 0.65 mol
124 2H,O
1 mol of white P, produces HCI = 12 mol 20. PCl1, reacts with finely divided silver on heating
and a white silver salt is obtained, which dissolves
0.6 mol of white P, will produce HCl = 12 x 0.6 = 6 mol
on adding excess aqueous NH, solution. Write the
Mass of HCl = 6 x 36.5 = 219.0 g
reactions involved to explain what happens.
16. Name three oxoacids of nitrogen. Write the
Ans. PCl, reacts with silver to form white silver salt (AgCl).
disproportionation reaction of that oxoacid of
This dissolves in aqueous ammonia to form soluble
nitrogen in which nitrogen is in +3 oxidation state.
complex.
Ans. Three oxoacids of nitrogen are
PCl, + 2Ag—> 2AgeC] + PCI,
(1) HNO,, Nitrous acid = (zz) HNO,, Nitric acid White ppt
(1121) Hyponitrous acid, H,N,O,
AgCl + 2NH, (ag) —> [Ag (NHg)o]* Cl”
Acid in which oxidation state of N is + 3, is HNO, Soluble complex

3HNO, ——sProportionation _, HNO, + H,O + 2NO 21. Phosphorus forms a number of oxoacids. Out
of these oxoacids phosphinic acid has strong
17. Nitric acid forms an oxide of nitrogen on reaction reducing property. Write its structure and also
with P,O,,. Write the reaction involved. Also write write a reaction showing its reducing behaviour.
the resonating structures of the oxide of nitrogen
. structure of phosphinic acid (Hypophosphorous acid) is
formed.
as follows:
ny 71130 MODERN'S abe + OF CHEMISTRY
-AXII

Reducing behaviour of phosphinic acid is observed when

it reacts with silver nitrate as:
4AgNO, + 2H,O + H,PO,—> 4Ag + 4HNO, + H,PO,.

Memory TEstT W

- In CIF, and SF,, Cl involves ......... hybridisation and $

i“ say True or False
involves ......0 hybridisation.
. The covalence of N,O, is five. 10. Among hydrides of oxygen family, the strongest reducing
- H,PO, 1s a dibasic acid. agent 18 ..........
. All the five bonds in PCI, are not equal. 11. Nitrogen is a gas because of its tendency to form ..........
12. In XeF,, xenon involves ......... hybridisation and its
BO.
CF
me The bleaching action of SO, is permanent while that of
shape 1s ..........
Cl, is temporary.
13. Oleum is formed when ......... is passed through conc.
. NH, is less basic than PH.
FigO,.
Oo»
oO Sulphuric acid has high boiling point and a high viscosity 14, The two neutral oxides of nitrogen are ......... and ..........
because it forms intramolecular hydrogen bonding.
15. In gaseous state nitric oxide is ......... while in the liquid
. In group 16, the volatility of hydrides first increases or solid state it is ..........
from H,O to H,5 and then decreases from H,5 to H,Te.
16. Among group 15 hydrides, ..... .... 18 most stable.
» Both pyrophosphoric acid and hypophosphoric acid have 17. P,O, and P,O,, dissolve in water to give ......... and
P_O_-P linkages.
. White phosphorous is most reactive while black 18.
phosphorus is least reactive.
10. In SF,, 5 involves sp*d hybridisation. 19. The oxide of nitrogen obtained on heating lead nitrate
11. Nitrogen cannot form compounds of the type R,N = O ee
while phosphorus can form compounds of the type R,P=O. 20. Phosphorus reacts with nitric acid to form ......... acid.
12. As,O, is amphoteric while Sb,O, is acidic. 21. Laughing gas is obtained on heating a mixture of NH,Cl
13. Concentrated H,SO, can be used to prepare HBr from NaBr. 1 but nitrogen gas is obtained when a mixture
of NH,CI and ......... is heated.
14, BrO,- and XeO, are isostructural.
22. Hypophosphoric acid is......... basic but pyrophosphorous
15. I, cannot liberate Cl, from aqueous KC] butit can liberate acid 18 ........ . basic.
CL, from KC1Q,.
Zoe Orthophosphorous acid on heating gives ......... and

I-38 Complete the missing links

2A, The nitrogen oxide which is blue liquid below 253K
1. Calcium phosphide on hydrolysis gives ..... .... and calc1um noes .is and which is brown gas is ..........
hydroxide. 25. The formula of epsom salt is ......... and that of baryte
. Sulphuric acid is viscous in nature due to ........ -
. Iodine dissolves in aqueous KI solution due to the
formation of ..........
. Concentrated nitric acid on dehydration with P,O,, gives . Reducing power of hydrides of group 16 increases/
decreases from 1 i a to H, Te.

. SF, molecule has square planar/see saw geometry.

. In brown ring test for nitrates, Fe** ion reduces NO, ion 3. Nitrogen gas is obtained by heating ammonium nitrite/
fe . which reacts with Fe** ion to form a brown ammonium nitrate.
ring complex having the molecular formula ..........
. PCl, in solid state exists as ionic compound having cation . Both In,O, and T1,O, are acidic/basic oxides.
ceueeeee . and anion ..........
5. In H,5,O0g,, the oxidation state of 5 is +6/+7.
. The strongest reducing agent among all the halide ions
EG weewsieceud
6. The negative electron gain enthalpy of F is less/more
than Cl.
p-BLOCK ELEMENTS

. Out of F, and Cl,, the stronger oxidising agent is F,/Ci,. 15. BrO, 1s stronger/weaker oxidising agent than ClO, .

- During electrolysis of molten ICI, both I, and Cl, are 16. The halogen which normally does not form oxoacid is
liberated at anode / cathode. fluorine /chlorine.

» HC1O, is less/more acidic than HC1O,. 17. In BrF,, Br involves sp?/sp%d hybridisation.
10. Hydrogen chloride gas can be dried over conc. sulphuric 18. The most abundant noble gas in atmosphere is argon/
acid /phosphorus pentoxide. helium.
11. When Cl, gas is passed through hot milk of lime, bleaching 19. The square pyramidal shape is of XeOF’,/XeO,F,.
powder/calcium chlorate is formed. 20. White phosphorus is less/more reactive than red
12. HI is stronger/weaker acid than HCl. phosphorus.

13. Bleaching action of SO, 1s permanent/temporary.

14, Dipole moment of SO, 1s higher/lower than that of SQ,.

Memory TEST W
14, True
15. False. I, is a weaker oxidising agent than Cl, and
Say True or False therefore cannot oxidise KCI to Cl,. However, KC1O, is a
stronger oxidising agent than I,, it oxidises I, to lO,” and
i False. Maximum covalence of nitrogen cannot be more itself gets reduced to Cl.,,.
than 4 because of absence of d-orbitals.
. False. H,PO, is monobasic because it has only one
2K, + I,—> 2KI0, + Cl,
ionisable hydrogen atom. Complete the missing links
. True.
. False. The bleaching action of Cl, is due to oxidation and 1. phosphine 2. hydrogen bonding 3. KI.
hence is permanent but that of SO, 1s due to reduction 4, N,O, 5. NH
and hence is temporary. 6. NO, [Fe(H,,0).NO]** 1. POPC
. False. NH, is more basic than PH,. 8. 9. sp°d, sp*d 10. H,Te
- False. High boiling point and viscosity of H,SO, is 11. multiple bonds 12. sp°d*, square planar 13. SO,
because its molecules are associated due to intermolecular 14. N,O, NO 15. paramagnetic, diamagnetic
hydrogen bonding and not due to intramolecular hydrogen 16. NH, 17. H,PO,, H,PO, 18. nitrolim
bonding.
19. NO, 20. phosphoric
. True
21. NaNO,, NaNO, 22. tetra, di
» False. Pyrophosphoric acid has P—O—P linkage but
hypophosphoric acid does not have P—O—P linkage. It has
. phosphoric acid, phosphine 24, N,O,, NO,
only P—P linkage. » MgSO,-7H,0, BaSO,.
. True 10. True 11. True
12. False. Acidic character decreases while basic character
increases down the group and therefore, As,O, is acidic 1. increases 2. seesaw 3. ammonium nitrite
while Sb,O, is amphoteric. 4, basic 5. +6 6. less a< Fy
8. anode 9. more 10. conc. sulphuric acid
13. False. Br, is produced instead of HBr because HBr is
11. calcium chlorate 12. stronger 13. temporary
a stronger reducing agent than H,SO,. Therefore, HBr
14, lower 15. stronger 16. fluorine 17. sp°d
reduces H,SO, to SO, and is itself gets oxidised to Br,,.
18. argon 19. XeOF, 20. more.

Higher Order Thinking Skills

=_ a Advanced Level
QUESTIONS WITH ANSWERS
Q.1. Why is SO, a better reducing agent in alkaline SO, +2H,O == H,SO,+2H
medium than in acidic medium ?
Alkali neutralizes the acid (H,5O,) and shifts the equilibrium
Ans. SO, acts as a reducing agent because of the liberation in the forward direction producing more nascent hydrogen.
of nescent hydrogen in the presence of moisture : However, in acidicmedium, the equilibrium issuppressed resulting
a 71132 MODERN’S abc + OF CHEMISTRY-XII

inalesser amount ofnascent hydrogen. Consequently, SO, is better (A) on heating with KOH liberates phosphine (C) which is
reducing agent in alkaline medium than in the acidic medium. poisonous gas with rotten fish smell.
Q.2. Elemental phosphorus does not exist as P, like B+ SKOH + 3H) ——+ PH, + 3KH,PO,
N,. Why? Phosphine
Ans. Nitrogen has a strong tendency to form multiple bonds (C)
because of its small size and high electronegativity. Therefore, White phosphorus (P,) burns with excess of Cl, to form
phosphorus pentachloride (D).
it exists as a diatomic molecule, N=N. On the otherhand,
phosphorus because of its large size and small electronegativity P,+10cl, —, APCI,
does not show any tendency to form multiple bonds and therefore, (D)
diatomic molecule like P=P is not formed. Instead, it prefers Hydrolysis of (D) gives phosphoric acid (E).
to form stable tetra atomic, P, molecules in which each Pis linked PCI, + 4H,@ ==» H,PO, + 5HCI
to three other P atoms by three single covalent bonds. The four (FE)
atoms in P, molecule lie at the corners of a regular tetrahedron.
Q.8. Concentrated sulphuric acid is added followed
Q.3. H,PO, and H,PO, act as good reducing agents but by heating to each of the following test tubes labelled
H,PO, does not. Why? (1)to (v).
—, ——$—,

Ans. The structures of H,PO,, H,PO, and H,PO, are:

| | |
O O

JIN UZIN LZIN OH

!
iF et Se a ’ ag

Cane Sodium Copper Sulphur’ Potassium

OH HO HO sugar bromide turnings powder chloride
Hypophosphorous Phosphorous Phosphoric
Identify in which of the above test tube the following
acid (H,PO,) acid (H,PO,) acid (H,PO,)
change will be observed. Support your answer with the
Due to the presence of P—H bonds, both H,PO, and H,PO, help of a chemical equation.
act as reducing agents. On the other hand, H,PO, does not (a) Formation of black substance
have any P—H bond and hence it does not act as a reducing agent. (6) Evolution of brown gas
Q.4. Why is nitrous oxide called laughing gas ?
(c) Evolution of colourless gas
Ans. When nitrous oxide(N,O)1is inhaledin minor quantities,
it causes hysterical laughter and therefore, it is called laughing (d) Formation of brown substance which on dilution
gas. becomes blue.

Q.5. What is the action of heat on (e) Disappearance of yellow powder along with
(4) Pyrophosphoric acid evolution of colourless gas.
(41) Metaphosphoric acid Ans. (a) In test tube (z) because of charring
(411) Phosphorous acid
Ans. (1) Pyrophosphoric acid (H,P,0,) on heating gives C410, ris tnoe i26
metaphosphoric acid. Black residue
H,P,0, —> 2HPO, + H,O (6) In tube (iz) because of evolution of brown gas
Metaphosphoric acid
2 NaBr + 3H,5O,——> 2NaHSO,+50, + Br, + 2H,O
(71) Metaphosphoric acid (HPO,) on heating gives phosphorus
pentoxide. (Brown gas)
2HPO, —fA@PoSs tf H,O (c) In tube (v) because of evolution of HCl gas
Phosphorus
pentaoxide KCl + H,SO, ——> KHSO,+ HCl
(1z2t) Phosphorous acid (H,PO,) on heating gives phosphine (d) In tube (i112), first the brown substance is presumably a
and phosphoric acid. mixture of unreacted copper turnings and colourless anhydrous
4H,PO, 8F°, 3H,.PO, + PH, copper sulphate. This brown substance on dilution turns blue
Phosphoricacid Phosphine due to the formation of hydrated copper sulphate.
Q.6. What structures does PCI. adopt in the solid Cu + 2H,SO, ——+ CusO, + SO, + 2H,O
state and vapour state ?
Ans. In the solid state PCl. is ionic compound consisting of CuSO, + 6H,O ——> CuSO,.6H,O
[PC1,]* (tetrahedral) and [PC1,]- (octahedral)ions. In vapour state, Hydrated copper sulphate (blue)
PCl, is monomeric having trigonal bipyramidal geometry.
(e) In tube (tv) due to evolution of SO,
Q.7. A translucent white waxy solid (A) on heating in
an inert atmosphere is converted to its allotropic form 8S + 2H,SO, ——> 350, + 2H,O
2
(B). Allotrope (A) on reaction with very dilute aqueous (Colourless pungent gas)
KOH liberates a highly poisonous gas (C) having rotten
Q.9. When a mixture of ammonium chloride and
fish smell. With excess of chlorine forms (D) which hy-
drolyses to compound (E). Identify compounds (A) to (E). potassium dichromate are heated, a stable colourless gas
Ans. (A) The white waxy solid (A) is white phosphorus. (A) was evolved which did not support combustion but
When white phosphorus is heated in an inert atmosphere magnesium continued to burn in it. The gas (A) reacted
at 573K, it changes to red phosphorus. with calcium carbide in an electric furnance forming a
(B) is red phosphorus. solid (B). The compound (B) was slowly hydrolysed by
p-BLOCK ELEMENTS

water forming an insoluble substance (C) and the solution

Cu + 4HNO, —“*> Cu(NO,), +2NO,1 + 2H,O
of substance (D) which turned Nessler’s reagent brown.
Brown gas
Identify (A) to (E) and give the reactions involved.
(A)
Ans.
(i) K,Cr,O, +2NH,Cl > (NH,),Cr,0, + 2KCl On cooling the gas A changes into a colourless gas (B), N,O,.
Ammonium dichromate
2NO, ——N,0,
(NE )Cr,0. __Heat_, N, + Cr,O, + 4H,O
(A) (B)
(A)
Q.11. Why does NCI, on hydrolysis give NH, and
N, does not support combustion but Mg burns in it
HOCI while PCI, on hydrolysis gives H,PO, and HCl.
3Mg+N, —Het, Mg.N,
(tz) Gas (A) reacted with CaC, Ans. This is because N does not have d-orbitals to accom-
modate the electrons donated by O of water. Therefore, attack of
CaC, +N, —@ CaCN, H,0O occurs on Cl atom which has d-orbitals to accommodate the
(B) extra electrons donated by H,O. As aresult, C1—O bond 1s formed
Calcium cyanamide leading to the formation of NH, and HOCI.
CaCN, + 3H,Q ——> CaCO,+2NH,
(C) (D)
(zit) D reacts with Nessler’s reagent to give borwn colour as
|
NH, + 2K,Hgl, + 3KOH ——-~ H,NHgOHgI+7KI+2H,O Cl
Nessler’s reagent Brown ppt.

Per)
Cl1— N ——~> 38HOCl+NH,
Q.10. When conc. H,SO, was added to an unknown
salt present in a test tube, a brown gas (A) was evolved. "| Ce
The gas intensified when copper turnings were also
added into this test tube. On cooling the gas A changed
into a colourless gas (B). H H
(4) Identify the gases (A) and (B). On the other hand, P and Cl both have d-orbitals to
accommodate electrons donated by H,O. But P—O bond is much
(it) Write the equations for the reactions involved.
stronger than Cl—O bond. Therefore, attack of H,O molecules
Ans. The given salt is a nitrate salt which on reaction with occur preferentially on P of PCI, to form H,PO, and HCl.
conc. H,5O, gives first vapours of HNO, which decompose to give HY “i
brown gas (NO,).
a. a C] +O Oy
2NaNO,+H,SO, —“*> Na,SO,+2HNO, — Cl—__p” ——-» —. —>
Colourless
Cl Cl
H
4HNO, —“> 4NO, + 2H,0+0,
Brown gas
(A) OH a OH
Cl—p—cl—=2>clI—-P > HO—P
+H,0 +H,0
The gas intensified when copper turnings were added due to
reduction of HNO, by Cu. OH OH
or PCI, +3H,O0 —» H,PO, + 3HCl

aa Revision Exercises
9. Which xenon compound is isostructural with ICL, ?
> Very Short Answer al SCTE [carrying
carrying 1Imark
mark |
| <4
(CBSE Sample Paper 2011)
Out of H,O and H,8 which has higher boiling point ? 10. Which one of PCl; and PCl, is not likely to exist and
: Arrange HCIO, HBrO and HIO in the decreasing order of why? (D.S.B. 2012)
their acidic strength. 11. Of PH, and H,S which is more acidic and why?
3. Which halogen has a tendency to form cation? (D.S.B. 2012)
4, What happens when sulphur heptoxide dissolves in 12. NH, has higher boiling point than PHg.
water?
(Chhatisgarh S.B. 2013)
5. Why is yellow phosphorus kept under water?
13. What happens when chlorine gas is passed through a hot
6. Give one example in which ammonia acts as an oxidising concentrated solution of NaOH? (Assam S.B. 2012)
agent.
14. Mention the basicity of H,PQ,. (Assam S.B. 2016)
7. Molten ICl, has high electrical conductivity. Explain.
15. Write the disproportionation reaction of H,PQO,.
(D.S.B. 2010)
8. Draw the structure of XeF, molecule. (D.S.B. 2011) (Assam S.B. 2013)
a 71134 MODERN'S abe + OF CHEMISTRY
-AXII

16. What is the covalency of nitrogen in N,O, ? (D.S.B. 2013) oO”. Which of the following oxide of nitrogen is called laughing
17. Draw the structure of H,PO, and explain why it is gas ?
monobasic. (Mizoram S.B. 2014) (a) NO, (6) N,O
18. What is the basicity of H,PO,? (D.S.B. 2015) (c) N,O, (d) NO, (.P.S.B. 2015)
19. Todine is more soluble in KI than in water. Why? 40. Among the following, which is the strongest oxidising
(Karnataka S.B. 2018) agent?
20. Complete the following equation: (a) Br, (b) I,
DOR eee: + 2HF (c) Cl, (d) F, (1. P.S.B. 2015)
(Karnataka S.B. 2018) Al. The basicity of H,PO, 1s
21. N, 1s known whereas P, is not known. Why? (a) 1 (b). 2
(Meghalaya S.B. 2018) (c) 3 (d) 4 (.P.S.B. 2016)
The basicity of phosphorous acid H,PO, is
»> CBSE QUESTIONS ‘<4 (a) Two
(c) One
(6) Three
(d) Zero (A.P.S.B. 2016)
22. Why is Bi(V) a stronger oxidant than Sb(V) ?
Which of the following is a neutral oxide of nitrogen?
(A.L.S.B. 2008; D.S.B. 2009)
(a) N,O (6) N,O,;
23. Nitrogen is relatively inert as compared to phosphorus.
Why ? (A.L.S.B. 2010) (c) NO, (dq) N,O, (Kerala S.B. 2017)
24, Fluorine does not exhibit any positive oxidation state. Among the trihalides of nitrogen, which one is least basic?
Why ? (A.L.S.B. 2010) (a) NI, (o) NBr,
205. Which is stronger reducing agent; SbH, or BiH, and why? (c), NCI, (dq) NF; (Mizoram S.B. 2017)
PASS aoe) The correct order of thermal stability of hydrogen halides
26. Name two poisonous gases which can be prepared from (FLX) is
chlorine gas. (A.fS_B. 2013) (a) HI > HBr > HCl > HF
27. What is the basicity of H,PO, and why ? (6) HF > HCl > HBr > HI
(A.LS.B. 2018, 2014) (c) HCl < HF < HBr < HI
28. Why does NH, act as a Lewis base? (A.LS.B. 2014) (7d) HI > HCl > HF > HBr (7.P.S.B. 2017)
29. Why does NO, dimerise? (A.LS.B. 2014) 46. Maximum covalency of nitrogen is :
350. Out of white phosphorus and red phosphorus, which one (a) 3 (b) 6
is more reactive and why? (ATSB. 2005) (c) 4 (d) 6 (Ar.S.B. 2017)
ol. On heating Pb(NO,), a brown gas is evolved which Al. In the following compounds which has minimum boiling
undergoes dimerization on cooling. Identify the gas. point?
(A.LS_B. 2016) (a) H,Se (6) H,Te
3o2. Write the formula of the compound of sulphur which is (c) H,O (d) H,8 (Ar.S.B. 2018)
obtained when conc. HNO, oxidises 8,. (AJ.S.B. 2017) The shape of XeF,, is
oo. Write the formula of the compound of phosphorus (a) square planar (6) tetrahedral
which is obtained when conc. HNO, oxidises Pa. (c) square pyramidal (d) trigonal bipyramidal
(ALS. AgQ0T7) (Mizoram S.B. 2018)
34, Write the formula of the compound of iodine which is
49, In the following which is dibasic acid?
obtained when conc. HNO, oxidises 1,. (A.J.S.B. 2017)
(a) H,PO, (6) H,PO,
(c) H,PO, (d) HClO,
MCQs from State Boards’ Questions (Ar. S.B. 2018)
3D. Which of the following compounds contains S—O and oO. In the following strongest reducing agent is:
©=5S bonds ? (a) PH, (6) BiH,
(a) Sulphuric acid (6) Thiosulphuric acid (c) SbH, (d) AsH,
(c) Sulphurous acid (d) Thiosulphurous acid. (Ar. S.B. 2018)

36.
oxidation state ?
(Maharashtra S.B. 2013)
Which of the following halogen shows only negative
> Short Answer Questions
1. Describe the trends in the elements of group 16 in order of
<4
(a) Chlorine (6) Bromine increasing atomic number:
(c) Fluorine (d) Iodine (t) Atomic radu (11) lonisation energy
(Meghalaya S.B. 2013, 2014) (zit) Oxidation state (iv) Catenation
of. Which of the following is the strongest acid? (v) Allotropy
(a) H,O (6) HS (Meghalaya 8.5. 2013, Jammu S.B. 2015)
(c) H,Se (dq) H,Te Draw the structures of white phosphorus and red
(Meghalaya S.B. 2014) phosphorus. Which one of these two types of phosphorus
38. The oxoacid of halogen having maximum acidic character 1s more reactive and why ? (D.S.B. 2010)
15 State reasons for each of the following :
(a) HClO, (6) HCIO, (1) The N—O bond in NO, is shorter than the N—O
(c) HClO, (d) HCIO bond in NO...
(Mizoram S.B. 2015) (iz) SF, 1s kinetically an inert substance.
p-BLOCK ELEMENTS

Or 14, (a) NCI, gets readily hydrolysed while NF, does not.
tate reasons for each of the following : Explain.
() All the P—Cl bonds1in PC1, molecule are not equivalent. (b) Write the structure of H,PO, and explain its diprotic
(it) Sulphur has greater tendency for catenation than nature. (Mizoram S.B. 2018)
oxygen. (D.S.B. 2011) 15. (a) stability of +5 oxidation state decreases and that. of
+3 oxidation state increases down the 15th group
. Draw the shape of P,O,,. element. Explain.
(a) Halogens are highly reactive. Why ? (b) H,PO, acts as a good reducing agent while H,PO,
(6) Complete the reaction : does not. Why? (Kerala S.B. 2018)
Al PEs? 16. (a) What is the formula of phosphine?
(c) Compare the acidic character of HCIO,, HC1O,, HCIO, (db) How is phosphine prepared in laboratory?
and HCI1O. (H.P S.B. 20183) (Kerala S.B. 2018)
. (a) Draw structures of H,PO, and H,PO, molecules. 17. (a) (1) NH, 1s astrong base but NF, does not show any
Also give their basicity. basic property. Why?
(6) Discuss abnormal behaviour of nitrogen. (it) What is laughing gas?
(Hr. S.B. 2018) (db) Draw the structure of XeF’,. What is the state of
(7) HF is a liquid while HCl, HBr and HI are gases. hybridisation of Xe in it? (Pb.S.B. 2015)
Explain. 18. (a) Why does bond angle decrease in the hydrides of
(11) How is nitric acid manufactured by Ostwald process? nitrogen family while going down the group?
Write the chemical equations involved. (db) Why are halogens coloured?
(Mizoram S.B. 2014) (c) How will ozone oxidise the following:
Kither (z) Lead sulphide to lead sulphate.
(a) Write the balanced chemical equation for the reaction (it) Potassium nitrite to potassium nitrate?
of CL, with hot concentrated NaOH. Is this reaction (Pb.S.B. 2015)
a disproportionation reaction? Justify. 19. (a) Why is ammonia more basic than phosphine?
Or (b) What is tailing of mercury?
(6) OF, should be called oxygen difluoride and not (c) All the five bonds in PCI, are not equivalent. Justify.
fluorine oxide. Why? (Meghalaya S.B. 2014) (d) H,PO, is monoprotic acid. Explain.
Give reason: Lr
(a) H,PO, is triprotic acid but H,PO, 1s diprotic acid. (a) Halogens have maximum negative electron gain
Why? enthalpy in their respective periods of the periodic
table. Explain.
(6) NCI, and PCI, are hydrolysed differently. Why?
(b) How will ozone oxidise the following:
(Pb. S.B. 2018)
(t) Copper sulphide to copper sulphate.
Explain, why
(it) Potassium manganate to potassium
(a) O, acts as a powerful oxidising agent. permanganate. (Pb.S.B. 2015)
(6) Why are the elements of Group 18 known as noble 20. (a) Explain why moist chlorine can bleach dry coloured
gases? articles but dry chlorine cannot.
Or
(b) Write down the structure of SO, and state with reason
(a) Why does NH, act as a Lewis base? whether it is polar or non-polar. (Kolkata S.B. 2016)
(6) Bond angle in NH,* is more than that in NH,. 21. (a) Complete the following reactions:
(H.P. SB. 2014) (t) NaOH (hot, conc.) + Cl, (¢) —>
10. Account for the following:
(iz) P, + SO, Cl, —>
(a) PCl, is more covalent than PCl.,.
(tit) NH,(excess) + Cl, —>
(6) Iron on reaction with HCI forms FeCl, and not FeCl,.
(b) Draw the structural formula of H,PO,. How do you
(c) The two O—O bond lengths in the ozone molecule are account for the reducing behaviour of H,PO, on the
equal. (D.S.B. 2014) basis of its structure?
11. Account for the following: Or
(a) Bi(V) is a stronger oxidizing agent than Sb(V). (a) When HCI reacts with finely powdered iron, it forms
(6) N—N single bond is weaker than P—P single bond. ferrous chloride and not ferric chloride. Explain why?
(c) Noble gases have very low boiling points. (b) What are interhalogen compounds? Give a method
(D.S.B. 2014) of preparation of any one interhalogen compound.
12. (a) Draw the structures of the following compounds: (Assam S.B. 2016)
(7) XeF, (iz) NO, 22. (a) Why is N, less reactive at room temperature?
(6) Write the structural difference between white (b) Explain why NO, dimerises. (Assam S.B. 2018)
phosphorus and red phosphorus. (D.S.B. 2014) 23. (a) Why does phosphorus exist as P, and nitrogen exists
135. () Explain the basic strength of hydrides of group 15 as N, gas?
elements. (b) Why has concentrated sulphuric acid high boiling
(zt) Give reason for the following: point?
(a) Nitrogen does not form pentahalide like phosphorous. (c) Fluorine exhibits only —1 oxidation state whereas
(6) Electron gain enthalpy of chlorine is higher than other halogens also show + 1, +3, +5 and +7 oxidation
fluorine. (Nagaland S.B. 2018) states. Explain. (H.P.S.B. 2016)
a 7/136 MODERN'S abe + OF CHEMISTRY
-AXII

24, Describe the Contact process for the manufacture of

sulphuric acid. (Jharkhand S.B. 2016)
(et) She el) kes ecco + 2HF
25. (a) What are interhalogen compounds? Give examples.
(Karnataka S.B. 2018)
(Ar.S.8. 2018, Jammu S.Z. 2018, Assam S.B. 2018)
356. (a) Write the chemical equation of the following reactions:
(6) Why are interhalogen compounds more reactive than
(1) Preparation of XeO, from XeF,.
halogens? (Ar.S.B. 2018)
(it) Mixing PtF, and Xe.
26. (a) Draw the structures of the following:
(d) H,0O 1s less acidic than H,S. Why?
(i) XeF,
(Kerala S.B. 2018)
(it) BrF,
of. (t) How is XeF’, prepared?
(b) HO, H,5, H,Se and H,Te, Arrange these in their
(11) Mention the types of hybridization of Xe in XeF’, and
increasing acidic character.
XeOF,,. Draw their structures.
(c) Bond dissociation energy of F’, is less than that of Cl.,.
(Nagaland S.B. 2018)
Why? (Ar.S.B. 2018)
38. Give reasons :
27. (a) Give the geometry of XeQ,.
(t) Thermal stability decreases from H,O to H,Te.
(bd) Describe the manufacture of H,5O, by Contact
process. (21) Fluoride ion has higher hydration enthalpy than
chloride ion.
(c) What is the basicity of H,PO, ?
(d) PCl, exists, while NCI, does not exist. Why ? (111) Nitrogen does not form pentahalide. (D.S.B. 2017)
(e) What is tincture of iodine and what is it used for? 359. Complete the following chemical equations :
(H.P.S.B. 2017) qr, n2crs—
28. (a) Discuss the structure of PF.. (tt), 2XeH) #2H,O —>
(b) What are main reasons for anomalous properties of Or
nitrogen ? What happens when
(c) How will you prepare HNO, by Ostwald process ? (1) HClis added to MnO,?
(Hr. S.B. 2017, Nagaland S.B. 2017) (71) PCI, is heated?
29. (a) Why does CIF, exist but FCI, not? Write the equations involved. (D.S_B. 2017)
(db) Why is IC1, more reactive than I,? (a) What are noble gases? Give any two reasons for the
(c) Using VBT theory describe shape of XeQO,. inertness of noble gases. (Mizoram S.B. 2018)
(Pb.S.B. 2018) (b) Why does fluorine show only —1 oxidation state
350. (a) Draw the structure of XeF,,. whereas other halogens show positive oxidation states
also? (Mizoram S.B. 2018, Assam S.B. 2018)
(bd) Define interhalogen compounds.
Draw structure of SF.
41. (a) Explain the various oxidation states of Group 17.
(c)
(db) What happens when chlorine is treated with slaked
(d) H,SO, is viscous in nature, why? (4.P.S.B. 2018)
lime and turpentine?
ol. (a) Interhalogens are more reactive than halogens, why?
(c) Write electronic configuration of noble gases.
(d) Out of HC1O and HBrO which is more acidic? (Jammu S.Z. 2018)
(c) Draw the shape of CIF. (A.P.S.B. 2018) 42. (i) Why is H,O a liquid and HS a gas at normal
32. Give reasons for the following: temperature?
(a) Bleaching by chlorine is permanent, while that by (21) What is oleum?
sulphur dioxide is temporary.
(111) Why have noble gases very low boiling points?
(db) NH, acts as a Lewis base.
(Assam S.B. 2018)
(c) NO, dimerises.
(d) In the reaction between HC] and powdered iron, ferric
chloride is not formed. (Assam S.B. 2017)
»> CBSE QUESTIONS <4
oo. (a) Draw the structure of H,5,O,. What 1s the oxidation 43. How would you account for the following :
state of sulphur in it? (t) NCI, is an endothermic compound while NF, is an
exothermic one.
(d) Write the balanced chemical equations for the following: (it) XeF, 1s a linear molecule without a bend.
(1) Excess of ammonia with chlorine (zit) The electron gain enthalpy with negative sign for
(it) Conc. H,5O, with calcium fluoride fluorine is less than that for chlorine, still fluorine
(Meghalaya S.B. 2018) is a stronger oxidising agent than chlorine.
34. Ozone is an oxidising as well as reducing agent.
(A..S.B. 2010)
44, How would you account for the following :
Support the statement by giving one example of each.
(Manipur S.B. 2017) (1) H,S is more acidic than H,O.
3D. Complete the following equations: (iz) Both O, and F, stabilize high oxidation states but
the ability of oxygen to stabilize the higher oxidation
(a) 2NaQH + Cl, — NaCl 4+ 2.0... + H.O
state exceeds that of fluorine. (A.LS.B. 2011)
(b) Nao 4+ 2QHCI1 - 2NaCl + H,O eee ee ee
p-BLOCK ELEMENTS

(zit) NF, is an exothermic compound but NCI, is not. Or

(iv) The acidic strength of compounds increases in the order : (d) Write down the preparation of ozone from oxygen.
Pie Bee EI Mention the conditions required to maximize the yield
of ozone.
(v) SF, is kinetically inert. (A.S.B. 2017)
(e) Write the structural formula of PCI, in solid state and
45. Give reasons for the following :
also indicate the hybridisation of phosphorus atoms.
(t) Where R is an alkyl group RK,P = O exists but
(f) What happens, when sulphur is treated with conc.
R,N = O does not.
HNO,? (Meghalaya S.B. 2014)
(it) PbCl, is more covalent than PbCl.,.
. (a) Give reasons for the following:
(121) Atroom temperature, N, 1s much less reactive.
() Bond enthalpy of F, is lower than that of Cl.,.
(A.LS_B. 2013)
(it) PH, has lower boiling point than NH,.
46. Give reasons for the following :
(6) Draw the structures of the following molecules:
(t) Though nitrogen exhibits +5 oxidation state, it does
(1) BrF, (11) (HPO,), (tit) XeF,
not form pentahalide.
Or
(it) Electron gain enthalpy with negative sign of fluorine
(a) Account for the following:
is less than that of chlorine.
(1) Helium is used in diving apparatus.
(111) The two oxygen-oxygen bond lengths in ozone molecule
are identical. (A.LS.B. 2013) (tt) Fluorine does not exhibit positive oxidation state.
(111) Oxygen shows catenation behaviour less than
47. Give reasons for the following:
sulphur.
(a) (CH,),P = O exists but (CH,),N = O does not.
(6) Draw the structures of the following molecules.
(6) Oxygen has less electron gain enthalpy with negative
(i) XeF, (22) H,5,0, (D.S.B.2013)
sign than sulphur.
Either
(c) H,PO, 1s a stronger reducing agent that H,PO,.
(a) Write the principle and conditions involved, giving
Ant er)
stepwise reactions, in the manufacture of H,SO, by
48. (a) Complete the following equations:
Contact process.
(Ct he conc)
(6) Give two examples of amphoteric oxide.
(i) XeF, + H,O —>
(c) HCl reacts with powdered Fe to give FeCl, and not
(6) Draw the structures of the following molecules:
FeCl,. Why?
(1) XeO, (} HLS, Pas Baie) (d) Give the chemistry of brown ring test.
49, Assign reason for the following: Or
(t) H,PO, is a stronger reducing agent than H,PO,.
(a) Mention the conditions required to maximise the yield
(it) Sulphur shows more tendency for catenation than
of ammonia 1n its synthesis by Haber’s process.
oxygen.
(121) Reducing character increases from HF to HI. (6) Which form of sulphur shows paramagnetism and
(A.IS.B. 2016) why?
50. Give reasons for the following : (¢) Unhke HCl, why HBr cannot be prepared by the action
(t) Red phosphorus is less reactive than white phosphorus. of concentrated sulphuric acid on sodium bromide?
(it) Electron gain enthalpies of halogens are largely Explain.
negative. (d) Write the reaction of white P with NaOH solution.
(iii) N,O, is more acidic than N,O,. (A.L.S.B. 2017) (Maghalaya S.B. 2014)
ol. (t) Draw the structures of the following : (a) State the hybridisation of the central atom and draw
the structure of PCl, and H,SO,.
(a) ESO, (6) HClO, (AI SB. 2077)
(it) Draw the structures of the following : (6) The first ionisation enthalpy of nitrogen is higher than
that of oxygen but the second ionisation enthalpy is
(a) XeF, (6) BrF. tae een Maung,
higher in oxygen than that of nitrogen. Explain.
52. Draw the structures of the following :
Or
Is Feb Bi (i) XeF, [Aer Boe (a) Give the laboratory preparation of sulphur dioxide
Da. Among the hydrides of group 15 elements, which have and write the chemical reaction involved.
the (6) SF4 is easily hydrolysed while SF, is not easily
(a) lowest boiling point? hydrolysed. (Mizoram S.B. 2015)
(6) maximum basic character? (a) Although electron gain enthalpy of fluorine is less
(c) highest bond angle? negative as compared to chlorine, fluorine is stronger
(dq) maximum reducing character? (A.LS.B. 2018) oxidizing agent than chlorine. Why?
(6) Dry chlorine does not act as a bleaching agent. Why?
Long Answer Questions <A (c) Why is H,PO, tribasic and H,PO, dibasic?
Or
(a) Write down the steps involved in the manufacture of (a) Why is ICI] more reactive than I, ?
HNO, by Ostwald process.
(6) Nitrogen exists as diatomic molecule, N, and
(6) Draw the structure of HCIO,. What is the oxidation phosphorus as P,. Why?
number of Clin this compound? Write the formula of (c) Write the principle and conditions involved giving
oxyacid of Cl in its +5 oxidation state. stepwise reactions in the manufacture of H»SO, by
(c) Write the reaction of XeF, with H,O. Contact process. (Meghalaya S.B. 2015)
a 7/138 MODERN'S abe + OF CHEMISTRY
-AXII

6. (a) Account for the following: (b) Explain with reasons:

(z) Acidic character increases from HF to HI. (:) HS is more acidic than H,O.
(it) There is large difference between the melting and (11) The electron affinity of chlorine is higher than
boiling points of oxygen and sulphur. that of fluorine.
(iit) Nitrogen does not form pentahalide. (111) Red phosphorus is more stable than white
phosphorus. (Tripura S.B. 2016)
(d) Draw the structures of the following: 10. (a) Account for the following:
(7) CIF, (11) XeF, (:) NH, acts as a Lewis base.
Or (iz) PCl, fumes in moist air.
(a) Which allotrope of phosphorus is more reactive and (111) Fluorine shows only —1 oxidation state.
why? (d) (1) Suggest any two fluorides of xenon.
(0) How are the supersonic jet aeroplanes responsible for (11) Write a method to prepare any one of the above
the depletion of ozone layer? mentioned xenon fluorides.
(c) F, has lower bond dissociation enthalpy than Cl,. Or
Why? (a) Account for the following:
(d) Which noble gas is used in filling balloons for (:) H,O 1s a liquid while H,5 is a gas.
meteorological observations ?
(11) Noble gases have very low boiling points.
(e) Complete the equation:
(tit) NO, dimerises to N,O,.
XeF, + PF,——> (D.S.B. 2015)
(d) (1) What are interhalogen compounds?
7. (a) Give the structure and basicity of H,PO,.
(11) Suggest any two examples of interhalogen
(b) SF, is known but SCI, is not. Why? compounds. (Kerala S.B. 2016)
(c) Give the shape of IF,. 11. (a) (:) Explain the steps involved in the manufacture of
sulphuric acid by Contact process.
Or
(it) Arrange the following oxoacids in decreasing order
(a) Why does nitric acid act as an oxidising agent? How of acidic strength: HClO, HC1O,, HC1O,, HCIO,,.
it oxidises Or
(t) carbon to carbonic acid (d) (1) How is XeF’, prepared?
(11) sulphur dioxide to sulphuric acid. (it) Draw the structures of XeF,, XeF,, XeOF,, and
mention the type of hybridization of Xe in each
(d) Give the structure of XeOF, and state of hybridization case. (Nagaland S.B. 2016)
of Xe in it. (Pb.S.B. 2016)
12. (a) Account for the following:
8. (a) Give the structure and basicity of H,PO..
(1) Ozone is thermodynamically unstable.
(b) SF, is known but 5H, is not. Why? (iz) Solid PC1, is 10n1c in nature.
(c) Give the shape of IF... (111) Fluorine forms only one oxoacid HOF.
Or (b) Draw the structure of

(a) Why does nitric acid act as an oxidising agent? How (1) BrF, (ii) XeF,
it oxidises Or
(z) sulphur to sulphuric acid. (a) Compare the oxidising action of F’, and Cl, by
considering parameters such as bond dissociation
(11) ferrous sulphate to ferric sulphate.
enthalpy, electron gain enthalpy and hydration
(d) Give the structure of XeO,F, and state of hybridization enthalpy.
of Xe in it. (Pb.S.B. 2016) (6) Write the conditions to maximize the yield of
9. (a) Write the structure of the following compounds: H,SO, by Contact process.
(2) H,8,0, (11) XeF, (c) Arrange the following in the increasing order of
property mentioned:
(dD) Explain with reasons:
(a) H,PO,, H,PO,, H,PO, (Reducing character)
(:) The negative electron gain enthalpy of oxygen is
less than that of sulphur. (6) NH,, PH,, AsH,, SbH,, BiH, (Base strength)
(D.S.B. 2016)
(it) the reducing power of phosphine is higher than
that of ammonia. 13. (a) PbCl, is known but PbCI1, is not known. Explain with
inert pair effect.
(zi) The majority of known noble gas compounds are
(b) Why is SF, much less reactive than SF, ?
those of xenon.
(c) Give hybridization and draw structure of XeF,,.
Or
Or
(a) Write the structures of the following compounds: Draw flow chart for Haber’s process for the
(a)
(t) H,PO, (iz) HClO, manufacture of ammonia.
p-BLOCK ELEMENTS

(b) Write down the reaction of ozone with potassium (c) H,S acts only as a reducing agent but SO, acts both
nitrite. as a reducing agent as well as an oxidizing agent.
(ce) Draw structure of IF... (Pb.S.B. 2017) Why? (Meghalaya S.B. 2018)

»>
14, (a) Unlike phosphorus, nitrogen shows little tendency
for catenation. Why? o}=f) =e] 0)oye)\tS <4
(b) SF, is known but 5H, is not known. Explain. 19. (a) Draw the structures of the following molecules :
(ce) Give hybridization and draw structure of XeF,. (:) HPO, (zt) CIF,
Or
(6) Explain the following observations :
(a) Explain the steps involved in manufacture of
sulphuric acid by Contact process. (1) Nitrogen is much less reactive than phosphorus.
(b) Write down the reaction of ozone with potassium (11) Despite having greater polarity, hydrogen fluoride
iodide. boils at a lower temperature than water.
(ce) Draw structure of CI1F,. (Pb.S.B. 2017) (111) Sulphur has greater tendency for catenation than
15. (a) Give a laboratory method of preparation of dinitrogen. oxygen in the same group.
(Assam S.B. 2017) Or
(b) Complete the following chemical equations (a) Draw the structures of the following molecules :

Mes he (7) N,O, (iz) HClO,

(6) Explain the following observations :
(ii) Ba(N,), decomposition (1) H,S is more acidic than H,O
(iii) (NH,),Cr,0,, Beat, ........ HF Sectetre LO (it) Fluorine does not exhibit any positive oxidation
(Assam S.B. 2017) state.
Or (111) Helium forms no real chemical compound.
(a) Explain why HNO, behaves both as oxidising as well (ALES 2072)
as reducing agent. (Assam S.B. 2017)
20. (a) Account for the following:
(b) Give chemical equations for the following processes :
(1) Interhalogens are more reactive than pure halogens.
(t) Decomposition of ozone at 523 K.
(iz) N, is less reactive at room temperature.
(it) Ozone oxidises lead sulphide to lead sulphate.
(tit) Reducing character decreases from NH, to BiH.
(zit) Ozone reacts with aqueous solution of potassium
iodide to liberate iodine. (Assam S.B. 2017) (6) Draw the structures of the following:
16. (a) Mention the conditions required to maximize the yield (1) H,P,O, (Pyrophosphoric acid)
of ammonia in its synthesis by Haber’s process. 7.
(b) Draw the structure of HCIO,. Or
(ce) Why does PCl, fume in moisture? (a) Which poisonous gas is evolved when white phosphorus
(d) Halogens have the maximum negative electron gain is heated with conc. NaOH solution? Write the chemical
enthalpy in the respective periods of the periodic equations involved.
table. Why? (6) Which noble gas has the lowest boiling point ?
Or (c) Fluorine is a stronger oxidizing agent than chlorine.
(a) Draw the structure of H,PO,. How do you account for Why?
the reducing behaviour of HPO, on the basis of its (d) What happens when H,PO, is heated?
structure ? (e) Complete the equation:
(b) What happens when (NH,), Cr,O0, is heated?
PbS + O, ———> (A. S_.B. 2075)
(c) How does ammonia react with a solution of Cu?*?
21. (a) Give reasons:
(d) Explain why fluorine forms only one oxoacid, HOF.
(.) When CL, reacts with excess of F,, CIF, is formed
(Meghalaya S.B. 2017)
and not FCIl,.
17. (a) F-atom is more electronegative than I-atom, yet HF (it) Dioxygen is a gas while sulphur is a solid at room
has lower acid strength than HI. Why? temperature.
(d) Explain why oxygen is a gas while other members of (6) Draw the structures of the following:
the same group are solids.
(i) XeF,
(c) For interhalogens of the type AX, (A, X = halogen (iz) HClO,
atoms; n = 1 or 3 or 5 or 7), what relation exists
between A and X ? How does their reactivity vary (c) Arrange the following in the decreasing order of their
reducing character:
with individual halogens? (Meghalaya S.B. 2018)
HF, HCL Gr, Hl
18. (a) Bleaching of flowers by chlorine is permanent while
that by sulphur dioxide is temporary. Explain. (d) Complete the following reaction:

(d) OF, should be called oxygen difluoride and not XeF, + SbF, ——> (A.L.S.B. 2018)
fluorine oxide. Why?
 MODERN'S abe + OF CHEMISTRY
-AXII

ints & Answers

for Revision Exercises
Very Short Answer Questions | a a ei form a soluble complex.
...
—————— ST ———_ 5

1. H,O because of hydrogen bonding 20. XeF,

2. HClO > HBrO > HIO . 3. lodine. XeF, + O,F, 143K XeF, +O,
4. Forms persulphuric acid 5,0; + H,O > H5.05 25. BiH, because BiH, is less stable than SbH, because of
5. Because it catches fire 1n air. larger size of Bi than Sb.
fp The high nena sayy of ICl is due to its ionization into 26. (i) Phosgene (COCI,)
ICL, and ICI, ions. (ii) Mustard gas (CICH,CH,SCH,CH,C)
2ICls, KCl, +ICl, 27. Two, because it contains two P—OH bonds and therefore,
9. XeF, can give two H* ions. . _
10. PCI; is not likely to exist because lone pair on P in PCl, 30. White P is more reactive because of angular strain in P,
can be donated to Cl* and not to CI. molecules where the angles are only 60°
11. H,S is more acidic because of weak S — H bonds. 31. NO,
12. NH, forms hydrogen bonds but PH, does not. 2Pb(NOg), A _.92PbO + 4NO, +0,
13. On treatment with hot concentrated NaOH, Cl, undergoes
disproportionation to form sodium chloride and sodium 2NO, ——~ >N.0 4
chlorate.
0 4 45 32. H,PO, 33. H,SO, 34, HIO, oo. (db)
3Cl, + 3NaOH(ag)
——-> 5NaCl + NaClO, + 3H,O 36. (c) 37. (d) 38. (a) 39. (0)
(hot) 40. (d) Al. (a) 42. (a) A3. (a)
14. two 15. 4H,PO, ——— 3H,PO, + PH, 44, (d) 45, (b) 46. (c) AT. (c)
16. Five 18. tribasic (3) 48. (a) AQ, (5) 50. (b)

onal Useful Information and Objective Questions

Competition }ul se
- J ADDITIONAL USEFUL INFORMATION / -
IMPORTANT REACTIONS sees
era 1. 10, + 5I- + 6H* ——-+ 31, +3H,O
Complete the following reactions : 2. I, +28,0,2 ——> S,0,2-4 21
1 =10,5+1F+H* ——-> 3. 2NaClO, +1, ——> 2Nal0, + Cl,
2 §8,0,* +1, —<—2 4, XeF,+H,O ——> XeOF,+2HF
38. NaClO, +1, ——? 5. Br, + 2Nal ——-> 2NaBr +l,
4. XeF,+H,O ——; 6. PCI, + 3H,O ——-+ H,PO, + 3HCl
5. Br, + Nal ——Se ‘8 SbCl, +H,O ——> SbOCl + 2HCI
6. PCl, + H,O —_—_5 Antimony
7. SbCl,+H,O —+ oxychloride
8 Ae oC 8. As, + 3Cl, ——> 4AsCl,
" 4 2
9. SCL, +NaF y Ss. 9. 25CL, + 4NaF ——> SF,+4NaCl+5
10. H,S,0,+H,O ——> 10. H,S,0, +H,O ——> 2H,SO,
11. P,O,,+H,0 Qs 11. P,O,, +6H,O ——+ 4H,PO,
600°C 12. H,P,0, ©0°°, sHPO O
12, H,P,O, — hail + He
13. 2HPO, —Heat, P.O, + H,O
18. HPO, — + s4
a 14, XeF,, + H,Q —————} XeOF, + 2HF
14. XeF,+H,O jase —
15. NCI, 4 H,O 5 15. NCI, + 3H,O ——_—_ NH, + 3HOCI

16. HNO, +P,0,, 16. 4HNO,+P,0,, ——> 4HPO, + 2N,0,

17. Zmsdil. HNO 17, 4Zn +10HNO, (dil.) ——_> 4Zn(NO,), +6H,O +N,O
18. P+NaOH+H,0 18. P,+3Na0OH+3H,O ——-> PH, + 3NaH,PO,
19. HgCl,+PH, ; 19. 3HgCl, + 2PH, ———> Hg.P, + 6HCl
20. P, + SO,CL, ; 20. P,+10S0,Cl, ——> 4 PCI, +1080,
p-BLOCK ELEMENTS

Ans. (a) HI > HBr> HCl> HF

ARRANGE THE FOLLOWING IN THE INCREASING
ORDER OF PROPERTY MENTIONED: (i) Cl > Br, >, = 1,
(co) BeOS 10 Slo S
(a) Acidic strength (in water) : HF, HCl, HBr, HI
(d) M—F > M-Cl > M—Br > M-I
(b) Bond dissociation enthalpy : Br,, Cl,, F,, I,
(c) Oxidising power: BrO,, 10,, ClO, (e) H,O > H,Te > H,Se > H,5
(d@) Ionic character of bond : M-F, M-Cl, M-Br, M-I (). NH, > PH, > AsH, > SbH,
(e) Boiling point : H,O, H,S, H,Se, H,Te (7) F-> Cr > Bros TT
(f) Base strength : NH., PH,, AsH., SbH, (ht) H,O > H,5 > H,Se > Ha fe
(g) Hydration enthalpy: F-, Cl, Br, [
(7) Cl>F>Br>I
(h) Bond angle : H,O, H,S, H,Te, H,Se
(4) Electron affinity : F, Cl, Br, I (7) BiH, > SbH, > AsH, > PH, > NH,
(7) Reducing character : NH,, AsH,, PH,, SbH,, Bil, (k) NH, > PH, > AsH, > SbH,
(k) Thermal stability : NH,, PH,, AsH,, SbH, (2) SO, > N,O, > CO, > S10,
(1) Acidic character : 5O,, CO,, Si0,, N,O, (m) HClO, > HClO, > HClO, > HClO
(m) Acidic strength : HC1O, HC1O,, HC1O,, HCIO,
(2) HClO > HBrO > HIO
(n) Acidic strength : HBrO, HC1O, HIO
(o) H,P,Of> HBEO > Fi.PO, > HPO,
(o) Oxidation state of P : H,PO,, H,PO,, H,P,0,, H,P,0,
(p) Boiling point : He, Ne, Ar, Kr (p) Kr > Ar > Ne> He
(q) Oxidation state of S : H,S,0,, H,SO., H,S,0, (q) H,8,0, > H,SO, > H,5,0,
(r) Melting point: F,, Cl,, Br,, I, (r) A, Sr, > Bf > F,.

IMPORTANT STRUCTURES

a a © oO
| 5. 5

i A O
eee
a
Vo
Se
ee
a | OOH Are SO
8 HO (OH L (uO Nay
Cc @ OH
Peroxodisulphuric Peroxomonosulphuric Thisulphurie acid
acid (or Marshall acid) acid (or Caro’s acid) (Pyrosulphurie acid) See-saw
H,S,0, H,SO; H,S,0, (sp°d hybridisation)

H,

f =
we
.U, F

f . i 1 Cl _ a
ATS a a
F

wy oO
west?
“0
—_ F
=<——6
fa —- F
- LY O

SF, Chlorie acid Perchloric acid IF.

Octahedral (HCIO,) (HC10,) Square pyramidal
(sp*d* hybridisation) (sp°d* hybridisation)

F F

a KS
|
1

-F«——— Cl FF ——_——_

aa kK
‘ —
‘ ‘. ae -
./f/-47

= FoF Cl

CIF, IF, ICl; ICl;

T-shaped Pentagonal bipyramidal Linear Square planar
(sp*d hybridisation) (sp°d° hybridisation) (sp°d hybridisation) (sp°d? hybridisation)
ne 71142 MODERN'S abe + OF CHEMISTRY
-AXII

BrF, ef,
Square pyramidal Linear Linear Square planar
(sp*d* hybridisation) (sp°d hybridisation) (sp°d hybridisation) (sp°d* hybridisation)
F

we YY
O

/ a

aA.
é F) af |

‘fo F oA
FC “1.
= f ~ ° a uy

F
XeF, XeOQ, XeOF, XeOF,
Distorted octahedral Pyramidal Square pyramidal T-shaped
(sp°d? hybridisation) (sp* hybridisation) (sp°d* hybridisation) (sp°d hybridisation)

OBJECTIVE TYPE QUESTIONS

M. C. Q.
AZ. Pure nitrogen gas is obtained from

at\wn 7FA (a) NH, + NaNO, (6) NH,Cl+ NaNO,

with only one correct answer (c) N,O + Cu (d) (NH,),Cr,O-.
Select the Correct Answer : A8. Which of the following is a coloured gas ?
(a) NO, (dD) N,0. (c) WO, (d) N,0.
Group 15 Elements
A9. The oxide of nitrogen obtained by dehydration of nitric acid
Al. The brown gas formed when HNO, is reduced by metals is with phosphorus pentoxide is
(a) N,O (6) N,O, (c) NO, (d) NO. (a) NO, (6) N,O, te) WO, (d) N,O.
A2,. The hydride of group 15 having largest bond angle is : A10. Among the trihalides of nitrogen, which one is least
(a) NH, (6) PH, (c) AsH, (d) Big. basic ?
A3. The oxoacid of P having oxidation state + 41s: (a) NF, (6) NCI, (ce) NEBr; (d) NI.
All. On heating ammonium dichromate, the gas evolved is
(a) Phosphorus acid (6) Hypophosphoric acid
(a) Oxygen (6) Ammonia
(c) Phosphoric acid (d@) Metaphosphoric acid.
(c) Nitric acid (d) Nitrogen.
A4, Nitric acid (conc.) oxidises phosphorus to
A12. The number of o—bonds in P,O,, is
(a) H,PO, (eo
(c) HPO, i) HP... (a) 6 (b) 16 (c) 20 (d) 7.
A5. Ammonia gas can be dried over Group 16 Elements
(a) CaCl, (6) Cone. H,SO,
A13. The oxidation state of sulphur in anion SO,7,, 5,0,?" and
(c) PC1, (dq) Quick lime S,0,7 follows the order :
A6. Of the following hydrides which is the strongest reducing
agent ?
(a) $,02-< S,0,2- <SO,2-
(a) NH, (6) SbH, (b) S,02 <SO2<8,02
(c) SO2 < SO2- <S,02

Answer
(c) AsH, (d) PHs.
(d) $0? <S,02- < S02

Al. (c) AZ. (a) As. (5) Ad. (a) A5. (d) A6. (5) AT. (5) A8. (a) AS. (6) Al0. (a)
All. (d) A112 (5) £AlS8. (5)
p-BLOCK ELEMENTS

Al4, Most volatile hydride of element of group 16 is A27. The chlorine atom in CIF involves
(a) H,O (6) HS (c) H,Te (d) H,Se. (a) sp? hybridisation (b) sp%d hybridisation
Al15. The oxoacid of sulphur which contains a lone pair of (c) sp*d? hybridisation (d) sp°d° hybridisation.
electrons on sulphur is
A28. Which of the following has maximum boiling point?
(a) Sulphurous acid
(a) HF (b) HCl (c) HBr (d) HI.
(6) Sulphuric acid
A29. When Br, is added to aqueous solution of NaF’, NaCl and
(c) Peroxodisulphuric acid
Nal separately
(d) Pyrosulphuric acid.
Al16. The boiling points of hydrides of group 16 elements are in (a) F,, Cl, and I, are liberated
the order: (6) only F, and Cl, are liberated
(a) H,O > H,5 > H,Te > H,Se (c) only Cl, is liberated
(6) H,Te > H,Se > H,S > H,O (d) only I, is liberated.
(c) H,O > H,Te > H,Se > H,S A30. Which of the following is strongest reducing agent?
(¢q) H,Te > H,O > H,5 > H,Se. (a) HCl (6) HI (c) HBr (d) HF.
A177. Which of the following has lowest reducing character?
A31. The low bond energy of F’, is best explained by:
(a) H,O (6) HS
(a) the attainment of noble gas configuration (F~)
(c) H,Te (d) H,Se.
(6) the low electron affinity of F
A18. Dehydration of formic acid with sulphuric acid gives
(c) repulsion by electron pairs on F
(a) CO (6) C
(d) the small size of F.
(c) CO and CO, (ay 4A.
A32. Which of the polyhalide ions is not known?
A19, Ozone oxidises moist iodine to
(a) 1,0, (6) 10, (a) Fy (6) Bry Cm be (d) Iz
(c) HIO, (d) HI A33. Which of the following halogen exhibits only one oxidation
A20. There is no S—S bond in state?
(a) 6,0,°° (6) 5,0,2- (a) Cl (6) Br (c) F (d) I
(c) 6,0 (oy gy A34, Cl,O, dissolves in water to give
A21. The number of S—S bonds 1n sulphur trioxide trimer (5,04) (a) HCIO, (6) HCIO,
18 (c) HClO + ClO, (d) ClO, + C10
(a) three (5) two (c) one (d) zero.
A22, Oxygen exhibits positive oxidation state in Group 18 Elements
(a) H,O, (6) OF, (c) N,O (d) NaO, A35. XeF’, reacts with water at — 80°C to give
A23. Bleaching action of SO, is due to: (a) XeOF, (b) XeOF,
(a) reduction (6) oxidation (c) XeO, (d) XeO,F,,.
(c) acidic nature (d) hydrolysis. A36. The geometry of XeOF, is :
A24, Chlorine oxidises Na,5,O, to
(a) Pyramidal (6) T-shaped
(a) Na,S,O, (6) Na,SO,, 50,
(c) Octahedral (d) Tetrahedral.
(c) Na,SO,,5 (dq) Na,SO,, Na,SQ,.
A37. Which of the following is called stranger gas?
Group 17 Elements
(a) Xe (b) Ne (c) Ar (d) Kr
A25. Out of all the halogen hydracids, the weakest in aqueous A38s. Among the following the square planar geometry 1s for:
solution is :
(a) XeOF, (5) XeF, (c) XeF, (d) XeQ,.
(a) HI (6) HBr (c) HF (d) HCl.
A26. Which of the following gives blue colour with starch A39. The noble gas compound prepared by Bartlett was:
solution? (a) XeOQ, (b) XePtF,
(a) F, (6) Cl, (c) Br, ay 1, (c) KrF, (d) XeF,.

Ansel
Ad40. Hydrolysis of XeF’, gives:
(a) XeOF, (6) XeOQ, (c) XeO,F, (d) XeOF,.

Al4, (5) A115. (a) Al6. (c) A177. (a) A18. (a) A19. (ec) A20. (d) A21. (d) A22. (6) A238. (a) A24. (c) A25. (c) A26. (d) A27. (c)
A28. (5) A29. (d) A380. (6) A8l1. (c) AS2. (a) ABS. (c) A384. (5) A85. (a) ASG. (6) A877. (a) A388. (5) AS9. (6) A40. (5)
a 71144 MODERN'S abe + OF CHEMISTRY
-AXII

B
B8. Which is the strongest acid in the following:
MULTIPLE CHOICE QUESTIONS (a) HCO, (6) H,SO,
from competitive examinations (c) H,SO, (d) HClO, (NEET 2013)
B9. Acidity of diprotic acids in aqueous solution increases in
AIPMT & Other State Boards’ the order
Medical Entrance (a) H,S <H,Se<H,Te (6) H,Se <H,5 <H,Te
(c) H,Te < H,S < H, Set), H,Se < H,Te < H,5
Bl The correct order of acid strength is (AIPMT 2014)
(a) HClO, < HClO, < HClO, < HC1O B10. Strong reducing behaviour of H.PO, 1s due to:
(6) HClO < HCIO, < HC1O, < HCIO, (a) High oxidation state of phosphorus
(6) Presence of two -OH groups and one P—H bond
(c) HClO, < HClO < HCl1O,< HClO, (c) Presence of one -OH group and two P—H bonds
(d) HC1O, < HCIO, < HCIO, < HClO (d) High electron gain enthalpy of phosphorus
(C_B.S.E. Med. 2005, 2007, NEET 2016) (AIPMT 2015)
Bil. Which of the statements given below is incorrect?
B2. Among the following which is the strongest oxidising agent?
(a) ONF is isoelectronic with O,N
(a) Br, (b) I, (6) OF, is an oxide of fluorine
(c) Cl, (a) FF, (C_B.S.E. Med. 2009) (c) Cl,O, 1s an anhydride of perchloric acid
Bs. The correct order of increasing bond angles 1n the following (d) QO, molecule is bent (AIPMT 2015)
species 1s:
B12. The variation of the boiling points of the hydrogen halides
is in the order HF > HI > HBr > HCl. What explains the
(a) ClO<ClO, <ClO, (6) ClO, < CLO < ClO, higher boiling point of hydrogen fluoride?
(c) ClLO<ClO,<ClO, (d) ClO, < C10 < ClO, (a) The bond energy of HF molecules is greater than in
(C.B.S.E. P.M.T. 2010) other hydrogen halides.
(6) The effect of nuclear shielding 1s much reduced in
BA, Sulphur trioxide can be obtained by which of the following fluorine which polarises the HF molecule.
reaction? (¢) The electronegativity of fluorine is much higher than
(a) CaSO, + C ——> (b) Fe,(SO,), —— for other elements in the group.
(d) There is strong hydrogen bonding between HF
(ec) S + H,50, = (d) H,SO, + PCl, —— molecules. (AIPMT 2015)
(A.I.P.M.T., 2012) B13. Nitrogen dioxide and sulphur dioxide have some properties
B5. Which of the following statements is not valid for oxoacids in common. Which property is shown by one of these
of phosphorus? compounds, but not by the other?
(a) Orthophosphoric acid is used in the manufacture of (a) Is soluble in water.
triple superphosphate. (6) Is used as a food preservative.
(c) Forms 'acid—rain.
(6) Hypophosphorous acid is a diprotic acid.
(c) All oxoacids contain tetrahedral four coordinated (d) Is a reducing agent. (AIPMT 2015)
B14. Which is the correct statement for the given acids?
phosphorus.
(a) Phosphinic acid is a monoprotic acid while phosphonic
(d) All oxoacids contain at least one P = O unit and one acid is a diprotic acid.
P—OH group. (A.I.P.M.T. 2012) (6) Phosphinic acid is a diprotic acid while phosphonic acid
B6. When Cl, gas reacts with hot and concentrated sodium is a monoprotic acid.
hydroxide solution, the oxidation number of chlorine (c) Both are diprotic acids.
changes from (d) both are triprotic acids. (NEET 2016)
(a) zero to + 1 and zero to—6 B15. Match the compounds given in column I with the
(6) zero to—1 and zero to +5 hybridisation and shape given in column IT and mark the
(c) zero to— 1 and zero to+3 correct option.
(d) zero to + 1 and zero to— 3 (A.L.P.M.T. 2012) Column I Column IT
B7. Roasting of sulphides gives the gas X as a by-product. This (A) XeF, (i) Distorted octahedral
is a colourless gas with choking damage to the respiratory (B) XeO, (it) oquare planar
organs as a result of acid rain. Its aqueous solution is (C) XeOF, (iiz) Pyramidal
acidic, acts as a reducing agent and its acid has never been (D) XeF, (zv) Square pyramidal
isolated. The gas ‘X’ is A B C D
(a) SO, (b) CO, (a) (tv) (i211) (z) (it)
(c) 5O, (d) HS (NEET 2073) (b) (iv) (z) (it) (111)
(c) (1) (i211) (tv) (it)
(d) (2) (it) (tv) (i112) (NEET 2016)
Answers
Bl. (b) B2. (d) B3. (5) B4. (5) B5. (0b) B6. (3) B7. (a) B8. (a) B9. (a) 510. (ec)
Bll. (6) B12 (¢@) Bis. (6) Bld (a) B15. (c)
p-BLOCK ELEMENTS

B16. Which one of the following order is correct for the bond B24. In the structure of CIF,, the number of lone pairs of
dissociation enthalpy of halogen molecules? electrons on central atom ‘CI’ is
(a) Br, > Lok, > Cl, (4) E> CL> Br,>1, (a) one (6) two
(ce) I> br = CLS, te) CLS bre f=,
(ec) four (d) three
(NEET 2016)
B17. When copper is heated with conc. HNO, it produces (NEET 2018)
(a) Cu(NQ,),, NO and NO, B25. Which of the following is the correct order of increasing
(6) Cu(NO,), and N,O enthalpy of vaporisation ?
(c) Cu(NO,), and NO, (a) NH, <PH,<AsH, (5) AsH, < PH, <NH,
(d) Cu(NO,), and NO (NEET 2016) (c) PH, < AsH, <NH, (d) NH, < AsH, < PH,
B18. Hot concentrated sulphuric acid is a moderately strong
oxidizing agent. Which of the following reactions does not
(ce) AsH, <NH, < PH, (Kerala P.M.T. 2007)
show oxidizing behaviour? B26. The maximum number of P—H bonds are contained in which
(a) Cu + 2H,50, > CuSO, + SO, + 2H,O of the following molecules?
(6) S + 2H,SO, — 380, + 2H,O (a) H,PO, (oy HPO,
(c) C+ 2H,50, > CO, + 250, + 2H,O (c) H,PO, (dq) H,P,0O, (A.M.U. Med 2010)
(d) CaF’, + H,S0, — CaSO, + 2HF (NEET 2016)
B27. Which of the following has — O — O — linkage ?
B19. Among the following, which one is a wrong statement?
(a) PH, and BiCl, do not exist. (a) H,S,0, (6) H,S,0,
(6) px-dz bonds are present in SO,. (cya S,Ce (dq) H,8,0, (A.M.U. Med. 2011)
(c) SeF’, and CH, have same shape. B28. When Br, is treated with aqueous solutions of NaF’, NaCl
(d) I, has bent geometry. (NEET 2016) and Nal separately
B20. Match the interhalogen compounds of column—I with the
(a) F,, Cl, and I, are liberated
geometry in column—II and assign the correct code.
Column-I Column-Il (6) only F, and Cl, are liberated
(A) XX’ (i) T-shape (ce) only I, is liberated
(B) XX (it) Pentagonal bipyramidal
(d) only Cl, is liberated
(C) XX. (zit) Linear
(D) XX, (tv) Square pyramidal (e) only Cl, and I, are liberated (Kerala PMT 2011)
(v) Tetrahedral B29. The basicity of pyrophosphorous acid is
Code : (a) 2 (b) 4 (c) 1
A B C D
(d) 5 (e) 3 (Kerala PMT 2011)
(a) (ut) =) (iv) (11)
B30. The oxidation state of phosphorus in cyclotrimetaphosphoric
(d) (v) (tv) (zit) (11)
acid is
(c) (zv) (i211) (it) (1)
(d) (zz) = (tv) (z) (zi) (NEET 2017) (a) +3 (b) 46 (ec) —3
B21. In which pair of ions, both the species contain S—S bond? (d) +2 (e) —-2 (Kerala PMT 2011)
(ey 0 02 (6) 5,0. Sao,”
B31. The oxyacid of sulphur that contains alone pair of electrons
ie) BO 8.0. (d) $,0,7°,, 5,0,7 (NEET 2017) on sulphur is
B22. The correct order of N-compounds in its decreasing order
(a) sulphurous acid (6) sulphuric acid
of oxidation states is
(a) HNO,, NO, N,, NH,Cl (c) peroxodisulphuric acid
(6) HNO,, NO, NH,ClL, N, (d) pyrosulphuric acid (A.M.U.Med. 2013)
(c) HNO,, NH,Cl, NO, N, B32. Which one of the following is used for the production of
(d) NH,Cl, N,, NO, HNO, (NEET 2018) UF, in the enrichment of U**°?
B23. Which of the following statements is not true for halogens? (a) CIF, (6) KF (c) KHF,
(a) All form monobasic oxyacids. (dq) HF (e) PF, (Kerala PMT 2014)
(6) All are oxidizing agents.
B33. The oxoacid of phosphorus that reduces silver nitrate into
(c) All but fluorine show positive oxidation states. metallic silver is
(d) Chlorine has the highest electron-gain enthalpy. (a) H,PO, (6) H,P,0, (c) H,PO,
(NEET 2078)
(d) H,P,O, (ec) (HPO,), (Kerala PMT 2015)
Arswets
B16. (¢@) B17. (ec) Bis. (@) B19. (ec) B20. (a) B21. (2) B22. (2) B23. (d) B24. (6) B25. (a)
B26. (2) B27. (6) B28. (c) B29. (a) B30. (5) B31. (2) B82. (2) B38. (a)
a 7/146 MODERN’S abc + OF CHEMISTRY-AXIl

JEE (Main) & Other State Boards’ (a) N,O and NO, (6) NO and NO,
Engineering Entrance (c) NO and N,O (d) NO, and N,O
B34. What products are expected from the disproportionation
(JEE Main 2016)
reaction of hypochlorous acid ? B43. The pairin which phosphorus atoms have a formal oxidation
state of +3 is
(a) HClO, and HClO, (6) HCland Cl,O
(a) orthophosphorous and pyrophosphorous acids
(c) HCl and HCIO, (d) HClO, and Cl,O (6) pyrophosphorous and hypophosphoric acids
(A.D E.E.E. 2006) (c) orthophosphorous and hypophosphoric acids
B35. In which of the following arrangements, the sequence is (d) pyrophosphorous and pyrophosphoric acids.
not strictly according to the property written against it ? (JEE Main 2016)
(a) CO, < S10, <Sn0O, < PbO,: Increasing oxidising power B44, Which of the following reactions 1s an example of a redox
(6) HF < HCl < HBr < HI: Increasing acid strength reaction ?
(c) NH, < PH, < AsH, < SbH, : Increasing basic strength (a) XeF, WO ee > Xe + O,
(dq) B< C<O<N:
Increasing first ionisation enthalpy. (b) XeF/ FPF, “[XeF]*PF,
(A.LE.E.E. 2009) (c) XeF, + HzO — XeOF, + 2HF
B36. Three reactions involving H,PO, are given below : (d) XeF, + 2H,O — XeO,F, + 4HF (JEE Main 2017)
B45. The products obtained when chlorine gas reacts with cold
(:) H,PO, + H,O —> H,O* + H,PO,-
and dilute aqueous NaOH are:
(ii) H,PO, + H,O —> HPO# + H,O*
(a) ClO” and ClO; (6) ClOZ and ClO;
(iit) H,PO, + OH’ —> H,PO, + O7-
(c) Cl and C1O- (d) CY and ClO;
In which of the above does H,PO, act as an acid ?
(JEE Main 2017)
(a) (zit) only (6) (z) only B46. The compound that does not produce nitrogen gas by the
(c) (az) only (dq) (t)and(i) (A LE.E.E 2010) thermal decomposition is:
B37. Which of the following statement is wrong ? (a) Ba(N,), (6) (NH,),Cr,0,
(a) The stability of hydrides increases from NH, to BiH, (c) NH,NO, (d) (NH,),50,
in group 15 of the periodic table. (JEE Main 2018)
(6) Nitrogen cannot form d1-pt bond. B47. Na,5,O, 1s reduced by I, to
(c) Single N—N bond is weaker than the single P—P bond. (a) Na,s (6) Na,SO,
(d) NO, has two resonance structures. (A... E.£.E. 2011) (c) NaHSO, (d) Na,5,0,
B38. Which of the following statement regarding sulphur is (Orissa BE. 2008)
incorrect ? B48. Sulphur trioxide gas when dissolved in H,SO,, the product
(a) 5, molecule is paramagnetic. obtained is
(6) The vapour at 200°C consists mostly of 5, rings. (a) H,SO, (b) H,SO,
(c) At 600°C the gas mainly consists of S, molecules. (c) 05,0, (d) H,S,O, (Orissa JEE 2010)
(d) The oxidation state of sulphur is never less than +4 1n B49. Which of the following contains P — O — P bond ?
its compounds. (A.LLELE.E. 2011)
(a) Hypophosphorous acid (6) Phosphorus acid
B39. Which of the following is the wrong statement?
(c) Pyrophosphoric acid (d) Orthophosphoric acid
(a) Ozone is diamagnetic gas.
B50. The least stable hydride of 15th group elements is
(6) ONC] and ON© are not isoelectronic
(a) NH, (6) PH,
(c) O, molecule is linear
(c) AsH, (d) SbH,
(d) Ozone is violet-black in solid state. (JEE Main 2013)
(e) BiH, (Kerala PET 2011)
B40. Which among the following is the most reactive?
B51. Pick out the wrong statement.
(a) I, (6) ICI
(a) Nitrogen has the ability to form pa-pr bonds with itself.
(c) Cl, (d) Br, (JEE Main 2015)
(6) Bismuth forms metallic bonds in elemental state.
B41. Which one has the highest boiling point?
(c) Catenation tendency is higher in nitrogen when
(a) Kr (b) Xe compared with other elements of the same group.
(c) He (d) Ne (JEE Main 2015) (d) Nitrogen has higher first ionisation enthalpy when
B42. The reaction of zinc with dilute and concentrated nitric compared with other elements of the same group.
acid, respectively produces (e) Arsenic forms di-dz bonds with transition metals.

Auswets (Kerala P_E.T. 2012)

B34. (c) B35. (c) B36. (c) B37. (a) B38. (d) B39. (c) B40. (bd) B41. (5) B42. (a) B43. (a)
B44. (a) B45. (c) B46. (d) B47. (d) B48. (c) B49. (c) B50. (e) B51. (c)
p-BLOCK ELEMENTS

re &

hi rar le

B52. Nitric acid can be obtained from ammonia via the formation Bé6él. In the solid state, PCl, exists as
of the intermediate compounds (a) [PCl1,] and [PC1,]° ions
(a) nitric oxide and nitrogen dioxide (6) covalent PCl, molecules only
(6) nitrogen and nitric oxide (c) [PC] AK and [PCI,] ions
(c) nitric oxide and dinitrogen pentoxide (d) covalent P,Cl,, molecules only. (WB JEE 2016)
(d) mtrogen and nitrous oxide (W.B.S_ELE. Engg. 2013) B62. Which one of the following group 16 element does not exist
B53. An inorganic salt (A) is decomposed on heating to give in —2 oxidation state?
two products (B) and (C). Compound (C) is a liquid at room (a) 8 (b) Se
temperature and is neutral to litmus while the compound (B) (c) O (d) Po
is a colourless neutral gas. Compounds (A), (B) and (C) are (e) Te (Kerala PET 2016)
(a) NH,NO,, N,O,H,O (6) NH,NO,, NO, H,O B63. Thermal decomposition of ammonium dichromate gives
(c) CaO, H,O, CaCl, (d) Ba(NO,),, H,O, NO, (a) N,, H,O and Crz,0, (6) N,, NH, and CrO
(eg) Mg(NQ,),, N,O,, H,O (Kerala P.E.T. 2018) (c) (NH,),CrO, and H,O (d) N,, H,O and CrO,
B54, If CL, is passed through hot aqueous NaOH, the products (Kerala PET 2016)
formed have Cl in different oxidation states. These are B64, The property which is not true about fluorine is
indicated as (a) most ofits reactions are exothermic
(a) —l and +1 (6) —1 and +56 (6) it forms only one oxo acid
(c) +1 and +65 (7q@) -land+3 (WB JEE 2014) (c) highest electronegativity
B55. The statement that is not correct is (d) high F—F bond dissociation enthalpy.
(a) Hypophosphorous acid reduces silver nitrate to silver (Karnataka C.E.T. 2016)
(dD) In solid state PCl, exists as [PCL,]* [PCl,]- B65. Select wrong chemical reaction among the following:
(c) Pure phosphine is non-inflammable (a) MnO, + 4HCl - MnCl, + Cl, + 2H,O
(d) Phosphorous acid on heating disproportionates to give (6) 8NH, + 38Cl, > 6NH,Cl + N,
metaphosphoric acid and phosphine. (c) 2NaOH + Cl, + 2NaCl + H, + O,
(Karnataka CET 2014)
(d) 2Ca(OH), + 2CL, > Ca(OCl), + CaCl, + 2H,O
B56. On heating with concentrated NaOH solution in an inert
(Karnataka C.E.T. 2017)
atmosphere of CO,, white phosphorus gives a gas. Which
of the following statements is incorrect about the gas? B66. Which of the following element forms pr — pr bond with
(a) Itis more basic than NH,. itself?
(6) Its solution inwater decomposes in the presence oflight. (a) N (b) Te
(c) Itis less basic than NH,. (c) P (d) Se (Karnataka C_E.T. 2017)
(d) Itis highly poisonous and has smell like rotten fish. B67. The shape of XeF; will be
(Karnataka CET 2015) (a) square pyramid (6) trigonal bipyramidal
B57. Sulphuryl chloride (SO,Cl,) reacts with white phosphorus (c) planar (d) pentagonal bipyramidal.
(P,,) to give (WB. J_ELE. 2017)
(a) PCI,, SO, (6) OPCI,, SOCI, B68. What is the hybridization and geometry of the given
ic}, PCL, 5D, 53CL (d) OPCl,,SO,, S,C1 species? The species are XeF, and ICI,.
“(WB JEE 2015) (a) sp*d and trigonal bipyramidal
B58. What is the basicity of orthophosphorus acid? (b) sp*d? and square planar
(a) One (6) Two (c) sp*d and linear
(c) Three (d) Four (MH-CET 2015) (d) sp? and irregular tetrahedron (J.K. CET 2018)
B59. Which of the following does not have S—S bond? B69. What will be the resultant products formed when the
(a) 5,0,7- 5.0," phosphorus halide PBr, splits up?
(c) 5,0, (d) 5,0,7- (MH-CET 2015) (a) [PBr,]° and Br (6) [PBr,] and [PBr,]”
B60. The boiling points of HF’, HCl, HBr and HI follow the order (c) [PBr,]* (d) [PBr,]
(a) HF > HCl > HBr > HI (J.K. CET 2018)
(6) HF > HI > HBr > HCl B70. Which of the following is the correct reason for HI solution
(c) HI > HBr > HCl > HF turning brown on exposure to air?
(a) HI reacts with H,O to form I,.
(2) HCl > HF > HBr
> HI (WE JEE 2076)
(6) HI dissolves NO,.
(c) HI reacts with O, to form I.
(d) HI reacts with N, and O, to form NO,.
Answers (J.K. CET 2018)

B52. (2) B58. (a2) B54. (6) B55. (dd) B56. (a) B57. (a) B58. (5) B59. (c) B60. (5) B61. (c)
B62. (2) B6s. (a2) Bed. (ad) B65. (ec) B66. (a) B67. (c) B68. (c) B69. (a) B70. (c)
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B71. CLO, is the anhydride of (c) liquefaction and fractional deistillation of liquid air
(a) HOCI (6) HCIO, (d) thermal decomposition of sodium azide
(c) HClO, (d) HClO, (WB JEE 2018)
(Karnataka CET 2018)
B72. At room temperature, the reaction between water and
fluorine produces
JEE (Advance) for ITT Entrance
(a) HF and H,0, (6) HF, O, and F,O,
(c) F,O, and H’ (d) HOF and HF. B79. The reaction of P, with X leads selectively to P,O,. The X is
(WB JEE 2018) (a) Dry O, (6) Amuxture of O, and N,
B73. When SO, gas is passed into aqueous Na,CQO,, the (c) Moist O,
product(s) formed is (are) (d) O, in the presence of aqueous NaOH W.1.T. 2009)
(a) NaHsO, (6) Na,SO, B80. Extra pure N, can be obtained by heating
(c) NaHSO, (d) Na,SO, and NaHsoO, (a) NH, with CuO (6) NH,NO,
(e) NaHsO, and Na,SO, (Kerala PET 2018) (c) (NH,),Cr,0, (d) Ba(N,), (117. JEE 2011)
B74, Select the correct option(s) for the following statements. B8s1. The reaction of white phosphorus with aqueous NaOH
1. Cl,O and ClO, are used as bleaching agents. gives phosphine along with another phosphorus containing
2. OCI salts are used as detergents. compound. Thereaction type; the oxidation states of phosphorus
3. OCI disproportionates in alkaline medium. in phosphine and the other product are respectively.
4. BrOjis oxidized in acidic medium. (a) redox reaction; — 3 and — 5
(a) 1, 2, 3 correct (6) 2,3, 4 correct (6) redox reaction; + 3 and +65
(c) 1, 2, 4 correct (dq) 1,3, 4 correct (ce) disproportionation reaction; — 3 and + 5
(e) All are correct (Kerala PET 2018) (d) disproportionation reaction; — 3 and +3
B75. Maximum number of covalent bonds formed by N and P (LT. J.EE. 2012)
are B82. Concentrated nitric acid, upon long standing, turns yellow-
(a) 8,65 (b) 3,6 brown due to the formation of
(c) 3,4,5 (d) 3,4,6 (Kerala PET 2018) (a) NO (6) NO,
B76. Consider the following statements concerning N,H,. (c) N,O (d) N,O,@.#.E. Advance 2013)
1. Itis an exothermic compound. B83. The product formed in the reaction of SOCL, with white
2. It burns in air with the evolution of heat. phosphorus is
3. It has kinetic stability. (a) PCI, (6) S5O,CL,
(c) SCI, (d) POC], (JEE Advance 2014)
4. It reduces Fe** to Fe** in acidic medium.
B84, Under ambient conditions, the total number of gases
Which of the following combination is correct? released as productsin the final step of the reaction scheme
(a) 2and3 arecorrect (6) 1 and 2 are correct shown below is
(c) All are correct (qd) 3 and 4 are correct Complete hydrolysis
XeF, T_T} P + other product
(e) 2,3 and 4 are correct
| OH/H,0
(Kerala PET 2018)
B77. Consider the following compounds
slow disproportionation
1 ANE or, 2. NH,NO,
| in OH /H,O
3. NH,VO, 4. NH,NO, products
Which compound(s) yield nitrogen gas upon heating? (a) O (b) 1
(a) land2 (6b) 2and3
(c) 2 (d) 3 (JEE Advance 2014)
(c) 3and4 (d) land4
B85. The order of the oxidation state of the phosphorus atom in
(e) All H,PO,, H,PO,, H,PO,, and H,P,O, is
(Kerala PET 2018) (a) HPO, > HPO, > HPO, > F,F,0,
B78. Very pure N, can be obtained by i) PO, Ss, SS AP,
(a) thermal decomposition of ammonium dichromate io) PO, > HPO, > HP), SBP
4°26
(6) treating aqueous solution of NH,Cl and NaNO,
(a) HPO, > FO, > H.PO,> H.PO,

Answers
(JEE Advance 2017)

B71. (d) B72. (c) B73. (d) B74. (a) B75. (a) B76. (e) B77. (a) B78. (d) B79. (6) B80. (d)
B81. (c) B82. (5) B83. (a) B84, (c) B85. (d)
p-BLOCK ELEMENTS

(6) is diamagnetic
(c) contains one N—N bond
with more than one correct answer (d) reacts with Na metal producing brown gas.
Cl. White phosphorus has (JEE Advance 2016)
(a) four P—P bonds (6) bond angle “PPP = 60° C7. The compounds with two lone pairs of electrons on the
(c) six P—P bonds (d) polymeric structure. central atom is/are
C2. A solution of colourless salt H on boiling with excess NaOH
(a) CIF, (6) BrF,
produces a non-flammable gas. The gas evolution ceases (c) XeF, (dq) SF, (JEE Advance 2016)
after some time. Upon addition of Zn dust to the same C8. The colour of the X, molecules of group 17 elements changes
solution, the gas evolution restarts. The colourless salt(s) gradually from yellow to violet down the group. This is due
H is (are) to
(a) NH,NO, (6) NH,NO, (a) the physical state of X, at room temperature changes
from gas to solid down the group
(c) NH,Cl (dq) (NH,),50, (.L.T. 2008)
(6) decrease in HOMO-LUMO gap down the group
C3. Nitrogen oxide(s) that contain(s) N—N bond(s) is (are)
(c) decrease in t*—o* gap down the group
(a) N,O (6) N,O,
(d) decrcease 1n ionization energy down the group.
(c) N,O, ay M0, (1.7. JEE 2009)
(JEE Advance 2017)
C4, Ionization potential values of noble gases decrease down
. The correct statement(s) about the oxoacids, HClO, and
the group with increase in atomic size. Xenon forms binary
HCLO, is(are)
fluorides by the direct reaction of elements. Identify the
(a) the conjugate base of HC1O, is weaker base than H,O
correct statement(s) from below:
(6) the central atom in both HClO, and HCO is sp
(a) Only the heavier noble gases form such compounds.
hybridized
(5) It happens because the noble gases have higher
(c) HCO, is formed in the reaction between Cl, and H,O
ionization energies.
(dq) HC1O, is more acidic than HClO because of the
(c) It happens because the compounds are formed with resonance stabilization of its anion.
electronegative ligands.
(JEE Advance 2017)
(ad) Octet of electrons provide the stable arrangements. C10. White phosphorus P, has the following characteristics
(J.B.E. Advanced 2015)
(a) 6 P—P single bonds
C5. The correct statement(s) regarding, (1) HClO, (71) HCIO,, (6) 4 P—P single bonds
(tit) HCLO, and (zv) HC1O,, is(are) (c) 4 lone pair of electrons
(a) The number of Cl=O bonds in (11) and (iii) together is (7d) P—P—P angle of 60° (WB JEE 2018)
two
Cll. The compound(s) which generate(s) N, gas upon thermal
(6) The number of lone pairs of electrons in Cl in (zi) and decomposition below 300 °C is (are)
(zit) together is three (a) NH,NO, (6) (NH,),Cr,0,
(c) The hybridization of Cl in (iv) is sp? (c) Ba(N,), (d) Mg.N, (JEE Advance 2018)
(d) Amongst (z) to (tv), the strongest acid 1s (2) C12. Based on the compounds of group 15 elements, the correct
(J.F.E. Advanced 2015) statement(s) 1s (are)
C6. The nitrogen containing compound produced in the reaction (a) Bi,O, is more basic than N,O,
of HNO, with P,O,, (6) NF, is more covalent than Bik,
(a) can also be prepared by reaction of P, and HNO, (c) PH, boils at lower temperature than NH,

Answer
(d) the N—N single bond is stronger than the P—P single
bond. (JEE Advance 2018)

C1. (5), (c) C2. (a), (0) C3. (a), (5), (c) CA. (a), (c) C5. (5), (ec) C6. (5), (d) C7.(a),(c) C8. (d), (c)
C9. (a), (6), (d) C10. (a), (c), (d) C11. (0), (c) C12. (a), (8), (e)

electronegativity. The presence of P—H group in these oxyacids

is responsible for their reducing properties. The structures of
some oxyacids are given below :
Passage I.
Phosphorus forms a variety of oxyacids. In all these, ° |
phosphorus is sp? hybridised and is tetrahedrally bonded to P Vin
four neighbouring atoms. These contain P—OH bonds, the N
hydrogen of which are ionisable giving acidic character to
10” “o HO 697°
meta-Phosphoric acid ortho-phosphoric acid
these compounds. These also contain P—H bonds in which
(A) (B)
hydrogens are not ionisable because P and H have nearly same
an 71150 MODERN'S abe + OF CHEMISTRY
-AXII

° 0 Oo.
|
(c) Between nitrates and phosphates, nitrates are less
abundant in earth’s crust
(d) Oxidation of nitrates 1s possible 1n soil.
Saft ye D7. Among the following, the correct statement is
HO on” on (a) Between NH, and PH., NH, is a better electron donor
because the lone pair of electrons occupies spherical ‘s’
Pyrophosphoric acid |§Hypophosphoric acid
orbital and is less directional.
(C) (D) (6) Between NH, and PH., PH, is a better electron donor

:
i
p=.
H
|Sale
SS OH
because the lone pair of electrons occupies sp° orbital
and is more directional
(c) Between NH, and PH,, NH, is a better electron donor
because the lone pair of electrons occupies sp? orbital
i on "a OH and is more directional
Hypophosphorus acid Phosphorus acid
(d) Between NH, and PH,, PH, is a better electron donor
(E) (F) because the lone pair of electrons occupies spherical ‘s’

i ot |
orbital and is less directional.
| D8. White phosphorus on reaction with NaOH gives PH, as
Aer ee one of the products. This is a
O H O—OH.
(a) dimerization reaction (5) disproportionation reaction
H a Nou Nou ge Now
(c) condensation reaction (d) precipitation reaction.
Pyrophosphorous acid Peroxomonophosphoric acid
Passage ITI.
(G) (H) The reactions of Cl, gas with cold-dilute and hot-concentrated
Answer the following questions: NaOH in water give sodium salts of two (different) oxoacids of
D1. The oxyacid of P having tetrabasicity is/are chlorine, P and Q, respectively. The CL, gas reacts with SO,
(a) CandH (b) CandE gas, in the presence of charcoal, to give a product R. RK reacts
with white phosphorus to give a compound 8. On hydrolysis, 5
(c) C andD (d) BandE
gives an oxoacid of phosphorus, T.
D2. Which of the acids show reducing properties ?
(a) E, FandG (6) E,GandH Answer the following questions:
(c) Eonly (dq) EandF D9. HK, 5 and T, respectively, are
D3. Monobasic oxyacids of phosphorus is/are (a) SO,C1,, PCl, and H,PO,
(a) HandE (6) AandE (6) SO,CL,, PCl, and H,PO,
(c) CandG (d) E only (c) SOCI,, PCl, and H,PO,
D4. Which of these can exist as polymeric ? (d) SOCI,, PCl, and H,PO,
(a) Aand E (6b) A only D10. P and Q, respectively are the sodium salts of
(c) CandG (d) H only. (a) hypochlorous and chloric acids
D5. Which of these is dibasic as well as reducing ? (6) hypochlorous and chlorous acids
(a) E (6) A (c) chloric and perchloric acids
(c) G (d) /¥. (d) chloric and hypochlorous acids. (.L.T. 2013)
Passage IT.
There are some deposits of nitrates and phosphates in earth’s Passage IV.
crust. Nitrates are more soluble in water. Nitrates are difficult to Upon heating KC1O, in the presence of catalytic amount of
reduce under the laboratory conditions but microbes do it easily. MnO,, a gas W is formed. Excess amount of W reacts with
Ammonia forms large number of complexes with transition white phosphorus to give X. The reaction of X with pure HNO,
metal ions. Hybridization easily explains the ease of sigma gives Y and Z.
donation capability of NH, and PH,. Phosphine is a flammable
gas and is prepared from white phosphorus. Answer the following questions :
D11. Y and Z are, respectively
Answer the following questions :
D6. Among the following, the correct statement is
(a) N,O, and HPO, (6) N,O, and H,PO,
(a) Phosphates have no biological significance in humans
(c) N,O, and H,PO, (d) N,O, and HPO,
(JEE Advance 2017)
(6) Between nitrates and phosphates, phosphates are less D12. W and X are, respectively
abundant 1m earth Ss crust (a) O, and P,O, (b) O, and PA.

wers (c) O, and P,O, (d) O, and P,O,,

Ans (JEE Advance 2017)
Passage I. D1. (c) D2. (a) D3. (d) D4. (a) D5. (d). Passage II. D6. (c) D7. (c) D8. (0d).
Passage III. D9. (a) D110. (a). Passage IV. D1l1.(a) D12. (0).
p-BLOCK ELEMENTS 7/151 >

pie

4, Assertion : P i is more reactive than N.,.

Assertion Reason Type Questions Reason : P—P single bond in P, is much weaker than
N=N in N, molecule.
The questions given below consist of an Assertion and
5. Assertion : Xenon forms fluorides.
Reason. Use the following key to choose the appropriate answer.
Reason i: Because 6d-orbitals are available for valence
(a) Ifboth assertion and reason are CORKECT and reason
is the correct explanation of the assertion. = a Chamaes
(6) Ifboth assertion and reason are CORRECT, but reason 6. Assertion : HCIO, is stronger acid than HCIO,.
is NOT THE CORRECT explanation of the assertion. Reason’ : Oxidation state of Cl in HCIO, is +7 and in
(c) If assertion is CORRECT but, reason is INCORRECT. HC10, 1s +6.
(d) If assertion is INCORRECT but, reason is CORRECT. 7. Assertion : Iodine dissolves in aqueous solution of
(e) If both assertion and reason are INCORRECT. eo epaide. |
i | Sa es Reason : Potassium iodide behaves as an organic
1. Assertion : Ozone is a powerful oxidising agent in : ie
comparison to O solvent and therefore, dissolves non-polar
Reason 7 but O, is paramagnetic.
=: Ozoneis diamagnetic
iodine.
(A.LLM.S. 2005) 8. Assertion : HC1O P is less acidic than HBrO =
2. Assertion : F, has low reactivity. Reason’ : HClO, ionises less in water than HBrO,.
Reason : F—F bondhas low bond dissociation enthalpy. 9. Assertion : H,PO, is a dibasic acid.
(A.LLM.S. 2002) Reason =: There are two H atoms directly bonded to P.
3. Assertion : F—F bond in F, molecule is strong. 10. Assertion : Reaction of SO, and H,S in the presence of
Reason : F atom is small in size. Fe,O, catalyst gives elemental sulphur.

Reason — : SO, is reducing agent.

Answets
1. (5) a. a) 3. (d) A, (a) 5. (a) 6. (dD) ae) 8. (e) 9. (c) 10. (5)

Matrix Match Type Questions

(A) Pyrophosphoric acid | (p) Dibasic
| Each question contains statements given in two columns, (B) Thiosulphurie acid (q) has oxidiation of +3 of
which have to be matched. Statements in Column I are labelled central atom
as A, B, C and D whereas statements st Column IT are labelled (C) Orthophosphoric acid] (7) has +5 oxidation state of
as p,g,r ands. Match the entries of Column I with appropriate qaibes |Fase
entries of Column II. Each entry in Column I may have one or (D) Phosphoric acid Steed
more than one correct option from Column II. The answers to
these questions have to be appropriately bubbled as illustrated 2. Match the compound in Column I with the property in
in the following example. Column I.
Pp q s4/,
“=

A (P) (p) has square pyramidal structure

(gq) does not exist
g1®i=
-
OOO (7) has +5 oxidation state of central atom
(s) gets hydrolysed.
© © © 3. Match each of the reactions given in Column I with the
D q) (r) (s) corresponding product(s) given in Column II.

If the correct matches are A-g, A-r, B-p, B-s, C-r, C-s and
D-g, then the correctly bubbled matrix will look like the (A) Cu + dil. H,SO, (p) NO
following: (B) Cu + cone. HNO, (q) NO,
1. Match the compound in Column I with the property in (C) Zn + dil. HNO; (7) N,O
Column II. (Dy) £n + cone. HNO, (s) Cu (NQO,),
(t) Zn(NO,),
Aaswes S (LLT. 2009)
WD ee lee) (B) —(p) (C)— (r), (s) (D)
— (p), (q@)
(2) : (A) —(s) (B) —(—), (rv), (s) (C) —(p), (s) (D)
— (q)
(3) : (A) —(p), (s) (B) — (q), (s) (C)-(r), @ (D)
— (q), @)
a 71152 MODERN'S abe + OF CHEMISTRY
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Matching Type Questions

Match the entries of column I[ with appropriate entries
of column IT and choose the correct option out of the four
options (a), (b), (c), or (d) given at the end of each question.
(LIT. (Advance) 2013)
1. The incomplete chemical reactions given in List I 2. Math the compound given in List I with structure and
show missing reagent or conditions (?) which are number of lone pairs in List IT.
provided in List Hf. Match List I with List IT and
select the correct answer using the code given below
1. T shaped, 2
the lists. 2. Square, 2
3. Square pyramidal, 1
4, Linear, 3
PbO, + H,SO, —> PbSO, + O,
Na,S,0, + H,O —>» NaHSO,
N,H, —> N, + other products
Aen —+ Xe + other products
(LET. Advance 2074)

Answess
1. (d) 2. (dD)

orthophosphoric acid, diphosphoric acid, metaphos-

Integer Type or Numerical Value Type Questions
phoric acid, peroxophosphoric acid, the acids having
+3 oxidation state of P are
Integer Type: The answer to each of the following question
is a single-digit-integer ranging from 0 to 9. The difference in the oxidation numbers of the two
types of sulphur atoms in Na,5,O, is
1. The number of molecules/ions having one lone pair of ULT. JEE 2011)
electrons among the following
Reaction of Br, with Na,CO, in aqueous solution gives
AsH,, XeOF,, CIF,, SF,, XeOf AQF,, SOM XeF,, sodium bromide and sodium bromate with evolution
ICL, BrO,-, XeOF,, XeF, 1s of CO, gas. The number of sodium bromide molecules
The number of oxoacids of sulphur having oxidation involved in the balanced chemical equation is
state of + 6 among : sulphuric acid, dithionous (LT. JEE 2011)
acid, pyrosulphuric acid, peroxomonosulphuric acid,
Among the following, the number of compounds that
sulphurous acid, thiosulphuric acid, peroxodisulphuric
can react with PCl, to give POCI, is O,, CO,, 5Q,,
acid is
Wo, HS; Fei,
The number of acidic oxides among N,O,, Cl,O., Al, Og,
(L.L.T. 2011)
CO, P,0,,, Fe,@,, MzOnee g SO,, SO,, NO, Na,O is
The difference between the number of lone pairs and
Total number of dibasic acids among H,PO,, H,P,0O.,
P — O bonds in P,O, molecule is
H,P,0,, H,PO,, AyPOAA,P.O,, H,PO, is
10. The total number of lone pairs of elections in N,O, is
Among phosphonic acid, phosphinic acid, pyrophospho-
(JHE Advance 2015)
rous acid, hypophosphorous acid, hypophosphoric acid,

Answer
| Pe 2. A. 3. 6. 4, 2. oD. 2. 6. » 45 8. 5 9.4 10.8
p-BLOCK ELEMENTS

Exemplar Problems //
Objective Questions
(6) It’s solution inwater decomposes 1n the presence of light.
Multiple Choice Questions (Type-l)
(c) Itis more basic than NHg.
- On addition of conc. H,SO, to a chloride salt, colourless (d) Itis less basic than NH,.
fumes are evolved but in case of iodide salt, violet fumes 9. Which of the following acids forms three series of salts?
come out. This is because | (a) HPO, (6) H,BO,
(a) H,SO, reduces HI tol, (6) HI is of violet colour (c) H.PO (d) H.PO
(c) HI gets oxidised tol, (d) HI changes to HIO Sh sad
wail : .
ee ae : 10. Strong reducing behaviour of H,PO, is due to
. In qualitative analysis, when H,5 is passed through an 4 < 3 2
aqueous solution of salt acidified with dil. HCl, a black (a) Low oxidation state of phosphorus
precipitate is obtained. On boiling the precipitate with dil. (6) Presence of two -OH groups and one PH bond
HNO,, it forms a solution of blue colour. Addition of excess of (c) Presence of one -OH group and two P—H bonds
aqueous solution of ammoniato this solution gives (d@) High electron gain enthalpy of phosphorus
(a) deep blue precipitate of Cu (OH), 11. On heating lead nitrate forms oxides of nitrogen and lead.
(6) deep blue solution of [Cu (NH,),]** The oxides formed are
(c) deep blue solution of Cu(NO,), (a) NO, PbO (b) NO,, PbO

° ee SO ee ee ee 12. Which of the following elements does not show allotropy?

and double bonds are present? (a) Nit (6) Bismuth
(a) 3 double bonds; 9 single bonds os Alpe eer
(6) 6 double bonds; 6 single bonds (c) Antimony (d) Arsenic
(c) 8 double bonds; 12 single bonds 13. Maximum covalency of nitrogen is
(d) Zero double bonds; 12 single bonds (a) 3 (6) 6
- Which of the following elements can be involved in px—dr (c) 4 (d) 6
bonding? ; 14, Which of the following statements 1s wrong?
(a) Carbon (6) Nitrogen
(o) Pihoephviti ia haben (a) Single N—N bond is stronger than the single P—P bond.
» Which of the following pairs of ions are isoelectronic and (0) PH; can act ieabas ligand in the formation of coordination
aepetuetucel? compound with transition elements.
(a) CO8-, NOZ (b) ClO, COZ (c) NO, is paramagnetic in nature.
(c) SOz, NO; (d) ClOZ, SO2- (d) Covalency of nitrogen in N,O, 1s four.
. Affinity for hydrogen decreases in the group from fluorine 15. A brown ring is formed in the ring test for NO, ion. It is
to 1odine. Which of the halogen acids should have highest due to the formation of
bond dissociation enthalpy? (a) [Fe(H,O), (NO)]2+ (b) FeSO,.NO,
(a) HF
(c) HBr
(b) HCl
(d) HI (c)
a
[Fe(H,O),(NO),]?*
| gant
(d) FeSO,.HNO,
. Bond dissociation enthalpy of E—H (E = element) bonds is se eae l of i ay Lean ished a ai . sas
given below. Which of the compounds will act as strongest soak ee ismut Seek ea eee eer eae
eae soni compound in +5 oxidation state. The compound is

_| NH; |PH; |AsH,| SbH,|

und (a) Bi,O, (b) BiF.
[Compo
Bg FT mak
= 17. =
On heating ammonium Bis,
dichromate and barium azide
(a) NH, (6) PH, separately we get
(c) AsH, (d) SbH, (a) N, in both cases
» On heating with concentrated NaOH solution in an inert (6) N, with ammonium dichromate and NO with barium
atmosphere of CO,, white phosphorus gives a gas. Which azide
of the following statement is incorrect about the gas? (c) N,O with ammonium dichromate and N, with barium
(a) It is highly poisonous and has smell like rotten fish. azide
| eS (d) N,O with ammonium dichromate and NO, with barium
Aaswe azide

ee) 2. (i) 3. (a) Ase) 5. (a) 6. (a) a. Aa) 8. (c) of te) 10. (c)
11. (d) 12. (a) 13. (c) 14, (a) 15. (a) 16. (bd) 17. (a)
a 71154 MODERN'S abe + OF CHEMISTRY
-AXII

i
t-

18. In the preparation of HNO,, we get NO gas by catalytic (a) —3 to +3 (6) —3 to 0

oxidation of ammonia. The moles of NO produced by the (c) —3 to +6 (d) Oto-—38
oxidation of two moles of NH, will be : 24, Inthe preparation of compounds of Xe, Bartlett had taken
O; PtF; as a base compound. This is because
(a) 2 (6) 3
(a) both O, and Xe have same size.
(c) 4 (d) 6 (6) both O, and Xe have same electron gain enthalpy.
19. The oxidation state of central atom in the anion of
(c) both O, and Xe have almost same ionisation enthalpy.
compound NaH,PO, will be (d) both Xe and O, are gases.
(a) +3 (b) +6 25. In solid state PCl. is a
fei a1 (d) —3 (a) covalent solid
20. Which of the following is not tetrahedral in shape? (6) octahedral structure
(a) NH; (b) SiCl, (c) ionic solid with [PCl,J* octahedral and [PCl1,]-
(c) SF, (d) SOP tetrahedra
21. Which of the following are peroxoacids of sulphur? (d) ionic solid with [PCl1,]* tetrahedral and [PC1,]~
(a) H,SO, and H,5,0, (6) H,SO, and H,8,0, octahedra
26. Reduction potentials of some ions are given below. Arrange
(c) H,S,0, and H,S,0, (dq) H,5,0, and H,S,0,
them in decreasing order of oxidising power.
22. Hot conc. H,SO, acts as moderately strong oxidising
agent. It oxidises both metals and non metals. Which of
the following element is oxidised by conc. H,5O, into two
toa J WE a0; |; | Bo;
Reduction 1.19V 1.65V 1L.74V
gaseous products? potential E7/V
(a) Cu (6) S (c) C (d) Zn
23. Ablack compound of manganese reacts with a halogen acid (a) ClO; > IO; > BrO,- (6) IO, > BrO > CIOL
to give greenish yellow gas. When excess of this gas reacts (c) BrO; > IO, > ClO, (d) BrO, > ClO, > 10,-
with NH, an unstable trihalide is formed. In this process
27. Which of the following is isoelectronic pair?

Answet
the oxidation state of nitrogen changes from :
(a) ICL, ClO, (®) BrO; , BrF,*
(c) ClO,, BrF (d) CN’, O,

18. (a) 19. (ec) 20. (c) 21. (a) 23. (a) 24, (c) 25. (d) 26. (c) 27. (0)

» ll. Multiple Choice Questions (Type-ll) (6) Leaving F—F bond, all halogens have weaker X—X
bond than X—X’ bond ininterhalogens.
(c) Among interhalogen compounds maximum number of
Note : In the following questions two or more options may be
correct. atoms are present 1n iodine fluoride.
28. If chlorine gas is passed through hot NaOH solution, two (d) Interhalogen compounds are more reactive than
changes are observed in the oxidation number of chlorine halogen compounds.
during the reaction. These are and 32. Which of the following statements are correct for SO, gas?
(a) Oto +5 (b) 0 to +3 (a) It acts as bleaching agent in moist conditions.
(c) Oto -1 (d) Oto +1 (6) It’s molecule has linear geometry.
29. Which of the following options are not in accordance with (c) It’s dilute solution is used as disinfectant.
the property mentioned against them? (d) It can be prepared by the reaction of dilute H,S5O, with
(a) F, > Cl, > Br, > L, — Oxidising power. metal sulphide.
(6) MI > MBr > MCl> MF - Ionic character of metal halide. 3a. Which of the following statements are correct?
(c) F, > Cl, > Br, > L, — Bond dissociation enthalpy. (a) All the three N—O bond lengths in HNO, are equal.
(6) All P—Cl bond lengths in PCl, molecule in gaseous
(dq) HI < HBr < HCl < HF — Hydrogen-halogen bond
state are equal.
strength.
(c) P, molecule in white phohsphorus have angular strain
30. Which of the following is correct for P, molecule of white therefore white phosphorus is very reactive.
phosphorus? (d) PCl, 1s ionic in solid state in which cation is tetrahedral
(a) It has 6 lone pairs of electrons. and anion is octahedral.
(6) It has six P—P single bonds. 34, Which of the following orders are correct as per the
(c) It has three P—P single bonds. properties mentioned against each?
(d) It has four lone pairs of electrons. (a) As,O, < S10, < P,O, < SO, — Acid strength.
31. Which of the following statements are correct? (6) AsH, < PH, < NH,— Enthalpy of vapouri-sation.
(a) Among halogens, radius ratio between iodine and (c) S<O<Cl<F— More negative electron gain enthalpy.
fluorine is Maximum. (d) H,O > H,S > H,Se > H,Te — Thermal stability.

Answess
26. iG co) 255 tine) Si (ood) ol. tae a) G2.) 33. (c, d) 34. (a, d)
p-BLOCK ELEMENTS

30. Which of the following statements are correct? (a) CaF, + H,SO,—-> CaSO, + 2HF
(a) S—S bond is present in 5,0. (6) 2HI + H,50,—> I, +50, + 2H,O
(6) In peroxosulphuric aci (H,SO.) sulphur is in +6
oxidation state. (c) Cu + 2H,SO, —> CuSO, + SO, + 2H,O
(c) Iron powder along with Al,O, and K,O is used as a (d) NaCl + H,SO, —> NaHsO, + HCl
of”. Which of the following statements are true?
catalyst in the preparation of NH, by Haber’s process.
(d) Change in enthalpy is positive for the preparation of (a) Only type of interactions between particles of noble
SO, by catalytic oxidation of SO,,. gases are due to weak dispersion forces.
36. In which of the following reactions conc. H,SO, is used as (6) lonisation enthalpy of molecular oxygen is very close
an oxidising reagent? to that of xenon.

Arse:
(c) Hydrolysis of XeF’, is a redox reaction.
(d) Xenon fluorides are not reactive.

35. (a, 5) 36. (5, c,) 37. (a, 8,)

» Matching Type Questions

<q Code:
(a) A(4) BG) C (1) D (2)
Note: Match the items of Column I and Column II in the
(6) A(3) BA) C (1) D (2)
following questions.
38. Match the compounds given in Column I with the (c) A(4) BD) C(2) D (8)
hybridisation and shape given in Column I] and mark the (dq) A(2) | B(1) C (3) D (4)
correct option. 41. Match the species given in Column I| with the shape given
in Column II and mark the correct option.

(A) XeF, (1) sp°d? — distorted octahedral

(B) XeO, (2) sp*d? — square planar
(1) Tetrahedral
(C) XeOF, (3) sp? — pyramidal
(2) Pyramidal
Eee (4) sp? d? -square pyramidal
(3) Sea-saw shaped
Code : (4) Bent T-shaped
(a) A(1) B (8) C (4) D (2)
(6) A(1) B (2) C (4) D (8) Code:
(c) A(4) B (3) C (1) D (2) (a) A(3) = B®) C (1) D (4)
(d) A(A4) B (1) C (2) D (8)
359. Match the formulas of oxides given in Column I with the type
(6) A(3) B(4) C (2) D(1)
of oxide given in Column IT and mark the correct option. ()AQ) BC) C (8) D (4)
(dq) AQ) BA) C (3) D (2)
(A) PbO, (1) Neutral oxide Match the items of Columns I and II and mark the correct
(B) N,O (2) Acidic oxide option.
(C) Mn,0, (3) Basic oxide
(D) Bi,O, (4) Mixed oxide (A) Its partial hydrolysis does not change
Code: oxidation state of central atom
(a) A(1) B (2) C (8) D (4) (B) It is used in modern diving apparatus
(6) A(4) B (1) C (2) D (38) (C) Itis used to provide inert atmosphere
(ec) A(8) B (2) C (4) D (1) for filling electrical bulbs
(d) A(A) B (3) C(1) D (2) (D) Its central atom is in sp°d?
40). Match the items of Columns | and IJ and mark the correct hybridisation
option.
Code:
(A) H,50, (1) Highest electron gain enthalpy (a) A(1) B (4) C (2) D (8)
(B) CCI,NO, (2) Chaleogen (6) A(1) B(2) C (8) D (4)
(CG) Cl, (3) Tear gas (c) A(2) B (1) C (4) D (8)
(D) Sulphur (4) Storage batteries (d) AQ) B (3) C (2) D (4)

Araswets
38. (a) 39. (5) AQ. (a) Al. (5) AZ. (c)
 MODERN'S abe + OF CHEMISTRY
-AXII

<q Reason : HNO, forms a protective layer of ferric nitrate

on the surface of iron.
In the following questions a statement of assertion Assertion : HI cannot be prepared by the reaction of KI
followed by a statement of reason is given. Choose the with concentrated H,SO,
correct answer out of the following choices. Reason: HI has lowest H—X bond strength among halogen
(a) Both assertion and reason are correct statements, and acids.
reason is the correct explanation of the assertion.
46. Assertion : Both rhombic and monoclinic sulphur exist as
(6) Both assertion and reason are correct statements, but
5, but oxygen exists as O,.
reason is not the correct explanation of the assertion.
Reason : Oxygen forms px — pm multiple bond due to
(c) Assertion is correct, but reason is wrong statement.
small size and small bond length but px — pm bonding is
(d) Assertion is wrong but reason is correct statement.
not possible in sulphur.
(e) Both assertion and reason are wrong statements.
47. Assertion : NaCl reacts with concentrated H,SO, to give
43. Assertion : N, is less reactive than P,.
colourless fumes with pungent smell. But on adding MnO,
Reason : Nitrogen has more electron gain enthalpy than the fumes become greenish yellow.
phosphorus. Reason : MnO, oxidises HCl to chlorine gas which is
4A, Assertion : HNO, makes iron passive. greenish yellow.
Assertion : SF, cannot be hydrolysed but SF, can be.

Answers43. (c) 44, (c) 45. (bd) 46. (a) AZ. (a) 48,
Reason : Six F atoms in SF, prevent the attack of H,O on
sulphur atom of SF,.

(a)

p l anations for
H i n t s & E x Difficult Objective Type Questions

A. mcq with only one correct answer

s—s—O- O—S—S—O-
A3. (6) : Hypophosphoric acid is H,P,O, |
O
oxidation state of P = +4.
Ad, (a): P, + 20HNO,(cone.)
—> 4H,PO, + 20NO, + 4H,O
O= ,
i O- Oe
1 4
AZ. (6) : Ammonium nitrite (NH,Cl + NaNO,) gives N, on
|
heating. O- -O O
A8. (a) : NO, is a brown coloured gas. A21. (d) : SQ, trimer has the structure:
-H,0
AY. (6) : 2HNO, 7, N,O, + Hoe
Al0. (a) : NF, is least basic because electron pair on N is least
O°
available due toi; electronegativity of F. o~
|
~Ole
Zo There is no S—S bond.
All. (d) : (NH,),Cr,O, _ Hee Cr,O, + N, + 4H,O0 OSS
Al12. (6) : No. of obonds = 16
Al13. (6) : O.S. of Sin SO? (+4), 5,0,7 (43), 5,07 (45) A22. (6) : In F,O, the oxidation state of oxygen is +2.
A24, (c) : Na,5,O, + Cl, + H,Q ——> Na,SO,+ 2HC1+5
Al4, (5) : In general, the boiling points of hydrides increase
A26. (d): Iodine gives blue colour with starch solution.
down the group. However, H,O has highest boiling
point due to hydrogen bonding. Therefore, the correct A29. (d): Bromine being stronger oxidising agent displaces
order of boiling points is: H,S < H,Se < H,Te < H,O weaker oxidising agent (1,) from its salt (Nal).
Therefore, most volatile hydride is H,5. 2Nal + Br, ——-> 2NaBr + I,
A32. (a) : Fj does not exist because of the absence of d-orbitals
Al8. (a) : HCOOH —224-5 CO +H,0 in F atom.
Al19. (c) : I,+ 60, + H,O——> 2HI1O, + 60, A384, (6): Cl,O, + H,O ——-> 2HCIO,
A20. (d) : 5,0,7> has no S—S bond because sulphur atoms A385. (a): XeF,+H,O °°, xXeOF, + 2HF
are linked through O-—atoms. All others have
A40. (6) : XeF, + 3H,0 ——-> XeO, + 6HF
58-5 bond.
p-BLOCK ELEMENTS

3
B24.
B. meq from Competitive Examinations F

Bas (6): fo, (80), — 2 5sFe,6, 2586, = zi *]

B5. (5) : Hypophosphorous acid is monoprotic acid. eee . !

F Se '
O
|
p
is ,

FE
ee
—"
B27. bay H,5,0, peroxodisulphurie acid (Marshall's acid) has
0 -1 +5
B6. (6) : 3Clg+ 6NaOH — NaCl +NaClO3 + 3H,O0 peroxo (— O — O —) linkage.
(hot & conc.)
B28. (c) : Br, reacts with Nal only to give [,.
: In this case, oxidation state of chlorine changes 2Nal + Br, —+ 2NaBr + I,.
from 0 to —1 and + 5 and hence is an example of
B29. (a) : Pyrophosphorous acid (H,P,O,) is a dibasic acid
disproportionation reaction.
because it contains two P— O-—H bonds:
B8. (a) : HClO, 1s the strongest acid. It has highest oxidation
state (+7 for Cl) and its conjugate base 1s resonance
A —
ro
— i : — FH
stabilised.
B10. (c) : Reducing behaviour of H,PO, is due to the presence OH OH
of one —OH bond and two P—H bonds. B30. (DIS Cyclotrimetaphosphoric acid is (HPO,),.
Bll. (6) : OF, is fluoride of oxygen not oxide of fluorine because Oxidation state of Pis
electronegativity of fluorine is more than that of +14x4+383(-2)=0 .x=46.
oxygen. B32. . CIF, is mainly used to produce UF,, as a part of
B13. (6) : NO, 1s not used as food preservative but SO, 1s used nuclear fuel processing and reprocessing.
as a food preservative. U(s) + 3ClF, (¢) —> UF, (g) + 3ClF (e)
B14. (a) : Phosphinic acid (H,PO,) is monoprotic and B33. fay = The P—H bond present in H,PO, imparts reducing
phosphonic acid (H,PO,) is a diprotic acid. property to the acid.
B17. (c) : Cu+4HNO, (cone.) —> Cu(NO,), + 2NO, + 2H,O 4 AgNO, +2H,O +H,PO,—-> 4Ag + 4HNO, + H,PO,
B18. (d) : During the reaction: CaF, + H,SO, —~+ CaSO, +1 —l +5
B34, (ec) : sHoc| —— 2HCl + HClO,
+ 2HF, the oxidation state of 5 remains same.
Therefore, it does not behave as an oxidising agent. s le} 2 On moving down the group, the size of central
atom increases. Due to this, availability of lone pair
B20. (a) : (A) XX’ (e.g. CIF): (ii) Linear of electrons decreases. Hence the basic character
(B) XX‘, (e.g. CIF): (2) T-shape decreases.
(C) XXZ (e.g. CIF): (iv) Square pyramidal . lel< (it) HPO, because it loses a proton and therefore,
(D) XX! (e.g. IF): (a) Pentagonal bipyramidal itis a Bronsted acid.
B21. (a) : 8,0,” and§,0,? contain S—S bonds. . tS The stability of hydrides decreases from NH, to
Bil, due to increase in size of the central atom.

|
“O—S—s—s—s—O_
| |S
a —_
B38. (d) : The oxidation state of sulphur in its compounds
varies from — 2 to + 6.
|
O
!
O
o7 \QO~° B39. (ce) : O, molecule is a bent molecule.
S,0,2-
46 50. B40. (b) : Interhalogen compoundd (ICI) are more reactive
because of weak bond between dissimilar atoms
than between similar atoms in halogens.
O O
B41. (bd) : Down the group, van der Waals forces of attraction
increase and hence Xe has the highest boiling point.
B42. (a) : 4Zn + 1OHNO, (dil.) —> 4Zn(NO,), + N,O + 5H,O
Zn + 4HNO, (cone.) —> Zn(NO,), + 2NO, + 2H,O
B43. (a) : Orthophosphorous acid: H,PO,
B22. (a) : HNO, (+6), NO (+2), N, (0), NH,Cl (—3) Oxidation state of P = +3
B28. (d) : Chlorine has the highest negative electron gain Pyrophosphorous acid : H,P,0,
enthalpy. Oxidation state of P = +3
a 7/158 MODERN'S abe + OF CHEMISTRY
-AXII

+4 +1 +6 0 B62. (d) : Po is a metal and therefore, it does not show any

B44, (a): Mek tO, ~ Ask. + 0 negative oxidation state.
Xe is oxidised from +4 to +6.
B63. (a) : (NH,),Cr,0;
—"— N, + Cr,0, + 4H,O
Oxygen is reduced from +1 to 0. Bé4, (d) : Fluorine has low F — F bond dissocation enthalpy.
This is a redox reaction. B65. (c) : NaCl and NaCl0O are formed when Cl, reacts with
B45. (c) : CL, + 2NaQH ——-> NaCl + NaClO + H,O cold dil. NaOH.
ld
2NaQH + Cl, a NaCl + NaClO + H,O

B46. (d) : Ba(N,), —“> Ba+8N, With hot NaOH, NaCl and NaClO, are formed.
6NaQOH + 38Cl, et 65NaCl + NaClO, + 3H,O
(NH,),Cr,0, ——> N, + 4H,0 + Cr,0, B66. (a) : Nitrogen forms pa-pz bonds with itself.
B67. (c) - XeF J is sp*d* hybridised with two lone pair of
NH,NO, —*—> N, +2H,O electrons. Its shape is pentagonal planar.
(NH,),SO, —> 2NH,+H,SO,
B47. (d) : 2Na,5,0, + 1, ———>Na,5,0, + 2Nal AY
Po Xe—>F
B50. (e) : Stability decreases down the group because size ry
‘ f
of central atom increases and its tendency to form
a =
covalent bond with small atom decreases.
B51. (ce) : In group 15, catenation tendency of P is higher as |
F oa Cl 4

LV
compared to other elements of the group. B68. {coer. LI

(a) : In Ostwald’s process, the formation of HNO, occurs

& =p
B52.
As:
ats | CO}
4NH, +60, 55> 4NO + 6H,0 + Energy oT
—a

2NO + O, —> 2NO,

3NO, + H,O —> 2HNO, + NO
-1
B54, ip) : 3Cl, + 6NaQH(ag) —-> 5NaCl + NaCl O,+3H,0 sp°d, linear a —
(Hot)
B69. (a) : PBr, —— [PBr,]* [Br]
B55. (d) : 4H,PO, -—“» 38H,PO, + PH,
Phosphorous Orthophosphoric Phosphine B70. (ec) : His a strong reducing agent and its aqueous solution
acid acid gets oxidised even by atmospheric oxygen.

B56. (a) : P, + 3NaOH + 3H,0O —*-» PH, + 3NaH, PO, AHI + O, ——-> 2H,0 + 21,
Pi. is less basic than NH.. B71. ia)2 CLO, + H,O ——> 2HCIO,
B57. (a) : Ps) + 10 50, C1, (2) —> 4 PCl(s) + 1050, Cl,O, 1s anhydride of HClO,
B58. (b) : Basicity of H,PO, 1s two because it has two ionizable B72. (ce) 2 2H,O + 2F, ——> 4HF+0O, or (Ht, F, O,)
H atoms
B73. (d) : 250,(¢g) + Na,CO,(aq) + H,OW) ———>
2NaHsSO,(aq) + CO,
Pe ta NaHsSO,(aqg) + Na,CO, ——-> Na,SO, + H,O + CO,
Now Both NaHSO, and Na,SO, are formed.
O O
B59. (ce) : I |
“O—S—sS—O o—s=s
| B74, : Cl,O and ClO, are both gases and are used to
prepare NaClO, which is used as a bleaching agent.
8,0," | B77. (a): (NH,),Cr,0, —*> Cr,0, + N, + 4H,O
8,0,"
NH,NO, —*—> N, +2H,O
O O 2NH,VO, —“—> V,O, + 2NH, + H,O
| |
Oo—sS—o—s—
1 |
—s—s—O NH,NO, —*—> N,O + 2H,O
| O
| | B78. Cas 2NaN, —*— 3N, + 2Na
(Dd) :
cenauhinalt;aearemneuiie
B79.
$,0,7° S,0,7
S,0,* does not have S—S bond.
B61. (c) : In solid state, PCI, exists as [PCL,]* [PC1,]~ P, +30, —2> P,O,
p-BLOCK ELEMENTS

(a) 1s wrong because number of Cl=O bonds in (zt) and (zzz)

B80. (d) : Ba(N,), —2"-> Ba +3N,. together is three.
B81. (c):
(6), (c) are correct.
+1 —3
P,(s) + 3NaOH(aq) + 3H,0 ———> 3NaH,PO,(ag) + PH,(g) (d), (tv)is the strongest acid.
Sodium Phosphine
hypophosphite C6. (6, d) : P,O,,+4HNO,—> 2N,0, +4 HPO,
+1 +5 —3 The nitrogen containing compound produced above is
3NaH,PO,(aq) ———*Na,PO, + 2PH, NOL:
In the above reactions, phosphorus undergoes It cannot be prepared by the reaction of P, and HNO,.
simultaneous oxidation and reduction to +5 and—3 Itis diamagnetic.
oxidation states respectively. The reaction in which It does not contain N—N bond.
species undergoes oxidation and reduction are called N,O, 1s decomposed by alkali metals.
disproportionation reactions. N,O, + Na—> NaNO, + NO,
B82. (5) : Nitric acid upon long standing turns yellow brown Brown gas.
due to decomposition by sunlight into NO,. CT. (acy:
i

4HNO, —Sumeht_, 4NO, + 2H,0 + O5 ’ i

F = ee ie

B83. (a) : P, +8 SOCI,—-> 4PCl, + 4SO, +2S,Cl, a D ey

cB LM!
# f i
(white)
— \ ! /
B84, (c) :XeF, + 3H,O ee XeO, + 6HF
(P) J
F

OH7/H,0O
F -
Ww. . Slow dis ortionation =
: KeOs + Xe (g) a LO HxXeO,
+H,O + O,(g) (Q)
Therefore 2 gases are released.
B85. (d) : The correct order is:
+5 +4 +35 +1
HPO, > H,P,0, > H,FO, > H,PO,
C8. (b,c): X(F,): KK(62s), (o*2s), (o2p,), (n2p,)” =(n2p,),
C. meq with more than one correct answer
(x°2p,)° =(x"2p,), (o2p,)°
Cl. (6,c) : P, has six PP bond and each 4 PPP is 60°.
HOMO (LUMO)
C2. (a, 6): NH,X + NaQH—-> NaxX + H,O + NH, “if
The colours of halogens arise because of absorption
Cc = NO,, NO, Cl, Saas) of light on promoting an electron from HOMO (1*)
to LUMO (o*). On descending down the group,
NO, +4 Zn + 7O0H-—->4Zn0,* + 2H,0 + NH,? the energy levels become closer and gap between
NO,” + 3 Zn + |0H- —+ 3Zn0,* + H,O + NH, HOMO and LUMO decreases.
C3. (a, b,c): N,O N=N—30 Cll. (6,c): NH,NO, ——>N,0+H,O0

O O (NH,),Cr,0, > N, + Cr,0, + 4H,O

N,O
93 N—N “36 Ba(N,), —> 3N, + Ba
Mg,N, —“<-» 3Mg +N,
Only (NH,),Cr,O, and Ba(N,), give N, on heating
N,O
oA Ayn
ox So below 300 °C.
C12. (a,b,c): Bi,O,1s more acidic than NO,
O = Pil
O NF, is more covalent than BiF, because of lesser
N,O
95 0 N—O—N So electronegativity difference.
C5. (8,c) : Boiling point of NH, is more than PH, because of
hydrogen bondingin NH,.
| P_P bond is stronger than N—N single bond because
0 Cle Cla Clay in N due to smaller size of atoms lone pair-lone pair
H~" No o~ No HO~ \~° aoe \>°
repulsions will be more.
H
(z) (iz) (tit) (tv)
an 7/160 MODERN'S abe + OF CHEMISTRY
-AXII

6. : N,O,,C1,0,, P,O,,, CO,,5O,, SO, are acidic oxides.

D. mcq based on passage/comprehension
: H,PO, and H,P,O, are dibasic acids.
D6. (c) : Nitrates being water soluble and as they get re-
duced by microbes so obviously its abundance will 2. : Phosphonic acid (H,PO,), pyrophosphoric acid
decrease. (H,P,0,) have oxidation state of +3 for phosphorus.
D7. (c) : NH, 1s a stronger Lewis base than PH,.
0 1 +3 O O
D8. (6) : P, + 3NaOH + 3H,O ——>3NaH, PO, + PH, l |
Here P, is oxidized to NaH,PO, and it is reduced to 6. 6. : Na 03 -@&
S wa
PH, O O
D9. (a) : R,S and T, are respectively, SO,Cl,, PCl., H,PO,
Sulphur has oxidation number = + 5, 0
Cl, + 2NaOH (dil) —“" ;NaCl + NaClO + H,O
(P) Difference in oxidation number = 5

3Cl, + 6NaOH (conc.) hot_, 5NaCl + NaClO, + 3H,O 3Br, + 3Na,CO, —-> 5NaBr + NaBrO, + 3CO,
(Q) Number of NaBr molecules = 5
P and Q are salts of hypochlorous acid (HCI1O) and 8 5.7 Fae 4f SO, —> POC], + SOC,
chloric acid (HC1O,) respectively.
Pcl, + H,O ——-=> POC,
C,.450, a Sack. PCl, + H,SO, ———> POC,
)
10 SO,Cl, + P,—— 4PCl, + 1050,
6PCl, + P,O, ———> 10 POC,
(8) PCI + O, —Heat_, poci, + Cl,
PCl, + 4H,O —-> H,PO, + 5HCl In the structure of P,O,.
For Questions D11 and D12,
2KCIO, —"_, 2KCl + 30,
MnO, cw)

SO,+ P, ae P49
(X)

P,O, 9+ 4AHNO, ———> 2N,0, + 4HPO,

1) (Z)
D11. (a)
D12. (5)

Number of lone pairs = 16

Matrix Match Type Questions
Number of P — O bonds = 12
3. (p, s): 3Cu + 8 HNO,—-> 38Cu(NO,), + 4H,0 + 2NOT Difference = 16-12 =4
(dil.) a :O: 10: :O%
10. 8:
(g, s): Cu+4 HNO, —> Cu(NO,), + 2H,O + 2NO,7T NF
Ni-N <—> \ N—N VA
“0 mA
(conc.)

(r, t): 4Zn + 10 HNO, —+ 4 Zn(NO,), + 5 H,O + N,OT It has 8 lone pairs of electrons.
(dil.)

(g, tf) : Zn+4 HNO £n(NO,), + 2H,O + 2NO,7

(conc.)
NCERT Exemplar Problems : MCQs Type-I
1.(c) : In case of iodine, the halogen acid obtained (HJ) is
Integer Type Questions oxidised to free iodine.
2Nal + 3H,SO, —— 2NaHSO, + SO, + L, + 2H,O
1. 7 : The molecules/ions having one lone pair of electrons
2.(6) : Cu2* + HS — >» CnuS + 2H",
are :
Black
AsH,, XeOF,,, SF,, XeO,, SO,, BrO,-, XeOF,,. CuS + dil HNO, —> Cu(NQ,),
2. A. : Sulphuric acid (H,SO,), pyrosulphuric acid Blue

(H,5,0,), peroxomonosulphuriec acid (H,SO,), Cu(NO,), + 4NH,OH —-> [Cu(NH,),]**

peroxodisulphuric acid (H,5,O,). Deep blue
p-BLOCK ELEMENTS

Oe lla Phosphorus involves pm — dr bonds. 22. (c): C + 2H,SO,—> 2S0,(g) + CO,(g) + 2H,O
Fa A because it has lowest bond dissociation enthalpy (E—H 23. (2): MnO, + 2HC1—-+ MnCl, + Cl, + 2H,O
bond) and hence strongest reducing agent. Greenish
2 te) 4P + 3NaOH + 3H,O —-+ NaH,PO, + PH, yellow
PH, 1s less basic than NH. NH, + 3Cl, —~> NCI, + 3HCl
Be71h Basicity of HPO, is three and it has three ionisable Oxidation state of N in NH, (—3) and in NCI, (+ 3).
OH.
25. (d): 2PCl, ——— uo rh [Perl
10. (@):: Strong reducing behaviour of H,PO, is due to the
presence of two P—H bonds. tetrahedral (octahedral)

11. (b): 2Pb(NO,), Heat, 9PbO + ANO, + O, 26. (c) : Higher the reduction potential, stronger the reducing
agent.
135. (e).: Maximum covalency of nitrogen is four.
27. (6): BrO; (86 +2 x 8+ 1=62)
and BrF} (36 + 2 x 9-1=62)
14, (a): Single P—P bond is stronger than N—N bond.
are isoelectronic.
16. (b): Only Bik. is known.
17. (a): (NH,),Cr,0, “> Cr,O, +N, + 4H,O, NCERT Exemplar Problems : MCQs Type-lI
Ba(N,), —"» Ba + 3N, 28. (a), (c) : BNaQH + 38CL,—-> 5NaCl+ NaClO, + 3H,O
18. (a): ANH, + 50, —> 4NO + 6H,O (O.N = 0) (O.N=—-1) (O.N = +5)

2 mol of NH, gives 2 mol of NO. 29. (0), (c) : Ionic character: HF > HCl > HBr > HI
19. (ec): NaH,PO, : Here +1 +2 (+1) +x + 2(-2) =0 Bond dissociation enthalpy : Cl, > Br, > F, > I,
or x =+1 30. (5), (d): It has six P—P bonds and four lone pairs of
20. (ce): SF, has see saw shape because it involves sp*d electrons.
hybridisation. 32. (a), (c) : SO, acts as a bleaching agent in moist conditions
21. (a): H,50, (peroxomonosulphuric acid) and H,5,0, and its dilute solution is used as disinfectant.
(peroxodisulphuric acid).

UU)
fen 62 MODERN'S abe + OF CHEMISTRY
-AXII

VY UnitPracticeTest ¢g

Time Allowed : 2 Hrs. Maximum Marks : 35

1. Which halogen has a tendency to form cations? (1)

2. Give the disproportionation reaction of H,PO,. (1)
3. Why is IC] more reactive than I,? (1)
4. Name the halogen which forms only one oxoacid and write the formula of the oxoacid ? (1)
5. Arrange H,O, H,S and H,Se in the decreasing order of acid strength? (1)
6. Why does R,P=O exist but R,N=O does not exist (R = alkyl group)? Explain. (2)
7. Comment on the nature of two S—O bonds formed in SO, molecule. Are the two S—O bonds in this molecule
equal? (2)
8. Draw the structures of
7) SF, (i) XeF, (2)
9. Give reasons for the following :
(1) SF, is not readily hydrolysed
(iz) Sulphur in vapour state is paramagnetic. (2)
10. What are interhalogen compounds ? Give examples. Why are these more reactive than halogens. (2)
11. (a) Considering the parameters such as bond dissociation enthalpy, electron gain enthalpy and hydration
enthalpy, compare the oxidising power of Cl, and F,.
(6) Why is helium used in diving apparatus? (3)
12. Explain the following :
(1) NH, is a stronger base than PH,.
(it) Sulphur exhibits greater catenation tendency than selenium.
(tit) HPO, is a diprotic acid. (3)
18. Write the four oxoacids of chlorine. Explain their relative acidic character. (8)
14. Explain the chemistry of manufacture of nitric acid by Ostwald’s process? How does it react with iodine? (8)
15. Complete the following chemical quations: (8)
(i) Ca,P, (s) + H,O @) > £
(i) Fig) (@) + H,0 @) f >
(iit) Ca,(PO,), +510, +C —>
16. (a) Nitrogen exists as diatomic molecule and phosphorus as P,. Why?
(6) Write the resonating structures of NO, and N,O,.
(c) Give two examples to show anomalous behaviour of fluorine.
(d) Why is BiH, the strongest reducing agent amongst all the hydrides of group 15? Explain.
(e) Draw the structure of P,O,,. (5)
 d-AND #-BLOCK
ELEMENTS
Building on.... Assessing.... Preparing for Competition....
@ Understanding Text 1 @ Quick Memory Test with @ Topicwise MCQs 69
¢ Conceptual Questions —-25, 37, 50 Seka Red ass ol A Se ean oe
7 ¢ HOTS van ve - | er ot oards
CHAPTER SUMMARY & QUICK QaneHina iat Aner bo | ee 71
CHAPTER ROUND UP 51 REVISION EXERCISES > JEE (Main) & Other State
NCERT FILE (with Previous Years’ CBSE Qs ; Boards’ Engineering Entrance 72
“Tugech es ee oa & Other State Boards Qs) g3. » JEE (Advance) for IIT Entrance
ecanoa sparta ¢ Hints & Answers for Revision 7
Solutions 53 Resins 69 a NCERT Exemplar Problems
# NCERT Exemplar Problems with (EITSSEG2: TESTE)
@ Hints & Explanations for
2
Answers & Solutions (Subjective) 57 UNIT PRACTICE TEST 86 Difficult Questions 82

The d-block consists of elements lying between s- and p-blocks i.e., between
Ah “groups 2 and 13, starting from fourth period and onwards. In these elements,
> the outermost shell contains one or two electrons in their s-orbital (ns)
f », — but the last electron enters the last but one d-subshell i.e., (n — 1)d.
_. The elements of this block have general characteristic properties
\. intermediate between the elements of s-block and p-block. The
\ dblock elements are also called transition elements. The study
\ of transition metals is important because the precious metals
\ such as silver, gold and platinum and industrially important
metals like iron, zinc, palladium, copper, titanium, nickel,
| chromium, etc. are transition elements.
The elements in which the last electron enters the forbital
of the atoms are called block elements. In these elements,
the last electron is added to the third to the outermost (called
antepenultimate) energy shell i.e., (n — 2) f. Therefore, these
elements are also called inner transition elements. These consist of
two rows of elements placed at the bottom of the periodic table and
are called lanthanoids and actinoids. These two series are generated
: by the filling of characteristic electrons in the 4f (lanthanoids) and 5f
_—f (actinoids) orbitals.
The names transition metals and inner transition metals are often used for the d- and # block elements respectively.

CHEMISTRY OF d-BLOCK ELEMENTS ~

TRANSITION ELEMENTS OR d-BLOCK ELEMENTS AND THEIR POSITIONS IN THE PERIODIC TABLE
The transition elements are those elements which have incompletely filled (partly filled) d-subshells in
their ground state or in any one of their oxidation states.
This definition covers coinage metals, Cu, Ag and Au (of group 11) as transition metals because in their commonly
occurring oxidation states, they have partly filled d-subshells. For example, Cu** has 3d° configuration, Ag** has 4d®
 MODERN'S abe + OF CHEMISTRY-All

configuration, Au** has 5d° configuration, although all these three atoms have
completely filled d-subshell in their elementary states (Cu : 3d19; Ag : 4d19; Au :
5d1"). However, it may be noted that the above definition does not include elements
of group 12 (previously called IT B) t.e., Zn, Cd and Hg. These elements do not have
partly filled d-subshells in their elementary state or in their commonly occurring
oxidation states. However, being the end members of three transition series, these
may be treated along with transition elements. They are quite similar to other
transition elements in some of their chemical properties.
The d-block or transition elements occupy position in between s and p-block in
eroups 3-12 in the periodic table (Fig. 1). The name ‘transition’ is given to these
elements of d-block because of their position between s and p-block elements. They
represent change (or transition) in properties from most electropositive s-block
elements to least electropositive (or most electronegative) p-block elements. In
their atoms, the d-orbitals of the penultimate (n—1) energy level receive electrons.

d-Block
Transition elements

AROARReD.
; @
22 + 24) 25] 26 | 27 29 | 30
1-2 Ti Crd Mn | Fe | Co | Cu | Zn
8-BlOCK |39 | 40 | 41 43 | 44| 45 | 46 | 47 | 48
Y | Zr |Nb Tc |Ru| Rh} Pd | Ag} Cd
57 |721 73 we 75 |76| 77 re | 79 | 80
La*| Hf Ta | Re | Os] Ir | Au Aig
1041105! 106! 1407| 108 110/411 1112
he Rf |Db| Sg | Bh |Hs Ds |Rg |Cn
f-Block
_—"—"_“7ia Inner Transition Elements ————————-
Nvablesendag 58 60 61 | 62 | 63 65 | 66 | 67 68 | 69 | 70 | 71
Ce Nd | Pm| Sm] Eu « Tb | Dy | Ho} Er Tm| YBa Lu
**Actinoid 90 | 91 | 92 | 93 | 94 | 95 | 96 | 97 | 98 | 99 100) |10
series Th | Pa| U | Np]| Pu| Am} Cm] Bk | Cf | Es | Fm| sa

Fig. 1 Position of d-block and f-block elements in the periodic table.

ELECTRONIC CONFIGURATIONS OF TRANSITION ELEMENTS
In the transition elements, the d-orbitals are successively filled. The general
electronic configuration for the atoms of d-block is: (m -— 1)d‘-!° ns! where
(7. — 1) stands for inner shell (or penultimate shell) and d-orbitals may have one
The general electronic configu-
to ten electrons and the s-orbital of the outermost shell (7) may have one or two
ration of d-block elements is : electrons.
(n-1)d)-"° ns Transition series
The transition elements consist of four rows of ten elements. These rows are
called first, second, third and fourth transition series which involve the filling
of 3d, 4d, 5d and 6d- orbitals respectively.
First transition series :Scandium (Z= 21) to Zine (Z = 30)
3d-orbitals are gradually filled.
Second transition series : Yttrium (Z = 39) to Cadmium (Z = 48)
4d-orbitals are gradually filled.
Third transition series : Lanthanum (Z = 57), Hafnium (Z = 72) to Mercury
(Z = 80)
5d-orbitals are gradually filled.
Fourth transition series : Actinium (Z = 89), Rutherfordium (Z = 104) to
Copernicium (Z = 112)
6d-orbitals are gradually filled.
Let us discuss the electronic configurations of individual members of these
series.
d-AND #BLOCK ELEMENTS

First transition series

The first transition series consists of elements from scandium, Sc (Z = 21)
to zine, Zn (Z = 30)i.e., scandium, titanium, vanadium, chromium, manganese,
iron, cobalt, nickel, copper and zinc. In scandium, the 3d-orbital starts filling
up and its electronic configuration is [Ar] 4s23d1. As we move from scandium
onwards, 3d-orbitals get filled up more and more till the last element, zinc, in
which the 3d-orbitals are completely filled, i.e., [Ar] 4s?3d1°.

Element Symbol Atomic Electronic

number configuration

Scandium Se ral [Ar] 3d14s?

Titanium Ti 22 [Ar] 3d74s?
Vanadium V 23 [Ar] 3d74s?
Chromium Cr 24 [Ar] 3d°4s1
Manganese Mn 25 [Ar] 3d°4s?
Iron Fe 26 [Ar] 3d°4s?
Cobalt Co 2a [Ar] 3d/4s?
Nickel Ni 28 [Ar] 3d*4s?
Copper Cu 29 [Ar] 3d1°4s1
Zine Zn 30 [Ar] 3d1°45

Exceptional configurations of Cr and Cu.

It may be noted that the configurations of chromium and copper
are anomalous. We know that halj-filled and completely-filled electronic
configurations (i.e., d° and d*") have extra stability associated with them.
Moreover the energy difference between 3d and 4s-orbitals is not large enough
to prevent the electron entering the 3d orbitals. Thus, to acquire increased
stability, one of the 4s-electrons goes to nearby 3d-orbitals so that 3d-orbitals
become half- filled in case of chromium and completely-filled in case of copper.
Therefore, the electronic configuration of Cr is [Ar] 3d°4s! rather than [Ar] 3d+
4s? while that of Cu is [Ar] 3d!9 4st instead of [Ar] 3d? 4s”.

Second transition series

The second transition series consists of elements from yttrium,
Y (Z=39)to cadmium, Cd (Z= 48), 7.e., yttrium, zirconium, niobium, molybdenum,
technetium, ruthenium, rhodium, palladium, silver and cadmium. This series
involves the filling of 4d-orbitals.
Element Symbol Atomic Electronic
number configuration

Yttrium ef 39 [Kr]4d‘5s? The element technetium (Tc)

Zirconium Zr 40 [Kr]4d75s? is a synthetic transition metal
Niobium Nb 41 [Kr]4d45s? which was made artificially. This
Molybdenum Mo 42 [Kr]4d°5s? was so named, because the word
Technetium Te 43 [Kr]4d%5s? technetium means artificial.
Ruthenium Ru A4 [Kr]4d‘5s+
Rhodium Rh A5 [Kr]4d°5s?
Palladium Pd 46 [Kr]4d™%5s°
Silver Ag AT [Kr]4d™%5s*
Cadmium Cd 48 [Kr]4d'"5s?

Third transition series

This series consists of elements lanthanum (Z = 57) and from hafnium
(Z = 72) to mercury (Z = 80) z.e., lanthanum (La), hafnium (Hf), tantalum (Ta),
tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au)
and mercury (Hg). In between lanthanum and hafnium, there are fourteen
elements called lanthanoids which involve the filling of 4f-orbitals and do not
 MODERN’S abe + OF CHEMISTRY-ill

belong to this series. The elements of this series involve the gradual filling of
REMEMBER
5d-orbitals.
The electronic configurations
of d-block elements have, Element Symbol Atomic Electronic
number configuration
in general, the following
characteristics: Lanthanum La 57 [Xe] 4f/°5d16s?
@ an inner core of electrons Hafnium Hf fie [Xe] 4f1*5d76s?
with noble gas configuration Tantalum Ta 73 [Xe] 4f1*5d?6s?
i.e., ns*np®. Tungsten W 74 [Xe] 4f1*5d*6s
(1 — 1) d orbitals are filled Rhenium Re 75 [Xe] 4f145d56s2
progressively. Osmium Os 76 [Xe] 4f145d56s2
Iridium Ir 77 [Xe] 4f145d76s”
Most of these have 2
electrons in the outermost Platinum Pt 78 [Xe] 4f!45d°6s!
i.e., ns-subshell. Some of the Gold Au po [Xe] 4f'45d19651
elements (e.g., Cr, Cu, Nb, Mercury Hg 80 [Xe] 4/450 10652
Mo, Tc, Ru, Rh, Ag, Pt, Au, Rg
etc.) have only one electron It may be noted that in the second and third transition series, there are
in ns subshell whereas many anomalous configurations in comparison to those of first transition series.
These are attributed to factors like nuclear-electron and electron-electron forces.
> Pd has no electron in
Fourth transition series
the ns-subshell.
It involves the filling of 6d-subshell starting from actinium (Z = 89); which
Pa (4 =46) > WKri 4q* os" has the configuration 6d17s*. It includes elements with atomic number 104
e In La (Z = 57) one electron onwards as given below :
goes to 5d-orbital before filling Element Symbol Atomic Electronic
of 4f-orbital (an exception number configuration
from Aufbau order).
Actinium Ac 89 [Rn] 5/°6d!7s2
Rutherfordium Rf 104 [Rn] 5f46d27s2
Hafnium Ha 105 [Rn] 5f**6d?7s*
Seaborgium Sg 106 [Rn] 5f46d4782
Bohrium Bh 107 [Rn] 5f1*6d°7s?
Hassium Hs 108 [Rn] 5f**6d°7s?
Meitnium Mt 109 [Rn] 5f**6d"7s?
Darmstadtium Ds 110 [Rn] 5f**6d°7s*
Rontgenium Rg WEL [Rn] 5f1*6d?°7s?
Copernicium Cn 112 [Rn] 5f!*6d"" 7s?

It may be noted that recently, the IUPAC has approved the name coper-
nicium with symbol Cn for the element with atomic number 112.

We have learnt that in all the transition metals, the ns-orbitals are filled before
the (n — 1) d-orbitals. For example, in scandium (Z = 21), the last electron goes
For K and Ca
to 4s-orbital rather than 3d-orbital because the 4s-orbital lies a little lower than
the 3d-orbital. However, it has been observed that a reversal of the relative
order of 3d- and 4s-orbitals occurs when the 3d-orbitals have been fed with
A)
qo some electrons. The change in energy levels of the various orbitals can be easily
level
——+
¥ understood by considering the effect of nuclear charge. The variation in relative
energies of various subshells with the change in atomic number is shown in
Energ
Fig. 2. It is observed that as the nuclear charge increases, the energies of the
subshells decrease. Upto argon (Z = 18), the expected sequence of 1s, 2s, 2p, 3s
40
Atomic number ——. and 3p is observed. After filling 3s and 3p-subshells we expect that the next
electron in potassium (Z = 19) should enter the 3d-subshell. But, at K (Z = 19)
Fig. 2. Change in energy levels
and Ca (Z = 20), 4s-orbital has lower energy due to its greater penetration
of various orbitals with increasing
nuclear charge. tendency than 3d-orbital. Therefore, in K and Ca, the outermost electron enters
d-AND #BLOCK ELEMENTS

the 4s-orbital. However after calcium, there is a sharp decrease in the energy of
3d-subshell and its energy becomes less than the 4s-subshell (shown in a circle
in Fig. 2). Therefore, the next electron after calcium goes to 3d-orbital. As the
nuclear charge increases from Ca (20) to Zn (30), the 3d-orbitals get filled and
become more effective in shielding the 4s-electrons from the nucleus.
Ionisation of atoms
The fundamental difference in
We have observed that after calcium, the energy of 4s-subshell is more than
the electronic configurations
3d-subshell (Fig. 2). Therefore, when electrons are to be removed from these atoms,
of transition elements and
the electrons will go from 4s-orbital rather than 3d-orbital, though the former
representative elements is that
was filled earlier. For example, in the representative elements
Fe(Z = 26) [Ar] 3d%4s? (belonging to s- and p-block), the
valence electrons are present only
Fe?* [Ar] 3d° and not [Ar] 4s?3d+
in the outermost shell. On the other
Ni(Z = 28) [Ar] 3d°4s? hand, in the transition elements,
Ni2* [Ar] 3d° the valence electrons are present in
The same trend is repeated for 5s, 4d and 6s, 5d-orbitals in second and third the outermost shell (ns) as well as
d-orbitals of penultimate (n—1) shell.
transition series. In the lanthanum, the energies of 4f, 5d and 6s-orbitals lie very
close to one another and one electron goes to 5d-orbital before 4f-orbitals. Its
configuration is 5d'6s. In the other elements, 4f-orbitals are stabilized relative
to 5d and electrons go into 4f-orbitals.
GENERAL CHARACTERISTICS OF TRANSITION ELEMENTS
The general characteristics of d-block elements are :
1. Nearly all the transition elements have typical metallic properties such
have high tensile strength, ductility, malleability, high thermal and
electrical conductivity and metallic lustre.
2. Except mercury which is liquid at room temperature, other transition
elements have typical metallic structures.
3. They have high melting and boiling points and have higher heats of
vaporisation than non-transition elements.
4. The transition elements have very high densities as compared to the
metals of groups | and II (s-block).
5. The first ionisation energies of d-block elements are higher than those
of s-block elements but are lesser than those of p-block elements.
They are electropositive in nature.
Most of them form coloured compounds.
They have good tendency to form complexes.
&
2PN
They exhibit several oxidation states.
10. Their compounds are generally paramagnetic in nature.
11. They form alloys with other metals.
12. They form interstitial compounds with elements such as hydrogen, boron,
carbon, nitrogen, etc.
18. Most of the transition metals such as Mn, Ni, Co, Cr, V, Pt, etc. and their
compounds have been used as good catalysts.
GENERAL PROPERTIES OF TRANSITION ELEMENTS
The properties of the transition metals show greater horizontal similarities
in contrast to the main group elements in the periodic table. They also show
similarities in groups but somewhat more irregularly than the main group
elements. The electronic configurations and other important properties of the
first series of the transition elements are given in Table 1.
 MODERN'’S abc + OF CHEMISTRY-Aill

Table 1. Electronic configurations and some other important

properties of the first series of transition elements.

Element Se Ti V Cr Mn Fe Co Ni An

Atomic number Al 22, 23 24 29 26 27 25 29 30

Electronic configuration
M 3d14s? 3d74s* 3TaeeRoe 3d°4s! 3d°4s? 3d°4s 3d'4s? 3d°4s* 3d1%451 3d1945
M* 3d14s! Sale 3d2%4s5! 3d° 3d°4s! 3d°4s! 38d‘4s1 3d°4s1 9d 10
3d1%4351
M2+ 3q1 3d? ae poe a0 346 3d! 3d° 3d? 9d 10

M** [Ar] Po le ae 3d* aq5 3d® 3d!

Enthalpy of atomisation
A, H*’/kJ mol- 326 469 515 398 279 418 427 431 309 130
A, , H* (kJ mol“) 15.9 15.5 17.6 13.5 14.6 15.3 15.2 17.6 13.0 Le
Aap H° (kJ mol) —-338.9 445.6 443.5 300.4 224.7 300.9 389.1 380.7 338.9 114.6
Ionisation enthalpy/A;H°/kJ mol
a 631 661 648 653 716 762 757 736 745 908
LeAe eT | 1235 1310 1370 1590 1510 1560 1640 1750 1960 1730
AH? Ill 2393 2657 2833 2990 3260 2962 32435 3402 3596 3829
Metallic/ionic M 164 147 135 129 137 126 125 125 128 137
radii (pm) M+ -— fe 82 82 five 74 70 73 75
M* 73 67 64 62 65 65 61 60
Standard
electrode M”*/M — — 1.65 —1.18 — 0.90 —1.18 — 0.44 — 0.28 — 0.25 + 0.34 — 0.76
potential M**/M* —- — 0.57 — 0.26 — 0.41 Ff 1.57 Pid op bee
E° (Vv)
Density (g em™*) 3.48 4.1 6.07 11g fea fie 8.7 eee 8.9 fia

Let us consider the general trends of some of the important properties.

1. Atomic Radii
The atomic radii of the transition elements are intermediate between those
of s- and p-block elements. The following trends in atomic radii of elements of
d-block are observed :
(a) The atomic radii of elements of a particular series decrease with increase
in atomic number but this decrease in atomic radit becomes small after midway.
For example, for the elements of first transition series, the atomic radii decrease
gradually from scandium to chromium but from chromium to copper, it remains
practically constant. The atomic radii of the d-block elements are given in
Table 2 and are also shown in Fig. 3.
Table 2. Atomic radii of d-block elements (in pm).
V
Se Th Cr Mn Fe Co Ni Cu An
164 147 135 129 137 126 125 125 128 137

Y Ae Nb Mo Te Ru Rh Po Ag Cd
180 160 146 139 136 134 134 137 144 154
La *HE Ta W Re Os Ir Pt Au Hg
187 158 146 139 13s7 135 136 138 144 157
* Includes 14 lanthanoid elements and has lanthanoid contraction.
Explanation. The atomic radius decreases in a period in the beginning,
because with increase in atomic number, the nuclear charge goes on increasing (by
d-AND #BLOCK ELEMENTS

unity) progressively. However, we know that the electrons

enter the penultimate (last but one) shell and the added
d-electrons screen the outermost s-electrons. The
shielding effect of d-electrons is small so that the net —e———®— 5d series
—e——_*®— 4d series
electrostatic attraction between the nuclear charge and pancoOo —$——-®— 3d series
the outermost electron increases. Consequently, the _
atomic radius decreases. As the number of d-electrons E
= =k=JoO
increases, the screening effect increases. This neutralises tH

the effect of increased nuclear charge due to increase —

1?)
in atomic number, and consequently, atomic radius
oO
ta Sa
ano
2
remains almost unchanged after chromium. E
2
Similar behaviour has been observed for the second < —kanOo

and third transition series.

(6) At the end of each period, there ts a slight increase
in the atomic radii. This is evident from Table 2.
Explanation. Towards the end of the series, there
are increased electron-electron repulsions between
Group ———>
the added electrons in the same orbitals which exceed
the attractive forces due to increased nuclear charge.
Fig. 3. Variation of atomic radii with atomic number of
Therefore, electron cloud expands and the size increases. transition elements.
The electron-electron repulsions can be understood
from the electronic configurations of these atoms. Upto
chromium (3d°4s!) electron-electron repulsions do not come into picture because
there is no pairing of electrons in d-subshell. However, from iron onwards,
the pairing of electrons (Fe: 3d®4s?) in d-orbitals results into electron-electron
repulsions which causes an increase 1n size. Now, the increased nuclear charge
makes the atom to shrink while electron-electron repulsions cause the size to REMEMBER
expand. In Fe, these two opposing effects almost counter balance each other JP peotytarrc etd op he ssc a
and, therefore, there is no change in size on going from Mn to Fe. In the last Peiimneenaicak cetera cnet race
elements, Zn, Cd and Hg, these electron-electron repulsions become predominant nearly same due to lanthanoid
and, therefore, there is increase in size. contraction, discussed later in
(c) The atomic radii increase while going down the group. Therefore, the this chapter.
atomic radii of transition metals of second series have large values than those
of the first transition series. However, the transition metals of third transition
series have nearly the same radii as metals of second transition series above them.
Explanation. The atomic radii of elements of second transition series are
more than those of first transition series because the electrons in the atoms
of second transition series elements occupy energy levels farther from the
nucleus. With the increase in number of outermost shell, size increases. The
similar atomic radii of elements of second and third transition series are due to
a special phenomenon known as lanthanoid contraction. This is associated
with the intervention of the 4f-orbitals which are filled before the 5d series of
elements starts. The filling of 4(-orbitals before 5d orbitals results in regular
decrease in atomic radii which compensates the expected increase in atomic
size with increasing atomic number. As a result of this lanthanoid contraction,
the elements of second and third transition series have almost similar atomic
radii (e.g., Zr 160 pm, Hf 159 pm). Because of this, these elements of two series
also have very similar physical and chemical properties. It is discussed later.
2. lonie Radii
The ionic radii follow the same trend as the atomic radii. Since the metals
exhibit different oxidation states, the radii of ions also differ. In general, the tonic
radi decrease with increase in oxidation state. For the same oxidation state, the
ionic radii generally decrease with increase in nuclear charge. For example, in the
first transition series, the radii of bivalent metal ions decrease as given ahead :
 MODERN’S abc + OF CHEMISTRY-XII

Table 3. Variation of ionic radii (pm) in transition series.

Metal (M) Se Ti V Cr Mn Fe Co Ni Cu 7n
rM2+ (pm) - — 79 82 82 17 14 70 ta 1S
r( M+) (pm) Ta 67 64 62 65 65 61 60 = -

The ionic radii of the transition metals are smaller than those of the main
sroup elements.
3. Metallic Character and Enthalpy of Atomization
All the transition elements are metals. They exhibit all the characteristics
of metals. They all have high density, hardness, high melting and boiling
points, high tensile strength, ductility, malleability, high thermal and electrical
conductivities and lustre. With the exception of zinc, cadmium and mercury,
the transition elements are much harder, less volatile and brittle than s-block
elements. They have simple hexagonal close packed (hcp), cubic close packed (ccp)
or body centred cubic (bcc), lattices which are characteristic of other metals. The
lattice structures of transition metals are given in Table 4. It is seen from the
table that except for Mn, Zn, Cd and Hg, all the transition metals have one or
more common metallic structures such as bee (body centred cubic), hcp (hexagonal
close packed) or ccp (cubic close packed) structures at normal temperatures.
Table 4. Lattice structures of transition metals.
First Transition Series
Group/Series 3 A 5 6 fi 8 J i ame IL [es
ad Se Ti V Cr Mn Fe Co NM Cu “Zn
hep hep bee Dee T Dee” [een cen? cen T
(bec) (bcc) (ccp) (hep) (hep) (hep)
Second Transition Series
Ad ae Zr Nb Mo Tc Ru Rh Pd Ag Cd
hep hep Bee. Ge) eg em cen ec teen T
(bec) (bec) (hep)
-~) Third series
Third Transition Series
Oo—————o Second series
© First series 5a La Hf Ta W Re Os Ir Pt Au Hg
hep hep nee. See Ter ied scent Grech. een T
(bec) (bec)
1
(ccp)
o
E
= *'T' represents a typical metallic structure at normal temperatures.
—
bs7 Explanation. The metallic character of transition elements is due to
their relatively low ionisation enthalpies and number of vacant orbitals in the
outermost shell. The hardness of these metals suggests the presence of strong
bonding due to overlap of unpaired electrons between different metal atoms.
Therefore, these elements exhibit high enthalpies of atomization as shown in
Atomic number —.
Fig. 4 (Table 1). In general, the greater number of unpaired d-electrons, greater
ts the number of bonds and therefore, greater is strength of these bonds. Thus,
Fig. 4. Trends in enthalpies of as we move from left to right in a particular d-series, the number of unpaired
atomization AH? (kJ mol!) of electrons increases from 1 to 6 and then decreases to zero in case of group 12.
transition elements.
The number of unpaired electrons in 3d-series are shown below :

Element

Electronic 3d14s*° 3d*4s* ad°4s* 3d°4s! 3d°4s* 3d°4s*— 3d‘4s" 3d®4s* 3d1°4s! = 3d1°4s?
configuration
No. of unpaired 1 2 3 6 +) 4 a 2 0
electrons
d-AND #BLOCK ELEMENTS

Cr, Mo and W have maximum number of unpaired electrons and, therefore,

these are very hard metals and have maximum enthalpies of atomization. The
elements Zn, Cd and Hg do not have any unpaired electrons, therefore, these
are not very hard. But they have one or more of typical metallic structures at
normal temperature.
Inspection of Fig. 4 also shows one interesting generalization. The metals of
Mercury is the only metal which
second (4d series) and third (5d series) have greater enthalpies of atomization
is liquid at room temperature.
of their corresponding elements of first transition series. This is an important
factor indicating more frequent metal-metal bonding in the compounds
of heavier transition elements (third series).
4, Density
All these metals have high density. Within a period, the densities vary
inversely with the atomic radit. As we move in a period, the densities increase
(as the radii decrease). For example, the density increases from titanium to
copper as given in Table 5. This is because as we move along a transition series
from left to right, the atomic radii decrease due to increase in effective nuclear
charge. Therefore, the atomic volume decreases, but, at the same time atomic
mass increases. Hence, density (atomic mass/atomic volume) increases.
Table 5. Variation of density (g cm™~) *) in first transition series.
Element Se Ti V Cr Mn Fe Co Ni Cu wn
Density 6.456 4.1 6.07 7.19 7.31 7.3 8.7 8.9 8.9 rie |

However, the densities increase upon descending a group. The densities of

second transition series are higher than those of first transition series and the
densities of third transition series are still higher. Osmium (22.57 g cm~) and
iridium (22.61 g cm~) have very high density among these elements.
Explanation. The atomic volumes of the transition elements are low because
the electrons are added in (n — 1) d-subshell and not in ns-subshell. Therefore,
the increased nuclear charge is partly screened by the d-electrons and the outer
electrons are strongly attracted by the nucleus. Moreover, the added electrons
occupy inner orbitals. Consequently, the densities of transition metals are high.
Therefore, decrease in atomic radius coupled with increase in atomic mass,
results in general increase in the density of these elements.
5. Melting and Boiling Points i series
The transition metals have very high melting and boiling
points. The melting points of the three transition series are shown
in Fig. 5. It is clear from the figure that the melting points of these
metals rise to a maximum value and then decrease with increase
in atomic number. However, manganese and technetium metals -— Second series
have abnormally low melting points.
Explanation. The high melting and boiling points of these
metals are due to strong metallic bonds between the atoms of
these elements.
This is also evident from the fact that these metals have high
enthalpies of atomization. The metallic bond is formed due to the
interaction of electrons in the outermost orbitals. The strength of
Transition metals
bonding is roughly related to the number of unpaired electrons.
In general, greater the number of valence electrons, stronger is
Fig. 5. Melting points of transition metals.
the metallic bonding, and consequently, melting points are high.
Therefore, as we move along a particular series, the metallic
strength increases upto the middle with increasing availability of unpaired Tungsten(W) has the highest melting
electrons upto d® configuration (e.g., Sc has 1, Tihas 2, V has 3, Cr has 5 unpaired point among the d-block elements.
electrons) and then decreases with decreasing availability of unpaired d-electrons (Fig. 5).
(e.g., Fe has 4, Co has 3 unpaired electrons and so on). Therefore, the melting
points decrease after the middle because of increase of pairing of electrons.
Since the alkali and alkaline earth metals have only one or two outer electrons
available, their melting points are relatively low in comparison to transition
ano MODERN'’S abe + OF CHEMISTRY-AXIl

metals. Similarly, the elements of group 12 (zinc, cadmium and mercury) are
quite soft with low melting points. Mercury is a liquid at room temperature
and melts at -38°C. These three elements behave typically because there
are no unpaired electrons available for metallic bonding and, therefore,
their melting points are low.

Inspection of Fig. 5 shows that there is a dip in the melting point curves at Mn and Te of first and second
row transition elements series. This unexpected observation is probably due to the fact that Mn has stable electronic
configuration (3d? half filled, 4s? fully filled). As a result, 3d electrons are more tightly held by the Mn atomic nucleus
and this reduces delocalisation of electrons resulting weaker metallic bonding than in the previous element Cr in
the series. The same trends are also observed in the second and third transition series with Te and Re, but are less
marked. Particularly, Re is refractory, having a melting point which is second only to that of tungsten amongst
transition elements.

6. lonisation Enthalpies
The following trends are observed in the ionisation enthalpies of the
d-block elements :
(t) The first tontsation enthalpies of d-block elements are higher than those
of s-block elements but are lesser than those of p-block elements. The tonisation
enthalpies increase as we move across each series, though not quite regularly.
The ionisation enthalpies of elements of first transition series are given in
Table 6.
Table 6. Successive ionisation enthalpies of elements of first
transition series.
i
i tion
Ioniza enthal al
hal py (kJ mol-*)

I i Hil

Explanation. The increase in ionisation enthalpy along a given transition

series is attributed to the effect of increasing nuclear charge which would tend
to attract the outer electron cloud with greater force. Consequently, ionisation
enthalpy is expected to increase. However, in case of transition elements, the
addition of electron takes place to the last but one 7.e., (7 — 1) d-subshell and
this, also increases the screening effect. With the increase in the electrons in
(n — 1) d-subshell, the outer electrons in ns-subshell are shielded more and
more. Thus, the effect of increasing nuclear charge is opposed by the additional
screening effect of the nucleus and consequently, tonisation enthalpy
increases from left to right but quite slowly among d-block elements.
The irregular trend in the first ionisation enthalpy of the first transition
serles elements is due to the fact that the removal of one electron alters the
relative energies of 4s and 3d orbitals. Therefore, there is a reorganisation
energy accompanying ionisation with some gains in exchange energy as the
number of electrons increases in the d” configuration and from the transference of
s-electrons into d-orbitals. Thus, there is expected general increasing trend in
the values of ionisation enthalpy because of increase in effective nuclear charge.
However, the value of chromium is lower because loss of one electron gives stable
(3d°) configuration. On the other hand, zine has high ionisation enthalpy
because electron has to be removed from 4s orbital of stable (8d!° 4s?)
d-AND #BLOCK ELEMENTS

configuration. Chromium and copper have

(iit) Table 6 also gives the first three ionization enthalpies of the elements of exceptionally high ionisation
first transition series. These values show that the second and third ionisation enthalpy values than those of
enthalpies also, in general, increase along a period. However, the magnitude of their neighbours. This is because
increase in the second and third ionisation enthalpies for the successive elements, of extra stability of half filled (in
is much higher. However, some exceptions are observed as given below : chromium 3d°) and fully filled (in
(a) Chromium and copper have exceptionally high ionisation enthalpy values
copper 3d").
than those of their neighbours. These exceptions are attributed to the extra
stability of half filled and completely filled set of d-orbitals in chromium (3d°*) and
copper (3d!") respectively. After the loss of first electron,
Cr and Cu acquire a stable configuration (3d° and 3d?") 4e) Third series
and the removal of second electron disrupts the stability @———@) Second series
and therefore, the removal of second electron is difficult. @- ooo @ First series

(6) The value of second ionisation enthalpy for zinc is Lo=] i

correspondingly low because the ionisation involves the

removal of an electron resulting stable 3d‘ configuration.
(c) The trend in third ionisation enthalpies is not
complicated by the 4s orbital factor and shows high values
for Mn** and Zn** because of stable 3d° and 3d" electronic
configurations. Similarly, the third ionisation enthalpy of mol!)
|.E.,(kJ
———»
Fe is very small because loss of third electron results in
stable 3d° configuration (IE, for Fe < IK, for Mn).
As is clear from Table 6, in general the third ionization
enthalpies are quite high. There ts break between the values Atomic number —————®
for Mn (ID and Fe (II). Moreover, the high values for
Fig. 6. Ionisa tion enthalpies of transition metals.
copper, nickel and zinc indicate that it is difficult to obtain
oxidation state more than two (+2) for these elements.
(iit) The ionisation enthalpies of elements of second and third transition
series are given in Table 7 and are shown in Fig. 6. Inspection of these values
shows that the first ionisation enthalpies of third transition series are higher
than those of first and second transition series.
Table 7. First ionisation enthalpies (kJ mol) of second and third
transition series.
Element EK. Element

Explanation. In the atoms of third transition series, there are filled

4f-orbitals. The 4f-orbitals have very poor shielding effect. As a result, the outer
electrons have greater effective nuclear charge acting on the outer valence
electrons. Therefore, their ionisation energies are higher.
7. Oxidation States
The transition metals exhibit a large number of oxidation states in their
compounds. This is one of the notable features of the transition elements. With
the exception of a few elements, most of these show variable oxidation states. These
different oxidation states are related to the electronic configuration of their atoms.
The existence of the transition elements in different oxidation states means
lan MODERN'’S abc + OF CHEMISTRY-Aill

that their atoms can lose different number of electrons. This is due to the
participation of inner (n — 1) d-electrons in addition to outer ns-electrons because,
the energies of the ns and (n — 1) d-subshells are almost equal. The lower oxidation
state is generally shown when only ns-electrons participate in bonding and higher
oxidation states are exhibited when both ns and (n — 1) d-electrons take part in
bonding.
For example, the oxidation states exhibited by the transition elements of
the first series are listed in Table 8 below.

Table 8. Different oxidation states of first transition series.

Outer Oxidation states

electronic configuration
+3
+2, +3, +4
+2, +3, +4, +5
+2, +3, (+4), (+5), +6
+2, 43, +4, (+5), +6,+7
+2, +3, (+4), (+5), (+6)
+2, +3, (+4)
+2, +3, +4
+1, +2
+2
*Oxidation states within brackets are unstable.
** Most common oxidation states are in bold type.
Variable oxidation states of second and third transition series. The
elements of second and third transition series also exhibit variable oxidation
states as given in Table 9.

Table 9. Different oxidation states of elements of second and third

transition series.
Second Transition Series

(+3) (+2) +2 +2 +2 uh
+4 (+3) +3 (+4) +3 +3
(+4) +4 (+5) +4 +4
+5 +5 (+5) (+6)
(+6)
+6 (+7)
(+8)

Third Transition Series

(+2) +2
(+3) (+3)
(+4) +4
+5 +5
+6

*The oxidation states in parentheses are uncommon.

It may be noted that the stability of a given oxidation state depends upon the
nature of the elements with which the metal is combined. The highest oxidation
states are found in compounds of fluorides and oxides because fluorine and oxygen
are most electronegative elements.
Some important conclusions regarding oxidation states of transition
elements.
d-AND #BLOCK ELEMENTS

The examination of the common oxidation states shown by different

transition metals reveals the following facts :
(t) The vartable oxidation states of transition metals are due to participation
of inner (n — 1) d and outer ns-electrons. The lowest oxidation state corresponds
to the number of ns-electrons. For example, in the first transition series, the
lowest oxidation states of Cr (3d°4s!) and Cu (3d1"4s!) are +1 while for others,
it is +2 (8d1-1%4s7).
(it) Except scandium, the most common oxidation state of the first row transition
elements is +2 which arises due to loss of two 4s-electrons. This means that after
scandium 3d-orbitals become more stable and, therefore, are lower in energy than
the 4s-orbitals. As a result, electrons are first removed from 4s-orbitals.
(iit) The elements which show the greatest number of oxidation states occur
in or near the middle of the series. For example, in the first transition series,
manganese exhibits all the oxidation states from +2 to +7. The small number of
oxidation states at the extreme left hand side end (Sc, Ti) is due to lesser number
of electrons to lose or share. On the other hand, at the extreme right hand side
end (Cu, Zn), it is due to large number of d-electrons so that only a fewer orbitals
are available in which the electron can share with others for higher valence.
For the first five elements, the minimum oxidation state is equal to the number
of electrons tn the s-orbitals and the other oxidation states are given by the sum
of outer s- and some or all d-electrons. The highest oxidation state is equal to the
sum of the outer s(ns) and (n — 1) d-electrons. (e.g., Ti'YO, VYO$,CrMO7 , Mn
Oj; , etc). For the remaining five elements, the minimum oxidation state is given
by the electrons tn s-orbital while the maximum oxidation state ts not related to
their electronic configurations, (e.g, Fe (II) and (III), Co (II) and (11), Ni dD, Cu (1)
and (II), Zn(1). The highest oxidation state shown by any transition metal is +8.
(iv) In the early elements of the series, scandium (IJ) is virtually unknown
and titanium (IV) is more stable than Ti (III) and Ti (11). At the other end, the
only oxidation state of zinc is +2 in which no d-electrons are involved.
(v) In the +2 and +3 oxidation states, the bonds formed are mostly tonic.
In the compounds of higher oxidation states (generally formed with oxygen
and fluorine), the bonds are essentially covalent. Thus, the bonds in +2 and
+3 oxidation states are generally formed by the loss of two or three electrons
respectively while the bonds in higher oxidation states are formed by sharing of
d-electrons. For example, in MnO, (Mn in +7) state all the bonds are covalent.
(vt) Within a group, the maximum oxidation state increases with atomic
number. For example, iron (group 8) shows common oxidation states of +2 and
+3 but ruthenium and osmium in the same group form compounds in the +4,
+6 and +8 oxidation states.
(vit) Transition metals also form compounds tn low oxidation states such as
+1 and 0 or negative. The common examples are [Ni(CO),], [Fe(CO),] in which
nickel and iron are in zero oxidation state.
(viii) The variability of oxidation states in transition elements arises because
of incomplete filling of d-orbitals in such a way that their oxidation states differ
by unity such as V!, VU yIV and VY. This behaviour is in contrast with the
variability of oxidation states of non-transition elements (p-block elements), where
oxidation states normally differ by a unit of two such as Sn**, Sn**, In* In*, etc.
(ix) Unlike p-block elements where the lower oxidation states are favoured
by heavier members (due to inert pair effect), the higher oxidation states are
more stable in heavier transition elements. For example, in group 6, Mo (VI)
and W (VI) are found to be more stable than Cr (VI). Therefore, Cr (VI) in the
form of dichromate in acidic medium is a strong oxidising agent whereas MoO,
and WO, are not.
(x) The transition elements show low oxidation states in some compounds
aC MODERN'’S abe + OF CHEMISTRY-AXIl

or complexes having ligands such as CO, which not only form sigma bonds with
the metal atoms but also have n-acceptor character (discussed in unit 9). For
example, nickel in Ni(CO), and iron in Fe(CO), have zero oxidation states.
8. Standard Electrode Potentials
The magnitude