Chemistry : p-Block Elements ALLEN®

Pre-Medical

Chapter No. 04
p-BLOCK ELEMENTS

S.No. Contents Page

01. Inert pair effect 139
02. Back bonding 140
03. Hydrolysis 142
04. Dimerisation / Polymerisation 144
05. Silicates / Silicones
EN 146
06. Allotropes 148
07. Boron family 150
08. Carbon family 156
LL

09. Exercise-I (Conceptual Questions) 160

10. Exercise-II (Previous Years Questions) 164
11. Exercise-III (Analytical Questions) 166
A

NEET SYLLABUS
p-Block Elements : General Introduction to p-Block Elements.
Group 13 elements : General introduction, electronic configuration, occurrence, variation of properties, oxidation states,
trends in chemical reactivity, anomalous properties of first element of the group; Boron, some important compounds:
borax, boric acids, boron hydrides. Aluminium: uses, reactions with acids and alkalies.
Group 14 elements : General introduction, electronic configuration, occurrence, variation of properties, oxidation states,
trends in chemical reactivity, anomalous behaviour of first element. Carbon, allotropic forms, physical and chemical
properties: uses of some important compounds: oxides. Important compounds of silicon and a few uses: silicon
tetrachloride, silicones, silicates and zeolites, their uses.

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OBJECTIVES
After studying this unit, you will be able to :

 appreciate the general trends in the chemistry of p-block elements;

 describe the trends in physical and chemical properties of group 13 and 14 elements;
EN
 explain anomalous behaviour of boron and carbon;
 describe allotropic forms of carbon;
 know the chemistry of some important compounds of boron, carbon and silicon;
 list the important uses of group 13 and 14 elements and their compounds.
LL

Perfection is not attainable , but if we chase perfection we can catch excellence.

Vince Lombardi
A

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p-BLOCK ELEMENTS
4.1 INERT PAIR EFFECT
 Inertness of ns2 electron to participate in chemical bond formation.
 On moving from 5th to 6th period in p-block there is an increment of 32 atomic number but due to poor
shielding effect of d and f electrons nucleus exert a strong attraction and therefore ns2 electron is tightly
held towards nucleus.
 ns2 electron will not be able to participate in chemical bond formation, this is called inert pair effect.
 It is observed in 6th period element.

Effect
 On moving down the group stability of lower oxidation state increases
B+ < Al+ < Ga+ < In+ < T+
C+2 < Si+2 < Ge+2 < Sn+2 < Pb+2
 T+3, Pb+4, Bi+5 acts as an oxidising agent

.
Illustrations
Illustration 1.
EN
Stability of trivalent cations of group III A will be in order.
(1) Ga3+ < In3+ < T3+ (2) Ga3+ > In3+ > T3+

(3) Ga3+ > In3+ < T3+ (4) T3+ > In3+ < Ga3+
Solution. Ans. (2)
LL
Illustration 2. A and Ga have the same covalent radius because of –
(1) Greater shielding power of s–electrons of Ga atoms.
(2) Poor shielding power of s–electrons of Ga atoms.
(3) Poor shielding power of d–electrons of Ga atoms.
(4) Greater shielding power of d–electrons of Ga atoms.
A

Solution. Ans. (3)

BEGINNER'S BOX-1
1. Which halide is unknown ?
(1) Tl(III) iodide (2) In(III) bromide
(3) Ga(III) fluoride (4) B(III) chloride

2. There is a tendency for the elements of groups 13 to 15 of higher periods, particularly period 6, to form
compounds with ions having a positive charge of _________ less than the group oxidation number.
(1) one (2) three (3) four (4) two

3. Which oxidation states are more characteristic for lead and tin ?
(1) For lead + 4, for tin + 2 (2) For lead + 2, for tin + 2
(3) For lead + 4, for tin + 4 (4) For lead + 2, for tin + 4

4. Which of the following pentahalide can not be formed :-

(1) PCl5 (2) AsCl5 (3) SbCl5 (4) BiCl5
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4.2 BACK BONDING
 It is a type of -coordinate bond.
 In this type of bond one element provide L.P. to the vacant orbital of other atom in the molecule and that
lone pair is delocalised in whole molecule.

ESSENTIAL CONDITION FOR BACK BONDING

 One atom should have L.P. to donate.
 Other atom should have vacant orbitals to accept L.P.
 One of the atom must belong to 2nd period. (either it can be a donar or it can be an acceptor)

EFFECT OF BACK BONDING

(i) Bond length
(ii) Hybridisation of central atom
(iii) Bond angle (may be same or may be increased)
(iv) Acidic and basic nature of molecule
(v) Regular geometry of molecule may or may not change.

TYPE OF BACK-BONDING
(a) p-p back-bonding EN
strength of back bonding
2p – 2p > 2p – 3p > 2p – 4p > 2p – 5p

F
j
j

F–donor
F–B B–acceptor
F
LL
j
j

F F F F
F B F B F B F B
F F F F
B.O=1.3
 due to Back bonding partial double bond character is developed i.e. why electron deficiency of B is
A

compensated i.e. why BF3 do not form dimer.

Lewis acidic strength of boron trihalide
BF3 < BCl3 < BBr3 < BI3

Example : Compare B–F Bond length in BF3 and in BF4–

–
F F
B B
F F F F F
Back Bonding No Back
is present Bonding
B.O = 1.33 B.O = 1.0

Hybridisation state = sp2 Hybridisation state = sp3

% s character = 33.33 % s character = 25
Bond order BF3 > BF4–
Bond length BF3 < BF4–

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(b) p – d Back Bonding (2p – 3d)
 
Example : (a) Why N (CH3)3 is more basic than N (SiH3)3
 
H3C–N–CH3 H3Si–N–SiH3
CH3 SiH3
Due to absence of vacant orbital in C. Due to presence of vacant orbital in Si.
No p–p Back Bonding p–d back bonding
Hybridisation-sp3 Hybridisation-sp2
Shape-pyramidal Shape-trigonal planar
L.P. is available to donate L.P. is not available on 'N' to donate
so it is more basic so it is less Basic


 SiH3– O –H
(b) CH3– O

–H 
Methyl alcohol Silyl alcohol
 No back bonding in conjugate base  Back bonding present in conjugate base
 Less acidic  More acidic

Illustrations
Illustration 1. Identify the compounds showing back bonding in the following :
(a) BF3 (b) NH3.BF3
EN (c) BF4– (d) NH2–BH2
(e) OF2 (f) NF3 (g) (SiH3)2O (h) (CH3)2O
Sol. (a)  (b)  (c)  (d) 
(e)  (f)  (g)  (h) 
Illustration 2. Compare the given properties of followings compounds
(a) BF3, BF4– (bond length)
LL
–
(b) BF3, BF4 (bond angle)
(c) BF3, BCl3, BBr3, BI3 (Lewis acid strength)
(d) (SiH3)2O, (CH3)2O (Bond angle)
(e) (CH3)3N, (SiH3)3N (basic character)
(f) (CH3)3N, (SiH3)3N (structure)
A

Sol. (a) < (b) > (c) increasing order

(d) > (e) > (f) Pyramidal, Trigonal planar

BEGINNER'S BOX-2
1. In BF3 :
(1) B-F bond has some double bond character and this bond is delocalised
(2) All the B–F bonds are single covalent in nature
(3) Bond energy and bond-length of B–F bond indicate its single bond character
(4) All of the bonds are ionic

2. Which of the following statements is incorrect in the context of the B–F bond in BF3 :-
(1) All the three B–F bond lengths are equal and each of them is shorter than the sum of the covalent radii
of boron and fluorine.
(2) The bond energy of the B–F bond is very high, higher than for any other single bond
(3) The unusual shortness and strength of the B–F bond may be explained by a p-p interaction between
boron and fluorine atoms.
(4) The unusual shortness and strength of the bonds may be explained by a p-d interaction between the
atoms of boron and fluorine.

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3. Which of the following structures correctly represents the boron trifluoride molecule :
F F
F F F
(1) B (2) B B
B B F F
F F F F F F F F

F F F F F– F

B+ B+
+ +
(3) B B (4) B B
F– – F F F–
F–
–
F F F F F F F

4. Trisilylamine [ N (SiH3)3] has a
(1) Planar geometry (2) Tetrahedral geometry
(3) Pyramidal geometry (4) None of these
4.3 HYDROLYSIS
Reaction of water molecules with covalent compound in such a way that H2O molecule break into H+ and OH– ion.
(A) Hydrolysis of halides :

Ionic Halides - Hydration

Covalent Halides - Hydrolysis
 Condition for hydrolysis EN
 Only those halide will undergo hydrolysis in which water molecule provide LP and other molecule
must have vacant orbital.
Mechanism :

Cl Cl H H
O OH OH
B 

+ H2 O B OH2 -2HCl
LL


Cl sp2 Cl Cl Cl -Cl
–
B +
-H B +2H2O B
Nucleophile Cl Cl Cl Cl HO HO
Intermediate
3
(sp )

Note : During hydrolysis formed intermediate involved one extra orbital than parent molecule.

1
 degree of hydrolysis  covalent character 
A

Ionic character

order of hydrolysis – NaCl < MgCl2 < AlCl3 < SiCl4

PCl5 > AsCl5 > SbCl5 > BiCl5
BF3 < BCl3 < BBr3 < BI3

P Cl3 + 3H OH  3HCl + H3PO3

+ –

LA LB LA LB
B Cl3 + 3H OH B(OH)3 + 3HCl
+ –

LA LB LA LB

 It is a neutralisation process of Lewis acid and Lewis base

(i) AlCl 3  3H  OH   Al(OH)3  3HCl

(ii) BeCl2  2H  OH   Be(OH)2  2HCl

(iii) MgCl2  2H  OH   Mg(OH)2  2HCl

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(B) Hydrolysis of metal carbide, metal nitride, metal hydride
(i) AlN  3H  OH   Al(OH)3  NH3

(ii) CaC2  2H  OH   Ca(OH)2  C2 H2

(iii) Mg2C3 + 4H+OH– 2Mg(OH)2 + C3H4
(iv) Al 4 C3  12H OH   4Al(OH)3  3CH4
(v) Mg3 N2  6H  OH   3Mg(OH)2  2NH3
(vi) Be2 C  4HOH  2Be(OH)2  CH4
(vii) NaH  H  OH   NaOH  H2
(viii) CaH2  2HOH  Ca(OH)2  2H2
(C) Metal oxide + H2O  Base
Na2O + H2O  NaOH
CaO + H2O  Ca(OH)2
(D) Non Metal oxide + H2O  Oxy acid
CO2 + H2O  H2CO3
SO3 + H2O  H2SO4
N2O5 + H2O  2HNO3 ENIllustrations
Illustration 1. Give the hydrolysis product of given compounds
(a) BCl3 (b) BeCl2 (c) PCl3 (d) MgCl2
(e) AlCl3 (f) CCl4 (g) SiCl4
LL
Sol. (a) H3BO3 + HCl (b) Be(OH)2 + HCl (c) H3PO3 + HCl (d) Mg(OH)2 + HCl
(e) Al(OH)3 + HCl (f) No hydrolysis (g) Si(OH)4 + HCl
Illustration 2. Which is correct order of hydrolysis
(a) NaCl < MgCl2 < AlCl3 < SiCl4 < PCl5 (b) CCl4 < SiCl4< GeCl4 < SnCl4 < PbCl4
A

(c) LiCl < BeCl2 < BCl3 (d) Both (a) and (c)
Sol. Ans. (d) covalent character rate of hydrolysis
Illustration 3. Why CCl4 do not undergo hydrolysis.
Sol. Due to absence of vacant orbital in central atom.
Illustration 4. Why SF6 do not undergo hydrolysis.
Sol. Due to steric crowding on central atom by the presence of 6 flourine atoms.
Illustration 5. Why NF3 do not undergo hydrolysis.
Sol. N & F both belong to 2nd period have lone pair to donate but both do not have vacant orbital to
accomodate lone pair.

BEGINNER'S BOX-3
1. The product formed in the reaction,
BCl3 + H2O  Product is –
(1) H3BO3 + HCl (2) B2O3 + HOCl (3) B2H6 + HCl (4) No reaction
2. AlCl3 on hydrolysis gives –
(1) Al2O3.H2O (2) Al(OH)3 (3) Al2O3 (4) AlCl3.6H2O

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3. Which one of the following compounds gives methane on treatment with water ?
(1) Al4C3 (2) CaC2 (3) Mg2C3 (4) SiC

4. The number of types of bonds between two carbon atoms in calcium carbide is :-
(1) One sigma, two pi (2) One sigma, one pi
(3) Two sigma, one pi (4) Two sigma, two pi

5. Which of the following gives propyne on hydrolysis

(1) Al4C3 (2) Mg2C3 (3) B4C (4) La4C3

6. Which of the following does not act as lewis acid ?

(1) BF3 (2) SnCl4 (3) CCl4 (4) SF4

4.4 DIMERISATION / POLYMERISATION

Types of Dimerisation

– –
3C—2e 3C—4e
B2H6 EN (BeCl2)2
(BeH2)2 (BeCl2)n
(BeH2)n (AlCl3)2
Al2(CH3)6
Ga2(CH3)6

(A) By banana Bond or by 3C–2e bond or by e– deficient bond

LL
(a) B2H6
Ht Hb Ht
x y
 = BA Ht= Terminal hydrogen
B  B 
x > y = BL Hb= Bridging hydrogen
Ht Hb Ht
A

2C – 2e– bonds = 4 3C – 2e– bonds = 2 


B2 H6   
 BH4  BH2
Hybridisation state = sp3
Electron deficient molecule (act as Lewis acid)
 All four terminal hydrogen are present in same plane both bridging H are present in perpendicular plane.
 If substitution reaction takes place then only 4 terminal H will be substituted.
B2H6 + 4CH3–Cl B2H2(CH3)4 + 4HCl
(b) (BeH2)2 (dimer of BeH2 in vapour state)
Hybridisation state = sp2
H
Be Planar
Ht Be Ht
electron deficient molecule
H

(c) (BeH2)n (polymer of BeH2 in solid state)

H H
Hybridisation state = sp3
Be Be Be Non-planar
H electron deficient molecule
H

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(B) By-coordinate Bond / 3C-4e bond
(a) Al2Cl6 (dimer of AlCl3 in liquid or solid state)
BA = 
Cl Cl x y Cl BL = x > y
Al (Al) Hybridisation state = sp3
Cl Cl Cl Non-planar
octet complete

(b) (BeCl2)2 (dimer of BeCl2 in vapour state)

Cl Hybridisation state = sp2
Cl Be Be Cl Planar
Cl electron deficient molecule

(c) (BeCl2)n (polymer of BeCl2 in solid state)

Cl Cl Cl
Hybridisation state = sp3
Be Be Be Non-planar
Cl Cl Cl EN octet complete

Note :
(i) BCl3, BBr3 and BI3 do not form dimer due to smaller size of boron & large size of halogen (due to
more steric repulsion)
(ii) BF3 cannot form dimer due to its back bonding.
LL
(iii) AlF3 cannot form dimer due to its ionic nature.
(iv) RCOOH forms dimer due to H-bonding.

BEGINNER'S BOX-4
1. Which of the following statements is incorrect in relation to the structure of diborane
A

(1) All the terminal B-H bond length are equal

(2) The terminal B–H bond is a 2-centre 3-electron bond

(3) The terminal B–H bond is a 2-centre 2-electron bond

(4) The bridge H is a 3-centre 2-electron bond

B B

2. Which of the following statements is correct in the context of diborane (B2H6) ?

(1) There are 12 valence electrons-three from each of the two boron atoms and six from the six hydrogen
atoms

(2) Two of the six hydrogen atoms form two bridges between two boron atoms

(3) The two bridging hydrogen atoms are in a plane perpendicular to the rest of the molecule and prevent
rotation between the two boron atoms

(4) All of these

3. Which of the following does not exist in free form ?

(1) BF3 (2) BCl3 (3) BBr3 (4) BH3

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4.5 SILICATES

Basic / structural unit : SiO4–4

SiO4–4 have a tendency of polymerisation

–
O
–
O
Si –
– O
Si
– O O
–

O –
–
O
O

Silicate No. of shared General Structure

Oxygen per unit Formula

Ortho silicate 0 SiO4–4 

Pyro silicate 1 Si2O7–6 



Single chain silicate

EN 2 (SiO3–2)n




LL

Cyclic silicate 2 (SiO3–2)n

 
A

 
Sheet silicate 3 (Si2O5–2)n
 

O
3–D silicate 4 (SiO2)n O Si O

Sodium Zeolite [Na2Al2Si2O8.xH2O]/[Na2O.Al2O3.2SiO2.xH2O]

(i) It is a 3-D silicate

(ii) Its used in softening of hard water

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Ex. Match the following

Silicate Type

(A) Beryl (Be3Al2Si6O18) (p) pyrosilicate

(B) Talc Mg3(OH)2(Si2O5)2 (q) orthosilicate

(C) Zircon ZrSiO4 (r) cyclicsilicate

(D) Hemi morphite Zn3Si2O7·Zn(OH)2·2H2O (s) sheetsilicate

Ans. (A) - r, (B) - s, (C) - q, (D) - p

4.6 SILICONES

Silicones are organo silicon polymer which contain R2SiO as a basic unit.

Properties :

(i) Silicones are chemically inert due to presence of strong sigma bond.

(ii) Silicones have water repelling nature due to presence of alkyl group.
EN
(iii) Silicones are insulator due to absence of free electrons.

Preparation :

Alkyl chloro silane 

 product  silicones
hydrolysis condensation

R3SiCl : dimer (used to stop chain formation)

LL

R2SiCl2 : linear polymer

RSiCl3 : cross link polymer

Dimer silicone:
A

–2HCl –H2O
2R3Si—Cl + 2H—OH R3Si—OH + HO—SiR3 R3Si—O—SiR3

Linear chain silicone

R R R R R
–2HCl HO—Si—OH + HO — Si — OH + HO—Si–OH
-nH2O
R2SiCl2 + 2H—OH O—Si––O—Si—O——
n
R R R R R
(R2SiO)n

Cross linked silicone

R R R
R SiCl3 + 3H OH HO Si OH O Si O Si O
OH O O
O Si O Si O
R R
(R2Si2O3)n

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BEGINNER'S BOX-5
1. Silicones have the general formula
(1) SiO44– (2) Si2O76– (3) (R2SiO)n (4) (SiO3)n2–

2. Consider the following route of reactions

R2SiCl2 + Water  (A) 
Polymerisation
(B)
Compound(B) in above reaction is
(1) Dimer silicone (2) Linear silicone
(3) Cross linked silicone (4) Polymerisation of (A) does not occur

4.7 ALLOTROPES
(A) Allotropes of Carbon

Crystalline Amorphous
Ex. Diamond (Hardest) Ex. Coke
Graphite Charcoal
Fullerene Coal
Lamp black (Softest)
EN
DIAMOND GRAPHITE

C
C
LL

C C
C
A

Each carbon bonded with 4 other carbon atom Each carbon bonded with 3 other carbon atom

sp3 hybridisation sp2 hybridisation

Tetrahedral structure Hexagonal layer structure

Insulator due to absence of free electrons Conductor due to presence of delocalised electrons

Hard due to presence of strong sigma bond Soft due to presence of weak van der Waals
& 3D structure forces between two layers

Density = 3.35 gm/cm3 Density = 2.22 gm/cm3

High melting point (giant molecule) Low melting point (w.r.t. diamond)

Bond length (C—C) = 1.54Å Bond length (C—C) = 1.41Å

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Special Point :

(i) Graphite is also known as plumbago (used in lead pencil )

(ii) Graphite is used as a dry lubricant.

Fullerene

 C-60 & C-70 are common fullerene.

 C-60 is also known as Buckminster fullerene (Bucky ball / soccer ball / football)

12 pentagonal
 There are 32 rings 32
20 hexagonal

 Each carbon atom bonded with 3 other carbon by sigma & double bond (resonance)

 sp2 hybridisation & aromatic in nature

Dangling Bond
EN
In diamond or graphite some surface carbon atom have free valency. These carbon atoms form new bonds
with impurities. These new bonds are known as dangling bond.
BEGINNER'S BOX-6
1. The false statement about the diamond will be

(1) The C-C bond length is larger than C=C, and CC
LL

(2) It is a molecular solid

(3) Dangling bond present along the surface and therefore have some impurities like hydrogen
(4) Diamond is bad conductor
A

2. Which one of the following is incorrect statement for graphite ?

(1) It has layer structure and each carbon atom sp2 hybridised
(2) It has a football like structure.
(3) Most stable allotropes of carbon
(4) None

3. Graphite is a soft solid lubricant extremely difficult to melt. The reason for this anomalous behaviour is that
graphite.
(1) is an allotropic form of diamond
(2) has molecules of variable molecular masses like polymers
(3) has carbon atoms arranged in large plates of rings of strongly bound carbon atoms with weak interplate
bounds.
(4) is a non crystalline substance

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BORON FAMILY
4.8 INTRODUCTION
The p-block elements are those elements of the periodic table in which the differentiating electron (or the
last electron) enters the p-subshell of the last (outermost) shell. Since the maximum capacity of any atomic
orbital is of two electrons with opposite spins (Pauli's principle), the maximum number of electrons that can
be accommodated in any p-subshell is six. As a result, the p-block of the periodic table consists of six group:
13 (III A), 14(IV A), 15(V A), 16(VI A), 17(VIIA) and 18 (zero group). On the basis of electronic
configuration, the element He is to be excluded from the p-block as its last electron enters the s-subshell of
the last shell.
BORON FAMILY
Boron is a typical non-metal, aluminium is a metal but shows many chemical similarities to boron, and
gallium, indium and thallium are almost exclusively metallic in character,
GENERAL CHARACTERISTICS
(A) Physical properties :
Boron is non-metallic in nature. It is extremely hard and black coloured solid. It exists in many allotropic
forms. Due to very strong crystalline lattice, boron has unusually high melting point. Rest of the member are
soft metals with low melting point and high electrical conductivity. Gallium with low melting point (303 K),
could exist in liquid state during summer. Its high boiling point (2676 K) makes it a useful material for
EN
measuring high temperatures. Density of the elements increases down the group from boron to thallium.
(B) Oxidation state
(a) These elements show +1 and +3 oxidation states.
(b) B & Al shows only +3 oxidation state. While other elements show +1 and +3 oxidation state.
(c) +1 oxidation state is more stable on moving down the group due to increase in inert pair effect.
(d) Relative stability of M+ and M3+ ions may be given as :
LL

B3+ > Al3+ > Ga3+ > In3+ > Tl3+

B+ < Al+ < Ga+ < In+ < Tl+
Tl+ ion is more stable than Tl3+ ion and thus, Tl3+ ion changes to Tl+ ion therefore acts as oxidising
agent.
Tl3+ compounds + 2e–  Tl+ compounds
A

(C) Chemical properties

(a) Reactivity towards air
Boron is unreactive in crystalline form. Aluminium forms a very thin oxide layer on the surface which
protects the metal from further attack. Amorphous boron and aluminium metal on heating in air form B2O3
and Al2O3 respectively. With dinitrogen at high temperature they form nitrides.
 
2E(s) + 3 O2 (g)   2 E2O3(s) ; 2E(s) + N2(g)   2 EN (s).
The nature of these oxides varies down the group. Boron trioxide is acidic and reacts with basic (metallic)
oxides forming metal borates. Aluminium and gallium oxides are amphoteric and those of indium and
thallium are basic in their properties.
BEGINNER'S BOX-7
1. Boron form covalent compound due to
(1) Higher ionization energy (2) Lower ionization energy
(3) Small size (4) Both (1) and (3)

2. Which of the following has highest non-metallic characteristic ?

(1) Gallium (2) Indium (3) Boron (4) Aluminium

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3. Which one of the following is a correct statement ?
(1) The hydroxide of aluminium is more acidic than that of boron
(2) The hydroxide of boron is basic while that of aluminium is amphoteric
(3) The hydroxide of boron is acidic while that of aluminium is amphoteric
(4) The hydroxides of both boron and aluminium are amphoteric

4. Boron reacts with air to give –

(1) B2O3 (2) BN (3) Both (4) None

4.9 CHEMISTRY OF BORON

(A) Structure of Boron: Elemental boron exists in the structures of B12

(B) Chemical properties : It exists in five allotropes, four of which are crystalline and one is amorphous. All
crystalline forms are very hard made up of clusters of B12 units. All crystalline forms are black in appearance
and chemically inert. However, it is attacked at high temperature by strong oxidising agents such as a
mixture of hot and concentrated H2SO4 and HNO3 or Na2O2. But amorphous form is brown and chemically
active.
(C) Compounds of Boron
(I) Borax (Na2B4O7.10H2O)
2Na+[B4O5(OH)4]–2.8H2O
EN
OH –2
B
O O
+
2Na HO B O B OH .8H2O
LL

O O
B
OH

Important points :
B–O–B linkage = 5
A

Total B–O bonds = 14

Two B-sp2 hybridised
Two B-sp3 hybridised
Properties :

(i) Borax is a white powder, less soluble in cold water due to stable H-bonds within the molecule of borax,
but more soluble in hot water, due to breaking of H-bonds present in borax, so that new H-bonds can
be easily form with water molecule.

(ii) Its aqueous solution is alkaline because of its hydrolysis to weak acid H3BO3 and strong alkali NaOH.

Na2B4O7 + 7H2O 4H3BO3 + 2NaOH

(iii) Action of heat.

When borax powder is heated, it first swells due to loss of water in the form of steam but at 740oC it
becomes converted into colourless transparent borax bead.


Na2B4O7.10H2O   Na2B4O7 + 10 H2O

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740 C
Na2B4O7   2NaBO2 + B2O3 (borax bead)
Borax-bead test :
Borax reacts with certain metal salts such as, Ni2+, Co2+, Cr3+, Cu2+, Mn2+ etc. to form coloured metaborates.
The colour of the metaborates can be used to identify the metallic ions (cations) in salts.

Na2B4O7·10H2O   Na2B4O7 
740ºC
 2NaBO2  B2 O3 ; CuO + B2O3  Cu(BO2)2 (blue bead)
10H2 O   
glassy mass

Ni2+ - Brown, Cu2+ - Pale blue, Co2+ - Dark blue, Mn2+ - Pink, Cr3+ - Green.
Uses : It is used
1. in borax bead test
2. in purifying gold
3. as flux during welding of metals and
4. in production of glass.
(II) ORTHO BORIC ACID [H3BO3/B(OH)3]
OH
B
OH OH

Na2B4O7 + 2HCl + 5H2O 2NaCl + 4B(OH)3

 Properties:
EN
It is a weak monobasic acid soluble in water and in aqueous solution the boron atom completes its octet by
accepting OH– from water molecules and thus liberate H+ of H2O.
B(OH)3(aq) + 2H2O() [B(OH)4]– (aq) + H3O+(aq). pK = 9.25.
LL
It, therefore, functions as a Lewis acid and not as a proton donor like most acids.
Heating effect :
When heated it first forms metaboric acid (HBO2) and then boron trioxide.
160°C
H3BO3 100°C
HBO2 H2B4O7 Red hot B2O3
Boric acid
A

Orthoboric acid is greasy to touch less soluble in cold water but more soluble in hot water. In the solid state,
the B(OH)3 units are hydrogen bonded together into two dimensional sheets with almost hexagonal
symmetry. The layers are quite a large distance apart (3.18 Å) and thus the crystal breaks quite easily into
very fine particles.
H
O

H B
O O
H H
O O
H B H H
O O
O
H B H B
H
O O O O
H H
Test for Borate radical :
When boric acid is heated with ethyl alcohol, the evolved gas is burned forming a green edged flame.
H3BO3 + 3C2H5OH B(OC2H5)3 + 3H2O
ethyl borate (volatile)

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 Uses :
1. It is an antiseptic and its water solution is used as an eyewash.
2. It is also used in glass, enamel and pottery industry.

(III) DIBORANE (B2H6)

Binary compounds of B with H are called boron hydrides or boranes.

Preparation :

(i) 4BF3 + 3LiAlH4 

ether
 2B2H6 + 3LiF + 3AlF3

2NaBH4 + 2  B2H6 + 2Na + H2

ether
(ii)
(iii) 2BF3 + 6NaH 
453 K

 B2H6 + 6NaF (Industrial method)

Properties :

(i) B2H6 is colourless gas and highly reactive (boiling point 183 K).

(ii) It catches fire spontaneously in air and explodes with O2. Reaction with oxygen is extremely
exothermic. EN
B2H6 + 3O2 B2O3 + 3H2O   H = – 2160 kJ mol–1

  Mixture of diborane with air or oxygen inflame spontaneously producing large amount of heat.
Diborane has a higher heat of combustion per unit weight of fuel than most other fuels. It is therefore
used as a rocket fuel.

 At red-hot, the boranes decomposes to give boron and hydrogen.

LL

(iii) Reaction with water is instantaneous.

B2H6 + 6H2O 2B(OH)3 + 6H2

(iv) The electron deficient 3c-2e B–H–B bridges are sites of nucleophilic attack.

 Small amines such as NH3, CH3NH2 and (CH3)2NH give unsymmetrical cleavage of diborane.
A

B2H6 + 2NH3 [H2B (NH3)2]+ + [BH4]–

 Large amines such as (CH3)3N and pyridine give symmetrical cleavage of diborane.

2(CH3)3N + B2H6 2H3B  N(CH3)3

The reaction with ammonia depends on conditions.

B2H6 + NH3 

Excess NH3
 B2H6 . 2NH3 or [H2B(NH3)2]+ [BH4]– (ionic compound).
low temperature


Excess NH3
 (BN)x boron nitride/(Inorganic graphite)/Borazone
higher temperature (  200ºC)


Ratio 2NH3 : 1 B2 H6
 B3N3H6 borazine/(Inorganic benzene)/Borazole
higher temperature (200ºC)

Borazine is much more reactive than benzene. Borazine readily undergoes addition reactions which do not
occur with benzene. Borazine also decomposes slowly and may be hydrolysed to NH3 and boric acid at
elevated temperature. If heated with water, B3N3H6 hydrolyses slowly.

B3N3H6 + 9H2O 3NH3 + 3H3BO3 + 3H2O

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Illustrations
–
Illustration 1. The geometry of [B(OH)4] ion is

(1) Triangular (2) Hexagonal

(3) Rectangular (4) Tetrahedral

Solution. Ans. (4)

In [B(OH)4]– boron is sp3 hybridised and it is tetrahedral.

Illustration 2. Orthoboric acid

(1) Donate proton to form H2BO3–

(2) Accept proton of form H4BO3+

(3) Donate OH– to form H2BO2+

(4) Accept OH– to form [B(OH)4]–

Solution. Ans. (4) EN

H3BO3 acts as a lewis acid and accepts an OH– ions to form [B(OH)4]–

Illustration 3. Boric acid heated to red hot gives

(1) HBO2 (2) H2BO2 (3) B2O3 (4) Borax

LL

Solution. Ans. (3)

Illustration 4. Boric acid is used in carom boards for smooth gliding of pawns because :-
A

(1) H3BO3 molecules are loosely chemically bonded and hence soft

(2) Its low density makes it fluffy

(3) It is chemically inert with the plywood

(4) H-bonding in H3BO3 gives it a layered structure

Solution. Ans. (4)

Illustration 5. Diborane readily reacts with water forming –

(1) Diborate and O2 (2) Boric acid and O2

(3) Boric acid and H2 (4) Diborate and H2

Solution. Ans. (3)

B2H6 + 6H2O  2H3BO3 + 6H2

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4.10 CHEMISTRY OF ALUMINIUM
Compounds of Aluminium
(a) Aluminium chloride – AlCl3 :
It is a colourless crystalline solid, soluble in water. It is covalent. Anhydrous AlCl3 is a deliquescent white solid.
Preparation :
(i) By dissolving aluminium, Al2O3, or Al(OH)3 in dilute HCl :
2Al + 6HCl 2AlCl3 + 3H2

Al2O3 + 6HCl 2AlCl3 + 3H2O

Al(OH)3 + 3HCl AlCl3 + 3H2O

The solution obtained is filtered and crystallized when the crystals of AlCl3.6H2O are obtained.
(ii) By heating a mixture of Al2O3 and coke and passing chlorine over it.
Al2O3 + 3C + 3Cl2 2AlCl3 (anhydrous) + 3CO
(b) Alum :
(i) Introduction :
(a) Alums are double salt of sulphates with their general formula M2SO4.M'2(SO4)3.24H2O
EN
where M= monovalent radical like Na+ , K+, NH4+ and M' = Trivalent radical like Al+3, Cr+3. Fe+3.
(b) The different alums are -
(i) Potash alum K2SO4.Al2 (SO4)3.24H2O
(ii) Chrome alum K2SO4 Cr2(SO4)3. 24 H2O
(iii) Iron alum (NH4)2SO4. Fe2(SO4)3. 24H2O
(iv) Ammonium alum (NH4)2SO4. Al2(SO4)3. 24H2O
LL

(c) In alums each metal ion is surrounded by six water molecules.

(d) Lithium does not form alum because Li ion is too small to have a coordination number of six.
(e) It is salt of (SA + SB) and (SA + WB) thats why aq. solution of alum is acidic.
(ii) Properties :
(a) It is a white crystalline solid highly soluble in water.
A

(b) On heating it undergoes dehydration and swells up.

(c) It is highly acidic in aqueous solution due to the hydrolysis of aluminium sulphate to sulphuric acid
(d) It is a double salt and its aqueous solution gives reaction of all the constituents ions K+, Al+3, SO4–2.
(iii) Uses :
(i) Alum is used to stop bleeding. (ii) It is used for purification of water.

BEGINNER'S BOX-8
1. Which of the following statements about H3BO3 is not correct
(1) It is a strong tribasic acid
(2) It is prepared by acidifying an aqueous solution of borax
(3) It has a layer structure in which planar BO3 units are joined by hydrogen bonds
(4) It does not act as proton donor but acts as a Lewis acid by accepting hydroxyl ion
2. The hardest substance amongst the following is
(1) Be2C (2) Graphite (3) B4C (4) SiC
3. Which of the following is known as inorganic benzene
(1) Borazine (2) Boron nitride (3) p-dichlorobenzene (4) Borazone
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CARBON FAMILY
4.11 PHYSICAL PROPERTIES
All group 14 members are solids. Carbon and silicon are non-metals, germanium is metalloid whereas tin
and lead are soft metals with low melting points. Melting points and boiling points of group 14 elements are
much higher than those of corresponding elements of group 13 due to stronger metallic bonding.
4.12 COMPOUNDS OF CARBON
(A) Carbon Monoxide (CO)
(I) Preparation
(i) It is formed together with CO2, when carbon or carbonaceous matter is oxidized by air or oxygen. It is
also produced when CO2 is reduced by red- hot carbon; this reaction is of importance in metal
extractions.
C(s) + CO2(g) 2CO(g)
(ii) In the laboratory it can be prepared by dehydrating methanoic acid with concentrated sulphuric acid .
HCOOH (liq) 
373 K
CO(g) + H2O
conc.H2 SO4

(iii) If oxalic acid is dehydrated in the same way, CO2 is formed as well.
conc. H2 SO4 , 
H2C2O4   CO + CO2
EN
– H2 O

(iv) On commercial scale it is prepared by the passage of steam over hot coke. The mixture of CO and H2
thus produced is known as water gas or synthesis gas.
473 1273 K
C (s) + H2O (g)   CO (g) + H2(g) (water gas).
When air is used instead of steam, a mixture of CO and N2 is produced, which is called producer gas.
1273 K
2 C (s) + O2 (g) + 4 N2 (g)   2 CO (g) + 4 N2 (g) (Producer gas).
LL

Water gas and producer gas are very important industrial fuels. Carbon monoxide in water gas or producer
gas can undergo further combustion forming carbon dioxide with the liberation of heat.
(II) Physical Properties
(i) Carbon monoxide is a colourless, odourless gas which burns in air with a blue flame, forming CO2. It is
sparingly soluble in water and is a neutral oxide. CO is toxic, because it forms a complex with
A

haemoglobin in the blood and this complex is more stable than oxy-haemoglobin. This prevents the
haemoglobin in the red blood corpuscles from carrying oxygen round the body. This causes oxygen
deficiency, leading to unconsciousness and then death.

(B) CARBON DIOXIDE (CO2)

Preparation :
(i) Complete combustion of carbon containing compounds.
CH4 + O2  CO2 + H2O
(ii) In the laboratory it can be conveniently made by the action of dilute hydrochloric acid on marble chips :
CO32-(aq) + 2H+(aq)  CO2(g) + H2O()
(iii) Industrially it is produced as a by-product during the manufacture of quicklime and in fermentation
processes:
CaCO3(s)  CaO(s) + CO2(g) ; C6H12O6(aq){glucose}  2C2H5OH(aq) + 2CO2(g)
Properties :
(i) It is a colourless, odourless and heavy gas which dissolves in its own volume of water at ordinary
temperature and pressure. Like all gases, it dissolves much more readily in water when the pressure is
increased and this principle is used in the manufacture of soda water and fizzy drinks.

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(ii) CO2 is easily liquefied (critical temperature = 31.1oC) and a cylinder of the gas under pressure is a
convenient fire extinguisher. When the highly compressed gas is allowed to expand rapidly solid carbon
dioxide (‘dry ice’) is formed. Solid carbon dioxide sublimes at –78oC and, since no massy liquid is
produced, it is a convenient means of producing low temperatures.
(iii) Carbon dioxide is the acid anhydride of carbonic acid, which is a weak dibasic acid and ionises in two
steps as follows : H2CO3(aq) + H2O () HCO3– (aq) + H3O+ (aq)

HCO3– (aq) + H2O () CO32– (aq) + H3O+ (aq)

H2CO3 / HCO3– buffer system helps to maintain pH of blood between 7.26 to 7.42.
A solution of carbonic acid in water will slowly turn blue litmus red and when the solution is boiled, all the
CO2 is evolved.
(iv) Carbon dioxide readily reacts with alkalies forming the carbonate and, if CO2 is in excess, the hydrogen
carbonate. This is the basis of the lime-water test for CO2 gas.
Ca(OH)2(aq) + CO2(g)  CaCO3(s) + H2O(liq) ; CaCO3(s) + H2O(liq) + CO2(g)  Ca(HCO3)2(aq)
The above reaction accounts for the formation of temporarily hard water.
(v) Carbon dioxide, which is normally present to the extent of ~ 0.03% by volume in the atmosphere, is
removed from it by the process known as photosynthesis. It is the process by which green plants convert
atmospheric CO2 into carbohydrates such as glucose. The overall chemical change can be expressed as :
h
6 CO2 + 12 H2O  
 C6H12O6 + 6 O2 + 6 H2O
Chlorophyll
EN
By this process plants make food for themselves as well as for animals and human beings. But the
increase in combustion of fossil fuels and decomposition of limestone for cement manufacture in recent
years seem to increase the CO2 content of the atmosphere. This may lead to increase in green house
effect and thus, raise the temperature of the atmosphere which might have serious consequences.
(vi) Gaseous CO2 is extensively used to carbonate soft drinks. Being heavy and non–supporter of combustion
LL
it is used as fire extinguisher. A substantial amount of CO2 is used to manufacture urea.
(C) Carbides :
Carbides are of three types according to the type of bonding
(i) Salt like carbides (ionic carbides)
(ii) Covalent carbides (giant molecular carbides)
A

(iii) Interstitial carbides (Metallic carbides).

(I) Salt like carbides (ionic carbides) :
(a) These are formed by strong electropositive elements of groups 1, 2 and 13
(b) These are transparent crystalline substances and do not conduct electric current in the solid state.
(c) These are easily hydrolysed by water or dilute acids to give aliphatic hydrocarbons,
(i) Methanides (Methides) – Methanides are the carbides which give methane on hydrolysis.
They contain C4– ions.
Be2C + 4H2O 2Be(OH)2+CH4
Al4C3 + 12H2O  4Al(OH)3+3CH4
(ii) Acetylides – These are the carbides which yield acetylene on hydrolysis.
They contain the ion C22  (CC)–2

e.g. : CaC2

CaC2 + 2H2O  Ca(OH)2 + C2H2 or C22  + 2H+  C2H2

Most of these carbides have ionic NaCl - type of structure.

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(iii) Allylides – These carbides give methylacetylene or allylene (CH3–CCH) on hydrolysis.

They contain C34  ions. The only example of this class is Mg2C3

Mg2C3 + 4H2O 2Mg(OH)2 + CH3–CCH

(II) Covalent carbides (giant molecular carbides)
(a) Covalent carbides are the compounds of carbon with elements having similar electronegativity.
(b) These are covalent, polymeric, thermally stable, extremely hard, high melting and technically inert solid.
(c) B4C and SiC are two main covalent carbides.
(III) Interstitial / Metallic carbides
Transition metals like Ti, Zr, Hf, V, Nb, Ta and Mo form these carbides. The metals retains their close
packed lattice and carbons are incorporated in their interstitial spaces. These carbides are extremely hard
and have very high melting points. The carbides of V and Ta are very hard hence they are used for
manufacture of high speed cutting tools.
Illustrations
Illustration 1. Which of the following is methanide –
(1) Be2C (2) Al4C3 (3) Mg2C3 (4) Both (1) and (2)
Solution. Ans.(4) EN
Both Be2C and Al4C3 has C4– ion and on hydrolysis gives CH4.
Illustration 2. Consider the following chemical reaction –
Fe2O3(s) + 3CO(g) 2Fe(s) + 3CO2(g)
(1) CO is an oxidising agent (2) CO is reducing agent
(3) CO is neutral towards litmus (4) CO acts as catalyst
LL

Solution. Ans.(2)
CO is reducing agent because it readily accepts oxygen to from CO2. CO is used as reducing
agent to reduce many metallic oxides into metals in metallurgy.
Illustration 3. Consider the following chemical reaction
A

HCOOH(aq.) 
X,
 CO(g) + H2O(g)
Formic acid
In the above reaction (X) is –
(1) Conc. H2SO4 (2) Conc. HCl (3) Conc. HNO3 (4) Dil. HNO3
Solution. Ans. (1)
Illustration 4. Living in the atmosphere of CO is dangerous because it –
(1) Reduces organic matter of tissues
(2) Dries up the blood
(3) Combines with haemoglobin of blood and makes it incapable to absorb oxygen
(4) Combines with O2 present inside to form CO2
Solution. Ans. (3)
Illustration 5. The ionic carbide is
(1) ZnC (2) TiC (3) SiC (4) CaC2

Solution. Ans. (4)

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ANSWER'S KEY
Que. 1 2 3 4
BEGINNER'S BOX-1
Ans. 1 4 4 4
Que. 1 2 3 4
BEGINNER'S BOX-2
Ans. 1 4 1 1
Que. 1 2 3 4 5 6
BEGINNER'S BOX-3
Ans. 1 2 1 1 2 3
Que. 1 2 3
BEGINNER'S BOX-4
Ans. 2 4 4
Que. 1 2
BEGINNER'S BOX-5
Ans. 3 2
Que. 1 2 3
BEGINNER'S BOX-6
Ans. 2 2 3
Que. 1 2 3 4
BEGINNER'S BOX-7
Ans. 4 3 3 3
Que. 1 2 3
BEGINNER'S BOX-8
Ans. 1 3 1

EN
LL
A

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