The d – and f- block Elements

KEY CONCEPTS
➢ The d- block of the periodic table contains the elements of group 3-12 in which last electron enter into d
subshell or d- orbital .
• Their general configuration is –
• (n-1) d1-10 ns1-2
➢ Those elements which have incompletely filled d orbital in its ground state or in any one of the oxidation
state are called Transition elements .
➢ Zinc, cadmium and mercury of group 12 have fully filled d10 configuration in their ground state as well
as in their common oxidation states and hence, are not regarded as transition metals .
➢ Atomic size - As we move from left to right in the series atomic size first decreases , then becomes
constant and again increases .
➢ Enthalpy of atomisation :- The transition elements exhibit higher value of enthalpy of atomisation
because due to presence of large no. of unpaired e- s in their atom they have stronger inter atomic
interaction and hence stronger bonding between atoms .
➢ Melting and Boiling point :- High melting and boiling points is due to the closed packed structures. In
these structures transition metal atom are held together by strong metallic bonds which have considerable
covalent character.
➢ Oxidation states -Transition element exhibits a large number of oxidation state in their compounds. This
is due to participation of inner (n-1) d e- s in addition to outer ns e- in bonding due to less energy
difference of ns and (n-1) d orbital .
*The transition element which exhibit a single O.S. is Sc (+3).
* The elements which show the greatest number of oxidation states occur in or near the middle of series
due to presence of maximum no. of unpaired e- .
* The compounds of metals with oxygen and fluorine exhibit highest oxidation state as F and O are most
electronegative element .
*The stability of oxygen to stabilize the highest oxidation state exceeds that of fluorine. This is due to
ability of oxygen to form multiple bonds .
*Oxidation state of p block element differ by +2 because their variable oxidation state can be explained
by exciting e-s from ns and np to (n-1)d orbitals whereas in transition elements it differ by one due to loss
of e- by s as well as d- orbitals .
➢ Catalytic properties -The catalytic activity is due to
i) Their ability to adopt multiple oxidation state .
ii) In no. of cases transition metal provide large surface area with free valencies on which reactants are
adsorbed.
➢ Magnetic properties - Most of the transition metals are paramagnetic in nature due to the presence of
unpaired electrons in d-subshell .

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 where n is the number of unpaired electrons .
➢ Formation of complex compounds - It is due to :-
• a) Small size.
b) High nuclear charge.
c) Availability of vacant d-orbitals of suitable energy to accept lone pair of electrons donated by ligands.
➢ Formation of coloured ions - The colour of transition metal compound is due to the presence of
unpaired electrons which undergoes d-d transition by absorption of light in visible region.
➢ Alloy Formation - Transition metals form a large number of alloys. It is due to their similar atomic sizes
.Due to this, atoms of one metal can easily take up the position in the crystal lattice of the other .
➢ Interstitial compounds – Transition metals forms a large number of interstitial compounds in which
small atoms like hydrogen, carbon , boron and nitrogen occupy the interstitial sites in their lattice.These
are non –stoichiometric compounds .
➢ Electrode potential –
For M2+/M :
There is irregular variation in electrode potential due to irregular variation in ionisation enthalpy
(IE1+IE2),sublimation energy and hydration enthalpy .
➢ f –block elements - Those elements in which differentiating electron enters into (n-2) f subshell are
called inner transition element or f block elements .
Their general electronic configuration is –
(n-2)f 1-14 (n-1)d0-1 ns2
➢ f- block consists of two series –
1) Lanthanoids
2) Actinoids
➢ Lanthanoids - The 14 elements which follow 57La from 58Ce to 71Lu in the periodic table are called
lanthanoids and in these filling of electrons occur in 4f subshell .
Their general electronic configuration is –
[Xe] 4f 1-14 5d0-1 6s2
➢ Lanthanoid Contraction - The regular decrease in the atomic and ionic radii of lanthanoids with
increasing atomic number is known as lanthanoid contraction .
Cause – This is due to the addition of electron in 4f subshell which has poor shielding effect .
➢ Consequences of Lanthanoid contraction – 1) Similarity in size of elements belonging to same group
of second and third transition series .
2) Decrease in basic strength from La(OH)3 to Lu(OH)3 .
3) Difficulty in separation of lanthanoids .
➢ Oxidation state -Most common O.S. for lanthanoid is +3 .
+2 and +4 is also exhibited by some elements which by losing 2 or 4 electrons acquire a stable
configuration .
*Ce and Tb exhibit +4 O.S. by losing 4 e-s .

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 58 Ce – [Xe] 6s2 4f1 5d1 Ce4+ – [Xe] 6s0 4f0 5d0
65Tb – [Xe] 6s2 4f9 Tb4+ – [Xe] 4f7
* Eu and Yb exhibit +2 O.S.by losing 2e-.
63 Eu – [Xe] 6s2 4f7 Eu2+ – [Xe] 4f7
70Yb – [Xe] 6s2 4f14 Yb2+ – [Xe] 4f14
* La ,Gd and Lu exhibit only +3 O.S .
➢ Colour - Most of the trivalent metal ions are coloured .The colour is due to absorption of light in the
visible region resulting in the f –f transition .

* La3+ and Lu3+ ions are colourless because of having f0 and f14 configuration respectively and hence no
f-f transition is possible .
➢ Magnetic property -Among lanthanoids La3+ and Lu3+ which have 4f0 and 4f14 configuration are
diamagnetic and all other trivalent lanthanoids are paramagnetic because they have unpaired electrons .
➢ Uses - 1) Lanthanoids are used in the production of an alloy misch metal which consists of a lanthanoid
metal (95%) , iron (5%)and traces of S , C, Ca and Al . It is used in Mg based alloy to produce bullets ,
shells and lighter flints.
2) Mixed oxides of lanthanoids are used as catalyst in petroleum cracking .
Frequently asked questions –
Q-1 What are transition elements ?
Ans –Incompletely filled d –orbital in ground state or in any one of their oxidation state.
Q-2 Why Zn ,Cd and Hg are not regarded as transition elements ?
Ans – Do not have partly fiiled d –orbital in ground state or in any one of their oxidation state.
Q-3 Why do transition elements exhibit higher enthalpy of atomization ?
Ans –Due to stronger interatomic interaction .
Q-4 Transition elements have high melting and boiling points ?
Ans – Due to strond metallic bond .
Q-5 Why Zn ,Cd and Hg are soft and have low melting and boiling points ?
Ans – Due to weak metallic bonds present in them as all the electrons in d-subshell are paired .
Q-6 Why do transition elements shows variable oxidation states ?
Ans –Due to participation of (n-1)d and ns electron in bond formation .
Q-7 Name a transition element which does not exhibit variable oxidation states .
Ans- Scandium .
Q-8 Which of the 3d series of the transition metals exhibits the largest number of oxidation states
and why ?
Ans - In 3d series Mn shows the highest oxidation state of +7 as it has maximum no. of unpaired e- .
Q-9Which metal in the first transition series exhibits +1 oxidation state most frequently and why ?

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Ans –Cu has the electronic configuration 3d10 4s1 .It can easily lose 4s1 electron to give the stable
3d10configuration .
Q-10 Why is the highest oxidation state of a metal exhibited in its oxide or fluoride only ?
Ans – Oxygen and fluorine have small size and high electronegativity .Hence, they can oxidize the metal
to the highest oxidation state .
Q-11 Cu+ is not stable in aqueous solution .Why ?
Ans- Many Cu(I) compounds are unstable in aqueous solution and undergo disproportionation.
2Cu+ → Cu2+ + Cu
The stability of Cu2+ rather than Cu+ is due to more –ve hydration enthalpy of Cu2+ than Cu+ which is
much more and compensate for the II ionisation enthalpy .
Q-12 Transition elements form colored compounds . Why ?
Ans- Due to d-d transition .
Q-13 Why is Cu2+ ion colored while Zn2+ ion is colorless in aqueous solution ?
Ans –Presence of unpaired e- showing d-d transition in Cu2+ while in Zn2+ there is no unpaired electron .
Q-14 Transition elements form alloys .Why ?
Ans – Due to similar metallic radii .
Q-15 Most of the transition elements are paramagnetic .Why ?
Ans – Due to presence of unpaired electron in (n-1) d subshell.
Q-16 Which is the stronger reducing agent Cr2+ or Fe2+ and why?
Ans – Cr2+ is the stronger reducing agent because in case of Cr2+ to Cr3+ change in configuration is from
d4 to d3 and in Fe2+ to Fe3+ the change is from d6 to d5. In medium like water d3 is more stable as
compared to d5 due to half filled t2g configuration.
Q-17 Why do transition metals and their compounds show catalytic activity ?
Ans- Because of multiple oxidation state / ability to form complex / having large surface area .
Q-18 Why transition metals form large number of interstitial compounds ?
Ans- Because small non metallic atoms (H,B,C,N etc) are able to fit in the interstitial sites of transition
metal lattice to form interstitial compounds .
Q-19 The 4d and 5d series of transition metals have more frequent metal –metal bonding in their
compounds than 3d series .Explain .
Ans –In the same group of d-block elements ,the 4d and 5d transition elements have larger size than that
of 3d element .Thus the valence electrons are less tightly held and hence can form metal metal bond more
frequently .
Q-20 The E0 (M2+/M) value for copper is positive (+0.34 v) .What is possible reason for this ?
Ans- Due to high enthalpy of atomization and low enthalpy of hydration .
Q-21 Co2+is stable in aqueous solution but in the presence of complexing agent ,it is easily
oxidised .Why ?
Ans-In the presence of complexing agent ,oxidation state of Co changes from +2 to +3 due to CFSE
which is more and compensate the ∆iH3 .
Q- 22 E0 for Mn3+/Mn2+ is more positive than for Fe3+/Fe2+ . Why ?
Ans – Mn3+has the configuration 3d4 while that of Mn2+ is 3d5 .So Mn3+ easily undergo reduction to Mn2+
having stable 3d5 configuration resulting in higher value of standard reduction potential .
Fe3+ is more stable than Fe2+ because of having 3d5 configuration and reduction to Fe2+ will not be
easy resulting in the decreased value of E0 .
Q-23 Zr and Hf have almost identical radii?
Ans - Due to filling of 4f orbitals which have poor shielding effect / lanthanoid contraction.

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 Q-24 La(OH)3 is a stronger base than Lu(OH)3?
Ans – As the size of lanthanoid elements decreases from La3+ to Lu3+ covalent character of hydroxide
increases hence basic strength decreases .
Q-25 The d1 configuration is very unstable in ions. Why ?
Ans – The ions with d1configuration have the tendency to lose the only electron present in d-subshell to
acquire stable d0 configuration .
Practice Questions –
Q-1 On what ground can you say that scandium (Z=21) is a transition element but Zinc (Z=30) is not ?
Q-2 Calculate the spin only magnetic moment of M2+ion (Z=27)
Q-3 Why transition elements have a strong tendency to form complexes?
Q-4 Sc3+ is colourless in aqueous solution whereas Ti3+ is coloured . Why ?
Q-5 Cr2+ is reducing in nature while with the same d-orbital configuration (d4) Mn2+ is an oxidising agent.
Explain .
Q-6 Mn2+ is much more resistant than Fe2+ towards oxidation .Why ?
Q-7 What is lanthanoid contraction ? Write two main consequences of Lanthanoid contraction .
Q-8 Why the metallic radii of the third(5d) series of transition metals are virtually the same as those of
the corresponding group members of the second (4d) series ?
Q-9 Name a member of lanthanoid series which is well known to exhibit +2 oxidation state.
Q-10 Name a member of lanthanoid series which is well known to exhibit +4 oxidation state.
Q-11 Ce4+ is a good oxidising agent and Eu2+ is a good reducing agent. Why ?
Q-12 Which is the most common oxidation state of Lanthanoids ?
Q-13 Give an example of disproportionation reaction .
Q-14 Which divalent metal ion has maximum paramagnetic character among the first transition metal.
Why?
Q -15 Iron has higher enthalpy of atomisation than that of copper. Assign reason .
Q- 16 E0 for Mn3+/Mn2+ is more positive than for Cr3+/ Cr2+. Why?
Q-17 The third ionisation enthalpy of Manganese (Z=25) is exceptionally high. Why ?
Q-18 The highest oxidation state is exhibited in oxo-anions of a transition metal. Suggest a reason.
Q-19 Why is the separation of Lanthanoids difficult?
Q-20 Name an important alloy, which contains some of the lanthanoid metals. Mention its uses .

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 COORDINATION COMPOUNDS
Coordination compounds are those addition molecular compounds which retain their identity in solid state as
well as in dissolved state. In these compounds. the central metal atom or ion is linked by ions or molecules with
coordinate bonds. e.g., Potassium ferrocyanide, K4 [Fe(CN)
21 6].

•
Double Salts: These are the addition molecular compounds which are stable in solid state but dissociate into
constituent ions in the solution. e.g., Mohr’S salt, FeSO4·(NH4)2SO4 . 6H2O get dissociated into Fe2+, NH+4 and
SO2-4 ions.
Terms Related to Coordination Compounds
1. Complex ion or Coordination Entity : It is an electrically charged species in which central metal atom or
ion is surrounded by number of ions or neutral molecules.
(i) Cationic complex entity It is the complex ion which carries positive charge. e.g., [Pt(NH3)4]2+
(ii) Anionic complex entity It is the complex ion which carries negative charge. e.g., [Fe(CN)6]4-
2. Central Atom or Ion : The atom or ion to which a fixed number of ions or groups are bound . It is also
referred as Lewis acid. e.g., in [NiCI2(H2O)4]. Ni is central metal atom.
3. Ligands : Ligands is electron donating species (ions or molecules) bound to the Central atom in the
coordination entity.These may be charged or neutral. Ligands are of the following types: (i) Unidentate It is a
ligand, which has one donor site, i.e., the ligand bound to a metal ion through a single donor site. e.g., H2O, NH3,
etc.(ii) Didentate It is the ligand. which have two donor sites.

(iii) Polydentate It is the ligand, which have several donor sites. e.g., [EDTA]4- is hexadentate ligand.
(iv) Ambidentate ligands These are the monodentate ligands which can ligate through two different sites, e.g.,
NO-2, SCN–, etc.

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(v) Chelating ligands Di or polydentate ligands cause cyclisation around the metal atom which are known as
chelates ,such ligands Uses two or more donor atoms to bind a single metal ion and are known as chelating
ligands.
More the number of chelate rings, more is the stability of complex.
The stabilisation of coordination compounds due to chelation is known as chelate effect.
4. Coordination Number : It is defined as the number of coordinate bonds formed by central metal atom, with
the ligands.
5. Coordination Sphere : The central ion and the ligands attached to it are enclosed in square bracket which is
known as coordination sphere.
IUPAC Naming of Complex Compounds
1. Name of the compound is written in two parts (i) name of cation, and (ii) name of anion.
2. The cation is named first
3. The dissimilar ligands are named in alphabetical order before the name of central metal atom.
4. For more then one similar ligands. the prefixes di, tri, tetra, etc are added before its name. If the di, tri, etc
already appear in the complex then bis, tris, tetrakis are used.
5. If the complex part is anion, the name of the central metal ends with suffix ‘ate’.
6. Names of the anionic ligands end in ‘0’, names of positive ligands end with ‘ium’ and names of neutral ligands
remains as such. But exception are there as we use aqua for H2O, ammine for NH3, carbonyl for CO and nitrosyl
for NO.
7. Oxidation state for the metal in cation, anion or neutral coordination compounds is indicated by Roman
numeral in parentheses.
8. The name of the complex part is written as one word.
9. If the complex ion is a cation, the metal is named same as the element.
10. The neutral complex molecule is named similar to that of the complex cation. eg.
(i) [Cr(NH3)3(H2O)3]Cl3 triamminetriaquachromium (III) chloride
(ii) [Co(H2NCH2CH2NH2)3]2(SO4)3 tris (ethane-l,2-diamine) cobalt (III) sulphate
(iii) [Ag(NH3)2] [Ag(CN)2] diamminesilver(I) dicyanoargentate(I)
(iv) K4 [Fe(CN)6] potassium hexacyanoferrate (II)
(v)[Pt(NH3)2CI(NO2)] . diamminechloridonitrito – N‐ platinum(II)
(vi) K3 [Cr(C2O4)3 ] potassium trioxalatochromate (III)
(vii) [CoCI2(en)2 ]CI dichloridobis(ethane1, 2diammine)cobalt(III) chloride
Bonding in Coordination Compounds
Werner’s Theory-Metals exhibit two types of valencies in the formation of complexes.
These are primary valencies and secondary valencies.

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 1. Primary valencies correspond to oxidation number (ON) of the metal and are satisfied by anions. These are
ionisable and non-directional.
2. Secondary valencies correspond to coordination number (CN) of the metal atom and are satisfied by ligands.
These are non-ionisable and directional. Hence, geometry is decided by these valencies.
Valence Bond Theory.( i) The suitable number of atomic orbitals of central metal ion (s, p, d) hybridise to
provide empty hybrid orbitals.

(ii) These hybrid orbitals accept lone pair of electrons from the ligands and are directed towards the ligand
positions according to the geometry of the complex.
(iii) When inner d-orbitals i.e. (n-1) d orbitals are used in hybridization, the complex is called – inner
orbital complex., they are formed due to strong field ligands or low spin ligands and hybridisation is d2sp3. eg
[Fe(CN)6]3-
(iv) outer orbital complexes When outer n d-orbital are used in bonding, the complexes are called outer
orbital complexes. They are formed due to weak field ligands or high spin ligands and hybridisation is sp3d2.
They have octahedral shape. [CoF6]3-.
Tetrahedral complex: A complex in which central atom/cation involves sp3 hybridisation.

Square planar complex: A complex which has a flat structure and central atom/ion has dsp2 hybridisation.

(v) There are two types of ligands namely strong field and weak field ligands. A strong field ligand is capable
of forcing the electrons of the metal atom/ion to pair up (if required). Pairing is done only to the extent which is
required to cause the hybridization possible for that Co-ordination number. A weak field ligand is incapable of
making the electrons of the metal atom/ ion to pair up.
Strong field ligands : CN–, CO, en, NH3,H2O, NO–, Py.
Weak field ligands : I–, Br–, Cl–, F–, NO3–, OH–, C2O42–, H2O

Magnetic Properties A substance which do not contain any unpaired electron is not attracted by magnet. It is said to be
diamagnetic. On the other hand, a substance which contains one or more unpaired e- in the electrons in the d-orbitals, is
attracted by a magnetic field. It is said to be paramagnetic. Paramagnetism can be calculated by the
expression, µs = √n(n+2) where μ = magnetic moment. S = spin only value and n= number of unpaired electrons.

Hence, if n = 1, µs = √1(1+2) = 1.73 B.M, if n = 3 µs = √3(3+2) = 3.87 B.M and so on

Geometry (shape) and magnetic nature of some of the complexes (Application of valence bond theory)

Crystal Field Theory (CFT): In this theory, ligands are treated as point charges in case of anions and dipoles in case of neutral
molecules. Due to approach of ligands, the five-degenerate d-orbitals split in two set of orbital t2g and eg,splitting of d-orbitals
depends on the nature of the crystal field.

[The energy difference between t2g and eg level is designated by Δ and is called crystal field splitting energy.]
Spectrochemical series

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Crystal field splitting in octahedral complexes energy separation is denoted by Δo .In octahedral complexes,
the six-ligands approach the central metal ion along the axis of d x2 – y2 and d z2 orbitals.
Energy of eg set of orbitals > energy of t2g set of orbitals.
The energy of eg orbitals will increase by (3/5) Δo and t2g will decrease by (2/5) Δo.
If Δo < P, the fourth electron enters one of the eg orbitals giving the configuration t32g e1g.

45
If Δo > P, it becomes more energetically favourable for the fourth electron to occupy a t2g orbital with
configuration t42g eog. (where, P = energy required for e– pairing in an orbital). Ligands which produce this effect
are known as strong field ligands and form low spin complexes.

Crystal field splitting in tetrahedral complexes , four ligands may be imagined to occupy the alternate comers
of the cube and the metal ion at the center of the cube.
Energy of t2g set of orbitals > Energy of eg set of orbitals. In such complexes d – orbital splitting is inverted and
is smaller as compared to the octahedral field splitting.
Colour in Coordination Compounds
The crystal field theory attributes the colour of the coordination compounds due to d-d transition of the electron,
i.e., electron jump from t2g level to higher eg level.
Assertion and Reason Type Questions

In the following questions, a statement of Assertion (A) followed by a statement of Reason (R) is given.
Choose the correct option out of the following choices.
(a) Assertion and Reason both are true, Reason is the correct explanation of Assertion.
(b) Assertion and Reason both are true but Reason is not the correct explanation of Assertion.
(c) Assertion is true, Reason is false.
(d) Assertion is false, Reason is true.

1. Assertion (A): Toxic metal ions are removed by the chelating ligands.
2. Reason (R): Chelate complexes tend to be more stable.
3. Ans: (a) When a solution of chelating ligand is added to solution containing toxic metals
ligands chelates the metal ions by formation of stable complex.

2. Assertion (A): [Cr(H2O)6]Cl2 and [Fe(H2O)6]Cl2 are reducing in nature.

46
Reason (R): Unpaired electrons are present in their d-orbitals.
Ans: (b) In the complexes, Co exists as Co2+ and Fe as Fe2+. Both of the complexes become
stable by oxidation of metal ion to Co3+ and Fe3+.
3. Assertion (A): Linkage isomerism arises in coordination compounds containing ambidentate ligand.
Reason (R): Ambidentate ligand has two different donor atoms.
Ans: (a) Linkage isomerism arises due to two different donor atoms in ambidentate ligand.
4. Assertion (A): (Fe(CN)6]3- ion shows magnetic moment corresponding to two unpaired electrons.
Reason (R): Because it has d2sp3 type hybridisation.
Ans: (d) (Fe(CN)6]3- ion shows magnetic moment corresponding to one unpaired electron.
5. Assertion(A) : [Co(NH3)Br]SO4 gives white precipitate with barium chloride.
Reason(R) : The complex dissociates in the solution to give Br - and SO4 2- . (Ans - c)
6. Assertion(A) : According to crystal field theory during complex formation, the d –
orbitals split and form two sets of orbitals t2g and eg.
Reason(R) : Splitting of d - orbitals occurs only in case of strong field ligands. (Ans - c)

7. Assertion(A) : [Fe(H2O)6] 2+ is sp3 d 2 hybridised and paramagnetic complex ion.

Reason(R) : It has four unpaired electrons. ( Ans - a)

8. Assertion(A) : Low spin tetrahedral complexes are not formed.

Reason(R) : For tetrahedral complexes, CFSE is lower than pairing energy. ( Ans - a)

9. Assertion(A) : [FeF6] 3- is paramagnetic.

Reason (R): F- is a weak field ligand, hence does not cause pairing of electrons. (Ans - a )

MCQ

1. Which of the following is a complex of metal other than transition metal?

(a) Haemoglobin (b) Chlorophyll (c) Ferrocene (d) Vitamin B12
2. Which of the following is not a double salt but a coordinate compound?
(a) KCl.MgCl2.6H2O (b) FeSO4.(NH4)2SO4.6H2O
(c) K2SO4.Al2(SO4)3.24H2O (d) 4KCN.Fe(CN)2
3. The donor atoms in ethylenediaminetetraacetate ion is
(a) two N and two O (b) two N and four O (c) four N and two O (d) three N and three O
4. The complex ion [Cu(NH3)4] +2 is
(a) tetrahedral and paramagnetic (b) tetrahedral and diamagnetic
(c) square planar and paramagnetic (d) square planar and diamagnetic
5. The hybrid state of Co in high spin complex, K3[CoF6] is
(a) sp3 d 2 (b) sp3 (c) d2 sp3 (d) sp3 d
6. In an octahedral crystal field, the t2g orbital are
(a) raised in energy by 0.4 ∆o (b) lowered in energy by 0.4 ∆o
(c) raised in energy by 0.6 ∆o (d) lowered in energy by 0.6 ∆o

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CHEMICAL DISTINCTION TEST FOR ORGANIC COMPOUND
1. Distinction test for carboxylic acid - (Sodium bicarbonate test)

R-COOH ------NaHCO3------------→ Brisk effervescence of CO2

Phenol --------NaHCO3 -----------→No brisk effervescence
Alcohol -------NaHCO3 -----------→ No brisk effervescence
2. Phenol
Phenol ---------Neutral FeCl3----→ Violet colour
RCOOH ---------Neutral FeCl3--→ No colour
Alcohol ----------Neutral FeCl3 -→ No colour
3. Formic acid (Methanoic acid)
Exceptionally give the test of aldehyde besides NaHCO3.
Formic acid ----------Tollens reagent ----→ Silver Mirror
Formic acid ----------Fehling solution ----→ Red Brown ppt of Cu2O
4. Distinction test for Aldehyde and Ketone
Aldehyde ----------Tollens reagent-----→ Silver Mirror
Ketone -------------Tollens reagent-----→ No colour
Aldehyde ----------Fehling solution ---→ Red brown ppt of Cu2O
Ketone -------------Fehling solution ---→ No colour

5. For Aliphatic and Aromatic Aldehyde

Aliphatic aldehyde ------Fehling solution ---→ Red Brown ppt of Cu2O
Aromatic aldehyde -----Fehling solution ---→ no colour obtained
6. Iodoform Test –
O.C. -------I2 + NaOH -------→ CHI3 (Yellow ppt)
Condition – (i) Any aldehyde or ketone having ( CH3-CO -)- group gives this test.
(ii) Alcohol having (CH3-CHOH-)- gives iodoform test.
(CH3CO-)- ------- I2 + NaOH -----→ CHI3 Yellow PPT
(CH3CHOH-)- ------- I2 + NaOH -----→ CHI3 Yellow PPT
That is it can be used to distinguish to
(i) Two Aldehyde
(ii) Two Ketones
(iii) Aldehyde and Ketones
(iv) Two alcohol
7. Primary, secondry and tertiary alcohol – (Lucas test)
Lucas reagent Anhyd. ZnCl2 and con. HCl
Tertiary alcohol gives turbidity immediately while secondry alcohol gives turbidity after
5 minute while tertiary alcohol gives no turbidity at room temperature.

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8. Amines - primary secondry and tertiary amines
(i) Carbyl amine test
To distinguish primary amine from secondry and tertiary amine.
Primary amine -------CHCl3 + NaOH-----→ R-NC (Foul smell)
Secondry amine -------CHCl3 + NaOH-----→ no smell
Tertiary amine -------CHCl3 + NaOH-----→ no smell
(ii) HNO2 Test –
Primary amine -----HNO2/ HCl ------→ N2(g)
Secondry amine -----HNO2/ HCl ------→ N2(g)
Tertiary amine -----HNO2/ HCl ------→ N2(g)
NOTE- Pimary Aliphatic amine and primary aromatic amine can distinguish by
this test only.
Primary aliphatic amine -----HNO2/ HCl ------→ N2(g)
Primary aromatic amine -----HNO2/ HCl ------→ Coloured azo dyes after
coupling reaction.
(iii) Hinsberg test – Benzene sulphonyl chloride
Primary amine -----benzene sulphonyl chloride ------→ product ----→ soluble in
alkali
Secondry amine --- benzene sulphonyl chloride ----→Product -→ not soluble in
alkali
Tertiary amine ----- benzene sulphonyl chloride ------→ No reaction
Practice Questions-
1. Acetic acid and ethyl alcohol
Hint:- By NaHCO3 or Iodoform
2. Phenol and Propanol
Hint:- Neutral FeCl3
3. Benzoic acid and phenol
Hint:- By NaHCO3 or by neutral FeCl3
4. Formic acid and acetic acid
Hint:- either by T.R. or F.S.
5. Formaldehyde and formic acid
Hint:- By NaHCO3 test
6. Propanal and propanone
Hint:- either by T.R. or F.S.
7. Ethanal and propanal
Hint:- Iodoform test
8. Acetophenone and benzophenone
Hint:- Iodoform test

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 9. 1-butanol and 2- butanol
Hint:- Iodoform test
10. Ethanol and ethyl ethanoate
Hint:- Iodoform test
11. Benzaldehyde and propanaldehyde
Hint:- By F.S. test
12. Benzaldehyde and acetaldehyde
Hint:- By F.S. test and iodoform test
13. Ethyl amine and N-methyl ethyl amine
Hint:- By carbyl amine test
14. Methanamine and Aniline
Hint:- By HNO2 test
15. N,N-demethyl amine and N-methyl amine
Hint:- By HNO2 test or by Hinsberg test
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SPECIFIC TEST
1) Phenol Test
(a) organic compound(O.C.) + Neutral Fecl3 → Violet or Green color solution
(b) organic compound(O.C.) + Benzene diazonium chloride(B.D.C.)+ ice → Orange color dye
2) Carboxylic acid test
(a)O.C. + NaHCO3(sol.) → Brisk effervescence is evolved → COOH is present
(b) O.C. + ethanol + few drops of conc. H2SO4 → Fruity smell of ester is formed – COOH is
present
3) Test of 10, 20, 30 alcohol (Lucas Test)
Organic Compound + Lucas Reagent(conc. HCL + ZnCl2) →
(a) If turbudity is formed at once = 10 alcohol
(b) If turbudity is formed within 5 minutes = 20 alcohol
(c) If no turbudity is formed at room temperature = 30 alcohol

4) 10 alcohol test (esterification test)

(a) O.C. + carboxylic acid + conc.H2SO4 → fruity smell of ester is formed (10 alcohol is
present)
5) Test of aldehyde
(a ) O.C. Tollen’s reagent + Heat→ Silvermiror is formed → Aldehyde is confirmed
(b) O.C. + Fehling solution + heat → Reddish brown precipitate is formed → Aldehyde is
confirmed
6) Test of Formic Acid (HCOOH)(Methanoic Acid)
Formic acid + Tollen’s Reagent placed (in water)→ A silver minor is formed after few minutes
7) Difference between 10, 20 and 30 Amines (Hinsberg test)
C6H5SO2Cl is known as Hinsberg Reagent (Benzene Sulphonyl Chloride)
O.C. Containing amines + Hinsberg Reagent

62
 O.C. Containing Amines
10 amine is present 20 amine is present 30 amine is present
A white precipitate is formed A white precipitate is formed No precipitate is formed.
which is soluble in aq. KOH. which is insoluble in aq.
KOH.
PROPANAL (CH3CH2CHO) PROPANONE O
||
(CH3-C-CH3)

(a) It gives silver mirror with Tollen’s reagent. (a) It does not give this test.

(b) It gives reddish brown precipitate of Cu2O when (b) It does not give this test.
react with fehling solution (A and B).

(c) It does not give this test. (c) It gives yellow precipitate of idoform and
NaOH (idoform test).

O O
ACETOPHENONE || BENZOPHENONE ||
CH3–C-C6H5 C6H5 –C-C6H5

It gives yellow precipitate of Idoform with I2 and

NaOH. (Idoform Test) It does not give this test.

PHENOL BENZOIC ACID

(a) It gives violet or green colour with FeCl3 (a) It does not give this test.
solution.
(b) It gives brisk effervescence of CO2 with
(b) It does not give this test. NaHCO3.

Pentan-2-one Pentan-3-one

CH3-C-CH2-CH2-CH3 CH3-CH2-C-CH2-CH2-CH3
|| ||
O O

It gives yellow precipitate idoform with I2 and It does not give this test.
NaOH (Idoform test).

BENZALDEHYDE ACETOPHENONE
(a) It does not give this test. (a) It gives yellow precipitate of idoform with I2
and
NaOH. (Idoform Test).
(b)It gives silver mirror with Tollen’s reagent.

63
 (b)It does not give this test.

BENZOIC ACID ETHYL BENZOATE

(a) It gives brisk effervescence of CO2 with (a) It does not give this test.
NaHCO3
solution.

FORMALDEHYDE ACETALDEHYDE
(a) It does not give this test. (a) It gives yellow precipitate of idoform with I2
and NaOH. (Idoform Test).

Methanol (CH3OH) Ethanol (CH3CH2OH)

(a) It does not give this test. (a) It gives yellow precipitate of idoform with I2
and NaOH. (Idoform Test).

Ethyl amine Dimethylamine

(a) It gives offensive smell of Isocyamide when
react with chloroform and alc.(KOH) (a) It does not give this test.
(Carbylamine test).

8) Idoform Test (M.Imp)

Compound containing CH3-CH- group and CH3-C- group

| ||
OH O

gives yellow precipitate of Idoform (CHI3) when react with I2 and NaOH.
Such as Ethanol, Ethanal, Propanone, Butanone, propan-2-ol, butan-2-ol, acetone, pentan-2-one,
Acetophenone.
9) All Primary amines gives Carbylamine test
10 amine + chloroform (CHCL3) + KOH ➔ An offensive smell of Isocyanide is evolved.
10) Test of aniline and phenol (Azodye test)
Aniline + Benzene diazonium chloride ➔ Yellow coloured dye is formed (Azodye)
Phenol + B.D.C. (Benzenedicarboxylate)➔ Orange colour dye is formed (Azodye)

*************************************************************************************

64
MECHANISM IN ORGANIC CHEMISTRY

65
66
Q1 Write the mechanism of the following acid catalysed reaction at 413K.

2CH3CH2OH. ————> CH3CH2OCH2CH3

Ans

Q2 Write the mechanism for the conversion of ethanol to bromoethane

67
MECHANISM OF ETHER FORMATION FROM ALCOHOL

Q3 Write the equations for the preparation of the following ethers from Williamson’s synthesis

1-Propoxypropane
2- Ethoxybenzene
3- 2methyl,2methoxypropane
Ans (1) 1- propoxypropane

(ii) Ethoxybenzene

68
iii) 2 methyl, 2 methxypropane

Q4 When 3methyl butan-2-ol is treated with HBr the product formed is 2-bromo,2 methyl. Butane. Give
mechanism for this reaction Ans-1

69
 DEHYDRATION MECHANISM OF ALCOHOLS

*************************************************************************************

70
 Reasoning Based Question and Answer in Organic Chemistry
Based on : Melting Point, Boiling Point, Nucleophilic – substitution and Electrophilic
substitution Reaction, Reactivity, solubility, Dipole moment etc.

M.P. of organic compounds depends on the following factors-

1. Lattice structure of compound .

2. Shape of molecule.
3. Dipole-dipole interaction between molecules.
4. Surface area of molecules.
(Branched chain isomers have lesser surface area hence low m.p. than straight chain
isomers with larger surface area.)
5. Vander Waal forces between molecule.
6. H-bonding between molecules if applicable.

Ques 1) B.P. of bromoethane is higher than that of chloroethane. Why?

Ans : Due to larger size and more mass of Br than that of Cl, the molecules of bromoethane have
greater magnitude of vander Waal forces of attraction than that in chloroethane. Hence B.P. of
bromoethane is higher than the B.P. of chloroethane.

Ques 2) n-Butybromide has higher B.P. than t-tubylbromide. Why?

Ans : n-Butylbromide has a straight chain hence larger surface area than t-butybromide that has a
branched structure.

Vander Waal forces of attraction is more when surface area is more. Hence n-Butyl bromide will
have higher B.P. than t-butyl bromide.

Ques 3) Alkyl halides, though polar, are immiscible with water. Why?

Ans: As alkyl halides are polar molecules they are held together by dipole-dipole attraction. The
molecules of water are held together by strong ‘H’ bonding. Since the force of attraction between
alkyl halide molecules and water molecules are weaker than the forces of attraction between alkyl
halide and alkyl halide molecules and water –water molecules, hence alkyl halides are immiscible
with water.

71
Ques 4) Why are haloalkanes very less soluble in water ?

Ans : Although haloalkanes are very polar molecule but neither they from ‘H’ bonds with water
molecules nor they can break ‘H’ bonding between water molecules. As a result haloalkanes are
very less soluble in water.

Ques 5) Out of ethyl bromide and ethyl chloride which has higher B.P. and Why?

Ans: Because of more mass and bigger size of ‘Br’ than ‘Cl’ the Vander wall force & attraction
are stronger in ethyl bromide than in ethyl chloride. Hence ethyl bromide has higher B.P. than
ethyl chloride.

Ques 6) Haloalkanes dissolve easily in organic solvents. Why?

Ans : Haloalkanes dissolve in organic solvents of low polarity, like petroleum-there, benzene,
diethyl ether, chloroform, CCl4, etc. because new force of attraction setup between haloalkanes
and solvent molecules are some as the force between haloalkanes-haloalkanes and between
solvent-solvent molecules.

Ques 7) p-Dichlorobenzene has more melting point (323k) than orhto and meta isomers.
Why?

Ans : p-Dichlorobenzene has more melting point than ortho and meta isomers due to better
symmetry and better molecular packing in crystal lattice than other two isomers.

Ques 8) Why are haloalkanes more reactive towards nucleophilic substitution reactions than
haloarenes?

Ans : Haloalkanes are more reactive than haloarenes towards nucleophilic substitution reaction
due to following reasons –

(a) Due to resonance in haloarenes, then C-X bond acquires a partial double bond character.
It makes the bond cleavage in haloarenes more difficult than in haloalkanes.
(b) The carbon of C-X bond is sp3-hybridised in haloalkanes while it is sp2-hybridiesed in
haloarenes. As such the C-X bond length in haloarenes in less than in haloalkenes. A
shorter bond is more difficult to break.
(c) The benzene ring is haloarenes is electron rich. This make it difficult for electron rich
nucleophiles to attack haloarenes.

Ques 9) Explain why propanol has higher boiling point than that of the hydrocarbon,
butane?

Ans: As butane is non-polar, the molecules of butane are held together by weak van der Waal’s
force of attraction while those of propanol are held together by stronger intermolecular hydrogen
bonding as shown below :

72
Therefore, the b. p. of propanol is much higher than that if butane.

Ques 10) Alcohols are comparatively more soluble in water than hydrocarbons of
comparable molecular masses. Explain this fact.

Ans: Alcohols can form H-bonds with water and break the H-bonds already existing between water
molecules. Therefore, they are in general, soluble in water.

On the other hand, hydrocarbons cannot from H-bonds with water and hence are insoluble in water.

Ques 11) Which of the following will have a higher boiling point and why: CH 3NH2 or
CH3OH?

Ans: CH3OH will have a higher boiling point than CH3NH2. This can be explained as follows.
Oxygen is more electronegative than nitrogen and atomic size of oxygen is less than that of
nitrogen. As such, the intermolecular forces in CH3OH are stronger than in CH3NH2. Therefore,
boiling point of CH3OH will be more than CH3NH2.

Ques 12) Alcohols are more soluble in water than the hydrocarbons of comparable molecular
masses.

Ans: Alcohols can from H-bonds with water and break the H-bonds already existing between water
molecules. Therefore, they are in general, soluble in water.

On the other hand, hydrocarbons cannot form H-bonds with water and hence are insoluble in water.

Ques 13) Why primary alcohols are more acidic than secondary alcohols?

73
Ans: As we move from primary to secondary alcohol, the number of alkyl groups attached to the
carbon having the –OH group increases.

Due to +I effect of alkyl group, the electron density on oxygen will be more in case of 2o alcohols
than in case of 1o alcohol. Hence the shared pair of electron of the O-H bond will be more displaced
towards the O atom in case of 1o alcohol than in case of 2o alcohol. Thus the release of proton
(H+) is easier in case of 1o alcohols than in case of 2o alcohol. Therefore, 1o alcohol is more acidic
than 2o alcohol.
Ques 14) Why are alcohols higher boiling point compounds than hydrocarbons of
corresponding molecular masses but have lower boiling point than corresponding acids?

Ans: The higher boiling point of alcohols than corresponding hydrocarbon are due to
intermolecular hydrogen bonding.

No such hydrogen bonding is present in hydrocarbons.

But alcohols have lower boiling points than corresponding acids because in acid there is stronger
intermolecular H-bonding due to the presence of two electronegative oxygen atoms. Thus acid
molecule dimerises.

Ques 15) Give reasons for the following :

(a) Benzoic acid does not give Friedel-Craft’s reaction.

(b) Carboxylic acid with more than five carbon atoms are insoluble in water.
(c) Acetic acid in vapors state shows a molecular mass of 120.

Ans: (i) The carboxylic group (-COOH) is an electron withdrawing group and therefore,
deactivates the benzene ring towards electrophilic attack. Therefore benzoic acid does not give
Friedel Craft’s reaction.

74
(ii) Carboxylic acid (RCOOH) dissolve in water due to hydrogen bonding between H-atom of –
COOH group and O-atom of water. As alkyl portion R- is non-polar and hydrophobic, this effect
predominates as –R gets larger (over five carbon atoms).

(iii) CH3COOH typically undergoes dimeric intermolecular hydrogen bonding as shown ahead.

It exists as a dimer in the vapour state. Therefore, its molecular mass comes out to be double than
the actual molecular mass of acetic acid (mol. Mass=60).

Ques 16) How would you account for the following:

(a) Aldehydes are more reactive than ketones towards nucleophiles.

(b) The boiling point of aldehydes and ketones are lower than of the
corresponding acids.
(c) The aldehydes and ketones undergo a number of addition reaction.

Ans : (i) Aldehydes are generally more reactive than ketones in nucleophilic more reactive than
ketones in nucleophilic addition reactions due to steric and electronic reasons. Sterically, the
presence of two relatively large substituents in ketones hinders the approach of nucleophile to
carbonyl carbon than in aldehydes having only one such substituent. Electronically, aldehydes are
more reactive than ketones because two alkyl groups reduce the electrophilicity of the carbonyl
carbon more effectively than in former.

(ii) Carboxylic acids are higher boiling liquids than aldehydes and ketones of comparable
molecular masses and ketones of comparable molecular masses. This is due to extensive
association of carboxylic acid molecules through intermolecular hydrogen bonding. The hydrogen
bonds are not broken completely even in the vapour phase. In fact, most carboxylic acid exist as
dimer as simmer in vapour phase or in the aprotic solvents.

Dimer in vapour state or in aprotic solvent

(iii) Aldehydes and ketones undergo a bumbler if nucleophilic addition reaction reactions such
as addition of HCN, NaHSO3, Grignard reagent etc. This can be explained as follows.

A nucleophilic attack the electrophilic carbon atom of the polar carbonyl group from a direction
approximately perpendicular to the plane of sp2-hybridised orbitals of carbonyl carbon.

75
The hybridization of carbon changes from sp2 to sp3 in this process, and a tetrahedral alkoxide
intermediate is produced. This intermediate captures a proton from the reaction medium to give
the electrically neutral product. The net result in addition of Nu- and H+ across the carbon oxygen
double bond.

Ques 17) Account for the following:

(a) Electrophilic substitution in benzoic acid takes place at meta position.

(b) Carboxylic acids have higher boiling point than alcohols of comparable molecular
masses.

Ans : Due to resonance in benzoic acid, there is comparatively higher electron density at meta
position than at ortho and para positions. Therefore, electrophilic substation in benzoic acid takes
place at the meta position.

(ii) This is because of stronger intermolecular hydrogen bonding in carboxylic acids than in
alcohols. This is due to the fact that O-H bond in carboxylic acid is more strongly polarized due to
the presence of adjacent electron withdrawing carbonyl group.

76
Ques 18) NH2 group is ortho and para-directing group, nitration of aniline give along
with ortho and para derivative, a good proportion of meta derivative also.

Ans: Direct narration of aniline with nitrating mixture (conc. HNO3 + conc. H2SO4) gives a
fair amount of m-derivative along with o-and p-product.

The NH2 group in aniline is o and p-directing. As such only o and p-substituted products are
expected in this reaction. The formation of a fair amount of m-derivative can be explained as
follows:

In strongly acidic medium (conc. HNO3+ conc. H2SO4-nitrating mixture) aniline is protonated to
form anilinium ion, which is meta directing.

Ques 19) Give plausible explanation for each of the following:

(a) The presence of a base in needed in the ammonolysis of alkyl halides.

(b) Aromatic primary amines cannot be prepared by Gabriel phthalimide synthesis.

Ans: (i) Ammonolysis of alkyl halides involves reaction of alkyl halide with ammonia to produce
1o, 2o or 3o amines (along with quaternary ammonium salts).

77
However, the product of the reaction is not an amine, rather it is its salt with HX, For example,

To obtain free amine from this salt a strong base (stronger than the amine) like NaOH or KOH is
needed.

(ii) In Gabriel phthalimide reaction phthalimide first react with a strong base (say KOH) to give
potassium salt which on ionization gives phthalimide ion. It is followed by nucleophilic
substitution of alkyl halide by phalimide ion to give N-alkyl phthalimide which on alkaline
hydrolysis gives the 1o amine.

Aromatic primary amines cannot be prepared by Gabriel phthalimide synthesis because aryl
halides do not undergo nucleophilic substitution with the anion formed by phthalimide.

Ques 19) p-Methoxy aniline is a stronger base than aniline while p-nitroaniline is a weaker
base than aniline. Why?

Ans: Methoxy group is an electron donating group. In p-methoxy aniline, methoxy group will
increase the availability of lone pair of electrons on nitrogen, thus making it more basic than
aniline. Nitro group is an electron it will decrease the availability of lone pair of electrons on
nitrogen, thus making it less basic than online.

78
Ques 20) Account for the following:

(a) pKb of aniline is more than that of methylamine.

(b) Ethylamine is soluble in water whereas aniline is not.
(c) Methylamine in water reacts with ferric chloride to precipitate hydrate ferric oxide.
(d) Aniline does not undergo Friedel-Crafts reaction.
(e) Diazonium salts of aromatic amines are more stable than those of aliphatic amines.
(f) Gabriel phthalimide synthesis is preferred for synthesizing primary amines.

Ans: (a) Aniline is a weaker base than methylamine in other words, Kb of aniline is less than Kb
of methylamine or pKb of aniline is more than pKb of methylamine (pKb=-log Kb or pKb=log
1/kb).
This can be explained on the basis of resonance and greater stability of aniline than anilinium ion.
Aniline is a resonance hybrid of following structure:

As a result of resonance, the lone pair on nitrogen gets delocalized over the ring. This decreased
the availability of electron pair for protonation. Therefore, aniline is weaker base than ammonia.
Aniline accepts a proton to form anilinium ion.

Anilinium ion is relatively less stable than aniline as it has only two resonating structures

On other hand, methylamine is a stronger base than ammonia. This is due to the +I effect of
methyl group which increases the availability of lone pair on nitrogen atom

79
 CH3--------->---------NH2

Thus, methylamine is much stronger base than aniline.

(b) Lower aliphatic amines like ethylamine are soluble in water. This is due to their ability to
from hydrogen bonds with water. This is due to their ability to form hydrogen bonds with water.

On the other hand, aromatic amines like aniline are insoluble in water. This is due to their larger
hydrocarbon part which hinders the formation of hydrogen bonds with water.

(c) Methylamine dissolve in water to give methylammonium hydroxide, which ionizes to give
methylammonium and hydroxide ions.

Due to the formation of OH-, ions they can precipitate out iron, aluminum, chromium etc., from
their salts.

Ferric hydroxide being unstable can be considered as hydrated ferric oxide.

2 Fe(OH)3=Fe2O3 + 3H2O

(d) Aniline does not undergo Friedel-Crafts acylation or alkylation. This is due to salt formation
between base i.e. aniline and Lewis acid i.e. anhydrous AICI3 used as catalyst in the reaction.

Due to this, nitrogen of aniline acquires positive charge and thus acts as a strong deactivating
group. This does not allow Friedel-Crafts reaction to occur.

(e) This greater stability of aromatic diazonium compounds than aliphatic diazonium compounds
is due to dispersal of the positive charges on the benzene ring, due to resonance.

80
Such resonance structure are not possible in case of aliphatic diazonium salts. As such
aliphatic diazonium salts are much less stable than aromatic diazonium salts.

(f) A reaction between alkyl halide and ammonia gives a mixture of amines (1o,2o, 3o) along with
tetraallyl ammonium halide. The components of this mixture are not easy to separate. To get pure
1o amine, Gabriel phthalimide synthesis is preferred. This is because in this case pure 1o amine is
obtained from alkyl halide and ammonia as shown below.

Phthalic acid or its salt obtained in the last step can again be converted into phthalimide needed
for the reaction.

Ques 21) Give plausible explanation for each of the following:

(a) Why are amines less acidic than alcohols of comparable molecular masses?
(b) Why do primary amines have higher boiling point than tertiary amines?
(c) Why are aliphatic amines stronger bases than aromatic amines?

81
Ans: (a) Consider a 1 ° amine and an alcohol of comparable molecular masses.

Due to the presence of lone pair of electrons. These can act as Lewis bases. However both 1 °
amine (say methylamine) and alcohol (say methyl alcohol) can also act as Bronsted acids. For
example, they react with sodium metal to give hydrogen.

However, 1 ° amines are less acidic than alcohols of comparable molecular masses. This can be
explained as follows :

Loss of proton form a 1° amine gives an alkyl amide ion while loss of a proton from alcohol gives
alkoxide ion. R—NT R—N + H+ 1° Amine Alkyl amide ion.

Since 0 is more electronegative than N, therefore, 0 in alkoxide ion can accommodate the -ve
charge more easily than N in alkyl amide ion. In other words is more stable than
Thus we can say that alcohols are more acidic than amines or amines are less acidic
than alcohols. It should be noted that only 1' and 2° amines show acidic character. As nQ H-atom
is attached to N-atom is 3° amines, 3°-amines cannot show acidic character.

(b) Boiling point of 1' amine is much higher than a tertiary amine of equal molecular mass. For
example l.p. of CH3CH2CH2NH2(n-propylamine - a 1' amine) is much higher than l.p. of (CH3)3
N (trimethylamine - a 30 amine). Due to the presence of two H-atoms, attached to N-atom there is
extensive intermolecular H-bonding in 1 ° amine. On the other hand in 30 amines as there is no H-
atom attached to N-atom, H-bonding is absent in 30 amine. More the H-bonding stronger the
intermolecular forces, and hence higher the boiling point.

82
(c) Alkyl amines are stronger bases than ammonia : All the three types of aliphatic amines are
stronger bases than ammonia (Kb = 1.8 x 10-5). This can be explained on the bases of the + I effect
or electron-donating effect of alkyl group or alkyl groups attached to the nitrogen atom. This
increases the electron density on the nitrogen atom. Thus, amines can donate the lone pair of
electrons more easily than ammonia. Moreover, electron releasing effect of alkyl groups stabilizes
the alkyl ammonium ion formed and hence, shifts the equilibrium in the forward direction making
the alkylamines stronger bases than ammonia.

Aromatic amines such as aniline are less basic than ammonia. Aromatic amines such as aniline
(Kb = 4.2 x 10-10) are less basic than ammonia (Kb = 1.8 x 10-5). The weaker basic character of
aniline can be explained as follows.

(i) Resonance effect : Resonance effect : Aromatic ring has electron withdrawing nature due to
resonance. This decreases the availability of electron pair on nitrogen, thereby, making it less basic
than ammonia. For example, aniline can I be regarded as a resonance hybrid of the following
structures.

As a result of resonance, the lone pair on nitrogen atom gets delocalized over the benzene
ring. This decreases the availability of electron pair for protonation. Therefore, aniline is a
weaker base than ammonia.

(ii) Lower stability of aryl ammonium ion than aryl amine : Amines accept a proton to
form conjugate acid,. For example, aniline accepts hydrogen to form anilinium ion.

Anilinium ion is relatively less stable than aniline because it is a resonance hybrid of only two
structures, whereas aniline is a resonance hybrid of five structures.

83
Thus we find that resonance stabilization of aniline is more than that of anilinium ion. Hence the
proton acceptability or basic nature of aniline would be less than that of ammonia. As such basic
character of aliphatic amines, aromatic amines and ammonia, in general, is in the order ; aromatic
amines < ammonia < aliphatic amines Thus, we can say that aliphatic amines are stronger bases
than aromatic amines.

Ques 22) Why do amines behave as nucleophiles?

Ans : Amines behave as nucleophiles. For example, amines react with alkyl halides,
acid chlorides etc.

It is due to the presence of lone pair of electrons on nitrogen.

Ques 23) Why is an alkyl amine more basic than ammonia?

Ans: This is because of the presence of electron releasing alkyl group (+I effect) which
increase the electron density on nitrogen.

Ques 24) Which of the following compounds will have the highest melting point and why?

Ans : Compound (II) is most symmetrical because it has both the CH3 group and Cl atoms p- to
each other. Therefore, it fits in the crystal lattice better than the other two isomers and hence it
has the highest melting point.

84
Ques 25) Which is a stronger acid, phenol or cresol? Explain.

Ans : Cresol is methyl phenol. It has three positional isomers : o-cresol, m-cresol and p-cresol,
Due to +I-effect of CH3 group, electron density in the O-H bond increases. Therefore, it becomes
difficult to break the O-H bond as compared to that in phenol and hence all cresols are less acidic
than phenol or phenol is a stronger acid than cresols.

Ques 26) How is that alcohol and water are miscible in all proportions?

Ans: Due to intermolecular H-bonding (as shown below) alcohol and water are miscible in all
proportions.

Ques 27)Why do alcohols have higher boiling points than haloalkanes of

comparable molecular mass ?

Ans: Alcohols undergo extensive intermolecular H-bonding. As a result, alcohols exist as

associated molecules as shown below:

Quite a large amount of energy is needed to break these H-bonds. Therefore, the boiling points of
alcohols are much higher than haloalkanes of comparable molecular mass because the molecules
of haloalkanes are held together only by weak dipole-dipole and van der Waals forces of attraction.
For example, the b.p. of methyl chloride is 249 K while that of methanol is 337.5.

Ques 28) Why is sulphuric acid not used during the reaction of alcohols with K1 in the
conversion of an alcohol to the alkyl iodide?

Ans: Alkyl iodides are formed when alcohols are heated with constant boiling hydriodic acid
(57%)

85
The HI needed for the purpose, however, cannot be prepared in situ by heating KI with H 2SO4.
The reason being that H2SO4 being an oxidizing agent, oxidizes HI to I2 before it is able to react
with alcohols to form alkyl iodides.

Ques 29) Why are phenols more acidic than alcohols? Give two reactions to show that
phenols are acidic in nature.

Ans: Since the phenoxide ion left after the removal of a proton is stabilized by resonance (refer to
page, 11/25) whereas alkoxide ion (left after the removal of a proton from alcohol) is riot.
Therefore, phenols are more acidic than alcohols.

The two reactions of phenol showing its acidic nature are :

(i) Phenols dissolve in NaOH forming sodium phenoxide.

(ii) Phenols react with metallic sodium to evolve H2 gas

Ques 30) Explain why phenols do not undergo Substitution of the -OH group like alcohols?

Ans: The C-0 bond in phenols has some double bond character due to resonance and hence cannot
be easily cleaved by a nucleophile. In contrast, the C-O bond in alcohols is a pure single bond and
hence can be easily cleaved by a nucleophile.

Ques 31) Explain why propanol has higher boiling point than that of the
hydrocarbon, butane ?

Ans: The molecules of butane are held together by weak van der Waals forces of attraction while
those of propanol are held together by stronger intermolecular hydrogen bonding.

Therefore, the b.p. of propanol is much higher than that of butane.

86
Ques 32) Alcohols are comparatively more soluble in water than hydrocarbons of
comparable molecular masses. Explain this fact.

Ans: Alcohols can form H-bonds with water and can also break the H-bonds already existing
between water molecules. Therefore, they are soluble in water.

On the other hand, hydrocarbons can neither form H-bonds with water nor can break the H-
bonds already existing between water molecules and hence are insoluble in water.

Ques 33) Explain why is ortho-nitrophenol more acidic than ortho-methoxyphenol?

Ans: Due to strong –R and –I-effect of the NO2 group, electron density in the O-H
bond decreases and hence the loss of a proton becomes easy.

Further, after the loss of a proton, the-nitro phenoxide ion left behind is stabilized by resonance,
thereby making o-nitrophenol a stronger acid.

In contrast, due to +R effect of the OCH3 group, the electron density in the O-H bond
increases thereby making the loss of a proton difficult.

Furthermore, the o-methoxy phenoxide ion left after the loss of a proton is destabilized
by resonance

87
Because the two negative repel each other thereby making o-methoxyphenol a weaker acid.
Thus, o-nitrophenol is more acidic than o-methoxyphenol.

Ques 34) Explain how does —OH group attached to a carbon of benzene ring activate
it towards electrophilic substitution?

Ans: Phenol may be regarded as a resonance hybrid of structures, 1-V. "As a result of +R-effect
of the OH group, the electron density in the benzene ring increases thereby facilitating the attack
by an electrophile. In other words, presence of OH group, activates the benzene ring towards
electrophilic substitution reactions. Further since the electron density is relatively higher at the two
o- and one p- position, therefore, electrophilic substitution occurs mainly at o- and p-positions.

Ques 35) Explain why is O = C = O nonpolar while R-O-R is polar.

Ans: CO2 is a linear molecule. The dipole moments of the two C = O bonds being equal and
opposite cancel out each other and hence CO2 is a non-polar molecule.

In contrast, in R-O-R molecule, the two dipoles of the R-O bonds are inclined to each other at
angle of 110°, i.e., the two dipoles do not cancel out and hence have a finite resultant. In other
words, R-O-R is a polar molecule.

Ques 36) Why is the reactivity of all the three classes of alcohols with conc. HCl and ZnCl2
(Lucas reagent) different ?

Ans: The reaction of alcohols with conc. HCl and ZnCl2 (Lucas reagent) occurs through
intermediate formation of carbocations. Obviously, more stable the carbocation, more reactive is
the alcohol. Since the stability of carbocations follows the order : 3° > 2° > 10, therefore, reactivity
of alcohols towards Lucas reagent follows the same order, i.e. , 3° > 2° > 1°.

Ques 37) Dipole moment of phenol is smaller than that of methanol. Why ?

Ans: In phenol, C-O bond is less polar due to electron-withdrawing effect of the benzene ring
whereas in methanol, C-O bond is more polar due to +I-effect of the CH3 group. As a result, phenol
has lower dipole moment (1.54 D) than methanol (1.71 D).

Ques 38) Why are aldehydes more reactive than ketones ?

88
Ans: Aldehydes are more reactive than ketones due to the following two reasons :

(i) Due to smaller +1-effect of one alkyl group in aldehydes as compared to larger +1-
effect of two alkyl groups, the magnitude of positive charge on the carbonyl carbon is
more in aldehydes than in ketones. As a result, nucleophilic addition reactions occur
more readily in aldehydes than in ketones.
(ii) Due to presence of a H-atom on the carbonyl group, aldehydes can be more easily
oxidized than ketones. As a result, aldehydes act as reducing agents and thus reduce
Tollens' reagent, Fehling's solution, etc.

Ques 39) Explain why o-hydroxybenzaldehyde is a liquid at room temperature while p-

hydroxybenzaldehyde is a high melting solid.

Ans: Due to intramolecular H-bonding (chelation), o-hydroxybenzaldehyde exists as discrete

molecules while due to intermolecular H-bonding, p-hydroxybenzaldehyde exists as associated

molecules. To break these intermolecular H-bonds, a large amount of energy is needed.
Consequently, p-hydroxy-benzaldehyde has a much higher m.p. and b.p. than that of o-
hydroxybenzaldehyde. As a result, o-hydroxybenzaldehyde is a liquid at room temperature while
p-hydroxybenzaldehyde is a high melting solid.

Ques 40) CH3CHO is more reactive than CH3COCH3 towards reaction with HCN ? Explain.
Or Propanone is less reactive than ethanal towards nucleophilic addition reactions. Give
reasons.
Ans: Due to electron-donating inductive effect (+ I-effect) of the two CH3 groups in CH3COCH3 as
compared to smaller + I-effect of one CH3 group in CH3CHO, the magnitude of the +ve charge on the
carbon atom of the carbonyl group in CH3CHO is more than in CH3COCH3. As a result, nucleophilic
addition reactions occurs more readily in CH3CHO than in CH3COCH3.

Ques 41) C6H5COCH3 is much less reactive than CH3COCH3 towards nucleophilic
addition reactions. Explain.

89
Ans: In C6H5COCH3, the electron-donating resonance effect (+R-effect) of the benzene ring
reduces the +ve charge on the carbon atom of the carbonyl group. Since +R-effect of benzene
ring is more pronounced than +I-effect of the CH3 groups, therefore, magnitude of the +ve
charge on the carbon atom of the carbonyl group in C6H5COCH3 is reduced to a much greater
extent than in CH3COCH3. As a result, C6H5COCH3 is much less reactive than CH3COCH3.

Ques 42) Acetone is highly soluble in water but benzophenone is not. Give reasons.

Ans: In acetone, C = O group easily forms H-bonds with water and hence acetone is highly
soluble in water. However, in benzophenone, the phenyl groups are bulky and hence C = O
group cannot form H-bonds with water due to steric hindrance and hence benzophenone is
insoluble in water.

Ques 43) Suggest a reason for the large difference in the boiling points of butanol and
butanal, although they have the same solubility in water.

Ans: The b.p. of butanol is higher than that of butanal because butanol has strong
intermolecular H-bonding while butanal has weak dipole-dipole attraction. However, both of
them form H-bonds with water and hence are soluble.

Ques 44) Why is benzoic acid less soluble in water than acetic acid ?

Ans: Due to polar nature of the C = O and O-H parts of COOH group, both CH3COOH and
C6H5COOH form H bonds with water. But due to large hydrocarbon part the extent of H-
bonding is much lower in benzoic acid than in acetic acid and hence benzoic acid is much less
soluble in water than acetic acid.

**********************************************************************************
SOME IMPORTANT CHEMICAL REACTIONS IN
ORGANIC CHEMISTRY
1. What happens when
I) Ethyl chloride is treated with Sodium Iodide (NaI )
II) Chlorobenzene is treated with Sodium metal in presence of dry ether.
III) Methyl Chloride is treated with KNO3
IV) n-butyl chloride is treated with alcoholic KOH.
V) 2,4,6-trinitrochlorobenzene is subjected to hydrolysis.
VI) Methyl chloride is treated with AgCN.
VII) Chlorobenzene is treated with Cl2 /FeCl3
VIII) Ethyl Chloride is treated with AgNO2
IX) 2-bromopentane is treated with alcoholic KOH.
X) Ethyl Chloride is treated with aqueous KOH

90
XI) Chlorobenzene is treated with CH3COCl in presence of anhydrous Alcl3
XII)Methyl chloride is treated with AgNO2.
XIII) Bromobenzene is treated with Ch3Cl in presence of anhydrous AlCl3
XIV) Ethyl chloride is treated with alcoholic KOH
XV) Chlorobenzene is treated with Ch3Cl in the presence of anhydrous AlCl3

ANSWERS
I) Ethyl Iodide is formed.

II- Biphenyl will be formed.

III- Methyl nitrite is formed.

IV-

V-

VI-

VII-

VIII-

IX- 2-pentene will be formed as major product

X- Ethyl Alcohol (ethanol) is formed

91
XI-

XII- Nitro methane is formed

XIII-

XIV-

XV-

2 .What happens when:

A). (CH3)3OCH3 is treated with HI
B). Anisole is treated with CH3COOCl/anhydrous ALCl3
C). Phenol is treated with Br2/CS2
ANSWERS

92
3. Convert the following:
A). benzoic acid to Benzene
B). Ethanoyl chloride to Acetone
C). Acetophenone to Ethyl benzene
D). propanone to propene
E). benzyl chloride to phenyl ethanoic acid
F). Propene to acetone
G). Propanoic acid to 2-hydroxypropanic acid

ANSWERS
A).

B).

C).

D).

E).

F).

G).

93
4.FILL IN THE BLANK:
A).

B).

C).

D).

E).

F).

G).

H).

I).Propanone to propene
J).

K).

L).

ANSWERS
A).

B).

94
C).

D).

E).

F).

G).

H).

I).

95
J).

K).

L).

5.WRITE THE PRODUCT

A).

B).

C).

D).

E).

F).

96
G).

H).

I).

J).

K).

L).

ANSWERS
A).

97
B).

C).

D).

E).

F).

G).

H).

98
J).

K).

L).

99
 BIOMOLECULES
KEY WORDS AND THEIR EXPLANATION
Carbohydrates Optically active, poly hydroxy aldehydes or ketones or the compounds
which yield such units upon hydrolysis.
Monosaccharides Cannot be hydrolyzed further. e.g.‐glucose, fructose, ribose
Reducing sugars Aldehydic/ ketonic groups free so reduce Fehling’s/ Tollen’s solution .
e.g.‐ all monosaccharides, maltose and lactose
Non reducing sugars Aldehydic/ ketonic groups are bonded so cannot reduce Fehling’s/
Tollen’s solution. Eg sucrose
Anomers. The two cyclic hemiacetal forms of glucose that differ only in the
configuration of the hydroxyl group at C1, called anomeric carbon
Such isomers, i.e., α –form and β ‐form, are called anomers.
Invert sugar Sucrose is dextrorotatory but after hydrolysis gives dextrorotatory
glucose and levorotatory fructose. Since the levorotation of fructose (–
92.4°) is more than dextrorotation of glucose (+ 52.5°), the mixture is
levorotatory. Thus, hydrolysis of sucrose brings about a change in the
sign of rotation, from dextro (+) to laevo (–) and the product is named
as invert sugar.
Essential amino acids Which cannot be synthesized in the body and must be obtained
through diet. Eg valine,leucine
Non-essential amino acids Which can be synthesized in the body, eg‐Glycine, Alanine
Zwitter ion In aqueous solution, amino acids exist as a dipolar ion known as
zwitter ion.
Peptide linkage Peptide linkage is an amide formed between –COOH group and –NH2
group of two successive amino acids in peptide chain.
Primary (10) str. Of Sequence of amino acids that is said to be primary structure of
proteins: proteins.
Secondary (20) str. Of secondary structure of protein refers to the shape in which a long
proteins polypeptide chain can exist. They are found to exist in two types of
structures viz. α‐helix andβ‐pleated sheet structure.
Tertiary structure of further folding of the secondary structure. It gives rise to two major
proteins: molecular shapes viz fibrous and globular.
Fibrous proteins Polypeptide chains run parallel, held together by hydrogen and
disulphide bonds, fiber– like structure. Water insoluble. Eg‐ keratin
(inhair, wool, silk) myosin (present in muscles).
Globular proteins chains of polypeptides coil around to give a spherical shape. water
soluble. Eg‐Insulin and albumin
Stable forces 2°& 3° Hydrogen bonds, disulphide linkages, van der Waals and electrostatic
structure of proteins forces of attraction.
Denaturation of Proteins When a protein is subjected to physical change like change in
temperature or chemical change like change in pH, the hydrogen
bonds are disturbed. Due to this, globules unfold and helix get
uncoiled and protein loses its biological activity. This is called
denaturation of protein. (During denaturation 2° and 30 structures are
destroyed but 10 structure remains intact.) eg‐ The coagulation of egg
white on boiling, curdling of milk etc.
DNA pentose sugar (D‐2‐deoxyribose) + phosphoric acid + nitrogenous
bases ( A , G , C, T )
RNA pentose sugar (ribose) + phosphoric acid + nitrogenous bases (A, G,
C, U)
Phosphodiester link Linkage between two nucleotides in polynucleotides
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Functions of Nucleic DNA reserve genetic information, maintain the identity of different
Acids species is capable of self-duplication during cell division, protein
synthesis.
Very Short Answer Questions
1. How many asymmetric carbon atoms are present in D (+) glucose?
2. Give the significance of (+)-sign in the name D- (+)-glucose.
3. Give the significance of prefix ‘D’ in the name D- (+)-glucose.
4. Name the linkage present in proteins.
5. Write the Zwitter ion form of amino acetic acid. (H2NCH2COOH).
6. How would you explain the amphoteric behavior of amino acids?
7. Which nucleic acid is responsible for carrying out protein synthesis in the cell?
8. The two strands in DNA are not identical but complementary. Explain.
9. What type of linkage holds together the monomers of DNA and RNA?
10. Mention the number of hydrogen bonds between adenine and thymine.
ANSWERS
1. 4
2. (+) sign indicates dextrorotatory nature of glucose.
3.‘D’ Signifies that –OH group on C-5 is on the right-hand side
4. Peptide linkage
5. NH3+CH2COO-
6. Amino acids are amphoteric due to the presence of both acidic and basic functional
groups.
7.RNA
8. complementary bases are prepared.
9. Phosphodiester linkage.
10. Two
Assertion –Reason based questions
A statement of assertion is followed by a statement of reason. Mark the correct choice from
the options given below:
(a) Both assertion and reason are true and reason is the correct explanation of assertion.
(b) Both assertion and reason are true but reason is not the correct explanation of assertion.
(c) Assertion is true but reason is false.
(d) Both assertion and reason are false.
1. Assertion : D - glucose is dextrorotatory whereas L - glucose is levorotatory.
Reason : D - compounds are always dextro and L - compounds are always laevo. ( Ans - b)
2. Assertion : Purine bases present in DNA are adenine and guanine.
Reason : The base thymine is present in RNA while base uracil is present in DNA. (Ans - c)
3. Assertion : α - Amino acids are the building blocks of proteins.
Reason : Natural amino acids are mostly α - amino acids. (Ans - b)
4. Assertion : The two strands of DNA are complementary.
Reason : Cytosine always pairs with guanine and thymine pairs with adenine. (Ans- a)
5. Assertion : Keratin is a globular protein.
Reason : Globular shape is due to secondary structure of proteins. (Ans- c)

Multiple Choice Questions

1. Antibodies are –
(a) carbohydrates (b) Proteins
(c) Lipids (d) Enzymes
Ans b

101
2. Which statement is incorrect about peptide bond?
(a) N bond length in proteins is longer than usual bond length of C – N bond
(b) Spectroscopic analysis shows planar structure of – CO – NH – group
© C – N bond length in proteins is smaller than usual bond length of C – N bond
(d) None of the above Ans a
3. The functional group which is found in amino acid is
(a) – COOH (b) – NH2
(c) – CH3 (d) both (a) and (b) Ans – d
4. Which base is present in RNA but not in DNA?
(a) Uracil (b) Cytosine
(c) Guanine (d) Thymine Ans d
5. ADP and ATP differ in the number of
(a) adenine base (b) ribose units
(c) phosphate units (d) nitrogen atoms Ans c
6. In both DNA and RNA, heterocyclic base and phospho diester linkages are at –
a. C5' and C2' respectively of the sugar molecule
b. C2' and C5' respectively of the sugar molecule
c. C1' and C5' respectively of the sugar molecule
d. C5' and C1' respectively of the sugar molecule
Ans c
6. Protein is a polymer made of
(a) carbohydrates (b) amino acids
© nucleic acids (d) carboxylic acids Ans- b
7. Nucleic acids are the polymers of
(a) Nucleosides (b) Nucleotides
© Bases (d) Sugars Ans- b
8. The specific sequence of amino acids in a polypeptide chain is known as
(a) Primary structure of proteins
(b) Secondary structure of proteins
(c )Tertiary structure of proteins
(d) Quaternary structure of proteins

9. Which of the following properties of glucose can be explained only by its cyclic structure
(a) Glucose forms pentaacetate
(b) Glucose reacts with hydroxylamine to form an oxime.
© Pentaacetate of glucose does not react with hydroxylamine.
(d) Glucose is oxidized by nitric acid to gluconic acid. Ans – c

10. Which of the following statements is not true about glucose ?

(a) It is an aldohexose
(b) On heating with HI it forms n- hexane
© It is present in furanose form
(d) It does not give 2,4-DNP test. Ans- c

Short Answer Questions

Q1. What is difference between reducing and non‐reducing sugars or carbohydrates?
(Ans) All those carbohydrates which contain aldehydic and ketonic group in the hemiacetal
or hemiketal form and reduce Tollen's reagent or Fehling's solution are called reducing
carbohydrates while others which do not reduce these reagents are called non‐reducing
sugars.
Q2. Explain the term mutarotation?
(Ans) Mutarotation is the change in the specific rotation of an optically active compound
with time, to an equilibrium mixture.
102
Q3. Why are carbohydrates generally optically active?
Ans. It is due to the presence of Chiral Carbon atoms in their molecules

Q4. How is globular protein different from fibrous protein?

Ans–
Globular Protein Fibrous Protein
1.they form α‐helix structure . 1. they have β‐pleated structure

2.they are water soluble. 2. they are water insoluble

3 they involve H bonding. 3. they have strong intermolecular

forces of attraction
Q5. (i) What products would be formed when a nucleotide from DNA containing thymine
is hydrolyzed?
Ans. Complete hydrolysis of DNA yields a pentose sugar, phosphoric acid and thymine.
(ii)How will you distinguish 1° and 2° hydroxyl groups present in glucose?
Ans- On oxidation with nitric acid, glucose as well as gluconic acid both yield a dicarboxylic
acid,
Q6. Explain tertiary structure of Protein.
Ans. Tertiary structure of proteins: The tertiary structure of proteins represents overall folding
of the polypeptide chains i.e., further folding of the secondary structure. It gives rise to two
major molecular shapes viz. fibrous and globular. The main forces which stabilize the 2° and
3° structures of proteins are hydrogen bonds, disulphide linkages, van der Waals and
electrostatic force of attraction.

103