CHEMISTRY

HIGHER SECONDARY - SECOND YEAR

VOLUME - II

Untouchability is a sin
Untouchability is a crime
Untouchability is inhuman

TAMILNADU
TEXTBOOK CORPORATION
College Road, Chennai - 600 006
© Government of Tamilnadu
First Edition - 2005
Second Edition - 2006
Revised Edition - 2007

CHAIRPERSON & AUTHOR

Dr. V.BALASUBRAMANIAN
Professor of Chemistry (Retd.)
Presidency College, (Autonomous), Chennai - 600 005.
REVIEWERS
Dr. M.KRISHNAMURTHI
Professor of Chemistry
Presidency College (Autonomous) Chennai - 600 005.
Dr. R. ELANGOVAN Dr. J.SANTHANALAKSHMI
Joint Director, Sarva Shiksha Abhiyan Professor of Physical Chemistry
College Road, Chennai - 600 006. University of Madras
Dr. M.KANDASWAMY Chennai - 600 025.
Professor and Head Dr. CHARLES CHRISTOPHER KANAGAM
Department of Inorganic Chemistry Professor of Chemistry
University of Madras Presidency College (Autonomous)
Chennai - 600 025. Chennai - 600 005.

AUTHORS
Mr. S.MUTHUKUMARAN, Mrs. N.KALAVATHY,
Lecturer in Chemistry P.G. Teacher in Chemistry,
Academy of Maritime Education & Training, J.G.G. Higher Secondary School
BITS (Ranchi) Ext. Centre, Virugambakkam, Chennai - 600 092.
Kanathur-603 112. Mrs. R.C.SARASWATHY,
Mr. V.JAISANKAR, P.G. Teacher in Chemistry,
Lecturer in Chemistry Govt. Girls Higher Secondary School
L.N.Government Arts College, Ashok Nagar, Chennai - 600 083.
Ponneri - 601 204. Dr. V. NARAYANAN,
Mrs. S.MERLIN STEPHEN, Lecturer in Inorganic Chemistry
P.G.Teacher in Chemistry University of Madras, Chennai - 600 025.
CSI Bain Mat. Hr. Sec. School Dr. K. SATHYANARAYANAN,
Kilpauk, Chennai - 600 010. P.G. Teacher in Chemistry,
Stanes Anglo Indian Hr. Sec. School,
Price : Rs. Coimbatore - 18.

This book has been prepared by the Directorate of School Education

on behalf of the Government of Tamilnadu.

This book has been printed on 60 G.S.M paper

Printed by Offset at :
(ii)
 PREFACE
Chemistry, a branch of science concerned with the properties, structures
and composition of substances and their reactions with one another. Inorganic
Chemistry studies the preparation, properties and reactions of all chemical
elements and their compounds, except those of carbon. Organic Chemistry studies
the reactions of carbon compounds, which are 100 times more numerous than
nonorganic ones. It also studies an immense variety of molecules, including those
of industrial compounds such as plastics, rubber, dyes, drugs and solvents. Physical
Chemistry deals with the Physical properties of substances, such as their boiling
and melting points.
The present book is included for the students of higher secondary second
year. For convenience sake this text book of chemistry is published in two volumes.
This text book is written after following the revised syllabus, keeping in view the
expectations of the National Council of Educational Research & Training
(NCERT). This book will provide an “inverted pyramid” model to gain knowledge
in all branches of chemistry. The topics such as Atomic Structure - II, Periodic
Classification - II, Solid State - II, Thermodynamics - II, Chemical equilibrium -
II, Chemical Kinetics - II, Electrochemistry - I and II are designed in such a way
that students should have a continuous access to these topics. Hence, the
knowledge gained in higher secondary first year will help the students to have a
continuous access to these topics. The knowledge gained in +1 will help the
students to achieve excellence in the path of quest for chemical knowledge. Many
problems are introduced in inorganic, physical and organic chemistry to enhance
the quantitative aptitude of students. The quantitative aptitude will enable the
students to understand the concepts well.
The importance of chemistry is well known. A knowledge of chemistry
will help anybody to understand biology, natural processes, geochemical concepts,
pharmaceutical and biochemical concepts. Hence this text book will enhance the
image of the students in such a way that they can face any competitive examination
in future. The problems in all branches of chemistry and many more mechanisms
of organic chemical reactions will help the students to understand the chemical
principles.
(iii)
 Much informations about nobel laureates are given. These informations
is not part of the syllabus. However, such information will help the students to
know a lot about the scientists.
The questions that are given at the end of every chapter can be taken
only as model questions. A lot of self evaluation questions, like, choose the best
answer, one or two sentence answer type and short answer types questions are
given in all chapters. While preparing the examination, students should not restrict
themselves, only to the questions and problems given in the self evaluation. They
must be prepared to answer the questions and problems from the entire text.
Learning objectives may create an awareness to understand each chapter.
Sufficient reference books are suggested so as to enable the students to
acquire more informations about the concept of chemistry.

Dr. V. BALASUBRAMANIAN
Chairperson
Syllabus Revision Committee (Chemistry)
& Higher Secondary Second Year Chemistry
Text Book Writing Committee

(iv)
 CONTENTS

UNIT NO. PAGE NO.

Physical Chemistry
11 Chemical Kinetics II 1
12 Surface Chemistry 28
13 Electro Chemistry I 55
14 Electro Chemistry II 98
Organic Chemistry
15 Isomerism in Organic Chemistry 123
16 Hydroxy Derivatives 146
17 Ethers 215
18 Carbonyl Compounds 230
19 Carboxylic Acids 282
20 Organic Nitrogen Compounds 323
21 Biomolecules 371
22 Chemistry in Action 388

(v)
 11. CHEMICAL KINETICS-II
LEARNING OBJECTIVES
@ To study about the order and rate of reactions. To derive the expression
for rate constant of first and pseudo-first order reactions.
@ To derive half life period and rate constant relations for nth order
reaction.
@ To know the experimental methods of determination of order of reaction.
Graphical method of determination of order and rate constant of a
reaction is also to be studied.
@ To learn about the effect of temperature on the rates and rate constants
of reaction. To know about Arrhenius equation and Arrhenius parameters
(Ea and A).
@ To differentiate between simple and complex reactions. To learn about
consecutive, opposing and parallel reactions.

The knowledge of rate of chemical reactions is valuable to understand

the chemistry and mechanism of reactions. The study of chemical kinetics
includes the experimental determination of rate or speed of a reaction, the
rate laws and the effects of temperature, pressure, concentration, catalyst
on the rates of reaction. It is possible to deduce the mechanism of the reaction
from the chemical kinetic data.

11.1 RATE AND ORDER OF A REACTION

For any reaction, the rate expression (or) the rate law equates the rate
of the reaction to the product of its rate constant and the concentrations of
the reactants raised to certain exponential powers. The rate law for a reaction
and the power (exponent) of the concentration terms involved in it must be
determined by experiment only.
In a general reaction, aA + bB products, the overall rate
expression can be written as,
1
 rate = k[A]p [B]q ... (11.1)
p = a or less than a
q = b or less than b
where k = rate constant of the reaction, p and q are the exponents or also
known as the orders with respect to reactants A and B respectively.
Therefore the term order can be defined as the sum of the powers of the
exponential powers to which each concentration term is raised in the
experimentally determined rate law of a chemical reaction.
In the rate expression (11.1),
rate = k[A]p, [B]q, p and q are called the orders of the reaction with
respect to reactants A and B respectively. The total order of the reaction,
n = p + q. Order with respect to A only p and order with respect to B only
is q.
It is found that the overall rate of a reaction, depends on the exponential
powers to which each concentration term is raised in the rate law. For
example, for a reaction with a rate law as rate = k[A]2, when the concentration
of A is doubled, the rate is increased by four times the initial rate. Thus,
chemical reactions and the over all rates are classified and studied according
to the magnitude of the order of their reactions.
Example
From the rate equations for the reactions given below determine the
order with respect to the overall reaction

(i) 2HCrO4– + 6I– + 14H+ 2Cr3+ + 3I2 + 8H2O

r = k [HCrO4–] [I–]2 [H+]2 ∴ Order = 1 + 2 + 2 = 5

(ii) H2O2 + 2I– + 2H+ I2 + 2H2O

r = k [H2O2] [I–] ∴ Order = 1 + 1 = 2

2
Characteristics of order of a reaction
(i) The magnitude of order of a reaction may be zero, or fractional or
integral values. For an elementary reaction, its order is never fractional
since it is a one step process.
(ii) Order of a reaction should be determined only by experiments. It cannot
be predicted interms of stoichiometry of reactants and products.
(iii)Simple reactions possess low values of order like n = 0,1,2, Reactions
with order greater than or equal to 3.0 are called complex reactions.
Higher order reactions are rare.
(iv)Some reactions show fractional order depending on rate.
(v) Higher order reactions may be experimentally converted into simpler
order (pseudo) reactions by using excess concentrations of one or
more reactants.

11.2 Rate equation for first order reactions

The reactions in which, the overall rate of the reaction is proportional to
the first power of concentration of one of the reactants only are called as
first order reactions. Consider the reaction
k1
A products

-d[A] = k 1.0
Rate of reaction = _____ 1[A]
dt
where k1 is the rate constant of the first order reaction.
At the beginning of the reaction, time ‘t’ = 0, let the concentration of A
be ‘a’ mole.lit–1. After the reaction has proceeded for some time ‘t’, let the
concentration of A that has reacted be x mole.lit–1. The concentration of
unreacted A remaining at time ‘t’ will be (a – x) mole.lit–1. The rate of the
reaction will be dx/dt. For a first order reaction,
rate = dx/dt = k1 (a – x) ... (11.2.)
upon integrating, equation 11.2 becomes,

3
 z dx
_____
(a – x)
= k1 z dt

which is, –ln(a – x) = k1t + c ... (11.3)

c = integration constant

at time, t = 0, x = 0.

∴ in equation 11.3,

– ln (a – 0) = k1 × 0 + C

or C = –ln a.

Substituting C value in equation 11.3

–ln (a – x) = k1t – ln a

1 a
Rearranging, k1 = ln a − x
t

2. 303 a
(or) k1 = log ... (11.4)
t a−x

Unit of k1 is sec–1.
This equation is known as the first order rate constant equation.
This equation can be used for determining the rate constant of a first
order reaction based on the experimental data of (a) and (a – x) at different
periods of time ‘t’. Sometimes, the following expression is also used.

2. 303 a − x1
k1 = t − t log a − x where x1 and x2 are the amounts reacted in
2 1 2
t1 and t2 periods of time.

4
Characteristics of first order reaction
(i) When the concentration of the reactant is increased by ‘n’ times, the
rate of reaction is also increased by n times. That is, if the concentration
of the reactant is doubled, the rate is doubled.
(ii) The unit of rate constant of a first order reaction is sec–1 or time–1.

rate mol.lit −1 sec −1

k1 = = = sec–1
(a − x ) mol.lit −1

(iii)The time required to complete a definite fraction of reaction is

independent of the initial concentration, of the reactant if t1/u is the
time of one ‘u’th fraction of reaction to take place then from equation
11.4,

2. 303 a
a log
x= and t1/u = k1 a
u a−
u

2. 303 u
∴ t1/u = k1
log
( u − 1)

since k1 = rate constant, t1/u is independent of initial concentration ‘a’.

Examples of first order reactions
1. All radioactive transformations follow first order kinetics. For example,
238 234 4
92U 90Th + 2He

2. Decomposition of sulphuryl chloride in the gas phase proceed by first

order kinetics.
SO2Cl2(g) SO2(g) + Cl2(g)
3. Inversion of sucrose in acidic aqueous medium follows first order
reaction.

H+
C12H22O11 + H2O C6H12O6 + C6H12O6
Glucose Fructose

5
 4. Decomposition of nitrogen pentoxide in CCl4 medium also exhibits
first order kinetics.
N2O5 2NO2 + ½ O2
There are many other reactions that proceed by first order kinetics. We
shall study some of the reactions that are experimentally followed by first
order kinetic expressions including the parameters that change with
concentration of the reactants or products which change with time of progress
of the reaction.
Let us consider some of the first order reactions in detail :
1. Decomposition of nitrogen pentoxide in CCl4

k1
N2O5 2NO2 + ½O2
At time t = 0, the volume of oxygen liberated is zero. Let Vt and V∞ be
the measured volumes of oxygen liberated after the reactant has reacted in
‘t’ time and at completion (t = ∞). Initial concentration of N2O5 is proportional
to total volume of oxygen liberated (i.e.,) (V∞).
(V∞-Vt) is proportional to undecomposed N2O5 at time ‘t’.

2. 303 V∞
∴ k1 = log sec −1
t (V∞ − Vt )

Example : From the following data on N2O5 decomposition in CCl4, at

298 K, show that the reaction is first order. Also evaluate the rate constant
of the reaction.
time (min) 10 15 20 ∞
Vol. of O2 (cc) 6.3 8.95 11.4 34.75
The first order rate constant k1 is given as,

2. 303 V∞
k1 = log sec −1
t (V∞ − Vt )

V∞ = 34.75 cc 1 min = 60 secs

6
 2. 303 V∞
t(min) (V∞ - Vt) k1 = t × 60 log V − V sec–1
o t

2. 303 34. 75
10 28.45 10 × 60 log = 2.079 × 10–4 sec–1
28. 45

2. 303 34. 75
15 × 60 log 25.8 = 1.530 × 10 sec
15 25.8 –4 –1

2. 303 34. 75
20 23.35 20 × 60 log = 1.267 × 10–4 sec–1
23. 35
Mean value = 1.6253 × 10-4 sec–1
k1 = 1.625 × 10–4 sec–1 is the rate constant of reaction. Since k1 values
are nearly constant at different timings, this is a first order reaction.
2. Decomposition of H2O2 in aqueous solution

Pt
H2O2 H2O + ½O2

The decomposition of H2O2 in aqueous medium in the presence of Pt

catalyst follows a first order reaction. The progress of the reaction is followed
by titrating equal volumes of the reaction mixture at regular time intervals
against standard KMnO4 solution.
Since volume of KMnO 4 used in the titration is a measure of
concentration of undecomposed H2O2, volume of KMnO4 consumed at
t = 0 is ‘Vo’ which proportional to ‘a’, the initial concentration of H2O2. Vt
is proportional to unreacted H2O2 which is similarly (a – x). Similarly
(Vo-Vt) is proportional to ‘x’, the concentration of H2O2 reacted in time
interval ‘t’. Vt is the volume of KMnO4 consumed after time ‘t’ of the reaction.
∴ The first order rate constant ‘k1’ of the reaction is,

2. 303 Vo
k1 = log V sec–1.
t t

7
 Example : From the following data, show that decomposition of H2O2
in aqueous solution follows a first order reaction. What is the value of the
rate constant?
time (min) 0 10 20 30 40
vol of KMnO4 25 20 15.6 12.7 9.4
(CC)

2. 303 Vo
time(min) Vt k1 = t × 60 log V sec–1
t

2. 303 25
10 20 log = 2.68 ×10–4 sec–1
10 × 60 15. 6

2. 303 25
20 × 60 log 15. 6 = 1.72 ×10 sec
20 15.6 –4 –1

2. 303 25
12. 7 = 1.42 × 10 sec
30 12.7 log –4 –1
30 × 60

2. 303 25
9. 4 = 1.43 × 10 sec
40 9.4 log –4 –1
40 × 60

Mean value = 1.81 × 10–4 sec–1

Since all the k1 are nearly constant. This is a first order reaction
k1 = 1.81 × 10–4 sec–1.

Half life period ‘t½’

Half life period, ‘t½’, of a reaction is defined as the time required to

reduce the concentration of a reactant to one half of its initial value. t½
values are calculated by using the integrated rate equation of any order of a
reaction.
For first order reaction,

8
 2. 303 a
k1 = log
t a−x

a
if amount reacted x = 2 then t = t½

2. 303 a
∴ t½ = k1
log
a−a / 2

2. 303log 2. 0
t½ = k1

0. 693
t½ = k1 secs.

Thus half life period of a first order reaction is independent of the initial
concentration of the reactant and also, inversely proportional to the rate
constant of the reaction.
Example : Compound A reacts by first order kinetics. At 25°C, the rate
constant of the reaction is 0.45 sec–1. What is the half life of A at 25°C.
What is the time required to have 12.5% unreacted A for first order reaction,

0. 693 0. 693
t½ = k1 = 0. 45

= 1.54 secs

No. of t½ Amount unreacted from 100%

1 50%

2 25%

3 12.5%
∴ Time of three half-life periods = 3 × 1.54
= 4.62 secs
9
 Example : Show that for a first order reaction time required for 99%
completion is twice the time required for 90% completion of the reaction.

2. 303 100 2. 303

t99% = log = log 100
k1 100 − 99 k1
2. 303 100 2. 303
t90% = log = log 10
k1 100 − 90 k1

t99% log 100 2. 0

t90% = log 10 = = 2.0
1. 0

∴ t99% = 2.0 t90%

Example : In the thermal decomposition of N2O at 764°C, the time

required to decompose half the reactant was 263 seconds, when the initial
pressure was 290 mm of Hg and 212 seconds at an initial pressure of 360
mm of Hg. What is the order of this reaction ?

t1 FG IJ
a2
n −1

Solution : t2 =
H K
a1

a1 = 290 mm of Hg t1 = 263 seconds

a2 = 360 mm of Hg t2 = 212 seconds

263 FG 360 IJ n −1

212
=
H 290 K
1.24 = (1.24)n–1
n–1= 1
n = 1+1=2
Hence, the reaction is of second order.
Example : In a first-order reaction, it takes the reactant 40.5 minutes to
be 25% decomposed. Find the rate constant of the reaction.

10
 Solution : Since the reactant is 25% decomposed in 40.5 min, the
remaining reactants is 75%, i.e. (a – x) = 0.75 a t 40.5 min.

2. 303 a 2. 303 a
k = log = log
t a−x 40.5 min 0. 75a

= 0.05686 log 1.33 min–1

= 0.05686 × 0.1249 min–1

= 7.1 × 10–3 min–1

Example : Show that for a first order reaction, the time required for
99.9% completion of the reaction is 10 times that required for 50%
completion.

2. 303 a
t = log
k a−x

2. 303 100
t99.9% = log
k 100 − 99. 9

2. 303 100
= log10
k 0.1

2. 303
= log10 1000 ... (1)
k

2. 303 100
t(50%) = log10
k 100 − 50

2. 303 100
= log10
k 50

2. 303
= log10 2 ... (2)
k

11
 2. 303
log10 1000
(1) t(99.9%) k
(2)
= t(50%) = 2. 303
log10 2
k

3. 000
= = 10
0. 3010
Example : The rate constant for a first order reaction is 1.54×10-3sec-1.
Calculate its half-life period.

0. 693
t½ =
k

0. 693
= = 450 seconds.
1.54 × 10−3 sec −1

11.3 PSEUDO-FIRST ORDER REACTIONS

In a chemical reaction involving more than one reactant, the overall
order of the reaction when experimentally determined by taking excess
concentrations of all the reactants except any one of the reactant, will be
found lower in magnitude than the overall order determined in presence of
smaller concentrations of all the reactants. The altered and the reduced order
of the reaction is called as the pseudo order of the reaction.
Thus in a second order reaction, when one of the reactants concentration
is in excess (10 to 100 times) of the other reactant, then the reaction follows
a first order kinetics and such a reaction is called pseudo-first order reaction.
In a reaction of the type,
k2
A+B= products ... (11.5)
Rate = k2 [A] [B] where k2 is the rate constant of the second order
reaction. If concentration of A is very large compared to concentration of
B, then during the reaction amount of A consumed will be equal to the
amount of B reacting with A. Since B concentration is smaller than that of

12
A, change in the concentration of A after the completion of reaction is
assumed to be negligible. Hence concentration of A is considered to remain
constant even after the completion of reaction. Hence equation 11.5 becomes,
Rate’ = k2'[B] ... (11.6)
where Rate’ = rate of the reaction with excess [A].
k2' = pseudo first order rate constant
= k2 [A] = second order rate constant × concentration of A.
Thus rate of the pseudo first order reaction alters when concentration
of B is altered, and shows a first order kinetics.

Determination of rate constant of acid catalysed hydrolysis of an ester

The hydrolysis reaction of an ester in pure water is a slow reaction and
when a mineral acid like hydrochloric acid is added, the rate of the reaction
is enhanced since the H+ ions from the mineral acid acts as the catalyst. The
acid catalysed hydrolysis of an ester follows pseudo first order kinetics. The
reaction can be represented as :

H+
CH3COOCH3 + H2O CH3COOH + CH3OH
Methyl acetate

The overall rate of the reaction depends on the concentrations of reactants

and also on the catalyst concentration.
Rate = k3 [ester] [H2O] [H+] ... (11.7)
k3 = rate constant of the third order reaction.
Therefore the true order of the reaction is 3.0. Since water is used as the
solvent, its concentration is excess.
Weight of 1 lit (1000 cc) of water = 1000 gm = 1 kg
(∴ density of water = 1 gm/cc)
1000
∴ No. of moles of water in 1 lit =
18
∴ Concentration of pure water = 55.55 moles
13
 If 1 molar aqueous solution of ester is used then, 1 mole of water will be
consumed for its complete hydrolysis. After the completion of hydrolysis,
55.55 – 1.0 = 54.55 moles water will be present in the medium. Therefore
change in the concentration of water considered as negligible and
concentration of water is assumed to be constant. Since acid acts the catalyst,
there will be, no change in the catalyst concentration before initial and after
the completion periods of times of the reactions. Hence [H+] is considered
as a constant value. Hence the expression 11.7 can be rewritten as
Rate = k3' [ester] where k3' = pseudo first order rate constant =
k3 [H+] [H2O]. In this rate expression rate of the reaction is directly
proportional to ester concentration only.

Procedure
Initially to a definite volume of (100 ml) hydrochloric acid (0.5 N),
10 ml of ester is added and the start of the reaction corresponds to time of
addition of ester. The rate of the reaction is followed by withdrawing a
definite volume of the reaction mixture consisting of the ester and acid at
various time intervals and arresting the further progress of reaction by adding
ice. The whole cold mixture is titrated with standard NaOH (0.1 N) using
phenolphthalein as the indicator.
Let the volume of alkali consumed at t = 0 be Vo cc which is equivalent
to the amount of hydrochloric acid present in the definite volume of the
reaction mixture drawn out at regular intervals of time. If Vt cc is the volume
of alkali consumed for the same definite volume of the reaction mixture
drawn out after reaction time ‘t’, then (Vt - Vo) cc is equivalent to the acetic
acid produced by the hydrolysis of ester in time ‘t’. A final titration is done
after about 8 hours or after refluxing the solution for 45 mins to complete
the hydrolysis which is V∞ cc. (V∞– Vo) cc is equivalent to acetic acid
produced from complete hydrolysis of ester.

Calculations
The initial concentration of ester = a ∝ (V∞– Vo) cc
Concentration of ester reacted at ‘t’ = x ∝ (Vt – Vo) cc
∴ Concentration of ester remaining at time ‘t’ = (a – x) ∝ (V∞– Vt)
14
 a (V∞ − Vo )
∴ (a − x ) = (V − V )
∞ t

∴ The first order rate expression for the hydrolysis of ester can be
written as

2. 303 (V∞ − Vo )
k = log10 (V − V )
t ∞ t

By substituting Vt values for various ‘t’ values, k is determined. These

values are found to be constant indicating k as the rate constant of the reaction.
Example : A certain amount of methyl acetate was hydrolysed in the
presence of excess of 0.05 M HCl at 25°C. 20 mL of reaction mixture were
removed and titrated with NaOH solution, the volume V of alkali required
for neutralisation after time ‘t’ were as follows :
t (min) 0 20 40 60 ∞
v (mL) 20.2 25.6 29.5 32.8 50.4
Show that the reaction is the first order reaction.

2. 303 (V∞ − Vo )
Solution : k = log (V − V )
t ∞ t

V∞ – Vo = 50.4 – 20.2 = 30.2

2. 303 50. 4 − 20. 2

when t = 20 mts. k = log 50. 4 − 25. 6
20

30. 2
= 0.1151 log
24.8

= 0.1151 log 1.2479

= 0.1151 × 0.0959 = 11.03 × 10–3 min–1

when t = 40 mts

15
 2. 303 50. 4 − 20. 2
k = log 50. 4 − 29.5
40

30. 2
= 0.0576 × log = 0.0576 × 0.1596
20. 9
= 9.19 × 10–3 min–1
when t = 60 mts

2. 303 50. 4 − 20. 2 30. 2

k = log 50. 4 − 32.8 = 0.03838 × log
60 17. 6

= 0.03838 × 0.2343 = 8.99 × 10–3 min–1

The constant values of k show that the reaction is of first order.

11.4 TEMPERATURE DEPENDANCE OF RATE CONSTANT

It is a common observation that rates of reactions increase with increase
in temperature of the reaction mixture. Keeping the concentration of the
reactants constant, the rate is found to be two times its initial value, when
measured at a temperature 10 K greater than the initial temperature. However,
the exact value of the rate constant determined at various temperature is
predicted by using Arrhenius equation. This expression is obeyed by most of
the reactions. Arrhenius equation is given as
k = A e–Ea/RT
where k = rate constant, Ea = activation energy, A = frequency factor,
R = gas constant, T = temperature in Kelvin. If k1 and k2 are the rate constants
measured at two different T1 and T² temperatures respectively, then Ea can
be determined as follows :
Arrhenius equation for two different temperatures T1 and T2 are :
Ea
log k1 = log A – 2. 303 R T ... (1)
1

Ea
log k2 = log A – 2. 303 R T ... (2)
2
16
where k1 and k2 are the rate constants at temperature T1 and T2 respectively.
(2) – (1)

Ea Ea
log k2 – log k1 = – 2. 303 R T + 2. 303 R T
2 1

Ea FG T − T IJ
H TT K
1 2
= – 2. 303 R
1 2

k2 Ea FG T − T IJ
H TT K
2 1
log k = 2. 303 R
1 1 2

If R = 1.987 cals.mol–1, then unit of Ea is 10–3 k.cal.

Also, a plot of log k against 1/T values gives a straight line with slope
value equals to –Ea/2.303 R and intercept value equals to log A. When Ea is
a positive value, and if T2 > T1 then k2 > k1. That is, rate constant value at
higher temperature is greater than rate constant value at lower temperature.
Under such conditions, plot of log k against 1/T gives a negative slope straight
line. From the slope of the straight line, Ea can be calculated.

log k
slope = –Ea/2.303 R.

1/T (K–1)

Reactant molecules come into contact through collisions for

transformation into product molecules. Since, not all collisions are successful
in producing the product molecules, all colliding molecules must possess
certain minimum energy called as the threshold energy which is needed to
make the collisions effective and successful. The additional energy required
17
by the molecules to attain the threshold energy in addition to the energy of
colliding molecules is called as activation energy ‘Ea’. Thus, activation
energy = threshold energy - Energy of colliding molecules. Generally,
this Ea value is higher than the potential energies of reactants and products.
Thus, Ea is considered as an energy barrier that must be crossed by the
reactant molecules before getting converted to actual product molecules.

Threshold energy
Energy

nts
acta

P.E. of products
Ea
f re
o
P.E.

Ea = activation energy

Reaction Co-ordinate
Potential energy diagram of a reaction. The molecular state present at
the Ea position in the potential energy diagram, is considered as the
intermediate product (or) the transition state. Thus Ea, is also the energy
required to form the activated state or the intermediate, which is necessary
to form the products. Ea is a characteristic value of a reaction. The rate, rate
constant, and their temperature dependance are determined by the value of
Ea. Higher the value of Ea, slower is the rate of the reaction.
Example : The following values for the first order rate constant were
obtained for a certain reaction :
Temp (°C) k × 10–5 sec–1
25 3.46
35 13.50
Calculate the Arrhenius frequency factor and activation energy ‘Ea’.
k2 Ea FG T − T IJ
H TT K
2 1
Solution : log k = 2. 303 R
1 1 2
18
 k1 = 3.46 × 10–5 sec–1 T1 = 298K
k2 = 1.35 × 10–4 sec–1 T2 = 308 K

1. 35 × 10−4 Ea FG 308 − 298 IJ

log
3. 46 × 10−5
= 2. 303 × 1. 987 H 308 × 298 K
2. 303 × 1. 987 × 308 × 298 1. 35 × 10−4
Ea = log
10 3. 46 × 10−5

= 2.4830 cals.

Ea
log k1 = 2. 303× RT + log A

−24830
log 3.46 × 10–5 = 2. 303 × 1.987 × 298 + log A

∴ log A = 13.7491
∴ A = 5.611 × 1013 sec–1
Examples : The activation energy of a certain reaction is 100 KJ/mole
what is the change in the rate constant of the reaction if the temperature is
changed from 25°C to 35°C ? Let the rate constants at 25°C be k1 and at
35°C be k2 respectively.

k1 Ea LM 1 − 1 OP
log k
2
=
2. 303 R NT T Q
2 1

k1 100000 J / mol LM 1 − 1 OP
∴ k
2
=
2. 303 × 8. 314 JK −1mol −1 N 308 298 Q
= –0.5745

k1
∴ k = antilog (–0.5745)
2

= 0.2664
19
 1
k2 = k = 3.75 times k1.
0. 2664 1
∴ k2, the rate constant at 35°C will be 3.75 times the rate constant at
25°C.
Example : Decomposition of ethyl bromide and propyl bromide follow
first order kinetics, and have the same frequency factor ‘A’. The rate constant
for decomposition of ethylbromide at 390°C is same as that for propylbromide
at 320°C. If the Ea of ethyl bromide reaction is 230 KJ/mole, what is the Ea
of propylbromide reaction ?
For ethyl bromide decomposition at 390oC

230000
log k = log A – 2. 303 × 8. 314 × 663 ... (1)

For propyl bromide decomposition at 320oC

Ea
log k = log A – 2. 303 × 8. 314 × 593 ... (2)

equations (1) and (2) are equal.

230000 Ea
∴ 2. 303 × 8. 314 × 663 = 2. 303 × 8. 314 × 593

230000 × 593
∴ Ea =
663
Ea = 205.7 kJ/mole.

11.5 SIMPLE AND COMPLEX REACTIONS

A simple reaction takes place in a single step. Simple reactions are also
known as elementary reactions. One step reactions are elementary reactions.
In some reactions many side reactions occur along with the main reaction
involving product formation.

20
 Reactions which do not take place in a single step but take place in a
sequence of a number of elementary steps are called as complex reactions.
Simple reactions Complex reactions
1. Occurs in single step Occurs in multi (or) many steps.
2. Overall order values are Overall order values are large and
small. Total and pseudo greater than 3.0. Sometimes
order values lie between fractional orders such as 1/2, 1/3,
0,1,2 and 3. 3/2 etc. are seen.
3. No side reactions Many side reactions are present.
4. Products are formed directly In some complex reactions
from the reactants products are not formed in steps
directly involving the reactants.
5. Experimental rate constant Experimental overall rate constant
values agree with the values differ from the calculated
calculated values. Theories values. Theories of reaction rates
of reaction rates apply well do not agree well on complex
on simple reactions. reactions.

Types of Complex reaction

(i) Consecutive reactions

The reactions in which the reactant forms an intermediate and the
intermediate forms the product in one or many subsequent reactions are
called as consecutive or sequential reactions. In such reactions the product
is not formed directly from the reactant. Various steps in the consecutive
reaction are shown as below :

k1 k2
A B C
A = reactant ; B = intermediate ; C = product. Initially only the reactant
A will be present. As the reaction starts, A produces an intermediate B
through k1 rate constant. As and when B is formed, it produces the product
C through k2 rate constant. After the completion of reaction only ‘C’ is
present and concentrations of A and B will be zero.

21
Example of consecutive reactions
Saponification of a diester in presence of an alkali :
k1 k2
R'OOC– (CH2)n–COOR R'OOC–(CH2)n–COOH HOOC – (CH2)n – COOH

(ii) Parallel reactions

In these group of reactions, one or more reactants react simultaneously
in two or more pathways to give two or more products. The parallel reactions
are also called as side reactions.
k1
B
A k2 C
k3 D

The reactant A reacts to give products B,C,D separately by following

three different reaction pathways involving different k1, k2, k3 rate constants
respectively. Among the many side reactions, the reaction in which maximum
yield of the product obtained is called as the main or major reaction while
the other reactions are called as side or parallel reactions.

Examples of parallel reaction :

(i) Bromination of bromobenzene :

Br
Br
+ HBr
Br
o-dibromobenzene

Br

+ HBr

Br
p-dibromobenzene

22
 (ii) Dehydration of 2-methyl-2-butanol
CH3 CH3
| |
H3C–C–CH2–CH3 CH3–C=CH–CH3
| 2-methyl 2-butene
OH
2-methyl-2-butanol CH3
|
CH2 = C–CH2–CH3
2-methyl1-butene
(iii) Opposing reactions
In opposing reactions the products formed react back simultaneously to
form the reactants. These reactions are also called as reversible reactions.
kf
A+B C + D,
kr

Examples of opposing reactions

(i) Reaction between CO and NO2 gases

kf
CO(g) + NO2(g) CO2(g) + NO(g)
kr

(ii) Isomerisation of cyclopropane to propene

CH2

kf
H2C – CH2 CH3 – CH = CH2
kr
(iii) Dissociation of hydrogen iodide in gas phase

2HI(g) H2(g) + I2(g)

23
 SELF EVALUATION
(A) Choose the correct answer :
1. Hydrolysis of an ester by dilute HCl is an example for
(a) second order reaction (b) zero order reaction
(c) pseudo first order reaction (d) first order reaction
2. The unit of zero order rate constant is
(a) litre mol–1 sec–1 (b) mol litre–1 sec–1
(c) sec –1 (d) litre2 sec–1
3. The excess energy which a molecule must posses to become active is
known as
(a) kinetic energy (b) threshold energy
(c) potential energy (d) activation energy
4. Arrhenius equation is
(a) k = Ae–1/RT (b) k = Ae–RT/Ea (c) k = Ae–Ea/RT (d) k = AeEa/RT
5. The term A in Arrhenius equation is called as
(a) Probability factor (b) Activation of energy
(c) Collision factor (d) Frequency factor
6. The sum of the powers of the concentration terms that occur in the rate
equation is called
(a) molecularity (b) order (c) rate (d) rate constant
7. Reactions in which the reacting molecules react in more than one way
yielding different set of products are called
(a) consecutive reactions (b) parallel reactions
(c) opposing reactions (d) chain reactions
8. The half life period of a first order reaction is 10 minutes. Then its rate
constant is
(a) 6.93 × 102 min–1 (b) 0.693 × 10–2 min–1
(c) 6.932 × 10 min
–2 –1 (d) 69.3 × 10–1 min–1
9. For a reaction : aA bB, the rate of reaction is doubled when the
concentration of A is increased by four times. The rate of reaction is
equal to
24
 (a) k [A]a (b) k [A]½ (c) k [A]1/a (d) k [A]
d [N 2 O5 ]
10. 2N2O5 4NO2 + O2, = k1[N2O5],
dt
d [N O2 ] d [O2 ]
= k2 [N2O5] and = k3 [N2O5], the relation between k1, k2
dt dt
and k3 is
(a) 2k1 = 4k2 = k3 (b) k1 = k2 = k3
(c) 2k1 = k2 = 4k3 (d) 2k1 = k2 = k3
11. For a reaction, Ea = 0 and k = 4.2 × 105 sec–1 at 300K, the value of k at
310K will be
(a) 4.2 × 105 sec–1 (b) 8.4 × 105 sec–1
(c) 8.4 × 105 sec–1 (d) unpredictable

(B) Answer in one or two sentences :

1. Define order of a reaction.
2. Derive the relationship between half-life period and rate constant for a
first order reaction.
3. What is activation energy ?
4. What is meant by zero order reaction ? What is the rate constant of such
a reaction ?
5. Write the Arrhenius equation and explain the terms.
6. Define half life period.
7. Give examples for first order reaction.
8. What are simple and complex reactions ?
9. Give examples for opposing reactions.

(C) Answer not exceeding sixty words :

1. Explain the experimental determination of rate constant of acid hydrolysis
of methyl acetate.
2. Write an account of the Arrhenius equation for rates of chemical reactions.

25
3. Write notes on (i) consecutive reactions, (ii) parallel reactions and
(iii) opposing reactions.
4. State the characteristics of order of reaction.
5. Explain the experimental determination of rate constant for decomposition
of H2O2 is aqueous solution.
(D) Solve the problems :
1. The specific reaction rates of a chemical reaction are 2.45 × 10–5 sec–1 at
273 K and 16.2 × 10–4 sec–1 at 303 K. Calculate the activation energy.
(Ans. 96.101 kJ/mole)
2. Rate constant of a first order reaction is 0.45 sec–1, calculate its half life.
3. (a) What are zero order reactions? (Ans. 1.5 sec)
(b) Give the units of first, third and zero order rate constants.
4. A first order reaction completes 25% of the reaction in 100 mins. What
are the rate constant and half life values of the reaction?
( Ans. k = 2.8773 × 10–3 min–1, t½ = 240.85 mins)
5. If 30% of a first order reaction is completed in 12 mins, what percentage
will be completed in 65.33 mins? (Ans.85.62%)
6. Show that for a first order reaction the time required for 99.9% completion
is about 10 times its half life period.
7. The half life period of a first order reaction is 10 mins, what percentage
of the reactant will remain after one hour? (Ans. 1.563%)
8. The initial rate of a first order reaction is 5.2 × 10–6 mol.lit–1.s–1 at
298 K. When the initial concentration of reactant is 2.6 × 10–3 mol.lit–1,
calculate the first order rate constant of the reaction at the same
temperature. (Ans. 2 × 10–3 s–1)

SUMMARY :
• Order is defined as the exponential power of the concentration term in
the experimentally determined rate expression :
rate = rate constant [A]p [B]q [C]r.
Total order = p + q + r

26
• Units of k and t½ depend on the order ‘n’.
Unit of k = lit(n–1) mole(1–n) sec–1
t½ ∝ (a)(1–n).
• Experimental determination of the pseudo first order rate constant from
the acid hydrolysis of ester is studied.
• Temperature dependance on the rate constant, Arrhenius equation and
the parameters, their significances and determinations are also learnt.
• Determination of activation energy Ea value from the plot of log k against
1/T and the analysis of the potential energy diagram to know the
significance of Ea are also learnt.
• Differences between simple and complex reactions are understood.
Consecutive, parallel and opposing studied.

REFERENCES :
1. Basic Physical Chemistry, by Walter J. Moore
Prentice Hall of India Pvt. Ltd.
2. Elements of Physical Chemistry, by P.W. Atkins
Oxford University Press.
3. Physical Chemistry, by Castellan
Macmillan India Ltd.
________

27
 12. SURFACE CHEMISTRY
LEARNING OBJECTIVES
@ To study the adsorption, classification of adsorption and factors
affecting adsorption.
@ To study the catalysis and types of catalysis
@ To learn the theories of catalysis
@ To study the preparation and properties of colloids
@ To understand about emulsions

12.1 ADSORPTION
Adsorption is a surface phenomenon. It is observed at the surface of the
solution. Adsorption is a phenomenon of concentration of substance on the
surface of a liquid or solid.
“The condition in which concentration of a substance in the interfacial
layers between two phases is greater than in the bulk of either phase, then
the substance is said to be adsorbed at the interface and the phenomenon is
known as adsorption”.
The process of adsorption of gases by solids is a common phenomenon.
The charcoal specially coconut charcoal has a great capacity of the adsorption
of gases. Silica gel is also utilised for the adsorption of number of gases. The
solid that takes up gas or vapour or solute from a given solution is called
adsorbent and the solute or gas which is held to surface of solid is known as
adsorbate.
Classification of adsorption of gases on solids
The adsorption of gases on solids has been divided in to two types based
on the nature of forces holding the gas molecules to the solids.
1. Physical adsorption (or) Vander waal’s adsorption
2. Chemical adsorption (or) chemisorption.
28
1. Physical adsorption
This adsorption is due to the operation of forces between solid surface
and the adsorbate molecules that are similar to vander waal’s forces between
molecules. These forces are generally undirected and relatively non specific.
Physical adsorption can also be defined as that type of adsorption where
physical forces hold the gas molecules to the solids.

2. Chemical adsorption
Chemical adsorption is defined as a type of adsorption in which chemical
bonds serve the function of holding gas molecules to the surface. It occurs
due to the stronger binding forces, comparable with those leading to formation
of chemical compounds. It is generally an irreversible process.
The main differences can be summarised as follows:-
Physical adsorption Chemical adsorption
1. It is due to intermolecular 1. It is due to chemical bond
Vander waal’s force. formation.
2. Depends on the nature of gas. 2. More specific than the physical
Easily liquefiable gases are adsorption.
adsorbed readily.
3. Heat of adsorption is small. 3. Heat of adsorption is large.
4. Reversible. 4. Irreversible.
5. If occurs rapidly at low 5. Increases with increase
temperature and decreases with of temperature.
increase of temperature.
6. Increase of pressure increases 6. Change of pressure has no
adsorption. effect.
7. Forms multimolecular layers 7. Forms unimolecular layer
on adsorbent surface.
Factors affecting adsorption
The magnitude of gaseous adsorption depends upon the following
factors:

29
 i. Temperature
ii. Pressure
iii. Nature of the gas and
iv. Nature of the adsorbent.

Effect of temperature and pressure

Adsorption is invariably accompanied by evolution of heat. Therefore,
in accordance with Le chatelier’s principle, the magnitude of adsorption
increases with decrease in temperature. Further, since adsorption of a gas
leads to decrease of pressure, the magnitude of adsorption increases with
increase in pressure. Thus, decrease of temperature and increase of pressure
both tend to cause increase in the magnitude of adsorption of a gas on a
solid.

Nature of the gas

It is observed that the more readily soluble and easily liquefiable gases
such as ammonia, chlorine and sulphur dioxide are adsorbed more than the
hydrogen, nitrogen and oxygen. The reason is that Vander waal’s or
intermolecular forces which are involved in adsorption are more predominant
in the former than in the latter.

Nature of the adsorbent

Adsorption is a surface phenomenon. Therefore, the greater the surface
area per unit mass of the adsorbent, the greater is its capacity for adsorption
under the given conditions of temperature and pressure.

12.2 CATALYSIS
A catalyst is a substance which alters the speed of a chemical reaction
without itself undergoing any chemical change and the phenomenon is known
as catalysis.
Example,
MnO2
2KClO3 2KCl + 3O2
In the above reaction, MnO2 acts as a catalyst.
30
General characteristics of catalytic reactions
The following characteristics are generally common to most of the
catalytic reactions.
1. The catalyst remains unchanged in mass and in chemical composition
at the end of the reaction.
2. Only a small quantity of catalyst is generally needed.
3. A catalyst cannot initiate a reaction. The function of a catalyst is only
to alter the speed of the reaction which is already occurring at a
particular rate.
4. A catalyst does not alter the position of equilibrium in a reversible
reaction.
5. The catalyst is generally specific in its action.

Types of catalytic reactions

Catalytic reactions are classified into two broad types;
1. Homogeneous catalysis
2. Heterogeneous catalysis

1. Homogeneous Catalysis
In these reactions, the reactants and catalyst remain in the same phase.
The following are some of the examples of homogeneous catalysis.
i. Oxidation of SO2 to SO3 with oxygen in the presence of nitric oxide
as the catalyst in the lead chamber process.
NO(g)
2SO2(g) + O2(g) 2SO3

ii. Hydrolysis of methyl acetate is catalysed by H+ ions furnished by

hydrochloric acid.

HCl(l)
CH3 COO CH3(l) + H2O(l) CH3COOH + CH3OH

31
2. Heterogeneous Catalysis
The catalytic process in which the reactants and the catalyst are in
different phases is known as heterogeneous catalysis. Some of the examples
of heterogeneous catalysis are given below.
i. Oxidation of SO2 to SO3 in the presence of Pt metal or V2O5 as catalyst
in the contact process for the manufacture of sulphuric acid.
Pt(s)
2SO2(g) + O2(g) 2SO3
The reactants are in gaseous phase while the catalyst is in solid phase.
ii. Combination between nitrogen and hydrogen to form ammonia in the
presence of finely divided iron in Haber’s process.
Fe(s)
N2(g) + 3H2(g) 2NH3
The reactants are in gaseous phase while the catalyst is in solid phase.

Types of catalysts
The catalysts have been divided into different types according to their
behaviour and pattern of action.

1. Positive catalyst
A catalyst which enhances the speed of the reaction is called positive
catalyst and the phenomenon is known as positive catalysis. Various examples
are given below :
i. Decomposition of H2O2 in presence of colloidal platinum

Pt
2H2O2 2H2O + O2

ii. Decomposition of KClO3 in presence of manganese dioxide.

MnO2
2KClO3 2KCl + 3O2
∆

32
2. Negative Catalyst
There are certain substances which, when added to the reaction mixture,
retard the reaction rate instead of increasing it. These are called negative
catalysts or inhibitors and the phenomenon is known as negative catalysis.
The examples are given below.
i. The oxidation of sodium sulphite by air is retarded by alcohol.

Alcohol
2 Na2SO3 + O2 2 Na2SO4
ii. The decomposition of hydrogen peroxide decreases in presence of
glycerine.

Glycerine
2 H2O2 2 H2O + O2

3. Auto catalyst
In certain reactions, it is observed that one of the products formed during
the reaction acts as a catalyst for that reaction. Such type of catalyst is called
auto catalyst and the phenomenon is known as auto catalysis.
In the oxidation of oxalic acid by potassium permanganate, one of the
products MnSO4 acts as a auto-catalyst because it increases the speed of the
reaction.
COOH
5 | + 2 KMnO4 + 3 H2SO4 2 MnSO4 + K2SO4 + 10 CO2 + 8H2O
COOH

4. Induced Catalyst
When one reactant influences the rate of other reaction, which does not
occur under ordinary conditions, the phenomenon is known as induced
catalysis.
Sodium arsenite solution is not oxidised by air. If, however, air is passed
through a mixture of the solution of sodium arsenite and sodium sulphite,
both of them undergo simultaneous oxidation. Thus sulphite has induced
the arsenite and hence is called induced catalyst.

33
Promoters
The activity of a catalyst can be increased by addition of a small quantity
of a second material. A substance which, though itself not a catalyst, promotes
the activity of a catalyst is called a promoter. Some examples of the promoters
are given below.
i. In the Haber’s process for the synthesis of ammonia, traces of
molybdenum increase the activity of finely divided iron which acts as a
catalyst.

Fe
N2 + 3 H2 2 NH3
+ Mo

Catalytic Poisons
A substance which destroys the activity of the catalyst is called a poison
and the process is called catalytic poisoning. Some of the examples are
(i) The platinum catalyst used in the oxidation of SO2 in contact process
is poisoned by arsenious oxide.

Pt
SO2 + O2 2 SO3
Poisoned
by As2O3

(ii) The iron catalyst used in the synthesis of ammonia in Haber process
is poisoned by H2S

Fe
N2 + 3 H2 2 NH3
Poisoned
by H2S

Active Centres
The catalytic surface has unbalanced chemical bonds on it. The reactant
gaseous molecules are adsorbed on the surface by these free bonds. This

34
accelerates the rate of the reaction. The distribution of free bonds on the
catalytic surface is not uniform. These are crowded at the peaks, cracks and
corners of the catalyst. The catalytic activity due to adsorption of reacting
molecules is maximum at these spots. These are, therefore, referred to as
the active centres. If a catalyst has more active centres, then its catalytic
activity is increased.

12.3 THEORIES OF CATALYSIS

There are two main theories to explain catalysis.
1. Intermediate compound formation theory
2. Adsorption theory
In general, the intermediate compound formation theory applies to
homogeneous catalytic reactions and the adsorption theory applies to
heterogeneous catalytic reactions.

The Intermediate Compound Formation Theory

According to this theory, the catalyst first forms an intermediate
compound with one of the reactants. The compound is formed with less
energy consumption than needed for the actual reaction. The intermediate
compound being unstable combines with other reactant to form the desired
product and the catalyst is regenerated.
For example, a reaction of the type

C
A + B AB
which occurs in presence of a catalyst C, may take place as
A + C AC
Catalyst Intermediate
compound

AC + B AB + C
Product Catalyst

Many catalytic reactions can be explained on the basis of this theory.

35
 The catalytic oxidation of SO2 to SO3 in the lead chamber process
probably takes place as;
2 NO + O2 2NO2
Catalyst Intermediate
compound

NO2 + SO2 SO3 + NO

Product Catalyst

Adsorption Theory
This theory explains the mechanism of heterogeneous catalysis. Here,
the catalyst functions by adsorption of the reacting molecules on its surface.

Fig. 12.1 Adsorption

In general, there are four steps involved in the heterogeneous catalysis.
Catalyst
A(g) + B(g) C(g) + D(g)

Step - 1. Adsorption of reactant molecules

The reactant molecules A and B strike the surface of the catalyst. They
are held up at the surface by weak vanderwaal’s forces or by partial chemical
bonds.

Step - 2. Formation of Activated complex

The particles of the reactants adjacent to one another join to form an
intermediate complex (A-B). The activated complex is unstable.
36
Step - 3. Decomposition of Activated complex
The activated complex breaks to form the products C and D. The
separated particles of the products hold to the catalyst surface by partial
chemical bonds.

Step - 4. Desorption of Products

The particles of the products are desorbed or released from the surface.

Applications of catalysis
The applications of catalysis are summarised as follows.
Process Catalyst
1. Haber’s process for the manufacture Finely divided iron. Molybdenum
of ammonia. as promoter.
2. Ostwald’s process for the manufacture Platinished asbestos
of nitric acid.
3. Lead chamber process for the Nitric oxide.
manufacture of sulphuric acid.
4. Contact process for the manufacture Platinised asbestos or vanadium
of sulphuric acid. pentoxide (V2O5).
5. Deacon’s process for the Cupric chloride (CuCl 2)
manufacture of chlorine.
6. Bosch’s process for the manufacture Ferric oxide (Fe 2O3). Chromic oxide
of hydrogen. as a promoter.
7. Hydrogenation of vegetable oils Nickel (finely divided).
Oil + H2 → Vanaspati ghee
8. Bergius process for the synthesis of Ferric oxide (Fe2O3)
petrol from coal.

12.4 COLLOIDS
Thomas Graham, in 1861, during his work on diffusion, found that while
certain substances, such as sugars, salts, acids and bases diffused readily
through a parchment membrane, others, such as gelatin, albumen and glue,
diffused at a very slow rate. The substances belonging to the former category
37
which generally exist in crystalline state, were called crystalloids while the
substances belonging to the second category were given the name colloids.
These observations led to the development of a new branch known as colloidal
science.
In a true solution as sugar or salt in water, the solute particles are
dispersed in the solvent as single molecules or ions. Thus the diameter of the
dispersed particles ranges from 1A° to 10A°. On the other hand, in a
suspension as sand stirred into water, the dispersed particles are aggregates
of millions of molecules. The diameter of these particles is of the order of
2000A° or more. The colloidal solutions are intermediate between true
solutions and suspensions. When the diameter of the particles of a substance
dispersed in a solvent ranges from about 10A° to 2000A°, the system is
termed a colloidal solution.

Types of Colloids
A colloidal system is made up of two phases. The substance distributed
as the colloidal particles is called the dispersed phase. The second continuous
phase in which the colloidal particles are dispersed is called the dispersion
medium. Depending upon the physical state of dispersed phase and dispersion
medium, the following types of colloidal solutions are possible.
Dispersed Dispersion Name Examples
phase medium
Solid Solid Solid-sol Ruby glass, alloys
Solid Liquid Sol paint, ink
Solid Gas Aerosol Smoke, haze
Liquid Solid Gel Curd, cheese
Liquid Liquid Emulsion Milk, Cream
Liquid Gas Liquid Aerosol Cloud, mist
Gas Solid Solid form Cork, pumice stone
Gas Liquid Foam Froths of air

38
 A colloidal solution of gas in gas is not possible as gases are completely
miscible and always form true solutions.

Lyophobic and Lyophilic Colloids

Colloidal solutions in which the dispersed phase has very little affinity
for the dispersion medium are termed as lyophobic (solvent hating) colloids.
Colloidal solutions of metals which have negligible affinity for solvents and
sulphur in water are examples of this type.
Colloidal solutions in which the dispersed phase has considerable affinity
for the dispersion medium are called lyophilic (solvent loving) colloids.
Gelatin, protein and starch are examples of this type.

12.5 PREPARATION OF COLLOIDS

1. Preparation of lyophilic sols: The colloidal solutions of lyophilic
colloids like starch, glue, gelatin etc., can be readily prepared by
dissolving these substances in water either in cold or on warming.
2. Preparation of lyophobic sols : Lyophobic sols are prepared by special
methods. These methods fall into two categories.
i. Dispersion methods: By splitting coarse aggregates of a substance
into a colloidal size.
ii. Condensation methods: By aggregating very small particles into the
colloidal particles.
Dispersion method Condensation methods
1. Mechanical dispersion 1. Exchange of solvents
2. Electro-dispersion 2. Change of physical state
3. Ultrasonic dispersion 3. Chemical methods
4. Peptization i. Double decomposition
ii. Oxidation
iii. Reduction
iv. Hydrolysis

39
Dispersion Methods

1. Mechanical dispersion using colloidal mill

The solid along with the
liquid is fed into a colloidal
mill. The colloidal mill consists
of two steel plates nearly
touching each other and
rotating in opposite directions
with high speed. The solid
particles are ground down to
colloidal size and then
dispersed in the liquid.
Colloidal graphite and printing
inks are made by this method.
Fig. 12.2 Colloid mill

2. Electro-dispersion method: (Bredig’s Arc Method)

This method is suitable for the preparation of colloidal solution of metals
like gold, silver, platinum etc. An arc is struck between the metal electrodes
under the surface of water containing some stabilising agent such as trace of
alkali. The water is cooled by immersing the container in a cold bath. The
intense heat of the arc vapourises some of the metal which condenses under
cold water.

Fig. 12.3 Electro-dispersion

40
3. Ultra-sonic dispersion :
The sound waves of high frequency are usually called ultra-sonic waves.
Ultrasonic waves are passed through the solution containing larger particles.
They break down to form colloidal solution.

4. Peptisation :
The dispersion of a precipitated material into colloidal solution by the
action of an electrolyte in solution is termed as peptisation. The electrolyte
used is called a peptizing agent.
A few examples are
i. Silver chloride can be converted into a sol by adding hydrochloric
acid
ii. Ferric hydroxide yields a sol by adding ferric chloride

II. Condensation methods

1. By exchange of solvent
If a solution of sulphur or phosphorus in alcohol is poured into water, a
colloidal solution of sulphur or phosphorus is obtained due to low solubility
in water.

2. By change of physical state

Colloidal solutions of certain elements such as mercury and sulphur are
obtained by passing their vapour through cold water containing a stabiliser.

3. Chemical Methods
The chemical methods involve chemical reaction in a medium in which
the dispersed phase is sparingly soluble. Some of the methods are
(i) Double decomposition: An Arsenic sulphide sol is prepared by
passing a slow stream of hydrogen sulphide gas through a cold solution of
arsenious oxide. This is continued till the yellow colour of the sol attains
maximum intensity.
As2O3 + 3 H2S As2S3 + 3 H2O
Yellow

41
 Excess hydrogen sulphide is removed by passing in a stream of hydrogen
(ii) Oxidation : A colloidal solution of sulphur is obtained by passing
H2S into a solution of sulphur dioxide.
2H2S + SO2 2H2O + 3 S
(iii) Reduction: Silver sols and gold sols can be obtained by treating
dilute solution of silver nitrate or gold chloride with organic reducing agents
like tannic acid or formaldehyde.
AgNO3 + tannic acid Ag Sol
AuCl3 + tannic acid Au Sol
(iv) Hydrolysis: Colloidal solutions of the hydroxides of Fe, Cr, Al etc
can be prepared by hydrolysis of their salts. A colloidal solution of ferric
hydroxide is obtained by boiling a dilute solution of ferric chloride.
FeCl3 + 3H2O Fe(OH)3 + 3HCl
red sol

PURIFICATION OF SOLS
In the methods of preparation stated above, the resulting sol frequently
contains besides colloidal particles appreciable amounts of electrolytes. To
obtain the pure sol, these electrolytes have to be removed. This purification
of sols can be accomplished by three methods:
(a) Dialysis
(b) Electrodialysis and
(c) Ultrafiltration

Dialysis
Animal membranes (bladder) or
those made of parchment paper and
cellophane sheet, have very fine
pores. These pores permit ions (or
small molecules) to pass through but
Fig. 12.4 Dialysis of a sol containing
not the large colloidal particles. ions and molecule

42
 When a sol containing dissolved ions (electrolyte) or molecules is placed
in a bag of semipermeable membrane dipping in pure water, the ions diffuse
through the membrane. By using a continuous flow of fresh water, the
concentration of the electrolyte outside the membrane tends to be zero.
Thus diffusion of the ions into pure water remains brisk all the time. In this
way, practically all the electrolyte present in the sol can be removed easily.
The process of removing ions (or molecules) from a sol by diffusion through
a permeable membrane is called Dialysis. The apparatus used for dialysis is
called a Dialyser.

Electrodialysis
In this process, dialysis is carried under the influence of electric field.
Potential is applied between the metal screens supporting the membranes.
This speeds up the migration of ions to the opposite electrode. Hence dialysis
is greatly accelerated. Evidently electrodialysis is not meant for non-
electrolyte impurities like sugar and urea.

Fig. 12.5 Electrodialysis

Ultrafiltration
Sols pass through an ordinary filter paper. Its pores are too large to
retain the colloidal particles. However, if the filter paper is impregnated
with collodion or a regenerated cellulose such as cellophane or visking, the
pore size is much reduced. Such a modified filter paper is called an ultrafilter.

43
 The separation of the sol particles from the liquid medium and electrolytes
by filtration through an ultrafilter is called ultrafiltration.
Ultrafiltration is a slow process.
Gas pressure (or suction) has to be
applied to speed it up. The colloidal
particles are left on the ultrafilter in
the form of slime. The slime may be
stirred into fresh medium to get back
the pure sol. By using graded
ultrafilters, the technique of
ultrafiltration can be employed to
separate sol particles of different
sizes.
Fig. 12.6 Ultra filtration
12.6 PROPERTIES OF COLLOIDS
The properties of colloids are discussed under three types
i. Kinetic property
ii. Optical property
iii. Electrical property

(i) Kinetic property

When sol is examined with an ultramicrosope, the suspended particles
are seen as shining specks of light. By following an individual particle, it is
observed that the particle is undergoing a constant rapid motion. It moves in
a series short straight line paths in the medium, changing direction abruptly.
The continuous rapid zig-zag chaotic
random and ceaseless movement executed by
a colloidal particle in the dispersion medium
is called brownian movement. This is due to
the unbalanced bombardment of the particles
by the molecules of the dispersion medium.

Fig. 12.7 Brownian movement

44
(ii) Optical property
When a strong beam of light is passed through a sol and viewed at right
angles, the path of light shows up as a hazy beam. This is due to the fact that
sol particles absorb light energy and then emit it in all directions. This
scattering of light illuminates the path of the beam. The phenomenon of the
scattering of light by the sol particles is called Tyndall effect.

Fig. 12.8 Tyndall effect

III. ELECTRICAL PROPERTIES

(i) Charge on Colloidal particles

The important property of colloidal dispersions is that all the suspended
particles possess either a positive or negative charge. The mutual forces of
repulsion between similarly charged particles prevent them from aggregating
and settling under the action of gravity. This gives stability to the sol.

Fig. 12.9 Adsorption of ions from dispersion

medium gives charge to sol particles which Fig. 12.10 Helmholtz Double layer
do not settle on account of mutual repulsions
45
 The surface of colloidal particle acquires a positive charges by selective
adsorption of a layer of positive ions around it. This layer attracts counterions
from the medium which form a second layer of negative charges. The
combination of the two layers of charges around the sol particle is called
Helmholtz double layer.

(ii) Electrophoresis
If electric potential is applied across two platinum electrodes immersed
in a hydrophilic sol, the dispersed particles move toward one or the other
electrode. The movement of sol particles under an applied electric potential
is called electrophoresis or cataphoresis. If the sol particles here negatively
charged, they migrate toward the positive electrode. On the other hand, if
they have positively charged they move toward the negative electrode. From
the direction of movement of the sol particles, we can determine the charge
of the sol particles.
The phenomenon of
electrophoresis can be demonstrated
by placing a layer of As2S3 sol under
two limbs of a U-tube. When a
potential difference of about 100
volts is applied across the two
platinum electrodes dipping in
deionised water, it is observed that
the level of the sol drops on the
negative electrode side and rises on
the positive electrode side (Fig.) This
shows that As2S3 sol has migrated
to the positive electrode, indicating
that the particles are negatively
charged. Fig. 12.11 Electrophoresis
of a sol
(iii) Electro osmosis
In a sol, the dispersion medium carries an equal but opposite charge to
that of the dispersed particles. Thus, the medium will move in opposite
direction to the dispersed phase under the influence of applied electric

46
potential. The movement of the dispersion medium under the influence of
applied potential is known as electro-osmosis.
The phenomenon of electro-
osmosis can be demonstrated by
using a U-tube in which a plug of wet
clay (a negative colloid) is fixed. The
two limbs of the tube are filled with
water to the same level. The platinum
electrodes are immersed in water and
potential applied across them. It will
be observed that water level rises on
the cathode side and falls on anode
side. This movement of the medium
towards the negative electrode,
shows that the charge on the medium
is positive. Similarly, for a positively
charged colloid electro-osmosis will
take place in the reverse direction.
Fig. 12.12 Electro-osmosis

12.7 APPLICATIONS OF COLLOIDS

Most of the substances, we come across in our daily life, are colloids.
The meal we eat, the clothes we wear, the wooden furniture we use, the
houses we live in, the newspapers we read, are largely composed of colloids.
The applications of colloid chemistry are limitless. These can be divided
mainly into two classes:
1. Natural applications and
2. Technical applications

1. Natural applications
(i) Blue colour of the sky : Colloidal particles scatter blue light. Dust
particles along with water suspended in air scatter blue light which reaches
our eyes and the sky looks blue to us.

47
 (ii) Fog, mist and rain : When a large mass of air, containing dust
particles, is cooled below its dewpoint, the moisture from the air condenses
on the surfaces of these particles forming fine droplets. These droplets being
colloidal in nature continue to float in the air in the form of mist or fog.
Clouds are aerosols having small droplets of water suspended in air. On
account of condensation in the upper atmosphere, the colloidal droplets of
water grow bigger and bigger in size, till they come down in the form of
rain. Sometimes, the rainfall occurs when two oppositively charged clouds
meet.
It is possible to cause artificial rain by throwing electrified sand or
spraying a sol carrying charge opposite to the one on clouds from an
aeroplane.
(iii) Food articles : Milk, butter, halwa, ice creams, fruit juices, etc.,
are all colloids in one form or the other.
(iv) Blood : Blood is a colloidal solution of an albuminoid substance.
The styptic action of alum and ferric chloride solution is due to coagulation
of blood forming a clot which stops further bleeding.
(v)Soils : Fertile soils are colloidal in nature in which humus acts as a
protective colloid. On account of colloidal nature, soils adsorb moisture and
nourishing materials.
(iv) Formation of delta : River water is colloidal solution of clay. Sea
water contains a number of electrolytes. When river water meets the sea
water, the electrolytes present in sea water coagulate the colloidal solution
of clay which get deposited with the formation of delta.

2. Technical Applications
(i) Electrical precipitation of smoke : Smoke is a colloidal solution
of solid particles such as carbon, arsenic compounds, dust, etc., in air. The
smoke, before it comes out from the chimney, is led through a chamber
containing plates having a charge opposite to that carried by smoke particles.
The particles on coming in contact with these plates lose their charge and

48
get precipitated. The particles thus settle down on the floor of the chamber.
The precipitator is called Cottrell precipitator.

Fig. 12.13 Cottrell smoke precipitator

(ii) Purification of drinking water : The water obtained from natural
sources often contains bacteria and suspended impurities. Alum is added to
such water so as to destroy the bacteria as well as to coagulate the suspended
impurities and make water fit for drinking purposes.
(iii) Medicines : Most of the medicines in use are colloidal in nature.
For example, argyrol is a silver sol used as an eye lotion. Colloidal antimony
is used in curing kalazar. Colloidal gold is used for intramuscular injection.
Milk of magnesia, an emulsion, is used for stomach disorders. Colloidal
medicines are more effective because these are easily assimilated.
(iv) Tanning : Animal hides are colloidal in nature. When a hide, which
has positively charged particles, is soaked in tannin, which contains negatively
charged colloidal particles, mutual coagulation takes place, which results in
the hardening of leather. The process is termed as tanning. Chromium salts
have been used in place of tannin.
(v) Photographic plates and films : The photographic plates or films
are prepared by coating an emulsion of the light sensitive silver bromide in
gelatin over glass plates or celluloid films.

49
 (vi) Rubber industry : Latex is a colloidal solution of rubber particles
which are negatively charged. Rubber is obtained by coagulation of latex.
(vii) Industrial products : Paints, inks, synthetic plastics, rubber,
graphite lubricants, cement, etc., are all colloidal solutions..

12.8 EMULSIONS
These are liquid-liquid colloidal systems, i.e., the dispersion of finely
divided droplets in another liquid. If a mixture of two immiscible or partially
miscible liquids is shaken, a coarse dispersion of one liquid in the other is
obtained which is called emulsion. Generally, one of the two liquids is water.
There are two types of emulsions.
(i) Oil dispersed in water (O/W type),
(ii) Water dispersed in oil (W/O type).
In the first system water acts as dispersion medium. Examples of this
type of emulsions are milk and vanishing cream. In milk, liquid fat is dispersed
in water.
In the second system oil acts as dispersion medium. Common examples
of this type are butter and cream.
Emulsions of oil and water are unstable and sometimes they separate
into two layers on standing. For the stabilization of an emulsion, a third
component called emulsifying agent is usually added. The emulsifying agent
forms an interfacial film between suspended particles and the medium. The
principal agents for O/W emulsions are proteins, gums, natural and synthetic
soaps, etc. For W/O emulsions, the principal emulsifying agents are heavy
metal salts of fatty acids, long chain alcohols, lampblack, etc.
Emulsions can be diluted with any amount of the dispersion medium.
On the other hand, the dispersed liquid when mixed, forms at once a separate
layer. The droplets in emulsions are often negatively charged and can be
precipitated by electrolytes. They also show Brownian movement and Tyndall
effect. Emulsions can be broken into constituent liquids by heating, freezing,
centrifuging, etc.
50
 SELF EVALUATION
(A) Choose the correct answer :
1. The migration of colloidal particles under the influence of an electric
field is known as
(a) electroosmosis (b) cataphoresis
(c) electrodialysis (d) electrophoresis
2. Which one is the correct factor that explains the increase of rate of reaction
by a catalyst
(a) shape selectivity (b) particle size
(c) increase of free energy (d) lowering of activation energy
3. Fog is a colloidal solution of
(a) gas in liquid (b) liquid in gas
(c) gas in solid (d) solid in gas.
4. The phenomenon of Tyndall’s effect is not observed in
(a) emulsion (b) colloidal solution
(c) true solution (d) None
5. The Tyndall’s effect associated with colloidal particles is due to
(a) presence of charge (b) scattering of light
(c) absorption of light (d) reflection of light
6. In case of physical adsorption, there is desorption when
(a) temperature increases (b) temperature decreases
(c) pressure increases (d) concentration increases
7. Colloidal medicines are more effective because
(a) they are clean
(b) they are easy to prepare
(c) the germs more towards, them
(d) they are easily assimilated and adsorbed
8. Oil soluble dye is mixed with emulsion and emulsion remains colourless
then, the emulsion is
(a) O/W (b) W/O (c) O/O (d) W/W
51
9. For selective hydrogenation of alkynes into alkene the catalyst used is
(a) Ni at 250°C
(b) Pt at 25°C
(c) Pd, partially inactivated by quinoline
(d) Raney nickel
10. For chemisorption, which is wrong
(a) irreversible
(b) it requires activation energy
(c) it forms multimolecular layers on adsorbate
(d) surface compounds are formed
11. An emulsion is a colloidal solution of
(a) two solids (b) two liquids
(c) two gases (d) one solid and one liquid
12. Colloids are purified by
(a) precipitation (b) coagulation
(c) dialysis (d) filtration

(B) Answer in one or two sentences :

1. Define adsorption.
2. Define colloidal solution.
3. What is electrophoresis?
4. What is catalysis ?
5. What are the two types of catalysis?
6. What are active centers ?
7. Why colloidal system in gas in gas does not exist ?
8. Why colloids are purified ?
9. What are emulsions ?
10. What is Tyndall effect ?

52
(C) Answer not exceeding sixty words :
1. Distinguish between physical adsorption and chemical adsorption.
2. Discuss the factors affecting adsorption.
3. Write notes on catalytic reactions
4. Write notes on
i. Positive catalyst
ii. Negative catalyst
iii. Auto catalyst
iv. Induced catalyst
5. Write briefly about the theories of catalysis.
6. Write the applications of catalysis.
7. Write briefly about the preparation of colloids by dispersion methods.
8. Write briefly about the preparation of colloids by condensation methods.
9. Write notes on
i. Dialysis
ii. Electrodialysis
iii. Ultrafiltration
10. Write notes on
i. Brownian movement
ii. Tyndall effect
iii. Helmholtz double layer
11. What is electro osmosis ? Explain.
12. Write the applications of colloids.

53
SUMMARY :
Adsorption is a phenomenon of concentration of substance on the surface
of a liquid or solid. The adsorption is classified into physical adsorption and
chemical adsorption.
A catalyst is a substance which alters the speed of a chemical reaction
without itself undergoing any chemical change and the phenomenon is known
as catalysis. Catalytic reactions are classified into homogeneous catalysis
and heterogeneous catalysis. The intermediate compound formation theory
and the adsorption theory are the two main theories which explain the catalytic
processes.
Colloids are intermediate between true solutions and suspensions.
Colloids are classified based on dispersion medium and dispersed phase.
Colloids are prepared by dispersion methods and condensation methods.
Colloids are purified by dialysis, electrodialysis and ultrafiltration. The
properties of colloids are discussed under the types namely, kinetic, optical
and electrical properties.

REFERENCES :
1. A text book of physical chemistry - A.S. Negi and S.C.Anand - Fifth
Print, 1997.
2. Essentials of physical chemistry - B.S. Bahl, G.D.Tuli and Arun-Bahl
- Reprint 2004.
3. Text book of physical chemistry - Louis and Glasstone.

______

54
 13. ELECTRO CHEMISTRY - I
LEARNING OBJECTIVES
@ To learn and differentiate among conductors, insulators and semi
conductors based on the conductivity differences of various substances.
@ To know about intrinsic and extrinsic semi conductors.
@ To study about the theory of electrical conductance specially about
the Arrhenius theory of weak electrolytes, lilmitations of Arrhenius
theory of electrolytic dissociation are also understood.
@ Onsagar equation will be known and

λC = λ∞ – (A + Bλ∞) C ,
the relation between equivalent conductance and concentration of
strong electrolytes will be studied.
@ Statements of Faraday’s laws of electrolysis and their significances
will be studied. Quantitative calculations on Faraday’s laws will be
learnt.
@ Definitions and explanations of specific resistance, equivalent and molar
conductances are to be studied.
@ Variations of conductance with dilution of strong and weak electrolytes
are to be explained and studied. Graphical representations of
conductance against concentrations are explained and understood.
@ Statement of Kohlraush’s law and its significances can be understood.
@ Buffer action, the nature of acidic and basic buffers, explanation of
Henderson equation, examples of buffer solutions in domestic and
industrial utilities will be explained and learnt.
@ Use of pH values, indicators with applications of different pH ranges
will be studied.
55
 The science of electrochemistry deals with the study of interconversion
of electrical and chemical energy.

13.1 CONDUCTORS , INSULATORS AND SEMI CONDUCTORS

All substances are classified into three types known as conductors,
insulators and semi conductors based on their ability to allow the electrical
current to pass through them.
Conductors : Those substances which allow electrical current to pass
through them completely are known as conductors.
Examples are metals, alloys and fused electrovalent compounds.
Insulators : Those substances which do not allow electrical current to
pass through them are known as insulators. Examples of insulators are wood,
silk, cotton, glass, rubber, organic compounds like benzene and carbon tetra
chloride.
Semiconductors : Those substances that allow the electrical current to
pass through them partially (or) possess very low electrical conductivity are
known as semi conductors. Examples of semi conductors are Silicon,
Germanium, oxides of Manganese, Cobalt oxide, Titanium dioxide etc.
Conductors of electricity are further classified into two types depending
on their mode of transport of electrical charges inside them. These are
electronic conductors and electrolytic conductors.
Metallic conductors : Metals and alloys conduct electricitiy due to the
movement (mobility) of delocalised outershell electrons present inside them
and are known as electronic conductors (or) metallic conductor. Electrical
conduction through metals do not bring about any chemical transformations.
Electrolytic conductor : Electrovalent (or) ionic compounds conduct
electrical current in their dissolved state (in solutions) or in their fused state
only. These compounds consists of ions of opposite charges and in aqueous
solution they exist as ions. In the presence of applied electrical field, these
ions migrate to respective electrodes exhibiting electrical conductivity. This
mobility of ions is responsible for conduction of electricity through
electrolytes and is referred as electrolytic conduction. Passage of current

56
through electrolytes is accompanied by chemical changes also. The differences
in the properties of electronic and electrolytic conductors are given below :
S.No. Electronic conduction Electrolytic conduction
1. Pure metals and their Electrovalent (or) ionic
solid solutions such as alloys compounds conduct electricity
are called as metallic conductors. through their ions present in
fused state or in dissolved state.
2. Free and mobile electrons of Ions with positive and negative
the metallic atoms or alloys charges conduct electricity and
are responsible for electrical move towards cathode and
conductance. anode respectively.
3. Positive holes in the metals Electrolysis occurs when
move in the opposite electrical current is passed
direction to electrons. through electrolytic solutions.
4. There is no chemical change in Chemical change occurs.
the material when electricity
is passed.
5. There is only flow of electrical There is actual transfer of
energy but there is no transfer matter since ions move towards
of matter. respective electrodes.
6. Conductivity of metal decreases The conductivity of electrolytes
with increase in temperature due increases with increase in
to the enhanced thermal vibration temperature. This is due to
of metal atoms disrupting the increase with ionic mobility.
movement of electrons passing
through them.

Semi conductors : Certain type of solids like pure silicon and germanium
which are poor conductors of electricity at normal temperature become good
conductors either at high temperatures or in the presence of impurities like
Arsenic or Boron. There are two types of semi conductors known as intrinsic
and extrinsic semiconductors.
Intrinsic semi conductors : In the intrinsic type, these solids have very
low conductivity at room temperature but at high temperatures one of the

57
interatomic covalent bonds between Silicon (or) Germanium atoms are
broken heterolytically such that free electrons and corresponding positive
holes are created. When electrical field is applied these electrons migrate
along the direction of the applied electricfield causing electrical conductivity
in them. The positive holes move in opposite direction to that of the movement
of electrons.
Extrinsic semi conductor : In the extrinsic type of semi conductors
addition of impurities like Arsenic or Boron causes appreciable increase in
the electrical conductivity. This effect can be obtained as follows :
N-type semi conductor : In silicon and germanium crystals, each atom
is covalently bonded to four neighbours so that all its four valence electrons
are tied down. Thus in the pure state these elements are poor conductors.
Suppose an atom of arsenic is introduced in place of silicon or germanium in
the crystal lattice. Arsenic has five valence electrons, four of which will be
utilised in the formation of covalent bonds and the remaining electron is free
to move through the lattice. This leads to enhanced conductivity.
p-type semi conductor : Now let a Boron atom be introduced in place
of Silicon atom in the crystal lattice. A Boron atom has only three valence
electrons. It can form only three of the four bonds required for a perfect
lattice. Thus it is surrounded by seven electrons (one of Si) rather than eight.
Thus electron vacancy or a ‘positive hole’ in the lattice is produced. Another
electron from the bond of the adjacent Si atom moves into this hole,
completing the four bonds on the B atom. This electron also leaves a hole at
its original site. In this way electrons move from atom to atom through the
crystal structure and the holes move in the opposite direction. Therefore the
conductivity of the material improves.
Semi conductors which exhibit conductivitiy due to the flow of excess
negative electrons, are called n-type semiconductors (n for negative).
Semiconductors which exhibit conductivity due to the positive holes,
are called p-type semiconductors (p for positive).

13.2 THEORY OF ELECTROLYTIC CONDUCTANCE

Arrhenius theory of electrolytic conductance is also known as Arrhenius
theory of ionisation since electrolytic dissociation into ions is considered
here.
58
 Postulates of Arrhenius Theory : 1. When dissolved in water, neutral
electrolyte molecules are split up into two types of charged particles.
These particles were called ions and the process was termed ionisation.
The positively charged particles were called cations and those having negative
charge were called anions.
The theory assumes that the ions are already present in the solid
electrolyte and these are held together by electrostatic force. When placed
in water, these neutral molecules dissociate to form separate anions and
cations.
A+ B– A+ + B–
For that reason, this theory may be referred to as the theory of electrolytic
dissociations.

2. The ions present in solution constantly reunite to form neutral

molecules. Thus there is a state of equilibrium between the undissociated
molecules and the ions.

AB A+ + B–

Applying the Law of Mass Action to the ionic equilibrium we have,

[A + ][B − ]
=K
[AB]

where K is called the Dissociation constant.

3. The charged ions are free to move through the solution to the
oppositely charged electrode. This is called as migration of ions. This
movement of the ions constitutes the electric current through electrolytes.
This explains the conductivity of electrolytes as well as the phenomenon of
electrolysis.
4. The electrical conductivity of an electrolyte solution depends on the
number of ions present in solution. Thus the degree of dissociation of an
electrolyte determines whether it is a strong electrolyte or a weak electrolyte.

59
 We know that electrolytes dissociate in solution to form positive ions
(cations) and negative ions (anions).
AgNO3 Ag+ + NO3–
CuSO4 Cu2+ + SO42–
H2SO4 2H+ + SO42–
As the current is passed between the electrode of the electrolytic cell,
the ions migrate to the opposite electrodes. Thus in the electrolytic solution
of AgNO3, the cations (Ag+) will move to the cathode and anions (NO3–)
will move to the anode. Usually different ions move with different rates. The
migration of ions through the electrolytic solution can be demonstrated by
the following experiments.

Fig. 13.1 Migration of ions through electrolytic solution to opposite electrodes

5. The properties of solution of electrolytes are the properties of ions.

The solution of electrolyte as a whole is electrically neutral unless an electric
field is applied to the electrodes dipped into it. Presence of hydrogen ions
(H+) renders the solution acidic while presence of hydroxide ions (OH–)
renders the solution basic.
6. There are two types of electrolytes. Strong electrolytes are those
when dissolved in water are completely dissociated (ionised) into ions of
60
positive and negative charges. The total number of cations and anions
produced are equal to those in the formula of the electrolyte.
(e.g.,) Al2 (SO4)3 2Al3+ + 3SO42–
NaCl, KCl, AgNO3 etc., are few examples of strong electrolytes.
In the case of weak electrolytes, there is partial dissociation into ions in
water and an equilibrium exists between the dissociated ions and the
undissociated electrolyte.
(e.g.,) CH3COOH CH3COO– + H+. Acetic acid is a weak
electrolyte in water and unionised acetic acid molecules are in equilibrium
with the acetate anions and H+ ions in solution.

Evidences of Arrhenius theory of electrolytic dissociation

1. The enthalpy of neutralisation of strong acid by strong base is a constant
value and is equal to –57.32 kJ. gm.equiv-1. This aspect is well explained
by adopting Arrhenius theory of electrolytic dissociation. Strong acids
and strong bases are completely ionised in water and produce H+ and
OH– ions respectively along with the counter ions. The net reaction in
the acid-base neutralisation is the formation of water from H+ and OH–
ions.
H+ + OH– H2O ; ∆Hro = –57.32 kJ.mol-1.
2. The colour of certain salts or their solution is due to the ions present.
For example, copper sulphate is blue due to Cu2+ ions. Nickel salts are
green due to Ni2+ ions. Metallic chromates are yellow due to CrO42–
ions.
3. Ostwalds dilution law, common ion effect and solubility product and
other such concepts are based on Arrhenius theory.
4. Chemical reactions between electrolytes are almost ionic reactions. This
is because these are essentially the reaction between oppositely charged
ions. For example,
Ag+ + Cl– AgCl ↓
5. Electrolytic solutions conduct current due to the presence of ions which
migrate in the presence of electric field.
61
6. Colligative properties depend on the number of particles present in the
solution. Electrolytic solution has abnormal colligative properties. For
example, 0.1 molal solution of NaCl has elevation of boiling point about
twice that of 0.1 molal solution of non-electrolyte. The abnormal
colligative properties of electrolytic solutions can be explained with theory
of electrolytic dissociation.

Ostwald’s dilution law for weak electrolytes

According to Arrhenius theory, weak electrolytes partially dissociate
into ions in water which are in equilibrium with the undissociated electrolyte
molecules. Ostwald’s dilution law relates the dissociation constant of the
weak electrolyte with the degree of dissociation and the concentration of
the weak electrolyte. Consider the dissociation equilibrium of CH3COOH
which is a weak electrolyte in water.

CH3COOH CH3COO– + H+

[H + ][CH 3COO − ]
Ka =
[CH 3COOH]

α is the degree of dissociation which represents the fraction of total

concentration of CH3COOH that exists in the completely ionised state. Hence
(1 – α) is the fraction of the total concentration of CH 3COOH, that exists in
the unionised state. If ‘C’ is the total concentration of CH3COOH initially,
then at equilibrium Cα, Cα and C (1 – α) represent the concentration of H+,
CH3COO– and CH3COOH respectively.

C α .C α α 2 C
Then Ka = =
C(1 − α ) 1 − α

if α is too small, then Ka = α2C and

Κa
α= . Also [H+] = [CH3COO–] = Cα.
C

FK I
=CG J
1/ 2

HCK
a
[H+] = (Ka.C)1/2 = K a .C
62
 α2 C
Ka = is known as the Ostwald’s dilution law. For weak bases,
1− α

α2 C Κb
Kb = and α = at α = small values. Kb = dissociation constant
1− α C
for weak base.
This law fails for strong electrolytes. For strong electrolytes, α tends to
1.0 and therefore Ka increases tremendously.

13.4 FARADAY’S LAWS OF ELECTROLYSIS

Electrolysis
When electric current is passed through an electrolyte solution, the ions
of electrolyte undergoes chemical changes at the respective electrodes. The
chemical reaction carried out by passing electricity is called as electrolysis.
There are two important laws of electrolysis proposed by Faraday and
the relation between the amount of products liberated at the electrodes and
the quantity of electricity passed through the electrolyte is established based
on these laws.

Faraday’s First law :

The mass of the substance (m) liberated at the electrodes during the
electrolysis is directly proportional to the quantity of electricity (Q) that
passes through the electrolyte.

Faraday’s Second law :

When the same quantity of electricity passes through solutions of different
electrolytes, the amounts of the substances liberated at the electrodes are
directly proportional to their chemical equivalents.

Electrochemical equivalent defined in First law

If m is the mass of substance (in grams) deposited on electrode by passing
Q coulombs of electricity, then
m∝Q ... First law
63
 We know that Q = I×t
or m = Z× I× t
where Z is the constant known as the Electrochemical equivalent of the
substance (electrolyte). If I = 1 ampere and t = 1 second, then
m=Z
Thus, the electrochemical equivalent is the amount of a substance
deposited by 1 ampere current passing for 1 second (i.e., one coulomb)

The Electrical unit Faraday

It has been found experimentally that the quantity of electricity required
to liberate one gram equivalent of a substance is 96,495 coulombs. This
quantity of electricity is known as Faraday and is denoted by the symbol F.
It is obvious that the quantity of electricity needed to deposit 1 mole of
the substance is given by the expression.
Quantity of electricity = n × F
where n is the valency of its ion. Thus the quantity of electricity required to
discharge :
one mole of Ag+ = 1 × F = 1F
one mle of Cu2+ = 2 × F = 2F
one mole of Al3+ = 3 × F = 3F
We can represent the reactions on the cathode as :
Ag+ + e = Ag
Cu2+ + 2e = Cu
Al3+ + 3e = Al
It is clear that the moles of electrons required to discharge one mole of
ions Ag+, Cu2+ and Al3+ is one, two and three respectively. Therefore it
means that the quantity of electricity in one Faraday is one mole of electrons.
Now we can say that,
1 Faraday = 96,495 coulombs = 1 Mole electrons

64
Importance of the First law of Electrolysis
With the help of the first law of electrolysis we are able to calculate :
1. the value of electrochemical equivalents of different substances ; and
2. the mass of different substances produced by passing a known quantity
of electricity through their solutions.
96495 coulomb of electricity liberates one gram equivalent weight of
the element.

equivalent mass
∴ 1 coulomb current liberates = g.coulomb-1
96495
∴ Z = electrochemcial equivalent mass

equivalent mass
=
96495 × 10-3 kg.coulomb-1

Electronic charge.
1 Faraday equal the quantity of electricity produced by 1 mole of
electrons.

96495
∴ Charge of an electron = 23
6.023 × 10

= 1.602 × 10-19 Coulomb.

Example 1. If 50 milli ampere of current is passed through copper
coulometer for 60 min, calculate the amount of copper deposited.
Solution : Electrical charge input = I × t coulombs
= 50 × 10-3 A × 60 × 60 sec
= 180 coulombs.
The chemical reaction is, Cu2+ + 2e Cu(s)
1 gm atom of copper requires 2F current

65
 63.5 g.mol −1 × 180 C
∴ amount of copper deposted =
2 × 96500 C

= 0.0592 gm.

Example 2. 0.1978 g of copper is deposited by a current of 0.2 ampere

in 50 minutes. What is the electrichemical equivalent of copper ?
Solution : Here, t = 50 minutes = 50 × 60 seconds ; I = 0.2 ampere.
Quantity of electricity used is
Q = I × t = 0.2 × 50 × 60 = 600 coulombs
Amount of copper deposited by 600 coulombs = 0.1978 g

0.1978
Amount of copper deposited by 1 coulomb = g = 0.0003296 g
600
Electrochemical equivalent of copper = 0.0003296 = 3.296 × 10–4gc–1
= 3.206 × 10–7 kg c–1

Example 3. What current strength in amperes will be required to

liberate 10 g of iodine from potassium iodide solution in one hour ?
Solution : 127 g of iodine (1g eqvt) is liberated by = 96,500 coulomb

96,500
10 g of iodine is liberated by = × 10 coulomb
127
Let the current strength be = I
Time in seconds = 1 × 60 × 60
We know that the quantity of electricity, Q, used is given by the expression
Q = I × time in seconds

Q 96,500 × 10
Curernt strength, I = = 127 × 60 × 60
t

= 2.11 ampere.
66
 Example 4. An electric current is passed through three cells in series
containing respectively solutions of copper sulphate, silver nitrate and
potassium iodide. What weights of silver and iodine will be liberated
while 1.25 g of copper is being deposited ?

Wt.of copper Eqvt.wt.copper

Solution : Wt.of Iodine = Eqvt. wt.of Iodine

1. 25 31.7 1. 25 × 127
or = , x=
x 127 31. 7
Hence, Wt. of Iodine x = 5.0 g of iodine

Wt.of Copper 1.25

Also, Wt.of Silver =
y

Eqvt.wt.of Cu ( = 31.7)
= Eqvt.wt.of Silver ( =108)

108 × 1.25
Wt. of silver (y) =
31.7
= 4.26 g

13.5 ELECTRICAL CONDUCTANCE QUANTITIES

The S.I. unit of electrical current is ampere. The unit of quantity of
electricity is coulomb. when one ampere of current is passed for one second,
then the quantity of current passed is one coulomb.
(i.e.,) Q = I × t Coulomb
Ohm’s law : This law can be stated as, at constant temperature, the
strength of the current flowing through a conductor is directly proportional
to the potential difference and inversely proportional to the resistance of the
conductor.

67
 V
Thus, I = , ∴ V = RI, V = Volts, I = ampere, R = ohms
R
Specific resistance : The resistance ‘R’ ohms offered by the material of
the conductor to the flow of current through it is directly proportional to its
length (l) and inversely proportional to the area of cross section (a). Thus,

l l
R∝ and R = ρ
a a
ρ is called the specific resistance and it is resistance in ohms which one
meter cube of material offers to the passage of electricitiy through it, unit of
specific resistance is ohm-meter.
Specific conductance : The reciprocal of specific resistance is called as
specific conductance (or) specific conductivity (κ) [κ is called ‘kappa’].
κ is defined as the conductance of one metre cube of an electrolyte
solution
1 1 l
∴κ = = .
ρ R a
Unit of specific conductance is ohm-1 m-1 (or) mho.m-1
Since ohm-1 = mho

1 m
κ= × = ohm-1.m-1
ohm m2
Also, 1 siemen = 1 mho. ∴ κ is also expressed as S.m-1.
Conductance is the reciprocal of resistance ‘R’.

1
Conductance =
R
l
is called as the cell constant (m-1) and is constant for a given
a
conductance cell.
68
 Thus specific conductance ‘κ’ = cell constant × conductance

Cell constant
=
Resistance
Equivalent conductance : Equivalent conductance (λC) is defined as
the conductance of an electrolyte solution containing one gram equivalent
of the electrolyte. It is equal to the product of specific conductance (κ) of
the solution and the volume (V) of the solution that contains one gram
equivalent of the electrolyte.
(λC) = κ × V
In general if an electrolyte solution contains N gram-equivalents in
1,000 cc of the solution the volume of the solution containing 1 gram
1000
equivalent will be
N × 10-6 m3 (1 cc = 10-6 m3)

10−3
∴ λC = κ mho.m2 gm.equiv.-1
N
for 1 : 1 electrolyte normality N equals to molarity ‘C’. Then

κ × 10−3
λC = mho.m2.(gm.equiv)-1
C
λC values depend on the type of the electrolyte, concentration of the
solution and temperature.
Molar conductance : Molar conductance ‘µC ’ is defined as the
conductance of a solution containing one mole of the electrolyte dissolved
in it.

κ × 10−3
∴ µC = mho.m2.mole-1
M
where M is the molarity of the electrolyte solution.
For 1 : 1 electrolyte like NaCl, equivalent conductance is equal to molar
conductance.

69
 Summary of electrochemical quantities.
Quantity Symbol Unit
Resistance R ohm (or) Ω
Resistivity (or) ρ ohm.m.
specific resistance
1
Conductance ohm-1 (or) Siemen
R
Specific conductivity κ ohm-1 m-1
(or) specific conductance
Volume (or) dilution V m3
Equivalent conductance λC ohm-1 m2 (gm.equiv)-1
Molar conductance µC ohm-1 m2 mole-1

13.6 VARIATION OF EQUIVALENT CONDUCTANCE WITH

CONCENTRATION
The effect of concentration on equivalent conductance can be studied
from the plots of λC values versus square root of concentration of the
electrolyte. By doing so, it has been found that different types of plots are
obtained depending on the nature of electrolyte. For strong electrolytes λC
decreases linearly with increase in C while for weak electrolytes, there is a
curve type of non linear decrease of λC with C .

C
Fig. 13.2 Variation of equivalent conductivity λC with C for
(a) strong electrolytes and (b) weak electrolytes.
70
 For strong electrolytes Debye, Huckel and Onsager equation can be
applied.

λC = λ∞ – (A + B λ∞ ) C to the linear plot of λC versus C for strong

electrolytes, the intercept value equals to λ∞ value which is obtained by
extrapolating the line to ‘y’ axis ( C = 0). The slope value equals to
(A + B λ∞). A and B are called as Debye constants for strong electrolytes.

In case of weak electrolytes, degree of dissociation (α) increases when

concentration decreases. Hence, (1 – α) value tends to zero at infinite dilution,
such that λC increases and tends to λ∞ value.

λ∞ of weak electrolytes are experimentally obtained by extrapolating

the upper arm of the curve to the Y axis and the intercept value corresponds
to λ∞. In the intermediate concentration range, λC is lower than λ∞ since the
weak electrolyte exists in partially ionised state. The degree of dissociation
α equals to the ratio of λC to λ∞ value. (i.e., α = λC / λ∞).

Example 1. The resistance of a 0.01 N solution of an electrolyte was

found to 210 ohm at 25oC using a conductance cell with a cell constant
0.88 cm -1 . Calculate the specific conductance and equivalent
conductance of the solution.
l
Solution : R = 210 ohm ; = 0.88 cm-1
a

l 1
Specific conductance κ = ×
a R

0.88 cm−1
= 210 ohm = 4.19 × 10-3 mho.cm-1

= 4.19 × 10–3 mho.m–1

Equivalent conductance, λ = κ × V
71
 V has 1 gram equivalent dissolved given is 0.01 N in 1000 ml.
1000
∴V = = 1,00,000 ml
0. 01
λ = 4.19 × 10-3 × 1,00,000
λ = 419.05 mho.cm2.gm.equiv.-1
= 4.1905 × 10–2 mho m2 (gm.equiv)–1
Example 2. 0.04 N solution of a weak acid has a specific conductance
4.23 × 10-4 mho.cm-1. The degree of dissociation of acid at this dilution
is 0.0612. Calculate the equivalent conductance of weak acid at infinite
solution.
Solution : Specific conductance κ = 4.23 × 10-4 mho.cm-1

κ1000 4. 23 × 10−4 × 1000

λC = C =
0. 04
= 10.575 mho.cm2.eq-1.
λC 10.575
α = 0.0612 = λ = λ
∞ ∞

∴ λ∞ = 172.79 mho.cm2.gm.equiv.-1

Example 3. Equivalent conductivity of acetic acid at infinite dilution

is 39.7 and for 0.1 M acetic acid the equivalent conductance is
5.2 mho.cm2.gm.equiv.-1. Calculate degree of dissociation, H + ion
concentration and dissociation constant of the acid.
λC 5. 2
Solution : α = λ = 390.7 = 0.01333 = 1.33%
∞

CH3COOH H+ + CH3COO–
C (1 – α) Cα Cα

∴ [H+] = Cα = 0.1 × 0.0133 = 0.00133 M

α2 C 0. 01332 × 0.1
K= = = 2.38 × 10-5 M
1 − α (1 − 0. 0133)
72
13.7 KOHLRAUSH’S LAW
This law states that, ‘‘at infinite dilution wherein the ionisation of all
electrolytes is complete, each ion migrates independently and contributes a
definite value to the total equivalent conductance of the electrolyte’’. Consider
an electrolyte AB in aqueous solution. It dissociates as
Am Bn mAn+ + nBm-
Then at infinite dilution, according to Kohlrausch’s law, the total
1 1
equivalent conductance of the electrolyte, λ∞ = + λA +
+ λ – where λ∞+
n m− B
and λ∞– are the cationic and anionic equivalent conductances at infinite
dilutions and n+ and m– correspond the valency of cations and anions furnished
from each molecule of the electrolyte.
λ∞ , NaCl = λ∞Na+ + λ∞ Cl–

λ∞ , BaCl2 = 1 λ Ba2+
∞ + λ∞ Cl–
2
λ∞ , AlCl3 = 1 λ∞ Al3+ + λ∞ Cl–
3
1
λ∞ , Al2(SO4)3 = 1 λ∞ Al3+ + λ∞ SO42–
3 2
For weak electrolytes,
λ∞ , CH3COOH = λ+∞ H+ + λ∞– CH3COO–
λ∞ , NH4OH = λ∞+ NH4+ + λ∞– OH–
Application of Kohlraush’s law : The important use of Kohlraush’s
law is to deduce the λ∞ value of the weak electrolytes correctly by
arithmetically combining the λ∞ values of strong electrolyte in appropriate
manner.
For example λ∞ of CH3COOH which is a weak electrolyte is deduced
from λ∞ values of NaCl, HCl, and CH3COONa in such a manner that λ∞ of
CH3COOH is obtained. Sodium acetate (CH3COONa) is a strong electrolyte
and it ionises to acetate (CH3 COO–) and sodium (Na +) ions at all
concentrations in water. Applying Kohlraush’s law,
73
 λ∞ CH3COONa + λ∞ HCl – λ∞ NaCl =
λ∞ CH3COO– + λ∞ Na+ + λ∞ H+ + λ∞ Cl– – λ∞ Na+ – λ∞ Cl–
λ∞ CH3COO– + λ∞ H+ = λ∞ CH3COOH
This method produces agreeable values of λ∞ for weak electrolytes.
Similarly λ∞ NH4OH can be deduced as,
λ∞ NH4OH = λ∞ NH4+ + λ∞ OH–
= λ∞ NH4+ + λ∞ Cl– + λ∞ Na+ + λ∞ OH– – λ∞ Na+ – λ∞ Cl–
= λ∞ NH4Cl + λ∞ NaOH – λ∞ NaCl
Molar conductances at infinite dilution : (µ∞) when an electrolyte
dissociates into γ+ number of cations and γ− number of anions then total
molar conductance at infinite dilution µ∞ of the electrolyte is given by
Aγ+ Bγ− γ+ A+ + γ− B–
then µ∞ = γ+ µ∞+ + γ− µ−∞
where µ−∞ and µ+∞ are the ionic conductances at infinite dilution.
∴ µ∞ BaCl2 = µ∞ Ba2+ + 2 µ∞ Cl–
µ∞ Na2SO4 = 2 µ∞ Na+ + µ∞ SO42–

Example 4 : Ionic conductances at infinite dilution of Al3+ and SO42–

are 189 ohm–1 cm2 gm.equiv.-1 and 160 ohm-1 cm2 gm.equiv.-1. Calculate
equivalent and molar conductance of the electrolyte at infinite dilution.
The electrolytes Al2(SO4)3

1 1
λ∞ Al2(SO4)3 = λ∞ Al3+ + λ∞ SO42–
3 2

189 160
λ∞ Al2(SO4)3 = + = 63 + 80 = 143 mho cm2 gm.equi–1
3 2
µ∞ Al2(SO4)3 = 2 × 189 + 3 × 160 = 858 mho cm2 mol–1

74
The common ion effect
When a soluble salt (say A+C–) is added to a solution of another salt
(A+B–) containing a common ion (A+), the dissociation of AB is suppressed.

AB A+ + B–

By the addition of the salt (AC), the concentration of A + increases.

Therefore, according to Le Chatelier’s principle, the equilibrium will shift to
the left, thereby decreasing the concentration of A+ ions or the degree of
dissociation of AB will be reduced.
The reduction of the degree of dissociation of a salt by the addition
of a common-ion is called the Common-ion effect.
Let us consider a few examples to illustrate the common-ion effect.
Example 1. In a saturated solution of silver chloride, we have the
equilibrium

AgCl(s) Ag+(aq) + Cl–(aq)

When sodium chloride is added to the solution, the concentration of Cl –

ions will increase. The equilibrium shown above will be shifted to the left to
form more of solid AgCl. Thus the solubility of AgCl, a typical sparingly
soluble salt, will decrease.
Example 2. When solid NH4Cl is added to NH4OH solution, the
equilibrium

NH4OH NH4+ + OH–

shifts to the left. Thereby the equilibrium concentration of OH– decreases.

This procedure of reducing the concentration of OH– ions is used in qualitative
analysis.
Example 3. The common-ion effect can also be applied to the ionic
equilibrium of a weak acid as HF.

HF H+ + F–

75
 NaF is added to the equilibrium mixture. The concentration of F –
(common ion) is increased. Thus the equilibrium shits to the left. In other
words, the degree of dissociation of HF decreases. It was found by experiment
that the degree of dissociation HF in 1M solution is 2.7 while the value
reduces to 7.2 × 10-4 after the addition of 1 M NaF.
Example 4. Find the degree of dissociation of HF in 1 M aqueous
solution. The value of K for the ionic equilibrium HF = H+ + F– is 7.2 × 10-4.
Solution : HF dissociates in water to form H+ and F– ions. On reaching
the equilibrium we have

HF H+ + F–

Thus one mole of HF taken initially dissociates to yield 1 mole of H+

and 1 mole of F–.
If x be the degree of dissociation, the concentration terms at equilibrium
are :
[HF] = (1 – x) mol/L
[F–] = x mol/L
[H+] = x mol/L
Substituting these values in the equilibrium expression, we have

[H + ][F− ] ( x) ( x )
K = 7.2 × 10-4 = = (1− x )
[HF]

If x is very small compared to 1, we can write :

x2
7.2 × 10-4 =
1. 00
∴ x = (7.2 × 10-4)1/2
= 2.7 × 10-2
Thus the degree of dissociation of HF in 1 M solution is 2.7 × 10-2.

76
13.8 IONIC PRODUCT OF WATER
Water is a weak electrolyte. The dissociation equilibrium of water can
be considered as,

2H2O H3O+ + OH–

According to law of mass action,

[H 3O+ ][OH − ]
Keq =
[H 2O]2

Since water as a solvent is always in excess and change in concentration

due its dissociation is negligible. Hence water concentration is assumed to
be constant.
∴ Keq [H2O]2 = [H3O+] [OH–] = Kw

The constant Kw is called as the ionic product of water and its value is
given by the product of concentrations of hydronium (H3O+) and hydroxide
(OH–) ions. At 298 K, Kw = 1 × 10-14 mol2.dm-6.

The pH of solutions
A knowledge of the concentration of hydrogen ions (more specifically
hydronium ions) is of the greatest importance in chemistry. Hydrogen ion
concentrations are typically quite small numbers. Therefore, chemists report
the hydrogen ion concentration of a solution in terms of pH. It is defined as
the negative of the base-10 logarithm (log) of the H+ concentration.
Mathematically it may be expressed as
pH = – log10 [H+]
where [H+] is the concentration of hydrogen ions in moles per litre
Alternative and more useful forms of pH definition are :

1
pH = log [H + ]

and [H+] = 10–pH

77
 The pH concept is very convenient for expressing hydrogen ion
concentration. It was introduced by Sorensen in 1909. It is now used as a
general way of expressing other quantities also, for example.
(a) Concentration of OH– ions in aqueous solution of a base is expressed
as
p [OH–] = – log10 [OH–]
(b) Equilibrium constant for water is written as
pKw = – log10 [Kw]
For any quantity X, we can write
pX = – log X
The ‘p’ in these expressions means ‘‘–log of the quantity’’.
The pH of a given solution can be measured with the help of an apparatus
called pH meter.
Knowing the pH of the solution its hydrogen ion concentration can be
calculated.

pH Scale
In order to express the hydrogen ion concentration or acidity of a solution,
a pH scale was evolved. The pH is defined as

pH = – log [H+] or [H+] = 10–pH

The hydrogen ion concentrations of different acidic solutions were

determined experimentally. These were converted to pH values using the
above relations. Then these pH values were computed on a scale taking
water as the reference substance. The scale on which pH values are
computed is called the pH scale.

Water dissociates to H+ and OH– ions to a very small degree so that we

have the equilibrium.

H2O H+ + OH–

78
 Since Kw = 1 × 10-14 mol2.dm-6.

[H3O+] = [H+] = [OH–] = 1 × 10−14 = 1 × 10-7 mol.dm-3

Thus the H+ ion and OH– ion concentrations in pure water are both
10-7 mol.dm-3 at 25oC and it is said to be neutral. In acidic solution, however,
the concentration of H+ ions must be greater than 10-7 mol. L-1. Similarly in
a basic solution, the concentration of OH– ions must be greater than 10-7
mol L-1. Thus we can state :
neutral solution [H+] = [OH–]
acidic solution [H+] > [OH–]
basic solution [H+] < [OH–]
Expressing the [H+] in terms of pH for the different solutions cited above,
we get what we call the pH scale. On this scale the values range from 0 to
14. Since pH is defined as –log [H+] and the hydrogen ion concentration of
water is 10-7, the pH of water is 7. All solutions having pH less than 7 are
acidic and those with pH greater than 7 are basic.

ACID NEUTRAL BASE

1 7 14
pH < 7 pH > 7

As shown by the pH scale, pH decreases with the increase of [H+]. The

lower the pH, higher is the [H+] or acidity.
To calculate [H+] and [OH–] from Kw. In any aqueous solution, the
product of [H+] and [OH–] always equal to Kw. This is so irrespective of the
solute and relative concentrations of H+ and OH– ions. However, the value
of Kw depends on temperature. At 25oC it is 1.0 × 10-14. Thus,

[H+] [OH–] = 1.0 × 10-14

Each of [H+] and [OH–] in pure water at 25oC is 10-7. The concentrations
of [H+] and OH– ions are expressed in gram moles per litre.

79
 The concentrations [H+] and [OH–] ions can be calculated from the
expressions :
Kw
[H+] =
[OH − ]
Kw
[OH–] =
[H+ ]

Relation between pH and pOH

pH concept can be used to express small quantities as [OH–] and Kw.
Thus
pOH = – log10 [OH–]
pKw = – log10 Kw
Let us consider the log form of the expression
Kw = [H+] [OH–]
That is log Kw = log [H+] + log [OH–]
or – log Kw = –log [H+] – log [OH–]
Thus pKw = pH + pOH
Since Kw = 1.0 × 10–14
pKw
=
–log (1.0 × 10–14) = 14.00
Hence, for any aqueous solution at 25oC, pH and pOH add up to 14.00.
That is,
pH + pOH = 14.00
In general, the pH problems may be of the following tpes :

Example 1. The hydrogen ion concentration of a fruit juice is

3.3 × 10-2 M. What is the pH of the juice ? Is it acidic or basic ?
Solution : The definition of pH is
80
 We are given [H+] = 3.3 × 10-2
Substituting into the definition of pH, we get
pH = – log (3.3 × 10-2)
= – (– 1.48) = 1.48
Since the pH is less than 7.00, the solution is acidic.

Example 2. If a solution has a pH of 7.41, determine its H+

concentration.
Solution : pH = – log [H+]
∴ [H+] = antilog [–pH] = antilog [–7.41]
∴ [H+] = 3.9 × 10–8 M

Example 3. pH of a solution is 5.5 at 25oC. Calculate its [OH–]

Solution : pH + pOH = 14.0 ∴ pOH = 14.0 – pH
= 14.0 – 5.5 = 8.50
pOH = 8.5 ∴ antilog [–pOH]
∴ [OH–] = antilog [–8.5] = 3.2 × 10–9 M

Example 4. Calculate the pH of 0.001 M HCl solution

HCl H+ + Cl–. HCl is a strong acid.
[H+] from HCl is very much greater than [H+] from water which is
1 × 10–7 M.
∴ [H+] = [HCl] = 0.001 M
∴ pH = –log (0.001) = 3.0
∴ That is acidic solution.

Example 5. Calculate the pH of 0.1 M CH3 COOH solution.

Dissociation constant of acetic acid is 1.8 × 10-5 M.
For weak acids,

81
 [H+] = Ka × C

= 1.8 × 10−5 × 0.1 = 1. 8 × 10−6

= 1.34 × 10–3 M

∴ pH = –log [H+] = log (1.34 × 10–3 )

∴ pH = 2.87

Example 6. Calculate the pH of 0.02 m Ba(OH)2 aqueous solution

assuming Ba(OH)2 as a strong electrolyte.
Ba(OH2) Ba2+ + 2OH–

∴ [OH–] = 2 [Ba(OH)2] = 2 × 0.02 = 0.04 M

∴ pOH = –log [OH–] = 1.398 = 1.40

∴ pH = 14 – 1.4 = 12.6

13.9 BUFFER SOLUTIONS

It is often necessary to maintain a certain pH of a solution in laboratory
and industrial processess. This is achieved with the help of buffer solutions,
buffer systems or simply buffers.
A buffer solution is one which maintains its pH fairly constant even
upon the addition of small amounts of acid or base.
In other words, a buffer solution resists (or buffers) a change in its pH.
That is, we can add a small amount of an acid or base to a buffer solution
and the pH will change very little. Two common types of buffer solutions
are :
1. a weak acid together with a salt of the same acid with a strong base.
These are called Acid buffers. (e.g.,) CH3COOH + CH3COONa.
2. a weak base and its salt with a strong acid. These are called Basic
buffers. (e.g.,) NH4OH + NH4Cl.
82
 Buffer action : Let us illustrate buffer action by taking example of a
common buffer system consisting of a solution of acetic acid and sodium
acetate (CH3COOH/CH3COONa).

CH3COOH H+ + CH3COO–

CH3COONa Na+ + CH3COO–

since the salt is completely ionised, it provides the common ions CH3COO–
in excess. The common ion effect suppresses the ionisation of acetic acid.
This reduces the concentration of H+ ions which means that pH of the solution
is raised.

It is stated that a buffer solution containing equimolar amounts (0.10 M)

of acetic acid and sodium acetate has pH 4.74. Now we proceed to discuss
how the addition of a small amount of HCl or NaOH to the buffer solution
affects its pH.
The pH of the buffer is governed by the equilibrium

CH3COOH CH3COO– + H+ ... (1)

The buffer solution has a large excess of CH3COO– ions produced by

complete ionisation of sodium acetate,

CH3COONa CH3COO– + Na+ ... (2)

1. Addition of HCl. Upon the addition of HCl, the decrease of H+ ions

is counteracted by association with the excess of acetate ions to form
unionised CH3COOH. Thus the added H+ ions are neutralised and the pH of
the buffer solution remains unchanged. However owing to the increased
concentration of CH3COOH, the equilibrium (1) shifts slightly to the right
to increase H+ ions. This explains the marginal increase of pH of the buffer
solution on addition of HCl.

83
 Fig. 13.3 Mechanism of Buffer action of an acid buffer.

2. Addition of NaOH. When NaOH is added to the buffer solution, the

additional OH– ions combine with CH3COOH to give CH3COO– and H2O.
Thus pH of the buffer solution is maintained almost constant. The buffer
NH4OH/NH4Cl can also be explained on the same lines as of an acid buffer
upon addition of HCl the H+ ions combine with NH4OH to form NH4+ and
H2O. pH is retained. Similarly when NaOH is added, the OH– ions combine
with NH4+ ions present in the buffer solution to give NH4OH and hence pH
is maintained.

Fig. 13.4 Mechanism of buffer action of a basic buffer

84
 Henderson equation : The pH of an acid buffer can be calculated from
the dissociation constant, Ka, of the weak acid and the concentrations of the
acid and the salt used.
The dissociation expression of the weak acid, HA, may be represented
as

HA H+ + A–

[ H + ][ A − ]
and Ka =
[ HA ]

[HA]Ka
or [H+] = ... (1)
[A − ]

The weak acid is only slightly dissociated and its dissociation is further
depressed by the addition of the salt (Na+ A–) which provides A– ions
(Common ion effect). As a result the equilibrium concentration of the
unionised acid is nearly equal to the initial concentration of the acid. The
equilibrium concentration [A–] is presumed to be equal to the initial
concentration of the salt added since it is completely dissociated. Thus we
can write the equation (1) as

[acid ]
[H+] = Ka × ... (2)
[ salt ]
where [acid] is the initial concentration of the added acid and [salt] that of
the salt used.
Taking negative logs of both sides of the equation (2), we have

[acid ]
–log [H+] = –log Ka – log ... (3)
[ salt ]
But –log [H+] = pH and –log Ka = pKa
Thus from (3) we have

85
 [acid ] [ salt ]
pH = pKa – log = pKa + log
[ salt ] [acid ]

[ salt ]
Hence, pH = pKa + log
[acid ]
This relationship is called the Henderson-Hasselbalch equation or
simply Henderson equation.
In a similar way, the Henderson-Hasselbalch equation for a basic buffer
can be derived. This can be stated as :
[salt]
pOH = pKb + log
[base]

Significance of the Henderson-Hasselbalch equation. With its help

1. The pH of a buffer solution can be calculated from the initial
concentrations of the weak acid and the salt provided Ka is given.
However, the Henderson-Hasselbalch equation for a basic buffer will
give pOH and its pH can be calculated as (14 – pOH).
2. The dissociation constant of a weak acid (or weak base) can be
determined by measuring the pH of a buffer solution containing equimolar
concentrations of the acid (or base) and the salt.
[ salt ]
pH = pKa + log
[acid ]
[ salt ]
Since, [salt] = [acid], log = log 1 = 0
[acid ]
pKa = pH
The measured pH, therefore, gives the value of pKa of the weak acid.
Likewise we can find the pKb of a weak base by determining the pOH of
equimolar basic buffer.
3. A buffer solution of desired pH can be prepared by adjusting the
concentrations of the salt and the acid added for the buffer.

86
 It is noteworthy that buffer solutions are most effective when the
concentrations of the weak acid (or weak base) and the salt are about equal.
This means that pH is close to the value of pKa of the acid (or pKb of the
base).
Example 1 : Find the pH of a buffer solution containing 0.20 mole
per litre CH3COONa and 0.15 mole per litre CH3COOH, Ka for acetic
acid is 1.8 × 10-5
Solution : Ka = 1.8 × 10–5
pKa = –log (1.8 × 10–5) = 4.7447
[ salt ]
pH = pKa + log
[acid ]
... Henderson - Hasselbalch equation
0. 20
= 4.7447 + log
0.15
4
pH = 4.7447 + log
3
= 4.7447 + 0.6021 – 0.4771 = 4.8697
Example 2 : The Ka of propionic acid is 1.34 × 10-5. What is the pH
of a solution containing 0.5 M propionic and 0.5 M sodium
proportionate ? What happens to the pH of the solution when volume
is doubled by adding water ?
Solution : Ka of propionic acid = 1.34 × 10–5
∴ pKa = –log Ka = – log (1.34 × 10–5)
= 4.87
By Herderson - Hasselbalch equation
[ salt ]
pH = pKa + log
[acid ]
0. 5
= 4.87 + log
0. 5
pH = 4.87

87
 Alternative solution : The dissociation equilibrium of propionic acid
will be
C2H5COOH C2H5COO– + H+

[C 2 H 5COO − ][ H + ] 0. 5 × [ H + ]
Ka = =
[ C 2 H 5COOH ] 0. 5
= [H+]
∴ pH = –log [H+]
= – log Ka = –log (1.34 × 10–5)
∴ pH = 4.87

13.10 pH INDICATORS
An indicator is a substance which indicates the completion of a reaction
by sharp colour change at the end point without taking part in the reaction.
The substances which are used to indicate the end point in acid-base reactions
are called as acid-base indicators. (e.g.,) phenolphthalein and methyl orange.
Those substances which change to specific colours in different pH range
values of the medium are called as pH indicators. Incidentally pH indicators
are used as acid-base indicators also.

Selection of pH indicators
Every pH indicator changes its colour specifically in a ranging pH which
is called as indicator range. For some of the indicators, the indicator ranges
are given as below.
Colour of the indicator
Indicator pH range Acidic solution Basic solution

Methyl orange 3.1 - 4.4 Pink Yellow

Methyl red 4.4 - 6.2 Red Yellow
Phenol red 6.8 - 8.4 Yellow Red
Phenolphthalein 8.3 - 10 Colourless Pink

88
 When a base is added to a solution of an acid, the H+ ions will be slowly
neutalised by the OH– ions of the base. Hence, there is a steady decrease in
the H+ ion concentration and pH value increases uniformly. At the end point
there is a steep rise in the pH value. The pH values can be plotted against the
volume of the base added and the curve so obtained is called titration curve.
The titration curves are useful in the choice of a suitable indicator in an acid-
base titration. A suitable indicator in an acid-base titration is one whose
range is well within the sharp rising portion of the titration curve. Thus the
choice of a suitable indicator for any titration depends on the nature of the
acid and base involved and the working range of the indicator.

1. Titration of a strong acid against a strong base :

(Example, HCl vs NaOH)
In this type of titration, the change in the pH value at the end point is
roughly from 4 to 10. Therefore any indicator which changes its colour
within this range may be used as a suitable indicator in the titration of strong
acid against strong base and phenolphthalein can be used as indicators for
this type of titrations.

2. Titration of a weak acid against a strong base :

(Example, Oxalic acid vs NaOH)
There is a little change in the pH value at the end point in this type of
titration. The pH value changes from 6.5 to 10. Thus phenolphthalein is the
suitable indicator for this titration as its working range is 8.3 – 10. Methyl
orange is not a suitable indicator. Since it has a working range below pH 5.

3. Titration of strong acid against weak base :

(Example, HCl vs Na2CO3]
When a strong acid like HCl is titrated against a weak base like Na2CO3,
the pH changes from 3.5 to 7.5 at the end point. The best indicator for this
type of titration is methyl orange which changes its colour within this pH
range.

89
 Volume of base Volume of base Volume of base
(a) strong acid vs (b) weak acid vs (c) strong acid vs
strong base strong base weak base

E-end point

4. Titration of weak acid against weak base :

(Example, CH3COOH vs NH4OH)
In this sypte of titration there is no sharp change in the pH value at the
end point. Therefore, in the titration of a weak acid against a weak base
none of the indicators shown in the table are quite satisfactory.
There are two theories to explain the function of acid-base indicators.

1. Ostwald’s theory
This theory was proposed by Ostwald’s in 1891. It is based on Arrhenius
theory. According to this theory, the acid-base indicator is either a weak
acid or a weak base. They are partially ionised in solution. The ionised and
unionised forms have different colours. The indicator exists predominantly
in one of the two forms depending on the nature of the medium and hence
there is colour change when the nature of the medium changes.
Phenolphthalein is a weak acid and it is partially ionised in solutions.

HPh H+ + Ph–
Unionised form ionised form
(colourless) (pink)

90
 In acidic medium, excess H+ ions are present which suppress the
dissociation of HpH due to common ion effect. Hence the indicator exists
predominantly in unionised form and it is colourless. In alkaline medium,
the OH– ion neutralises H+ ion to form water. Consequently the dissociation
of HpH is favoured and the indicator is predominantly in the ionised form
and it is pink in colour.

Methyl orange is a weak base and its ionisation can be written as

MeOH Me+ + OH–
Unionised form ionised form
(yellow) (pink)
In the presence of a base excess OH– ions suppress the dissociation of
MeOH due to common ion effect. Hence in basic medium, the indicator is
mostly in unionised form which is yellow.

In acidic solution the H+ ions combine with OH– ions to form unionised
water. Hence in acidic solution, the indicator is mostly in ionised form and
has pink colour.

This theory also explains why phenolphthalein is not a suitable indicator

in the titration of a strong acid against a weak base. The reason is the OH–
ions produced by the weak base at the end point is too low to cause the
ionisation of phenolphthalein. Hence, the pink colour does not appear exactly
at the equivalence point. The pink colour appears only after a sufficient
excess of the weak base is added.

For a similar reason, methyl orange is not a suitable indicator in the

titration of a strong base against a weak acid. The weak acid does not furnish
sufficient H+ ions to shift the equilibrium towards the right. A sufficient
excess of the weak acid has to be added to get the colour change.

Quinonoid Theory
According to this theory the colour change of an acid-base indicator
arises as a result of structural change. It is supposed that an indicator exists
as an equilibrium mixture of two tautomeric forms namely, benzenoid and
quinonoid forms.

91
 benzenoid form quinonoid form
One form exists in acidic solution and the other form in basic solution.
At least one of the tautomers is a weak acid or a weak base. The two forms
possess two different colours and as the pH of the solution containing the
indicator is changed, the solution shows a change of colour. The colour
change is due to the fact that one tautomer changes over to the other.
For example, phenolphthalein is tautomeric mixture of the two forms.
O O
|| ||
C C
O O
OH–
C C
H+

OH O–

OH OH

Benzenoid form, colourless, O

exists predominantly in acidic ||
medium C
O–

OH
Quinonoid form, pink,
exists predominant
in basic medium
92
 SELF EVALUATION
(A) Choose the correct answer :
1. The process in which chemical change occurs on passing electricity is
termed as ...............
(a) neutralisation (b) hydrolysis
(c) electrolysis (d) ionisation
2. The laws of electrolysis were enunciated first by ...............
(a) Dalton (b) Faraday (c) Kekule (d) Avogadro
3. When one coulomb of electricity is passed through an electrolytic solution,
the mass deposited on the electrode is equal to ...............
(a) equivalent weight (b) molecular weight
(c) electrochemical equivalent (d) one gram
4. Faraday’s laws of electrolysis are related to ...............
(a) atomic number of the cation (b) atomic number of the anion
(c) equivalent weight of the electrolyte (d) speed of the cation
5. The specific conductance of a 0.01 M solution of KCl is 0.0014
ohm-1 cm-1 at 25oC. Its equivalent conductance is ...............
(a) 14 ohm–1 cm2 eq–1 (b) 140 ohm–1 cm2 eq–1
(c) 1.4 ohm–1 cm2 eq–1 (d) 0.14 ohm–1 cm2 eq–1
6. The equivalent conductivity of CH3COOH at 25oC is 80 ohm-1 cm2
eq-1 and at infinite dilution 400 ohm-1 cm2 eq-1. The degree of dissociation
of CH3COOH is ...............
(a) 1 (b) 0.2 (c) 0.1 (d) 0.3
7. When sodium acetate is added to acetic acid, the degree of ionisation of
acetic acid ...............
(a) increases (b) decreases
(c) does not change (d) becomes zero
8. NH4OH is a weak base because ...............
(a) it has low vapour pressure (b) it is only partially ionised
(c) it is completely ionised (d) it has low density

93
9. Which one of the following formulae represents Ostwald’s dilution law
for a binary electrolyte whose degree of dissociation is α and
concentration C.

(1− α ) C α 2C (1 − α ) C α 2C
(a) K = (b) K = (c) K = (d) K =
α 1− α α2 (1 − α ) C
10. Ostwald’s dilution law is applicable in the case of the solution of ...............
(a) CH3COOH (b) NaCl (c) NaOH (d) H2SO4
11. Which one of the following relationship is correct ?
1
(a) pH = (b) pH = log10 [H+]
[H+ ]
1
(c) log10 pH = [H+] (d) pH = log10
[ H+ ]
12. When 10–6 mole of a monobasic strong acid is dissolved in one litre of
solvent, the pH of the solution is ..............
(a) 6 (b) 7 (c) less than 6 (d) more than 7
13. When pH of a solution is 2, the hydrogen ion concentration in moles
litre-1 is .............
(a) 1 × 10–12 (b) 1 × 10–2 (c) 1 × 10–7 (d) 1 × 10–4
14. The pH of a solution containing 0.1 N NaOH solution is ..........
(a) 1 (b) 10–1 (c) 13 (d) 10–13
15. A solution which is resistant to changes of pH on addition of small
amounts of an acid or a base is known as .............
(a) buffer solution (b) true solution
(c) isohydric solution (d) ideal solution
16. The hydrogen ion concentration of a buffer solution consisting of a
weak acid and its salt is given by .............
[Acid ]
(a) [H+] = Ka (b) [H+] = Ka [Salt]
[Salt ]
[Salt ]
(c) [H+] = Ka [Acid] (d) [H+] = Ka
[ Acid ]
94
17. Indicators used in acid-base titrations are ...........
(a) strong organic acids
(b) strong organic bases
(c) weak organic acids or weak organic bases
(d) non-electrolysis
18. For the titration between oxalic acid and sodium hydroxide, the indicator
used in ...........
(a) potassium permanganate (b) phenolphthalein
(c) litmus (d) methyl orange
(B) Answer in one or two sentences :
1. Differentiate between electrolytic conductor and metallic conductor.
2. Define Faraday.
3. Define electrochemical equivalent.
4. What are insulators. Give examples.
5. State Ostwald’s dilution law.
6. What is common ion effect. Give examples.
7. What is a buffer action ?
8. What are indicators ?
9. Define specific and equivalent conductance. How are they related ?
10. What is Henderson equation ?

(C) Answer not exceeding sixty words :

1. Write an account of the Arrhenius theory of electrolytic dissociation.
2. Explain Faraday’s laws of electrolysis.
3. Explain Ostwald’s dilution law.
4. Explain buffer action with example.
5. Derive Henderson equation.
6. Write notes on (i) Ostwald’s theory of indicators, (ii) Quinonoid theory
of indicators.

95
7. Define molar, equivalent and specific conductance and describe the effect
of dilution.
8. State and explain Kohlrausch’s law.
9. State and explain Debye-Huckel-Onsager equation.

(D) Solve the problems :

1. What is the electrochemical equivalent of a substance when 150 gm of it
is deposited by 10 ampere of current passed for 1 sec ? [Ans. 15.0]
2. The electrochemical equivalent of an electrolyte is 2.35 gm. amp-1
sec-1. Calculate the amount of the substance deposited when 5 ampere is
passed for 10 sec ? [Ans. 117.5 gm]
3. To 1 M solution of AgNO3, 0.75 F quantity of current is passed. What is
the concentration of the electrolyte, AgNO3 remaining in the solution ?
4. 0.5 F of electric current was passed though 5 molar solutions of AgNO3,
CuSO4 and AlCl3 connected in series. Find out the concentration of each
of the electrolyte after the electrolysis ?
[Ans. AgNO3, 4.5 M ; CuSO4 ; 4.75 M ; AlCl3 ; 4.839 M]
5. To one molar solution of a trivalent metal salt, electrolysis was carried
out and 0.667 M was the concentration remaining after electrolysis.
Calculate the quantity of electricity passed. [Ans. 1F]
6. A conductance cell has platinum electrodes, each with 5 cm2 area and
separated by 0.5 cm distance. What is the cell constant?[Ans. 0.1 cm-1]
7. Using a conductivity cell with 0.9 cm-1 cell constant, the conductance
was observed to be 2.5 × 10-3 mho for 0.07 M KCl solution. What is the
specific conductance of the solution ? [Ans. 2.25 × 10–3 mho.cm-1]
8. Specific conductance of 1 M KNO 3 solution is observed to be
5.55 × 10-3 mho.cm-1. What is the equivalent conductance of KNO3
when one litre of the solution is used ?[Ans. 5.55 mho.cm2.gm.equiv-1]
9. Explain why on dilution does the conductivity decrease whereas molar
conductivity increases for an electrolytic solution.

96
10. The equivalent conductances at infinite dilution of HCl, CH3COONa
and NaCl are 426.16, 91.0 and 126.45 ohm-1 cm2 gm.equivalent-1
respectively.. Calculate the λ∞ of acetic acid.
[Ans. 390.71 ohm-1. cm2 gm equiv-1]

SUMMARY :
+ Differences between electronic, electrolytic and semiconductors are
studied. Intrinsic and extrinsic semi conductors are learnt.
+ Arrhenius theory of weak electrolytes and its limitations are known.
+ Onsager’s equation for equivalent conductors of strong electrolytes is
learnt and its dependence with C is studied.
+ Statements of Faraday’s laws of electrolysis and their significances are
studied.
+ Quantitative calculation on amount of electricity and mass deposited at
the electrodes are learnt.
+ Definitions and mathematical expressions of resistance, conductance,
specific, equivalent and molar conductances are learnt and studied.
+ Variations of conductances with dilution for strong and weak electrolytes
are leant and understood.
+ Kohlrausch’s law is defined and studied. It’s significances are also
understood.
+ Buffer action, nature of acidic and basic buffers, Henderson equation are
studied.
+ Use of pH values, indicators with applications of different pH ranges are
studied.

REFERENCES :
(i) Electrochemistry By S. Glasstone Tata McGraw Hill publication.
(ii) Physical Chemistry by S.W. Castellan.
______

97
 14. ELECTROCHEMISTRY - II
LEARNING OBJECTIVES
@ Properties and nature of cells will be understood. The differences between
electrolytic and electrochemical cells will be learnt. Interconversion of
electrical and chemical energy will be emphasized.
@ Metal - metal ion electrode and standard hydrogen electrode construction
and the electrode potential will be learnt. Nernst equation will be learnt.
∆G = – nFE and the interconversion of change in free energy and
electrode potentials will be explained.
@ Construction of cells with specific electrodes and the EMF calculations
will be studied. Daniel cell, and its representation, EMF of cell from
two half cell potentials will also be calculated.
@ Complete electrochemical cell representation and writing oxidation and
reduction half cell reactions will be studied with suitable example.

14.1 CELLS
In electrochemistry, the interconversion of chemical energy and electrical
energy is an important aspect that possesses numerous applications. For
example, batteries supply electrical energy stored in the form of chemical
energy for the operation of torch, radio, calculators etc. Conversely, electrical
energy is used to bring about certain chemical reactions which are industrially
important such as purification of metals like copper, aluminium, generation

98
of gaseous chlorine, oxygen, hydrogen, electroplating, metal coatings etc.
The electrochemical or electrolytic processes are carried out in a device
known as a cell. An electrolytic (or) electrochemical cell consists of two
conducting metal electrodes in contact with an electrolyte solution which
separates them (or) placed separately in compartments containing suitable
electrolytes. The electrolyte may be an aqueous solution containing mostly
the salt of the metal with which the electrode is made of (or) it may be an
ionically conducting solid.
There are two types of cells known as electrolytic cell and electrochemical
cell. Each of them possesses different characteristics and used in different
application.

Generally at the anode oxidation reaction occurs and at the cathode

reduction reaction occurs. When the electrodes are connected externally
through a wire and electrons flow through them, the electrical circuit is said
to be an open circuit. If the electrodes are not connected externally and the
electrons do not flow from one electrode into the other, the electrical circuit
is said to be a closed circuit.
Daniel cell : Daniel cell or a galvanic cell is an example of electrochemical
cell. The overall reaction taking place in the cell is the redox reaction given
as
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)
This overall reaction is made of the summation of two half reactions
such as oxidation half reaction and reduction half reaction.
The oxidation half reaction occurring at the zinc electrode in contact
with the aqueous electrolyte containing Zn2+, accumulates the electrons at
the zinc rod.
Zn(s) Zn2+(aq) + 2e–
The reduction half reaction occurring at the copper electrode in contact
with the aqueous electrolyte containing Cu2+ ions receives the electrons
from the zinc electrode when connected externally, to produce metallic copper
according to the reaction as,
99
 Cu2+ + 2e– Cu(s)
The decrease in the energy which appears as the heat energy when a
zinc rod is directly dipped into the zinc sulphate solution, is converted into
electrical energy when the same reaction takes place indirectly in an
electrochemical cell. The zinc sulphate is placed in the porous pot while
copper sulphate is placed in a glass vessel.
The Daniel cell is also called as the voltaic cell. However for continuous
supply of current for a long period, the two half cells each comprising the
metal electrode and its aqueous electrolyte kept in separate containers and
can be connected externally as below :

Fig. 14.3 A simple voltaic (galvanic) cell

When the cell is set up, electrons flow from zinc electrode through the
wire to the copper cathode. As a result, zinc dissolves in the anode solution
to form Zn2+ ions. The Cu2+ ions in the cathode half cell pick up electrons
and are converted to Cu atoms on the cathode.

Cell Terminology
Before taking up the study of the electrochemical cells, we should be
familiar with a few common terms.
Current is the flow of electrons through a wire or any conductor.

100
 Electrode is the material : a metallic rod/bar/strip which conducts
electrons into and out of a solution.
Anode is the electrode at which oxidation occurs. It sends electrons
into the outer circuit. It has negative charge and is shown as (–) in cell
diagrams.
Cathode is the electrode at which electrons are received from the outer
circuit. It has a positive charge and is known as (+) in the cell diagrams.
Electrolyte is the salt solution in a cell.
Anode compartment is the compartment of the cell in which oxidation
half-reaction occurs. It contains the anode.
Cathode compartment is the compartment of the cell in which reduction
half-reaction occurs. It contains the cathode.
Half-cell. Each half of an electrochemical cell, where oxidation occurs
and the half where reduction occurs, is called the half cell.

Cell diagram or Representation of a Cell

A cell diagram is an abbreviated symbolic depiction of an electrochemical
cell. For this purpose, we will consider that a cell consists of two half-cells.
Each half-cell is again made of a metal electrode in contact with metal ion in
solution.
IUPAC Conventions. In 1953 IUPAC recommended the following
conventions for writing cell diagrams. We will illustrate these with reference
to Zinc-Copper cell.
(1) a single vertical line (|) represents a phase boundary between metal
electrode and ion solution (electrolyte). Thus the two half-cells in a voltaic
cell are indicated as

Phase
Boundary
Zn | Zn2+ Cu2+ | Cu
ANODE HALF-CELL CATHODE HALF-CELL

101
 It may be noted that the metal electrode in anode half-cell is on the left,
while in cathode half-cell it is on the right of the metal ion.
(2) A double vertical line represents the salt bridge, porous partition or
any other means of permitting ion flow while preventing the electrolyte from
mixing.
(3) Anode half-cell is written on the left and cathode half-cell on the
right.
(4) In the complete cell diagram, the two half-cells are separated by a
double vertical line (salt bridge) in between. The zinc-copper cell can now
be written as
Salt
Bridge
Zn | Zn2+ || Cu2+ | Cu
ANODE HALF-CELL CATHODE HALF-CELL
(5) The symbol for an inert electrode, like the platinum electrode is
often enclosed in a bracket. For example,

Inert
Mg | Mg2+ || H+ | H2(Pt) Electrode

ANODE HALF-CELL CATHODE HALF-CELL

(6) The value of emf of a cell is written on the right of the cell diagram.
Thus a zinc-copper cell has emf 1.1 V and is represented as

Zn | ZnSO4 || CuSO4 | Cu E = + 1.1 V

Direction of electron flow
If the emf acts in the opposite direction through the cell circuit it is
denoted as a negative value.

Cu | CuSO4 || ZnSO4 | Zn E = – 1.1 V

Direction of electron flow

The negative sign also indicates that the cell is not feasible in the given
direction and the reaction will take place in the reverse direction only. The

102
overall cell reaction for E = –1.1 V of the daniel cell is
Cu(s) + Zn(aq)2+ Cu(aq)2+ + Zn(s)
The reversal of the cell current is accompanied by the reversal of direction
of the cell reaction. Thus a reversible cell is defined as that operates by
reversal of cell reactions when the direction of flow of current is reversed.
The reversible behaviour operates only for infinitesimal changes in e.m.f. of
the cell on the positive and negative sides from the balance point which
corresponds to the actual emf of the cell.

14.2 SINGLE ELECTRODE POTENTIAL

An electrochemical cell consists of two half-cells. With an open-circuit,
the metal electrode in each half-cell transfers its ions into solution. Thus an
individual electrode develops a potential with respect to the solution. The
potential of a single electrode in a half-cell is called the Single electrode
potential. Thus in Daniel cell in which the electrodes are not connected
externally, the anode Zn/Zn2+ develops a negative charge and the cathode
Cu/Cu2+, a positive charge. The amount of the charge produced on an
individual electrode determines its single electrode potential.
The single electrode potential of a half-cell depends on : (a) concentration
of ions in solution ; (b) tendency to form ions ; and (c) temperature.

Standard emf of a cell

The emf generated by an electrochemical cell is given by the symbol E.
It can be measured with the help of a potentiometer. The value of emf varies
with the concentration of the reactants and products in the cell solutions and
the temperature of the cell. When the emf of a cell is determined under
standard conditions, it is called the standard emf. The standard conditions
are : (a) 1 M solutions of reactants and products ; and (b) temperature of
25o C. Thus standard emf may be defined as the emf of a cell with 1 M
solutions of reactants and products in solution measured at 25o C. Standard
emf of a cell is represented by the symbol Eo. For gases 1 atm. pressure is a
standard condition instead of concentration. For Zn-Cu voltaic cell, the
standard emf, Eo is 1.10V.
Zn | Zn2+(aq, 1M) || Cu2+(aq, 1M) | Cu Eo = 1.10 V

103
Determination of emf of a half-cell
By a single electrode potential, we also mean the emf of an isolated
half-cell or its half-reaction. The emf of a cell that is made of two half-cells
can be determined by connecting them to a voltmeter. However, there is no
way of measuring the emf of a single half-cell directly. The emf of the newly
constructed cell, E is determined with a voltmeter. The emf of the unknown
half-cell Eo can then be calculated from the expression
Emeasured = ER – E L

If the standard half-cell acts as anode, the equation becomes

ER = Emeasured (Q EL = 0)
On the other hand, if standard half-cell is cathode, the equation takes
the form
EL = – Emeasured (Q ER = 0)
The standard hydrogen half-cell or Standard Hydrogen Electrode (SHE),
is selected for coupling with the unknown half-cell. It consists of a platinum
electrode immersed in a 1 M solution of H+ ions maintained at 25oC.
Hydrogen gas at one atmosphere enters the glass hood and bubbles over the
platinum electrode. The hydrogen gas at the platinum electrode passes into
solution, forming H+ ions and electrons.

Fig. 14.4 The standard hydrogen electrode

104
 The emf of the standard hydrogen electrode is arbitrarily assigned the
value of zero volts. So, SHE can be used as a standard for other electrodes.
The half-cell whose potential is desired, is combined with the hydrogen
electrode and the emf of the complete cell determined with a voltmeter. The
emf of the cell is the emf of the half-cell.
For example, it is desired to determine the emf of the zinc electrode,
Zn | Zn2+. It is connected with the SHE. The complete electrochemical cell
may be represented as :

Zn | Zn2+ || H+ | H2 (1 atm), Pt

The emf of the cell has been found to be –0.76 V which is the emf the
zinc half-cell. Similarly, the emf of the copper electrode, Cu2+ | Cu can be
determined by pairing it with the SHE when the electrochemical cell can be
represented as :

Pt, H2 (1 atm) | H+ || Cu2+ | Cu

The emf of this cell has been determined to be 0.34 V which is the emf
of the copper half-cell.
Eocell = EoCu/Cu2+ – EoSHE
= 0.34 – Zero
= 0.34 V
The two situations are explained as follows :
When it is placed on the right-hand side of the zinc electrode, the
hydrogen electrode reaction is
2H+ + 2e– H2
The electrons flow to the SHE and it acts as the cathode.
When the SHE is placed on the left hand side, the electrode reaction is
H2 2H+ + 2e–
The electrons flow to the copper electrode and the hydrogen electrode
105
as the anode. Evidently, the SHE can act both as anode and cathode and,
therefore can be used to determine the emf of any other half-cell electrode
(or single electrode).

According to IUPAC convention, the standard reduction potentials alone

are the standard potentials. The values of the standard potentials at 25oC
(298 K) for some common Reduction Half-reactions are listed in Table below.
Standard Reduction Potentials at 25oC (298K)
Reduction Half - reaction EoV
F2 + 2e– 2F– 2.87
H2O2 + 2H+ + 2e– 2H2O 1.78
PbO2 + SO42– + 4H+ + 2e– PbSO4 + 2H2O 1.69
Au3+ + 3e– Au 1.50
Cl2 + 2e– 2Cl– 1.36
Ag+ + e– Ag(s) 0.80
Cu2+ + 2e– Cu(s) 0.34
2 H+ + 2e– H2(g) 0.00
Pb2+ + 2e– Pb(s) –0.13
Zn2+ + 2e– Zn(s) –0.76

Predicting Cell EMF

The standard emf Eo, of a cell is the standard reduction potential of
right-hand electrode (cathode) minus the standard reduction potential of the
left-hand electrode (anode). That is,
Eocell = Eoright – Eoleft
= Cathode potential – Anode potential
Let us predict the emf of the cell
Zn(s) | Zn2+(aq) || Ag+(aq) | Ag

106
 by using the Eo values from the table.

Eocell = EoR – EoL

= 0.80 – (– 0.763)

= 0.80 + 0.763 = 1.563 V

Predicting Feasibility of Reaction

The feasibility of a redox reaction can be predicted with the help of the
electrochemical series. The net emf of the cell reaction, Ecell, can be calculated
from the expression
Eocell = Eocathode – Eoanode
In general, if Eocell = + ve, the reaction is feasible
Eocell = –ve, the reaction is not feasible.
Example 1 : Predict whether the reaction
2Ag(s) + Zn2+(aq) 2Ag+(aq) + Zn(s)
is feasible or not.
Solution : The cell half reactions are
Anode : 2Ag(s) 2Ag+(aq) + 2e– Eo = 0.80 V
Cathode : Zn2+(aq) + 2e– Zn(s) Eo = –0.763 V
Eocell = Eocathode – Eoanode
Eocell = –0.763 V – 0.80 V
= –1.563 V
Since Eocell is negative, the given reaction is not feasible.
Example 2 : Determine the feasibility of the reaction
2Al(s) + 3Sn4+(aq) 2Al3+ + 3Sn2+(aq)
Solution : The given reaction consists of the following half reactions

107
 Anode : 2Al(g) 2Al3+ + 6e–
Cathode : 3Sn4+ + 6e– 3Sn2+ Eo = –1.66 V
Eocell = 0.15 – (– 1.66) Eo = + 0.15 V
= 1.81 V
Since Eocell is positive, the reaction is feasible.
Metal displacement : (Predicting whether a metal will displace
another metal from its salt solution or not).
As already shown, the metals near the bottom of the electrochemical
series are strong reducing agents and are themselves oxidised to metal ions.
On the contrary, the metal lying higher up in the series are strong oxidising
agents and their ions are readily reduced to the metal itself. For example,
zinc lying down below the series is oxidised to Zn2+ ion, while copper which
is higher up in the series is produced by reduction of Cu2+ ion.
Zn Zn2+ + 2e–
Cu2+ + 2e– Cu ↓
Thus when zinc is placed in CuSO4 solution, Cu metal gets precipitated.
In general we can say that a metal lower down the electrochemical series
can precipitate the one higher up in the series.
Silver cannot precipitate Cu from CuSO4 solution, since both metals
have positions higher up in the series and are strong oxidising agents.
Hydrogen displacement : (Predicting whether a metal will displace
hydrogen from a dilute acid solution.)
Any metal above hydrogen in the electrochemical series is a weaker
reducing agent than hydrogen and will not convert H+ to H2. This explains
why Zn lying below hydrogen reacts with dil. H2SO4 to liberate H2, while
Cu lying above hydrogen does not react.
Zn + 2H+ (dil.H2SO4) Zn2+ + H2↑
Cu + 2H+ (dil. H2SO4) Cu2+ + H2

108
 Example 1 : Calculate the standard e.m.f. of the cell : Cd, Cd2+ || Cu2+,
Cu and determine the cell reaction. The standard reduction potentials of
Cu2+, Cu and Cd2+, Cd are 0.34V and –0.40 volts respectively. Predict the
feasibility of the cell reaction.
Eocell = Standard EMF of the cell
= Eoright – Eoleft
= [Std. reduction potential of Cu2+, Cu]
– [Std. reduction potentials of Cd2+, Cd]
= EoCu2+,Cu – EoCd2+,Cd
= 0.34 V – (– 0.4 V)
= + 0.74 Volts.
Left hand electrode (oxidation half cell) reaction is
Cd(s) Cd2+ + 2e
Right hand electrode (reduction half cell) reaction is
Cu2+ + 2e Cu(s)
The cell reaction is
Cd(s) + Cu2+(aq) Cd2+(aq) + Cu(s)
Eocell is positive. ∴ The cell reaction is feasible.
Example 2 : Determine the standard emf of the cell and predict its
feasibility.
Ag, Ag+ || H+, H2(g)1atm, Pt.
The standard reduction potential of Ag+, Ag is 0.80 volts.
The right hand side electrode is SHE.
∴ Eocell = EoRight – EoLeft
Eocell = [Std. reduction potential of SHE]
– [Std. reduction potential of Ag+, Ag]
= 0 – (+ 0.8 V) = – 0.8 Volts.
Since Eocell is negative, the cell reaction is not feasible.

109
Relation between EMF and free energy
When a cell produces a current, the current can be used to do work - to
run a motor, for instance. Thermodynamic principles can be employed to
derive a relation between electrical energy and the maximum amount of
work, Wmax, obtainable from the cell. The maximum amount of work
obtainable from the cell is the product of charge flowing per mole and
maximum potential difference, E, through which the charge is transferred.
Wmax = – n FE ... (1)
where n is the number of moles of electrons transferred and is equal to
the valence of the ion participating in the cell reaction. F stands for Faraday
and is equal to 96,495 coulombs and E is the emf of the cell.
According to thermodynamics, the maximum work that can be derived
from a chemical reaction is equal to the free energy (∆G) for the reaction,
Wmax = ∆G ... (2)
Therefore, from (1) and (2), we can write
∆G = – n FE ... (3)
Thus only when E has a positive value, ∆G value will be negative and
the cell reaction will be spontaneous and the e.m.f. of the cell can be measured.

Here E refers to the Ecell.

Thus, the electrical energy supplied by the cell is (nFE) equal to the free
energy decrease (–∆G) of the cell reaction occurring in the cell.

Example : Determine the standard emf of the cell and standard free
energy change of the cell reaction.

Zn, Zn2+ || Ni2+, Ni. The standard reduction potentials of Zn2+, Zn and
Ni2+, Ni half cells are – 0.76 V and – 0.25 V respectively.

Eocell = EoR – EoL = – 0.25 – (– 0.76)

= + 0.51 V Eocell is + ve. ∴ ∆Go = – ve.

110
 ∴ ∆Go = – n FEocell

n = 2 electrons

∴ ∆Go = –2 × 96495 × 0.51 = –97460 Joules = – 97.46 kJ.

Thermodynamics of a reversible cell

Nernst equation : Suppose the reaction occurring in a reversible cell is
represented by the equation
A + B C + D

The decrease in free energy, – ∆G, accompanying the process is given

by the well known thermodynamic equation
– ∆G = – ∆Go – RT ln J
where – ∆Go is the decrease in free energy accompanying the same
process when all the reactants and products are in their standard states of
unit activity and J stands for the reaction quotient of the activities of the
products and reactants at any given stage of the reaction.
Substituting the value of J, we have
aC × aD
– ∆G = – ∆Go – RT ln a × a
A B

If E is the E.M.F. of the cell in volts and the cell reaction involves the
passage of ‘n’ faradays (i.e.,) nF coulombs, the electrical work done by the
cell is in nFE volt-coulombs or Joules. Hence free energy decrease of the
system, –∆G, is given by the expression
– ∆G = nFE
aC × aD
nFE = – ∆Go – RT ln a × a
A B

aC × aD
= nFEo – RT ln a × a
A B

RT aC × aD
E = Eo – ln a × a
nF A B

111
where Eo is the E.M.F. of the cell in which the activity, or as an approximation,
the concentration of each reactant and each product of the cell reaction is
equal to unity. Eo is known as the standard E.M.F. of the cell.

RT aC × aD
E = Eo – ln a × a is often referred to as the Nernst equation
nF A B

Replacing activities by concentrations, as an approximation, the Nernst

equation may be written as

RT [C] [D]
E = Eo – ln [A][B]
nF

where the quantities in parantheses represent the concentration of the species

involved. Replacing [C] [D]/[A] [B] as equal to K, the equilibrium constant
in the molar concentration units,

RT
E = Eo – ln K.
nF
This equation is known as Nernst equation.

RT
E = Eo – 2.303 log K,
nF
where Eo = standard electrode potential
R = gas constant
T = Kelvin temperature
n = number of electrons transferred in the half-reaction
F = Faraday of electricity
K = equilibrium constant for the half-cell reaction as in
equilibrium law.

Calculation of Half-cell potential

For an oxidation half-cell reaction when the metal electrode M gives
Mn+ ion,
M Mn+ + ne– ...(1)
112
 the Nernst equation takes the form

2. 303 RT [M n+ ]
E = Eo – log ... (2)
nF [M]

The activity of solid metal [M] is equal to unity. Therefore, the Nernst
equation can be written as

2. 303 RT
E = Eo – log [Mn+]... (3)
nF
Substituting the values of R, F and T at 25oC, the quantity 2.303 RT/F
comes to be 0.0591. Thus the Nernst equation (3) can be written in its
simplified form as

0. 0591
E = Eo – log [Mn+] ... (4)
n
This is the equation for a half-cell in which oxidation occurs. In case it is
a reduction, the sign of E will have to be reversed.
Example 1 : What is the potential of a half-cell consisting of zinc
electrode in 0.01 M ZnSO4 solution 25oC. Eo = 0.763 V.
Solution : The half-cell reaction is
Zn Zn2+ + 2e–
The Nernst equation for the oxidation half-cell reaction is

0. 0591
E = Eo – log [Zn2+]
n

The number of electrons transferred n = 2 and Eo = 0.763 V.

Substituting these values in the Nernst equation we have

0. 0591
E = 0.763 – (–2)
2

= 0.763 + 0.0591 = 0.8221 V

113
 Calculation of Cell potential
The Nernst equation is applicable to cell potentials as well. Thus,
0. 0591
Ecell = Eocell – log K
n
K is the equilibrium constant of the redox cell reaction.
Example 2 : Calculate the emf of the cell.
Zn | Zn2+ (0.001 M) || Ag+ (0.1 M) | Ag
The standard potential of Ag/Ag+ half-cell is + 0.80 V and Zn/Zn2+ is
–0.76 V.
Solution :
Step 1 : Write the half-cell reactions of the anode and the cathode.
Then add the anode and cathode half reactions to obtain the cell reaction
and the value of Eocell.
Cathode : 2Ag+ + 2e– 2Ag Eo = + 0.80
Anode : Zn Zn2+ + 2e– Eo = –0.76 V

Cell : Zn + 2Ag+ Zn2+ + 2Ag Eo = 1.56 V

[Zn2 + ]
Step 2. K for the cell reaction =
[Ag + ]2
Substituting the given values in the Nernst equation and solving for
Ecell, we have
0. 0591
Ecell = Eocell – log K
n
0. 0591 [Zn2 + ]
= 1.56 – log
2 [Ag + ]2

0. 0591 [10−3 ]
= 1.56 – log
2 [10−1 ]2
= 1.56 – 0.02955 (log 10-1)
= 1.56 + 0.02955
= 1.58955 V

114
Calculation of Equilibrium constant for the cell reaction
The Nernst equation for a cell is

0. 0591
Ecell = Eocell – log K
n

n Eocell
or log K =
0. 0591
Example 3 : Calculate the equilibrium constant for the reaction between
silver nitrate and metallic zinc.
Solution :
Step 1 : Write the equation for the reaction

2Ag+ + Zn Zn2+ + 2Ag Eocell = 1.56 V

Step 2 : Substitute values in the Nernst equation at equilibrium

n Eocell
log K =
0. 0591
0 = 2 × 1.56 – 0.03 log K

– 1.56 × 2 = – 0.03 log K

−1.56 × 2
log K = = 52.79
−0. 03

K = 6.19 × 1052

Example 4 : Calculate the E.M.F. of the zinc - silver cell at 25oC when
[Zn2+] = 0.10 M and [Ag+] = 10 M. (Eo cell at 25oC = 1.56 volt]
Solution : The cell reaction in the zinc - silver cell would be

2Ag+ + Zn 2Ag + Zn2+

The Nernst equation for the above all reaction may be written as :

115
 RT [Ag]2 [Zn2 + ]
Ecell = Eocell – ln
nF [Ag + ]2 [Zn]

(since concentrations of solids are taken as unity)

[Zn2 + ]
= Eo cell – ln [Ag + ]2

Substituting the various values in Nernst equation, we have

2. 303 × 8. 314 × 298 0.1

Ecell = 1.56 – 2 × 96495
log
(10)2
= 1.648 volts.
Example 5 : Write the cell reactions for the following cells.

(i) Zn | ZnO22–, OH– | HgO | Hg

(ii) Pb | PbSO4 | H2SO4 | PbSO4 | PbO2 | Pt

(iii) Pt | H2 | HCl | Hg2Cl2 | Hg | Pt

Solution : (i) The electrode reactions are
Zn(s) + 4OH– + 2e– ZnO22– + 2H2O
HgO(s) + H2O + 2e– Hg(s) + 2OH–
Cell reaction is
Zn(s) + HgO(s) + 2OH– ZnO22– + Hg(s) + H2O

(ii) The electrode reactions are

Pb(s) + SO42– PbSO4(s) + 2e–
PbO2(s) + SO42– + 4H+ + 2e– PbSO4(s) + 2H2O

Cell reaction is
Pb(s) + PbO2(s) + 4H+ + 2SO42– 2PbSO4(s) + 2H2O

116
(iii) The electrode reactions are
2H+ + 2e– H2(g)
Hg2Cl2(s) + 2e– 2Hg(l) + 2Cl–
The cell reaction is
Hg2Cl2(s) + H2 2Hg(l) + 2H+ + 2Cl–
Example 6 : Calculate the potential of the following cell at 298 K
Zn/Zn2+ (a = 0.1) // Cu2+ (a = 0.01) / Cu
EoZn2+ / Zn = – 0.762 V
EoCu2+ / Cu = + 0.337 V
Compare the free energy change for this cell with the free enegy of the
cell in the standard state.
Solution : The overall cell reaction is
Zn + Cu2+ (a = 0.01) Zn2+ (a = 0.1) + Cu
The cell potential given by nernst equation

RT aZn 2 + aCu
Ecell = Eocell – ln
2F aZn aCu2 +

RT aZn 2+
= Eocell – ln a 2+
2F Cu
(Since activity of a pure metal is unity)
Eocell = 0.337 – (– 0.762) = 1.099 V
0. 0591 0.1
Ecell = 1.099 – 2 log 0. 01

0. 0591
= 1.099 – 2 log 10

= 1.099 – 0.02956
= 1.0694 V
117
 The free energy change ∆G is given by ∆G = – nFE
∆G = – (2 equi/mol) (1.0694 V) (96495 coulombs equiv–1)
= – 206.4 kJ mol–1
The standard free energy change :
∆Go = – (2 equi/mol) (1.099V) (96495 coulomb/equiv)
= –212.1 kJ/mol.
Example 7 : Calculate the standard e.m.f. of the reaction
Fe3+ + 3e– Fe(s). Given the e.m.f. values of
Fe3+ + e Fe2+ and Fe2+ + 2e Fe(s) as + 0.771V and –
0.44 V respectively.
Solution : Let E1 = 0.771V for Fe3+ + e Fe2+
E2 = – 0.44V for Fe2+ + 2e Fe(s)
then E1 + E2 = 0.331 V and this e.m.f. corresponds to
Fe3+ + 3e Fe(s).
Example 8 : The standard electrode potentials of the half cells Ag+ / Ag
and Fe3+, Fe2+ / Pt are 0.7991 V and 0.771 V respectively. Calculate the
equilibrium constant of the reaction :

Ag(s) + Fe3+ Ag+ + Fe2+

Solution : The cell formed is Ag / Ag+ ; Fe3+, Fe2+ / Pt

At anode : Ag(s) Ag+ + e
At cathode : Fe3+ + e Fe2+
Overall reaction : Ag(s) + Fe3+ Fe2+ + Ag+
emf of the cell is given by (ER – EL)
Eocell = 0.771 – 0.7991 = – 0.0281 V

RT aAg + aFe 2+
At equilibrium, Ecell = Eocell – n F ln aFe 3+

118
 Since activity of solid silver is 1.0.
aAg + aFe 2+
∴ n = 1 and Keq = aFe 3+

0. 0591
∴ Eocell = n log Keq

0. 0281× 1
∴ log Keq = 0. 0591 = 0.4751

∴ Keq = 0.335

SELF EVALUATION
(A) Choose the correct answer :
1. The potential of a single electrode is a half cell is called the
(a) Reduction potential (b) Half-wave potential
(c) Single electrode potential (d) cell potential
2. The relationship between free energy change and e.m.f. of a cell is
(a) ∆G = –nFE (b) ∆H = –nFE (c) ∆E = nFG (d) ∆F = nEG
3. The feasibility of a redox reaction can be predicted with the help of
(a) Electronegativity (b) Electrochemical series
(c) Electron affinity (d) Equivalent conductance
4. The metals near the bottom of the electrochemical series are
(a) strong reducing agents (b) strong oxidising agents
(c) weak reducing agents (d) weak oxidising agents
5. The emf of a cell with 1 M solutions of reactants and products in solution
at 25o C is called
(a) Half cell potential (b) Standard emf
(c) Single electrode potential (d) Redox potential
6. The relationship between equilibrium constant and standard emf of a
cell is
(a) Eo = 0.0591 log K (b) 0.0591 E o = log K
o
(c) nE = 0.0951 log K (d) nEo = 0.0591 log K

119
(B) Answer in one or two sentences :
1. The standard reduction potentials of Fe3+/Fe and Fe2+/Fe electrode
systems are –0.035 V and –0.44V respectively. Predict which of the two
oxidations is easy : Fe3+/Fe and Fe2+/Fe. [Ans. Fe2+/Fe]
2. What are the types of changes in the cathode and anode in electrolytic
and electrochemical cells.
3. Write the electrochemical cell for the overall cell reaction
Zn(s) + 2AgNO3 2Ag(s) + Zn(NO3)2.
4. The standard reduction potential of Fe3+, Fe2+/Pt is + 0.771V. This half
cell is connected with another half cell such that e.m.f. of the cell is
0.771V. What is the other half cell ? [Ans. SHE]
5. Write the cell reaction for the half cell Cl–(aq) / AgCl(s) Ag.
[Ans. AgCl(s) + e– Ag(s) + Cl–]
6. What are two types of cells ?
7. What is single electrode potential ?
8. Define standard emf of a cell.
9. How to predict the feasibility of a cell reaction ?
10. Write the Nernst equation.

(C) Answer not exceeding sixty words :

1. Write the differences between electrolytic and electrochemical cells.
2. How emf of a cell is determined ?
(D) Solve the problems :
1. The standard reduction potential for the reaction Sn4+ + 2e Sn2+
is + 0.15 V. Calculate the free energy change of the reaction.
[Ans. 28.95 kJ]
2. Write the Nernst equation for the half cell Zn2+(aq) / Zn(s).

[Ans. E Zn2+ / Zn = E Zn2+ /Zn – RT ln [Zn2+]

o
2F

120
3. The emf of the cell : Cd/CdCl2 . 25H2O / AgCl(s) Ag is 0.675 V. Calculate
∆G of the cell reaction. [Ans. n = 2 ; ∆G = –130.335 kJ]
4. The standard free energy change of the reaction M +(aq) + e M(s)
is –23.125 kJ. Calculate the standard emf of the half cell.
[Ans. Eo = + 0.25 V]
5. The emf of the half cell Cu2+(aq)/Cu(s) containing 0.01 M Cu2+ solution is
+ 0.301 V. Calculate the standard emf of the half cell.
[Ans. n = 2, EoCu2+/Cu = 0.359 V]
0. 0591 1
[Hint : ECu2+/Cu = EoCu2+/Cu– log ]
2 [Cu2+ ]
6. If E1 = 0.5 V corresponds to Cr3+ + 3e– Cr(s) and E2 = 0.41 V
3+
corresponds to Cr + e 2+
Cr reactions, calculate the emf
2+
(E3) of the reaction Cr + 2e Cr(s) [Ans. 0.955V]
3E1 − E2
[Hint : E3 = ]
2
7. Calculate the standard emf of the cell having the standard free energy
change of the cell reaction is –64.84 kJ for 2 electrons transfer.
[Ans. Eo = 0.336 V]
8. Calculate the emf of the cell Zn/ZnO2–, OH–(aq), HgO/Hg given that Eo
values of OH–, ZnO2– / Zn and OH–, HgO/Hg half cells are –1.216 V
and 0.098 V respectively.
[Hint : Eo = EoR – EoL ; Eo = 1.314V]
9. The equilibrium constant of cell reaction :
Ag(s) + Fe3+ Fe2+ + Ag+ is 0.335, at 25oC. Calculate the standard
emf of the cell Ag/Ag+ ; Fe3+, Fe2+ / Pt. Calculate Eo of half cell Fe 3+,
Fe2+/Pt if Eo of half cell Ag+/Ag is 0.7991V. Calculate Eo of Fe3+, Fe2+/
Pt half cell. [Ans. EoFe3+/Fe2+ = 0.771V]
10. Calculate the emf of the cell having the cell reaction
2Ag+ + Zn 2Ag + Zn2+ and Eocell = 1.56 V at 25oC when
concentration of Zn2+ = 0.1 M and Ag+ = 10 M in the solution.
RT [Zn2 + ]
[Hint : Ecell = Eocell – n F ln [Ans. 1.648 V]
[Ag + ]2

121
11. The emf values of the cell reactions Fe3+ + e– Fe2+ and
Ce2+ Ce3+ + e– are 0.61V and –0.85 V respectively. Construct
the cell such that the free energy change of the cell is negative. Calculate
the emf of the cell. [Ans. Ecell = 0.24 V]
12. A zinc rod is placed in 0.095 M zinc chloride solution at 25oC. emf of
this half cell is –0.79V. Calculate Eo Zn2+ /Zn . [Ans. –0.76 V]

SUMMARY :
The interconversion of chemical energy and electrical energy is an
important aspect that possesses numerical applications. The differences
between electrolytic and electrochemical cells are discussed. Standard
hydrogen electrode construction and its electrode potential is given. The
relationship between free energy change and emf of a cell is obtained. IUPAC
convention for representation of a cell is discussed.

REFERENCES :
1. Electrochemistry for chemists by S. Glasstone, TMH publications.
2. Physical Chemistry by G.M. Barrow E.E.C. Publications
3. Physical Chemistry by P.W. Atkins, Oxford University Press.
_____

122
 15. ISOMERISM IN ORGANIC CHEMISTRY
15.1 ISOMERISM
Isomers are compounds having same molecular formula but differ in
physical or chemical or both physical and chemical properties. This
phenomenon is known as isomerism.
Isomerism is of two types - (i) Structural isomerism (ii) Stereoisomerism.
Structural isomerism arises out of the difference in the arrangement of
atoms in a molecule, (without referring to space), type of linkage and the
atoms which are linked to each other in the moelcule. Stereoisomerism arises
out of the difference in the arrangement of atoms in the molecule, with
reference to each other in space.
Stereoisomers (have the same structure) differ in the way the atoms are
oriented in space. They have the same structure and hence do not differ
much in properties.
There are two types of Stereoisomerism. They are (i) Geometrical
isomerism and (ii) Optical isomerism.

(i) Geometrical Isomerism :

Isomerism that arises out of difference in the spatial arrangement of
atoms or groups about the doubly bonded carbon atoms is called Geometrical
isomerism. These isomers are not mirror images of each other. Rotation
about C=C is not possible at normal conditions and hence the isomers are
isolable.
If different atoms or groups are bonded to the ‘C=C’ bond in a molecule,
more than one spatial arrangement is possible. For example, 2-butene exists
in two isomeric forms.

H CH3 H CH3
C C

C C
H I CH3 H3C II H
Cis isomer Trans isomer

123
 The isomer in which similar groups lie on the same side is called ‘cis
isomer’ (I). The other in which similar groups lie in opposite direction is
called ‘Trans isomer’ (II). This isomerism is called ‘Cis-Trans’ isomerism.
The two groups attached to the carbon atoms need not be same, it may
be different also. e.g.,

2-pentene H CH2CH3 H CH2CH3

C C

C C
H CH3 H3C H
Cis Trans
This isomerism arises out of the hindrance to rotation about the C=C
bond in such molecules.
The cis-trans isomers do not differ much in chemical properties. They
differ in physical properties like boiling point, melting point, crystal structure,
solubility and refractive index. Highly substituted olefin is more stable than
less substituted olefin. Among substituted olefins, trans olefin is more stable
than cis olefin. In the cis isomer because similar groups are very near each
other, Vander Waals repulsion and steric hindrance make the molecule much
unstable. In the trans isomer, similar groups are diagonally opposite to each
other. Hence there is no such steric interaction. Generally trans isomer is
more stable than cis isomer. Hence reactivity of cis isomer may be little
higher than the trans isomer. The energy of the cis isomer is greater than that
of trans isomer.
Though at room temperature, cis and trans isomers are stable and are
not interconvertible, on heating to a certain temperature, trans isomer can
be converted to cis isomer and vice-versa. ‘Breaking of carbon-carbon
π-bond and its reformation is responsible for the interconversion.’
∆
Trans isomer Cis isomer
Consider unsaturated dicarboxylic acid - Maleic acid and Fumaric acid.
These are geometrical isomers.

124
 H COOH H COOH
C C

C C
H COOH HOOC H
Cis Trans
[Maleic acid] [Fumaric acid]
‘Cis-trans’ system of nomenclature may not be suitable for many
substituted olefins.
For example,
H3C H
C

C
H3CCH2 CH3

A newer system based on the priority of groups is the Cahn-Ingold-

Prelog convention. This system is called the (E-Z) system, applies to alkene
diastereomers of all type. If the two groups of higher priority are on the
same side of the double bond, the alkene is designated ‘Z’ (from the German
word Zusammen-meaning together). If the two groups of high priority are
on opposite sides of the double bond, the alkene is designated ‘E’ (from the
German, entgegen, meaning opposite)
The priorities follow the order of decreasing atomic number of the atom
directly bonded to the carbon.
For some compounds the priority is shown by numbers as
1 2 1 2
H3C H H3C H
C C
Z-isomer E-isomer
C C
H3CCH2 CH3 H3CCH2 CH2CH2CH3
1 2 2 1

125
 1 2 2 1
H3C H H3C Cl
C C

C E-isomer C Z-isomer
F Cl H CH2CH3
2 1 2 1

Dipolemoment studies is one of the best methods of identifying cis-

trans isomers. Generally cis isomers have larger dipolemoment than trans
isomers. Often DPM of trans isomer is zero. e.g., Trans 2-butene and Trans
2,3-dibromo-2-butene. (Refer Chapter on disubstituted benzene)

1,3 - butadiene
CH2=CH–CH=CH2
This molecule can exist in two forms.
CH2 = CH CH2 = CH
| |
CH = CH2 and CH2 = CH
I II
Though these two forms do not differ very much in their energy and
stability, the (I) form, which is similar to ‘trans’ is more stable than (II) form
which is similar to ‘cis’. These two forms do not arise out of the hindrance
to rotation about C=C, instead the restricted rotation about C–C. In order
to indicate that, this cis-trans isomerism is due to restricted rotation about
C–C bond, they are named as,

S-trans S-cis
These are easily interconvertible and exist in equilibrium.

126
 S-trans form is also called ‘transoid form’
S-cis form is also called ‘cisoid form’.
The energy of S-trans form is 3 Kcals less than the S-cis form.
These two forms differ in chemical reactivity. Very often they give
different products in reactions.

Conformation in cyclic systems :

The different forms that arises out of the rotation about C–C single
bond are called conformers. Free rotation about C–C single bond is not
always possible. Very often the rotation is restricted depending upon the
nature and the size of atoms or groups bonded to each carbon atom. The
different conformers differ in energy though not appreciably.
Restriction to free rotation about C–C single bond is much pronounced
in cyclic systems. In these cases, the restriction to rotation is so appreciable
as to make the different forms isolable or identifiable.
Thus cyclopropane is flat, cyclobutane can form butterfly shape while
cyclopentane can form an open-envelope shape.
H H H
H H H
H
H
H H
H H H H
H H H H
H
H H

H H
H
Cyclopropane Cyclo butane Cyclo pentane
[Planar conformation] [non planar conformation] [non planar conformation]

Cyclohexane :
As early as 1890, Sachse suggested that cyclohexane ring exists in two
non planar forms (i.e.,) boat and chair conformations. The energy difference
between these two forms was found to be only 6.5 K.cal/mole by Pitzer. The
energy difference is small enough for interconversion to take place.
127
 Both the boat form and chair form are free of angle strain called Baeyer’s
strain (i.e., the valence bond angle is 109o28']
a
f s

x x

Chair conformation Boat conformation

a = axial, e = equatorial f = flagpole, s = bowspirit,
x-x = pair of eclipsing hydrogen atoms

Chair conformation :
There are two types of C–H bonds.
Types of C–H bonds

Axial Equatorial
[Six C–H bonds parallel [Six C–H bonds subtending
to the axis of the an angle of about 70o
molecule] and 110o with the axis

3-axial bonds 3-axial bonds 3-equatorial 3-equatorial

facing upward facing downward bonds facing bonds facing
β-axial α-axial upward downward
β-equatorial α-equatorial
Every pair of carbon atoms (Two carbon atoms directly bonded to each
other) in chair form exists in skew form.
Boat conformation
This form has two pairs of carbon atoms with eclipsing bonds. This
eclipsing interaction destabilies boat form.
Though the chair form is stable, it is sufficiently flexible to turn itself
upside down called ring flipping so that all bonds which are axial originally
become equatorial and vice versa.
128
 R
R
H
R
H

H
There exists an equilibrium between these two chair forms with boat
form as intermediate.
A mono substituted cyclohexane like cyclohexanol exists in the two
chair forms. These two forms are interconvertible and exist in equilibrium.

OH

OH
I II
In one form (I) the –OH group is axially oriented. In the other form (II)
the –OH group is equatorially oriented. The energy of the axial conformer is
little higher than that of the equatorial conformer. Because the axial
substituent experiences steric interaction with the axial H-atoms present at
the third carbon atoms. This decreases the stability of the axial conformer.
This is called 1 : 3-diaxial interaction. This interaction is absent in the
equatorial conformer. Hence equatorial cyclohexanol is present to an extent
of about 90% in the equilibrium mixture. The axial isomer is present only to
10%.
Energy level diagram for axial and equatorial alcohols

E
Boat

11 KCals

Axial

0.7 KCal Equatorial

129
Optical activity and optical isomerism :
Light is propagated in the form of waves. Ordinary monochromatic light
is supposed to consist of waves vibrating in all planes. If such a light is
passed through a Nicol prism, the emergent light is found to consist of waves
vibrating in only one plane. Such a light is called plane polarised light.

Ordinary light with Nicol Emergent light consisting

waves vibrating in prism of wave vibrating in
all planes. only one plane
[plane polarised light]
When the plane polarised light is passed through certain substances or
solutions (such as lactic acid), the emergent light is found to be vibrating in
a different plane. This is called optical rotation.

or

p-p light Sample Clockwise Anti-Clockwise

direction direction
Such substances are called optically active substances. This property of
such substances is called ‘Optical activity’.
If the rotation is towards the right side [clockwise] it is called dextro-
rotation and the substance is said to be dextrorotatory. Dextrorotation is
indicated by the symbol (+) or ‘d’.
If the rotation is towards the left side [Anticlockwise] it is called laevo-
rotation and the substance is said to be laevo rotatory. Laevorotation is
indicated by the symbol (–) or ‘l’.
130
Conditions of optical activity :
Not all substances are optically active. For example substances like
CHCl3, CH3CH2OH, CH3CH2CH=CH2, CH3CH2COCH3 are not optically
active. On the other hand substances like CHIBrCl, CH3CHBr–CH=CH2,
CH3CH(OH)COCH3, CH3CHDOH are found to be optically active.
When the structures of the compounds which are optically inactive and
optically active, are compared, one thing is clear. All the optically active
compounds, mentioned above have atleast one carbon atom that is bonded
to four different atoms or groups.
A carbon atom attached to four different atoms or groups is called
‘‘asymmetric carbon atom’’.
Pasteur suggested that optical activity arises from molecular dissymmetry
which is supported by Vant-Hoff and LeBel. According to them, a carbon
atom has its four valencies directed towards the four corners of a regular
tetrahedron. In this situation a molecule with an ‘asymmetric carbon atom’
becomes asymmetric.
It so happens that an asymmetric molecule is not superimposable on its
mirror image. That means an optically active molecule has more than [atleast
two] one configuration. [configuration refer to three dimensional arrangement
of atoms in a molecule] that is, an optically active molecule exhibits isomerism
which is called optical isomerism.
Consider ethanol and deuterated ethanol
CH3CH2OH CH3CHDOH
CH3 CH3 CH3

C H C C H
H OH OH OH
H D D
(ethanol-symmetric (deuterated ethanol-
molecule) asymmetric and
non-superimposable)
The isomers-called optical isomers have configurations which are non
super imposable.
131
 Hence the criteria for a molecule to be asymmetric (hence optically active)
is that its configuration is non superimposable on its mirror image. Such
molecules are also called ‘chiral’ molecules.
‘Chirality’ is ‘the essential and the sufficient’ condition for a molecule
to be optically active.
Chirality means handedness or non superimposability. Right hand and
left hand, Right leg shoe and left leg shoe are examples of objects having
handedness or the property of chirality and non superimposability.
The molecules which are optically inactive are ‘achiral’.
Simple optically active molecules like lactic acid, are said to have ‘‘chiral
carbon’’ or ‘‘chiral center’’.
CH3
e.g.,

H C*
COOH
HO
The carbon with ‘‘astreik’’ is called the chiral carbon.
All the α-amino acids (except glycine) have chiral centres (chiral carbon)
and are optically active.
CH3 CH3
R

H C* H OH HO H

H2N COOH

COOH COOH
α-amino acid
d,l pair of lactic acid

Optical isomers :
Chiral molecules can have two different configurations. Each
configuration stands for one optical isomer. Thus dextrorotatory isomer has
configuration which is the mirror image of the laevorotatory isomer. Such
optical isomers which differ only in the sign of (or direction of) optical rotation
are called ‘‘enantiomers’’.
132
 When equal amounts of d-isomer and l-isomer are mixed one gets a
‘‘racemic mixture’’ and this process is called racemisation. A racemic mixture
becomes optically inactive. Because, in this mixture rotation towards
clockwise direction by the dextro isomers is compensated by the rotation
towards the anticlockwise direction by the laevo isomers. The optical
inactivity of a racemic mixture is said to be due to ‘external compensation’.
Any how an optically inactive racemic form can be separated into two active
forms. This process of separation is called ‘‘resolution of the racemic
mixture’’.

A molecule with more than one chiral carbon

A molecule can have more than one chiral centres. Correspondingly the
number of isomers is increased. In general for a molecule with n-different
chiral centres, 2n-isomers are possible. A molecule can have more than one
identical asymmetric carbon atoms. (e.g.,) butane -2,3-diol and tartaric acid.
CH3 COOH

H OH H OH

HO H HO H

CH3 COOH
Diol Tartaric acid
In such cases the number of optical isomers is not 22 = 4, it is less than 4
(i.e.,) 3.
Isomerism in Tartaric acid :
Tartaric acid is dihydroxy dioic acid, having two identical chiral carbon
atoms. COOH COOH

H OH HO H

HO H H OH

COOH COOH
(d, l pair of tartaric acid)

133
 The enantiomers of tartaric acid, have the same magnitude but different
sign of optical rotation. They have object-mirror image relationship.
In the d-isomer, each of the two asymmetric carbon atoms rotate the
plane of the polarised light towards right leading to overall dextro rotation.
In the same way in the l - isomer, the overall rotation is laevo.
There is another optical isomer for tartaric acid in which one asymmetric
carbon atom is dextrorotatory and the other laevorotatory-both rotating to
the same extent in opposite directions. The net result is, that this isomer
becomes optically inactive and is called the ‘‘Meso’’ isomer.
COOH

H OH

H OH

COOH
Though the Meso isomer has two asymmetric carbon atoms the
configuration of one carbon is the mirror image of the other, the net result
being the molecule as a whole becomes symmetric. This molecule is said to
have a symmetric plane, which divides the molecule into two equal halves.
The molecule becomes ‘‘achiral’’. It has configuration which is super-
imposable on its mirror image.
The optical inactivity of the ‘Meso’ isomer is due to the internal
compensation. It is due to the inherent symmetry in the molecule. Mesoform
cannot be separated into optically active enantiomeric pairs. This form is a
single substance and not a mixture.
Racemic form Meso form
1. It is a mixture that can be It is a single compound and
separated into two optically hence cannot be separated.
active forms.
2. Optically inactive due to Optically inactive due to
external compensation. internal compensation.
3. Molecules of isomers Molecules are achiral.
present are chiral.

134
 When equal amounts of d-tartaric acid and l-tartaric acid are mixed, we
get racemic tartaric acid which is an optically inactive mixture. This can be
separated into two optically active forms.
d- and l-isomers have the same magnitude but different sign of optical
rotation, hence they are called enantiomers. The Meso tartaric acid differs in
the magnitude of optical rotation from the d- or l- isomer. Hence Mesoform
is said to be a ‘‘diastereomer’ of the active form.
Enantiomer Diastereomer

1. Optical isomers having the same Differ in the magnitude of

magnitude but different sign of optical rotation.
optical rotation.
2. They have configuration with They are never mirror images.
non-super imposable object mirror
image relationship.
3. Enantiomers are identical in all Diastereomers differ in all
properties except the sign of physical propeties.
optical rotation.
4. Separation of enantiomers is a Separation from the other
tedious process. pairs of enantiomers is
easy.
Representation of configurations of the molecule :
In order to indicate the exact spatial arrangement of atoms or groups in
a molecule having asymmetric carbon atom, Fischer proposed DL-system
of nomenclature. Glyceraldehyde was taken as the standard. The dextro
isomer and laevo isomer of glyceraldehyde are designated as D and L as
follows. These are Fischer’s projection formulae.
CHO CHO

H OH HO H

CH2OH CH2OH

Sign of rotation : d or (+) glyceraldehyde l or (–) glyceraldehyde

Designation of
configuration : D L

135
 In general more oxidised group is shown at the top and the reduced
group at the bottom. The chiral molecule is viewed in such a way that H, X-
lie above the plane of the paper and R1, R2-lie below the plane of the paper.
The D, L-configurations are shown as :
R2 R2

H C X X C H

R1 R1

D L
R2 = Oxidised group - COOH, CHO, CO... (In the projection formula, the broken
lines indicate the bonds that are going
R1 = Reduced group CH3, CH2OH ...
below and thick lines, the bonds
X = a heteroatom or a group with hetero atom coming above the plane of the paper)
(i.e.,) Cl, Br, I, –OH, –NH2, etc.,

The above projection formulae can be understood from the following

diagram.
R2 R2

C* C*

H H
X X
R1 R1

D L
Thus D and L lactic acids are
COOH COOH

H OH HO H

CH3 CH3
D L
136
and tartaric acid - (R-stands for the remaining half portion of the molecule)
COOH R COOH

H OH
≡ HO H ≡ H OH
HO H

D-configuration COOH COOH R

R = –CH(OH)COOH
COOH R COOH

HO H
≡ H OH ≡ HO H
H OH

L-configuration COOH COOH R

This system of designating configuration is of limited applicability.

In Fischer’s projection formula any two exchanges of groups attached
to the asymmetric carbon atom, are allowed, then the configuration is not
changed.
i.e.,
R R R
Exchange Exchange
–H by –OH H by COOH
HO H H OH COOH OH
1 2

COOH COOH H

I II
Though I and II appears to be different but both represent the same
configuration. Both are identical.

Disubstituted benzene :
When any two hydrogen atoms of the benzene ring are replaced by any
other atoms or groups disubstituted benzene is obtained.
(e.g.,) C6H4Cl2, C6H4 (OH)2, CH3 C6H4Br, HOC6H5NO2

137
 The disubstituted benzenes can exist in three isomeric forms.
X X X
X

X
X = any substituent
These are three distinct forms differing in many properties though they
have the same formula. Hence they are said to exhibit isomerism. In these
three structures the isomers differ in the relative position of the substitutents.
Hence they are called position isomers.

When the substituents are in adjacent positions in the benzene ring, it is

called ortho isomer.

When the two substituents are exactly opposite to each other, it is a

para isomer.

When the angle between two substituents is 120o. It is a meta isomer.

Example,
Cl Cl Cl
Cl

Cl

Cl
Ortho dichloro Meta dichloro Para-dichloro
benzene benzene benzene

Isomers can also be named using the number of the carbon atom thus
Ortho isomer is 1,2-dichloro benzene
Meta isomer is 1,3-dichloro benzene
Para isomer is 1,4-dichloro benzene

138
 It should be remembered that there are two ortho and two meta and
only one para position to the substituent already present in a molecule of
benzene.
Cl Cl CH3 CH3
Cl O2N
Cl NO2

and (OR) and

These two are identical and are not isomers. Similarly the following two
represent one and the same compound and are not non-superimposable mirror
images.
Cl Cl CH3 CH3

Cl and (OR) and

Cl NO2 O2N

Ortho, meta and para isomers differ mainly in physical properties like
melting point, refractive index, solubility. Their behaviour under an applied
electric field differs widely. This behaviour is measured by a quantity called
‘Dipole moment’. For disubstituted benzenes the magnitude of DPM depends
on the angle between the two substituents. For example, for dichloro benzene.
Cl Cl
Cl
Cl

Cl

Cl
angle θ = 60o θ = 120o θ = 180o
Their DPM, is in the order.
Ortho isomer > Meta isomer > Para isomer
for para dichloro benzene DPM = 0.
Hence dipole moment measurement is the best method of distinguishing
the three isomers of disubstituted benzenes.

139
 SELF EVALUATION
Choose the correct answer :
1. Identify chiral molecule among the following :
(a) isopropyl alcohol (b) isobutyl alcohol
(c) 2-pentanol (d) 1-bromo-3-butene
2. Which among the following is not having an asymmetric carbon atom ?
(a) 2-chloro butane (b) 2-bromo-3-butene
(c) 2-hydroxy propanal (d) isobutyric acid
3. Which among the following can be a chiral center ?
(a) C+ of a cabocation (b) carbon of a radical
2
(c) an sp carbon (d) an sp3 carbon
4. Give the structural formulae for the simplest chiral.
(a) alkane (b) alkene (c) alkyne (d) alcohol
(e) aldehyde (f) ketone (g) carboxylic acid (h) amine.
GEOMETRICAL ISOMERISM
1. Which among the following exhibit geometrical isomerism ?
(a) isobutyraldehyde (b) 1-butene
(c) 1,1-dichloro ethylene (d) 1-chloro-2-bromo ethylene
2. Which among the following does not exhibit geometrical isomerism ?
(a) CH3CH=CHBr (b) CH2Br CH2I
C=C
H3C CH2Br

(c) (CH)3C = CHC2H5 (d) CH3CH = CHCHO

3. Give E/Z-designation for
(a) CH3 CH2CH3 (b) BrCH CH3
2

C=C C=C
H H H3C CH2CH3

140
 H CH3 H H
(c) C=C (d)
C=C
Cl H Br Br

4. Arrange the following in the increasing order of stability.

CH3CH2CH=CH2, CH3CH=CHCH3 (cis), CH3CH=CHCH3 (trans)
CH3
C = CH2
CH3
5. How many linear chain isomers are possible for each of the following
olefins ?
Practice Questions
(a) C4H8 (b) C5H10 (c) C3H6 (d) C6H12
6. Draw the cis, trans isomers for the following and designate them as E or Z.
(a) HOH2C–CH = CHCH2CH3 (b) CH3CH=CHCO2H
(c) CH3CH = CH – CHO (d) CHCl = CHBr
7. Identify each of the following alkenes as being either cis or trans.

ClCH2 Cl Cl Br
(a) C=C (b)
C=C
H H H H

OHC H
H COOH
C=C
(c) (d) C=C
H CHO
H COOH

8. Which of the following can exist as geometric isomers ?

(a) ClCH2C ≡ CCH3 (b) ClCH2–CH = CH–CH2Cl
(c) CH2 = CHCHO (d) CH2 = C–CH2CH3
|
CH3

141
9. Label the following as, E, Z isomers.
CH3 CH2OH
C CH3 H

(a) (b) C=C

C H COOH

HOCH2 H

H CHO Cl H

(c) C=C (d) C=C

CH3 CH2Cl Br F

10. Give the structure of Z and E forms of cinnamic acid.

CONFORMATION
1. Which among the following can have different conformations ?
(a) CH4 (b) CHCl3 (c) CH3COOH (d) CH3CH2OH
2. Arrange the following conformation of n-butane with increasing order of
energy, staggared (anti), partially eclipsed, eclipsed and skew
conformations.
3. The eclipsed form of which of the following has the highest energy.
Ethane, propane, n-butane, ethylene dibromide.
4. What is the relative composition of the equilibrium mixture of all the
conformers of n-butane ?
5. Draw the different conformation of cyclohexane clearly indicating the
various C–H bonds.
6. Explain the energy level diagram for axial-equitorial cyclo hexanol
conformational changes.
7. Describe the conformations of cyclohexanol. Comment on their stability.
Short answer questions.
1. Explain the following with examples.
(a) cis-trans isomerism (b) optical isomerism.

142
2. Distinguish enantiomers and diasteromers ?
3. What is a racemic mixture ? Explain with suitable example.
4. Mesotartaric acid is an optically inactive compound with chiral carbon
atoms. Justify.
5. Distinguish racemic form from Mesoform.
6. Describe the D, L-system of designation of configurations.
OPTICAL ACTIVITY - KEY
1. (b) CH3CH2CH2–CH(OH)CH3
2. (d) CH3
|
CH3–CH–COOH
3. (d) sp3 carbon
4. (a) CH3CH2–CH (CH3)CH2 CH2 CH3
(b) CH3CH2–CH (CH3) – CH=CH2
(c) CH3
|
CH3CH2CH – C≡CH
(d) CH3CH2– CH (OH) CH3
(e) CH3CH2–CH (CH3)CHO
(f) CH3COCH(CH3)CH2CH3
(g) CH3CH2CH(CH3)COOH
(h) CH3CH2CH (CH3)NH2
Geometrical isomerism
1. (d) CHCl=CHBr
2. (c) CH3 H
C=C
H3C C2H5

143
3. (a) Z (b) E (c) E (d) Z
4. CH3CH2CH=CH2 < (CH3) CH=CH2CH3 (cis)
< (CH3)2 C =CH2 < CH3CH=CHCH3 (trans)

5. (a) CH3CH2CH=CH2
CH3CH=CHCH3 (cis, trans)

(b) CH3CH2CH2CH=CH2, CH3CH2CH=CH CH3 (cis, trans)

(c) CH3CH=CH2 one

(d) CH3CH2CH2CH2CH=CH2(1), CH3CH2CH2CH=CHCH3 (cis, trans)

CH3CH2CH=CHCH2CH3 (cis, trans)

CONFORMATIONS
1. (d)
2. Staggard < skew < partially eclipsed < eclipsed.
3. Ethylene dibromide (Br has larger size than CH3- group).
4. eclipsed < partially eclipsed < skew < staggard.
5. refer energy level diagram of equitorial - axial cyclohexanol

SUMMARY :
ISOMERISM IN ORGANIC CHEMISTRY

Isomerism - Stereoisomerism - Geometrical isomerism and optical

isomerism
Geometrical isomerism - difference in the relative orientation of groups
attached to C = C Condition.
Stereoisomers which are not mirror images - Cis and trans isomers -
E, Z nomenclature - examples.
Conformation - rotation about C – C bond - Conformation of
cyclopropane, cyclobutane and cyclopentane.
144
 Non-coplanar arrangement of carbon atoms in cyclo-hexane - chair and
boat conformation - relative stability
Cyclohexanol - conformation - axial and equitorial alcohol - energy level
diagram.
Optical isomerism - the phenomenon of optical activity - cause of optical
activity - asymmetric carbon atom
Chirality - Chiral centre - Chiral molecules - isomers with nonsuper-
imposable object - mirror image relationship - dextro rotatory and
laevorotatory isomers - enantiomers -
Racemic mixture - mixture of enantiomers - optically inactive.
Optical isomers with more than one asymmetric carbon atom - Tartaric
acid - enantiomers and diastereomer - mesoform - optically inactive.
Designation of configuration - D, L - notation.
Position isomerism - disubstituted benzene - ortho, meta and para isomers
- Identification - Dipole moment.

REFERENCES :
1. Problems in sterochemistry and conformations by Samuel Delvin.
2. Stereochemistry of organic compounds by Eliel.
3. Organic chemistry by Morrison Boyd.
_____

145
 16. HYDROXY DERIVATIVES
LEARNING OBJECTIVES
@ Alcohols - structure - isomerism.
@ Nomenclature - Common system, Carbinol system, IUPAC system of
naming alcohols.
@ Classification - monohydric, dihydric and trihydric alcohols -
Recognising primary, secondary and tertiary alcohols.
@ Learning general methods of preparation.
@ Uses of Grignard reagent in the preparation of alcohols.
@ Physical and Chemical properties - related to structure - uses.
@ Distinction between primary, secondary and tertiary alcohols.
@ To learn the methods of preparation, physical and chemical properties
and uses of dihydric and trihydric alcohols - ethylene glycol and glycerol.
@ Oxidation of glycol and glycerol - different methods.
@ Learning the methods of preparation, properties and uses of aromatic
alcohol - benzyl alcohol.
@ Phenols - classification - preparation, properties
@ Resonance in phenol - acidic property, difference from alcohol - uses.

146
16.1 HYDROXY COMPOUNDS
These are compounds having hydroxyl group directly linked to a carbon
atom. These comprise a variety of organic compounds starting from simple
alcohols and phenols to complex naturally occuring substances like starch
and cellulose.
Alcohol is one of the most important class of compounds. Nearly every
other kind of aliphatic compounds like - alkenes, ethers, aldehydes, ketones,
acids, esters and a host of other compounds can be made from alcohol. They
are not only used as raw materials but frequently as solvents in which reactions
are carried out and from which products are crystallised.
This chapter on alcohol deals with the study of (a) structure and
classification, (b) nomenclature, (c) isomerism, (d) general methods of
preparation, (e) properties - physical and chemical - relating to structure
and (f) uses of alcohols.

16.2 CLASSIFICATIONS AND STRUCTURE

Alcohols are compounds having hydroxy group directly bonded to a
saturated carbon atom, having the general formula R–OH.
‘R’ can be (i) aliphatic saturated - ethyl alcohol
(ii) unsaturated - allyl alcohol
(iii) aralkyl - benzyl alcohol
A compound can have more than one hydroxy group such as ethylene
glycol, a dihydric alcohol and
CH2 – CH2
| |
OH OH

Glycerol a trihydric alcohol. CH2– CH – CH2

| | |
OH OH OH
Alcohols can be further classified as primary, secondary and tertiary
according to the kind of carbon to which the –OH group is linked.

147
 R R
R – CH2OH CHOH R C–OH
R R
Primary Secondary Tertiary
1o 2o 3o
They differ in the rate and mechanism of reaction, often in reactions
which directly involve the hydrogen atom attached to the carbon bearing the
–OH group an entirely different course for each class of alcohol take place.

16.2.1 NOMENCLATURE
Alcohols are named by three systems of nomenclature.
1. For simple alcohols common names are often used. A common name
consists of the name of the alkyl group followed by the word alcohol.
2. The carbinol system of nomenclature considers alcohols as being derived
from methanol (called carbinol) by the replacement of one or more
hydrogen by alkyl group.
3. In the IUPAC system a set of rules is followed.
(a) the longest carbon chain that contains the –OH group is taken as
the parent structure.
(b) The name is arrived at by replacing the terminal ‘e’ of the
corresponding alkane by -ol.
(c) Indicate the number and position of the –OH group in the parent
chain using the lowest possible number.
M.F Common Carbinol IUPAC
name name name
CH3CH2OH ethyl alcohol methyl carbinol ethanol

CH3CH2CH2OH n-propyl alcohol ethyl carbinol 1-propanol

CH3–CHOHCH3 isopropyl alcohol dimethyl carbinol 2-propanol

CH3CH2–CH–OH secondary butyl ethyl methyl

| alcohol carbinol 2-butanol
CH3

148
 CH3–CH–CH2OH Isobutyl alcohol isopropyl carbinol 2-methyl-
| 1-propanol
CH3
CH3
|
H3C–C–OH tert-butyl alcohol trimethyl carbinol 2-methyl-
| 2-propanol
CH3

C6H5CH2OH Benzyl alcohol phenyl carbinol phenyl methanol

CH3CH2CHOHCH2CH2CH3 --- ethyl, propyl carbinol 3-hexanol
CH3 CH3
| |
CH3– C – C– CH3
| |
H OH ---- dimethyl isopropyl 2,3- dimethy1-2
carbinol butanol

Isomerism : Alcohols exhibit three kinds of isomerism.

1. Chain isomerism : arising out of the difference in the carbon chain
structure of the parent hydrocarbon.
CH3
4 3 2 1 |
CH3– CH2– CH2– CH2OH CH3– CH – CH2OH
1-butanol 2-methyl-1-propanol
(linear chain) (branched chain)

2. Position isomerism : arising out of the difference in the position of

–OH group, the hydrocarbon chain being the same.
CH3CH2 – CHOH – CH2CH3 CH3CH2CH2CHOHCH3
3-pentanol 2-pentanol

CH3CH2CH2CH2CH2OH
1-pentanol

3. Functional isomerism :
Alcohols are isomeric with ethers, having the same formula with different
functional groups.
CH3CH2CH2OH CH3OCH2CH3
n-propyl alcohol ethyl methyl ether

149
16.3 GENERAL METHODS OF PREPARATION
Simple alcohols are obtained from natural sources. Thus methyl alcohol
is obtained from the liquid formed by the destructive distillation of wood.
Hence it is called wood spirit.
Ethyl alcohol is manufactured by the fermentation of sugar present in
grains and fruits and hence called ‘grain alcohol’. Other alcohols can be
prepared by using any one of the following methods.
In the light of mechanism involved, alcohol can be prepared by
(1) addition reaction, (2) substitution reaction.
(1) Addition reactions
(a) Markownikoff’s addition of water to olefins in presence of dilute
sulphuric acid.

H2SO4
CH3CH = CH2 + H2O CH3– CHOH – CH3
propylene

Hydration normally proceeds by protonation of olefins to form

carbocation, followed by nucleophilic attack by water.
+ + OH2
H+ H2O
R – CH = CH2 R– CH CH3 |
R – CH – CH3

– H+
OH
|
R–CH–CH3
Simple alcohol (C2H5OH) can be prepared by absorbing olefin in con.
H2SO4 with the formation of ethyl hydrogen sulphate, which undergoes
hydrolysis to give alcohol.
353K
C2H4 + H2SO4 C2H5 HSO4

H2O : + C2H5 HSO4 HOC2H5 + H2SO4

150
 (b) Grignard addition : Grignard reagent adds to carbonyl compounds
forming adducts which on hydrolysis form alcohols.
Primary alcohols from formaldehyde.
H H H OH X

XMg – R C=O R – C–O MgX RCH2OH + Mg

H H OH

It is a nucleophilic addition where the nucleophile is the carbanion (R–)

generated by the Grignard reagent (RMgX).
(c) By catalytic hydrogenation of aldehydes and ketones

R H2/Pt R H2/Pt
C=O RCH2OH ; C=O R2CHOH
H R

(d) By the reduction of aldehydes and ketones using hydrides.

R LiAlH4 R R NaBH4 R
C=O CH2 ; C=O CHOH
H HO R R

(2) Nucleophilic substitution

(a) Alkyl halides undergo the nucleophilic substitution reaction. Thus
alkyl halides are converted to alcohols by aqueous alkaline solution or silver
oxide suspended in water. The nucleophile is OH– ion and the leaving group
is the halide ion.
H2O
RX + NaOH R–OH + NaX
RX + AgOH R–OH + AgX
(b) Aliphatic primary amines react with Nitrous acid forming alcohols.
Diazonium ion is formed as an intermediate.
–H2O H2O
RNH2 + HONO [R–N=N+] N2 + R–OH
unstable

151
 The nucleophile is water and the leaving group is Nitrogen molecule.
(c) Hydrolysis of esters by either acid or alkali.

H+
R'COOR + H2O R'COOH + ROH
OH–
R'COOR + NaOH R'COONa + R–OH
The above reactions proceed with nucleophilic addition to carbonyl
carbon atom by water or OH– ion followed by elimination of ROH.
(d) Ethers can be cleaved to alcohols and alkyl iodide by treating with
HI.
+
I–
R–O–R + HI R–O – R R–OH + R–I
|
H
First step involves protonation which is followed by nucleophilic
displacement by Iodide ion.
Ethers can also be hydrolysed by treating with dilute H2SO4 under
pressure.

H2SO4 +
HO
C2H5–O–C2H5 + H2O C2H5–O–C2H5 2
2C2H5OH + H+
|
H
Protonation of ether oxygen, followed by nucleophilic displacement of
ethyl alcohol by water.
16.3.1 Physical Properties
(a) Alcohols are neutral substances whereas inorganic hydroxides are
basic in nature. Physical properties of an alcohol are best understood if we
recognise that structurally an alcohol is a composite of an alkane and water.
R–H H–OH R–OH
Hence alcohol contains alkane like alkyl group and water like hydroxyl
group. The OH– group gives the alcohol its characteristic properties and the
alkyl group modifies it.
152
 The hydroxy group contains highly electro negative element oxygen
bonded to hydrogen. Hence this group is polar. This is capable of forming
hydrogen bond as shown.
R R R H
| | | |
O–H ......O–H , O–H .....O–H
Many of the physical properties are affected by hydrogen bonding.
1. The boiling point of alcohols are far higher than the hydrocarbons
having the same molecular weight and structure.
Compound Mol.wt. Boiling point. K
CH3OH 32 333
CH3CH3 30 184.4
C2H5OH 46 351.5
C3H8 44 228.5

This is because alcohols are associated liquids. Their abnormal boiling

points are due to the greater energy needed to break the hydrogen bonds
that hold the molecules together.
Hence lower members are colourless mobile liquids. Higher members
are oils, liquids or waxy solids.

(b) Solubility
Alcohols are soluble in water and other hydroxy compounds in contrast
to hydrocarbons. This is also explained on the basis of intermolecular
hydrogen bonding. The energy required to break intermolecular forces
between alcohol molecules is provided by the formation of hydrogen bond
between a water molecule and an alcohol molecule. Lower members are
completely miscible with water and the solubility decreases with increase in
molecular weight. This is because of the increase in size of the hydrophobic
alkyl group in the alcohol.

153
Chemical Properties
Alcohols can be considered to be derived from alkane as well as water.
CH3H CH3OH HOH
This is easily seen as the alcohols have properties in between methane
and water.
Properties Methane Methanol Water
m.p 89 K 176.8 K 273 K
b.p 159 K 338 K 373 K
Solubility insoluble soluble insoluble in
in water in water in water and hydro
slightly soluble carbon
in hydro carbon.
Similar to water forming hydrate with salts, lower alcohols also form
addition compounds with salts (e.g.,) CaCl2.4C2H5OH, MgCl2. 6CH3OH
In chemical reactions also alcohols bear striking resemblance to water
and alkane.
Properties due to the acidic nature of hydrogen of the –OH group.
1. Alcohols are weaker acid than water because of +I effect of alkyl
groups. Hence alcohols react only with electro positive metals evolving
hydrogen.
R–OH + Na RONa + ½ H2
(Sodium alkoxide)

2C2H5OH + 2Na 2C2H5ONa + H2

(Sodium ethoxide)

The acid strength decreases in the order 1o > 2o > 3o because of the
electron releasing effect of the alkyl groups.
2. Strongly basic substances like organometallic compounds are
decomposed by alcohol.
R–OH + CH3MgBr RO–Mg–Br + CH4

154
 Hence alcohols cannot be used as a solvent for Grignard’s reagents.
3. Alcohols react with acid chlorides and acid anhydrides to form esters.
This involves nucleophilic attack by alcohol on the carbonyl carbon. The
leaving groups are Cl– or CH3COO–
H
|
R–OH + R'CO–Cl R–O–CO–R' + Cl–
+

–H+
R–O–CO–R'

H
CO–R' |
R–O–H + O R – O – CO–R' + R' COO(–)
CO–R' +

–H+
H+ + R–O–CO–R'
Reactions in which the –OH group is involved.
1. Alcohols react with carboxylic acids in presence of con. sulphuric
acid. Alcohol molecule brings forth a nucleophilic attack on the carbonyl
carbon to form ester.
O
||
R–OH + H – O–C–R' H+ R–O–CO–R' + H2O
..

H+
C2H5OH + CH3COOH CH3COOC2H5 + H2O
(ethyl acetate)
2. Alcohols form alkyl chlorides. When treated with anhydrous zinc
chloride and hydrogen chloride.
ZnCl2
R–OH + HCl R–Cl + H2O

155
 This reaction involves protonation of the alcohol followed by nucleophilic
attack by chloride ion. Protonation weakens the C–O bond considerably.
The removal of water from the protonated species is facilitated by
anhydrous zinc chloride. Reactivitiy in this reaction with respect to alcohols
is 3o > 2o > 1o. This reaction is used in Lucas Test.

con.HCl
(CH3)3 COH (CH3)3 C–Cl + H2O
anhyd. ZnCl 2 (Turbidity appears immediately)
3o alcohol
at room temperature

con.HCl
(CH3)2 CHOH (CH3)2CHCl + H2O
anhyd. ZnCl2
2o alcohol (Turbidity appears after 5-10 minutes)
at room temperature

Conc. HCl
CH3CH2OH CH3CH2Cl + H2O
anhydrous ZnCl2
1o alcohol (No turbidity appears easily)
but only on heating

3. Similarly alcohols are converted to alkyl chlorides by thionyl chloride

in presence of pyridine.

Pyridine
RCH2OH + SOCl2 RCH2Cl + SO2 + HCl
HCl is removed by pyridine and sulphur dioxide, being a gas escapes.
Hence there is no separation problem in this method.
This reaction involves the formation of alkyl chloro sulphite as
intermediate.
RCH2OH + ClSOCl RCH2–O–SO–Cl
Intramolecular nucleophilic attack by the chlorine in the intermediate,
on the carbinol carbon atom, results in the removal of sulphur dioxide forming
alkyl chloride with retention of configuration.

156
 R–CH2–O–SO –Cl RCH2Cl + SO2
This reaction belongs to SNi (Nucleophilic substitution internal)
4. Alcohols are converted to their halides by the action of phosphorous
halides.
R–OH + PCl5 RCl + POCl3 + HCl

3C2H5OH + PCl3 3C2H5Cl + H3PO3

Similarly alkyl bromide by phosphorous and bromine, alkyl iodide by

phosphorous and iodine can be made.
In all these cases an intermediate is formed, which undergoes nucleophilic
displacement reaction with halide ion.

+
H
RCH2OH + PCl5 RCH2 – O + Cl(–)
PCl4

+
H
R–CH2 – O R CH2Cl + POCl3 + HCl
Cl– PCl4
5. Dehydration
(a) Alcohols undergo intermolecular dehydration by treating with
con. H2SO4 acid to give ethers. In the first step alkyl hydrogen sulphate is formed
which with excess alcohols undergoes nucleophilic displacement reaction.
410K
C2H5OH + H2SO4 C2H5 . HSO4 + H2O

+ H
C2H5 – HSO4 C2H5 – O + HSO4–
C2H5
C2H5–O–H

157
 H
+
C2H5– O C2H5–O–C2H5 + H+
C2H5
(b) Intramolecular dehydration takes place leading to the formation of
olefins. This reaction involves β-elimination. It is E1 reaction and the
intermediate is carbonium ion.

H+ +
(CH3)3 COH (CH3)3 C + H2O

(CH3)3 C+ (CH3)2 C = CH2 + H+

It follows E2 mechanism if the ethyl hydrogen sulphate is involved as
shown.

H–CH2–CH2–HSO4 CH2=CH2 + H2SO4

Thus ethyl alcohol gives ethylene on treating with excess con. H 2SO4
acid at 440 K.
(c) Dehydration can also be carried out by passing the alcohol vapour
over alumina at 620 K.

Al2O3
CH3CH2OH CH2=CH2
620 K

(d) Alcohols react with ammonia in presence of heated Alumina or thoria

catalyst at 633 K to form mixture of amines.

Al2O3 ROH ROH

R–OH + NH3 RNH2 R2NH R3N
633 K

Heated alumina removes the water formed.

158
16.3.2 Methods of distinction between three classes of alcohols
(1o, 2o and 3o)
Reaction involving hydrogen α- to the –OH group.
Since primary, secondary and tertiary alcohols differ in the number of
α-hydrogen atoms, these reactions can be used to distinguish them.
1. Oxidation
Oxidation of alcohols with acidified potassium dichromate gives different
oxidation products.
(O)
CH3–CH–O + (O) CH3–CH=O CH3–COOH
| | –H2O
aldehyde
H H
(primary alcohol)

CH3 CH3
| | (O)
CH3 – C – O + (O) CH3–C=O CH3COOH
–H2O
| | (Ketone) (acid with lesser
H H carbon atoms)
(secondary alcohol)

CH3 CH3
| H+ | (O)
H3C – C – OH CH3 – C = CH2 CH3COCH3 + HCOOH
|
CH3
(tertiary alcohol)
CH3COOH

As the number of α-hydrogen decreases, reactivity with respect to

oxidation also decreases.
Hence the presence of α-hydrogen is essential for normal oxidation
reactions of alcohols.

159
 Acidified potassium permanganate oxidises the alcohols directly to the
carboxylic acid.

(O) (O)
CH3CH2OH CH3CHO CH3COOH

The breath analysis test for the detection of ethanol involves the oxidation
of alcohol in the breath of a person who has consumed alcohol, by acidic
potassium dichromate and observing the change in the colour of the chromium
ion (CrVI) from yellow orange to Cr(III) which is blue green colour.
2. Reaction with chlorine water
When alcohols are treated with chlorine water, or sodium hypochlorite
or bleaching powder solution, they are oxidised.
Primary alcohols are oxidised to aldehydes

(O)
CH3CH2OH CH3CHO + H2O
Ethyl alcohol Acetaldehyde

Secondary alcohols are oxidised to ketones.

CH3 (O)
CH3
CHOH CO + H2O
CH3 CH3
Isopropyl alcohol Acetone

Tertiary alcohols do not undergo this reaction because it does not contain
α-hydrogen which is involved.
The carbonyl compounds formed undergo further chlorination forming
chlorinated aldehydes and ketones.

Cl2
CH3CHO CCl3 CHO (chloral)

Cl2
CH3COCH3 CCl3 COCH3
Trichloro acetone

160
 When alcohols containing CH3CHOH- group is treated with iodine and
potassium hydroxide, yellow crystals of iodoform is formed. The tri-iodo
carbonyl compound formed is decomposed by the alkali to give iodoform
and potassium salt of an acid.
I2/KOH I2 KOH
C2H5OH CH3CHO CI3CHO CHI3 + HCOOK
I2/KOH I2 KOH
CH3CHOHCH3 CH3COCH3 CI3COCH3 CHI3 + CH3COOK
The formation of haloform in general by this procedure is called haloform
reaction. Since methanol does not contain CH3CHOH group, it does not
undergo haloform reaction.
2. Catalytic dehydrogenation :
Dehydrogenation of alcohols by passing the vapours over heated copper
at 573 K.
Cu/573K
CH3 CH – O CH3CHO + H2
| | (aldehyde)
H H
Primary alcohol

CH3 CH3
| Cu/573 K |
CH3 – C – O CH3 – C = O + H2
| | (acetone)
H H
Secondary alcohol

CH3 OH CH3
Cu/573K
C C=CH2 + H2O
dehydration
CH3 CH3 CH3
Tertiary alcohol Isobutylene
Absence of α-hydrogen in tertiary alcohol under the above condition
leads to only dehydration to olefin.
3. Victor Meyers Test
This test consists of the following steps.
(a) Alcohol is converted into alkyl iodide by treatment with P/I2
(b) The alkyl iodide is then converted into nitro alkane by silver nitrite
(AgNO2).
161
 (c) The nitro alkane is treated with Nitrous acid (HNO2) and then with
aqueous KOH.
The alcohols are identified from the colour of the product.
(a) Primary alcohol:
P/I2 AgNO2
CH3CH2OH CH3CH2I CH3–C H2O = N–OH
primary alcohol |
NO2
KOH
CH3– C=NOH CH3–C=N–OK+
| |
NO2 NO2
(Nitroxime or nitrolic acid) Potassium salt of nitrolic acid
(red colour)

(b) Secondary alcohol :

CH3 CH3 CH3 NO2
P/I2 AgNO2
CHOH CHI C + HON=O

CH3 CH3 CH3 H

Secondary alcohol

CH3 NO2 KOH

C No Reaction but blue colour
CH3 N=O remains.
(Pseudo nitrol)
blue colour

(c) Tertiary alcohol :

CH3 CH3 CH3

P/I2 AgNO2
HNO2
CH3 – C – OH CH3 – C – I CH3 – C – NO2 No reaction

CH3 H3C CH3

Nitro compound
colourless

Absence of α-H in tertiary alcohol makes it inactive to nitrous acid.

162
USES OF ALCOHOLS
(a) Methyl alcohol is used as an industrial solvent (b) as an antifreeze in
automobile radiators, (c) for the manufacture of formaldehyde.
Methanol is poisonous in nature and when taken orally can cause
blindness and even death. Ethanol which contains 5% methanol is known as
methylated or denatured spirit. It is used as a fuel in spirit lamp and as a
solvent for wood polish, methanol is used as a motor fuel along with petrol.
Ethyl alcohol one of the most extensively used organic compound (a) in
alcoholic beverage, (b) industrial solvent, (c) in pharmaceutical preparation,
(d) as a preservative for biological specimens, (e) in the preparation of large
number of other organic compounds like ether, iodoform, acetaldehyde etc.,
and (f) as a good solvent for recrystallisation and extraction of plant materials
etc.

16.4 DIHYDRIC ALCOHOLS

Compounds having two hydroxyl groups are known as dihydric alcohols
or diols. If two hydroxyl groups are linked to the same carbon atom, it is
called ‘gem diols’. These are unstable. The relative position of the two
hydroxyl groups can be 1, 2 or 1, 3 or 1, 4 and so on.
Example,
OH
|
CH3 – C – OH CH3 – C = O + H2O
| |
H H
‘Gemdiol’

CH2OH CH2OH
| |
CH2OH CH2
1,2 ethane diol |
CH2OH
1,3 propane diol

Nomenclature of 1,2-diols
1. In the common system, the name is arrived at by adding the word
‘glycol’ to the name of the olefin from which it is derived.

163
 HOCH2– CH2OH CH3CH(OH)CH2OH
ethylene glycol propylene glycol

2. In the IUPAC system, the suffix ‘diol’ is added to the name of parent
alkane.
HOCH2– CH2OH CH3CH(OH)CH2OH
ethane-1,2-diol propane-1,2-diol

ISOMERISM
Position Isomerism
Diols having the same molecular formula differ in the position of the
hydroxyl groups.
CH3CH(OH)CH2OH propane-1,2-diol
CH2(OH)CH2CH2OH propane 1,3-diol
Functional Isomerism
Diols are isomeric with ethers or hydroxy ethers.
CH3CH(OH)CH2OH is isomeric with
CH3OCH2OCH3 and CH3OCH2CH2OH
Dimethoxy methane 2-methoxy-ethanol

16.4.1 GENERAL METHODS OF PREPARATION OF GLYCOLS

1. By addition reactions
(a) Dihydroxylation
By the action of cold dilute alkaline potassium permanganate solution
which is known as Baeyer’s reagent on olefins, diols are formed.
RCH = CH2 + H2O + (O) RCHOH – CH2OH
(b) Addition of oxygen to form olefin oxide from olefin followed by
acid hydrolysis to give glycol.

H3O+
RCH = CH2 + ½ O2 R–CH–CH2 R – CH – CH2
| |
O OH OH

164
 Thus ethylene forms ethylene epoxide.

Ag
CH2 = CH2 + ½ O2 CH2– CH2
473-673 K
O

This is hydrolysed to ethylene glycol by dil. HCl or sulphuric acid at

333 K.
H3O+
CH2 – CH2 CH2OH – CH2OH
O
This reaction proceeds via the nucleophilic attack by water on the
protonated epoxide.

CH2 + CH2 – OH CH2OH

H2O : | OH + | –H+ |
CH2 H2O – CH2 CH2OH

(c) Olefins are converted to chlorohydrins and are then hydrolysed with
milk of lime. Ethylene glycol itself is prepared as follows :
CH2 CH2OH Ca(OH)2 CH2OH
|| + HOCl | |
CH2 CH2Cl CH2OH

In the above, first step involves addition across the double bond and
the second step a SN2 attack by the OH– ion.
The latter two methods are of commercial importance.
2. By substitution reactions :
1,2-dihaloalkanes are hydrolysed with aqueous sodium carbonate.
(a) Ethylene dibromide is heated with moist silver oxide or aqueous
sodium carbonate solution to form ethylene glycol.

165
 CH2Br H2O CH2OH
| | + 2 NaBr + CO2
CH2Br Na2CO3 CH2OH

This reaction involves SN2 attack by OH– and the leaving group is
Br–.
(b) Action of nitrous acid on ethylene diamine leads to ethylene glycol.
CH2NH2 2HNO2 CH2OH
| | + 2N2 + 2H2O
CH2NH2 CH2OH
An unstable diazonium ion is formed in the first step, which undergoes
nucleophilic attack by OH– to form glycol.
3. By Reduction reactions
This procedure is similar to the preparation of alcohol by ‘Bouveault-
Blanc Reduction’ where aldehyde or ketone or ester can be reduced to
alcohol by sodium and ethanol. Thus ethylene glycol is prepared from diethyl
oxalate.
COOC2H5 8(H)
CH2OH
| | + 2 C2H5OH
COOC2H5 CH2OH

CHO 4 (H)
CH2OH 2 (H)
CHO
| | |
CHO CH2OH CH2OH
glyoxal glycolic aldehyde

16.4.2 PROPERTIES
Because of the presence of two hydroxyl groups the intermolecular
hydrogen bonding is made much stronger. Hydrogen bond can be formed
between both OH groups resulting in a polymeric structure.

166
 H
|
CH2 – O -------- H – O
| |
-------- O – CH2 CH2– CH2– O --------
| |
H H
This leads to high viscosity and boiling point (470 K). This is miscible
with water and alcohol in all proportions but immiscible with ether. Water
or alcohol forms stronger H-bonding with glycol, breaking the polymeric
structure. This explains the ‘hygroscopic’ nature of glycol. It is a colourless
liquid with sweet taste, but toxic in effect.

CHEMICAL PROPERTIES
The molecule of ethylene glycol contains two primary alcoholic groups.
It exhibits the general chemical characteristics of primary alcohols twice
over. However in most of the reactions both these groups are not equally
reactive. One hydroxyl group reacts completely before the other one
participates in the reaction. In general this resembles a primary alcohol in all
chemical reactions.
1. Replacement of acidic hydrogen
The hydrogen atom of the –OH group is replaced by electropositive
metals like sodium step by step, with evolution of hydrogen.

CH2OH CH2ONa CH2ONa

Na Na
| | |
323 K
CH2OH CH2OH 433 K CH2ONa
Monosodium Disodium
glycolate glycolate

2. Reactions in which –OH group is replaced

(a) Reaction with organic and inorganic acids to form esters.
(i) In all these reactions, protonation of the –OH is followed by
nucleophilic attack by the anion of the acid.

167
 CH2OH H+
+ H
| X– CH2 –– O
HX
CH2OH | H
CH2OH
X – CH2 + H2O
|
CH2OH
Ethylene glycol reacts with hydrogen chloride gas as follows :
CH2OH HCl / 433 K
CH2Cl HCl / 473 K
CH2Cl
| | |
CH2OH –H2O CH2OH –H2O CH2Cl
ethylene chlorohydrin ethylene
dichloride

(ii) On heating with nitric acid in presence of catalytic amount of con.

sulphuric acid, ethylene glycol forms ethylene dinitrate, an explosive liquid.
CH2OH H2SO4
CH2– O – NO2
| + 2HNO3 | + 2H2O
CH2OH ∆ CH2– O – NO2
(iii) Ethylene glycol reacts with organic acids like acetic acid in presence
of mineral acid, forming glycol mono and diacetate.
CH2OH CH2OCOCH3 CH2OCOCH3
H+ CH3COOH
| + CH3COOH | |
CH2OH -H2O CH2OH H+ CH2– OCOCH3
glycol monoacetate glycol diacetate

Acetyl chloride, acetic anhydride also form the same products with
ethylene glycol.
(iv) Reaction of ethylene glycol with dicarboxylic acid.
Both glycol and dicarboxylic acid being molecules with two functional
groups, react forming condensation polymers. Thus with Terephthalic acid,
ethylene glycol forms the polymer ‘Terylene’ (also known as dacron or
terene), which is extensively used as a synthetic fibre.

168
nHO – CH2 – CH2 – OH + n HOOC COOH

HO–[–CH2–CH2–O–CO CO–O–]n H + (2n – 1) H2O

(v) With phosphorous halides
Ethylene glycol forms ethylene chlorohydrin and ethylene dichloride with
either PCl5 or PCl3.
CH2OH CH2Cl CH2Cl
| | |
CH2OH CH2OH CH2Cl
Similarly PBr3 forms mono and dibromide.
CH2OH CH2Br CH2Br
| | |
CH2OH CH2OH CH2Br
ethylene bromohydrin ethylene dibromide

With PI3, it forms ethylene diiodide, which being unstable decomposes

to form ethylene.
CH2OH CH2I CH2
-I2
| | ||
CH2OH CH2I CH2
unstable

3. DEHYDRATION
Ethylene glycol undergoes dehydration under different conditions to
form different products.
(i) When heated alone up to 773 K it forms ethylene oxide or ethylene
epoxide. This is an intra molecular reaction in which a water molecule is
eliminated from the two –OH groups.
CH2 – OH –H2O
CH2
| | O
CH2 – OH 773K CH2

169
 (ii) When heated with anhydrous zinc chloride, ultimately acetaldehyde
is formed. This involves β-elimination.
H H
| | H
H – C– OH C–O–H |
ZnCl2
| –H2O
|| C=O
H – C – OH CH2 |
| CH3
H
In the second step hydrogen migrates from –OH group to CH2 carbon.
(iii) Intermolecular dehydration
When heated with conc. phosphoric acid, ethylene glycol eliminates a
molecule of water forming diethylene glycol.
HO – CH2 – CH2 – O H HO – CH2 – CH2
H3PO4
∆
O
HO – CH2 – CH2 – OH HO – CH2 – CH2

This involves the nucleophilic attack by the –OH group of one molecule,
to displace the protonated –OH group of another molecule.
(iv) Concentrated sulphuric acid being more powerful acid and
dehydrating agent removes two molecules of water forming dioxan.
HO – CH2 – CH2 –O H H O–CH2–CH2 H2SO4 CH2–CH2
H2SO4
O O O
HO–CH2–CH2– OH HO –CH2–CH2 CH2–CH2

4. OXIDATION REACTION
Ethylene glycol contains two primary alcohol groups, hence number of
oxidation products are possible. That depends on
(i) The nature of the oxidising agent.
(ii) The quantity of the oxidising agent used.

170
 (iii) Whether one or both the primary alcoholic groups are oxidised.
(a) Acidified potassium dichromate or potassium permanganate is very
powerful oxidising agent. Hence they are capable of cleaving the C–C bond
forming formic acid.
CH2OH HCOOH
3(O)
| + + H2O
CH2OH HCOOH
(b) Periodic acid is a specific reagent to bring about such a C–C bond
cleavage by oxidation.
CH2OH 3(O)
HCOOH
| + + H2O
HIO4
CH2OH HCOOH
This undergoes cleavage at carbon-carbon single bond forming two
molecules of aldehyde. This further gets oxidised to acids.
Both these reactions involve the formation of cyclic diester with the
reagent, as intermediate.
(c) Dilute nitric acid or alkaline KMnO4 oxidises ethylene glycol to the
following oxidation products. The first step involves the formation of
aldehyde by the oxidation of one –CH2OH group. The second step may
involve (i) oxidation of the other –CH2OH group to aldehyde or (ii) the
further oxidation of –CHO group to –COOH group. Ultimately oxalic acid
is formed.
CHO
|
CHO
CH2OH CHO glyoxal COOH COOH
| | | |
CH2OH CH2OH CHO COOH
glycol glycolic glyoxalic oxalic
aldehyde acid acid
COOH
|
CH2OH
glycollic acid

171
16.4.3 Uses :
(i) As an antifreeze in automobile radiators.
(ii) As a coolant in aeroplane engines.
(iii) As an explosive.
(iv) In the preparation of synthetic fibre, terylene.
(v) As a solvent and preservative.
(vi) In the preparation of numerous compounds like dioxan.

16.5 TRIHYDRIC ALCOHOLS

The compounds containing three hydroxyl groups are known as
Trihydric alcohols. These three hydroxyl groups are attached to three
different carbon atoms for stability of the compound. The most important
compound of the series is glycerol.
3 2 1
CH2OH – CHOH – CH2OH
This is also known as propane-1,2,3-triol in IUPAC system. This was
first discovered by Scheele in 1779 who obtained it by the hydrolysis of
olive oil.
It occurs in the combined state as glyceryl ester of higher fatty acids in
almost all vegetable and animal oils and fats. The higher fatty acids present
in glyceryl esters (oils or fats) are usually palmitic acid (C15H31COOH),
olecic acid (C17H33COOH) and stearic acid (C17H35COOH).
The general formula of triester of glycerol is
CH2OCOR
|
CHOCOR' R, R' and R" can be same or different.
|
CH2OCOR"
The triester is called triglyceride. If R=R'=R'' it is called simple
triglyceride, if different it is called mixed triglyceride.

172
Saponification Reaction
Glycerol is prepared in a large scale by the hydrolysis of oils or fats
either by using alkali (in soap industry) or by super heated steam (in candle
industry). Hydrolysing with alkali, forms sodium or potassium salt of higher
fatty acids as solids. These are called soaps.
In general hydrolysis of esters using alkali is called ‘Saponification’
reaction.
CH2OCOR CH2OH
| |
CHOCOR + 3NaOH CHOH + 3RCOONa
| | (soap)
CH2OCOR CH2OH
Glycerol is formed as byproduct in the soap industry. When the oil is
hydrolysed using steam, higher fatty acids are formed as solids. These are
used in candle industry.
CH2OCOR H2SO4
CH2OH
| + 3H2O Steam |
CHOCOR CHOH + 3RCOOH
| | (solid)
CH2OCOR CH2OH
Glycerol is the other product formed in this.
3. Synthesis of Glycerol
Starting from propylene (obtained in the cracking of petroleum) glycerol
is synthesised as given below :
CH2 CH2 CH2 CH2OH
|| Cl2
|| Na2CO3
|| HOCl
|
CH CH CH CHCl
| 773 K | 773 K/12 atm | |
CH3 CH2Cl CH2OH CH2OH
propylene allyl chloride allyl alcohol glycerol
chlorohydrin
CH2OH
| NaOH
CHOH + NaCl
| ∆
CH2OH
173
 I step involves the (chlorination) substitution of the methyl hydrogen
forming allyl chloride.
II step involves hydrolysis - Nucleophilic substitution reaction.
III step addition of hypochlorous acid to olefinic part of allyl alcohol.
IV step hydrolysis with Nucleophilic displacement of chlorine by hydroxyl
group.
16.5.1 Physical Properties :
It is a colourless and odourless liquid. It is a highly viscous and
hygroscopic liquid with high boiling point (536 K). The latter properties can
be explained on the basis of intermolecular hydrogen bond leading to
complex polymeric structure. It is miscible with water and alcohol in all
proportions but insoluble in organic solvents.
Chemical Properties
Glycerol molecule contains two primary alcoholic groups and one
secondary alcoholic group. However both alcoholic groups are not equally
reactive though in many of the reactions it resembles alcohol and glycol.
1. Reaction with electropositive metals like sodium :
Monosodium glycerolate is readily obtained and the disodium glycerolate
at higher temperature. The secondary alcoholic group does not react.
CH2OH CH2ONa CH2ONa
| | |
CHOH Na CHOH Na CHOH
| | |
CH2OH CH2OH CH2ONa
2. Reaction with hydrogen halides :
Glycerol reacts with hydrogen chloride at 383 K to give both α and
β-mono chloro derivative.
CH2OH CH2Cl CH2OH
| | |
CHOH HCl CHOH + CHCl
| 383K | |
CH2OH CH2OH CH2OH
glycerol glycerol β-chlorohydrin
α-chlorohydrin
174
 With excess of hydrogen chloride, α, α' - and α, β dichlorohydrins
are obtained.
CH2Cl CH2OH CH2Cl CH2Cl
| | Excess
| |
CHOH + CHCl CHOH + CHCl
HCl
| | | |
CH2OH CH2OH CH2Cl CH2OH
α-α' dichlorohydrin α,β- dichloro
hydrin

3. Phosphorous pentachloride forms glyceryl trichloride :

CH2OH CH2Cl
| PCl5
|
CHOH CHCl
| |
CH2OH CH2Cl

Hydrogen bromide and phosphorous tribromide react in the same way.

With hydrogen iodide or phosphorous triiodide, allyl iodide is formed.
An unstable triiodide is formed as an intermediate which loses iodine to give
allyl iodide.
CH2OH CH2I CH2
| HI or
| -I2 ||
CHOH CHI CH
| PI3 or I2 | |
CH2OH CH2I CH2I

With excess of the reagent allyl iodide further reacts giving ultimately
isopropyl iodide.
CH2 CH3 CH3 CH3
|| HI
| –I2 | HI
|
CH CHI CH CHI
| | || |
CH2I CH2I CH2 CH3
propylene isopropyl
I Step II Step III Step iodide

175
 The first and the third step involves Markownikoff’s addition of HI to
the carbon-carbon double bond. The second step involves β-elimination of
iodine.
5. With a well cooled mixture of concentrated sulphuric acid and
fuming nitric acid, nitroglycerine is formed.

CH2OH CH2ONO2
| conc.H2SO4
|
CHOH + 3HONO2 CHONO2 + 3H2O
| |
CH2OH CH2ONO2
Nitroglycerine
or
Glyceryl trinitrate

Similarly with acetic acid, acetic anhydride (or) acetyl chloride mono,
di and tri acetates are formed depending upon the amount of reagent used.
CH2OCOCH3 CH2OCOCH3 CH2OCOCH3
| | |
CHOH CHOH CHOCOCH3
| | |
CH2OH CH2OCOCH3 CH2OCOCH3
Glycerol Glycerol Glycerol
Monoacetate Diacetate Triacetate
6. Dehydration :
When glycerol is heated with potassium bisulphate or conc. sulphuric
acid or phosphorous pentoxide dehydration takes place. Two β-elimination
reaction takes place to give acrolein or acrylic aldehyde.

H – CH – OH CH2 CH2
| KHSO4
|| ||
H – C – OH C CH
| || |
H – CH – OH CHOH CHO
unstable acrolein
7. Action with oxalic acid :
Depending upon the temperature, glycerol is converted to allyl alcohol
or formic acid. At 383 K glycerol mono formate is formed.

176
 CH2OH HO – C = O CH2 – O – C = O
| | | | decarboxylation
383K
CHOH + CO – OH CHOH CO–OH
| |
CH2OH CH2OH – CO2
monooxalate

CH2OCOH
|
CHOH glycerol mono formate
|
CH2OH
This on hydrolysis gives formic acid.
CH2OCOH CH2OH
| |
CHOH CHOH + HCOOH
| | formic acid
CH2OH CH2OH
In this reaction glycerol acts as a catalyst.
(b) At 533 K, glyceryl dioxalate is formed which eliminates two molecules
of carbondioxide forming allyl alcohol.
CH2OH CH2 – O – CO CH2
| HO–CO | | ||
533K
CHOH + | CH – O – CO CH + 2CO2
| HO–CO | |
CH2OH CH2OH CH2OH
unstable allyl alcohol

The elimination of two molecules of carbondioxide takes place by the

cyclic reorganisation of bonds in the diester.

8. Oxidation :
Theoretically glycerol can give rise to a large variety of oxidation
products. The actual product obtained depends upon the nature of the
oxidising agent and their concentration.

177
 (a) With dil. Nitric acid glyceric acid is formed.
(b) With con. Nitric acid glyceric acid and tartronic acids are formed.
(c) Bismuth nitrate converts glycerol to Mesoxalic acid.
(d) Milder oxidising agents like bromine water or Fenton’s reagent
[FeSO4 + H2O2] or sodium hypobromite-oxidises glycerol to ‘glycerose’ -
a mixture of glyceraldehyde and dihydroxy acetone.
(e) Strong oxidising agents like warm acidified permanganate convert
glycerol to oxalic acid and carbondioxide.
Note :
[O] [O]
–CH2OH – CHO –COOH
primary alcohol aldehyde acid

[O] [O]
–CHOH– > C=O –COOH + CO2
Secondary alcohol Ketone etc.

Oxidation reaction of glycerol

CHO COOH COOH

| | |
CHOH (O) CHOH (O) CHOH (O)
| | |
CH2OH CH2OH CH2OH COOH
| glyceraldehyde glyceric acid tartronic acid
CHOH (O)
|
CH2OH CH2OH COOH
| |
CO (O)
CO
| prolonged
|
CH2OH COOH
dihydroxy acetone mesoxalic acid

(O)
(O) COOH
2 CO2 + H2O | + CO2
COOH
oxalic acid

178
16.5.1 Uses :
1. In the manufacture of explosives like TNG.
2. as an antifreeze in automobile radiators.
3. as a sweetening agent in beverages.
4. in moisturising creams and other cosmetics.
5. in copying inks and stamp pad inks.
16.6 AROMATIC ALCOHOL
Benzyl alcohol :
Aromatic compounds containing hydroxyl group in the side chain are
called aromatic alcohols. A typical example is Benzyl alcohol –C6H5CH2OH.
It is also called ‘phenyl carbinol’ or in the IUPAC system phenyl methanol.
CH2OH

The structure is

It can be considered as an arylated aliphatic alcohol. Benzyl alcohol

occurs in nature either in free form or in the form of esters in jasmine oil. It
is isomeric with cresols and anisole.

16.6.1 Methods of preparation :

1. By the hydrolysis of benzyl chloride
Obtained by the chlorination of Toluene followed by hydrolysis with
aqueous NaOH.

Cl2 NaOH
C6H5CH3 C6H5CH2Cl C6H5CH2OH + NaCl
Toluene –HCl Benzyl chloride Benzyl alcohol

The formation of benzyl alcohol from benzyl chloride involves

nucleophilic substitution.
This method is used in the large scale preparation of benzyl alcohol.
2. Reduction of benzaldehyde
Benzaldehyde is reduced to benzyl alcohol on treatment with sodium
amalgam and water or zinc and hydrochloric acid or Lithium aluminium
hydride.
C6H5CHO + 2 [H] C6H5CH2OH
179
3. By Cannizzaro Reaction :
Simple Cannizzaro reaction of benzaldehyde or a crossed Cannizzaro
reaction of a mixture of benzaldehyde and formaldehyde is effected by treating
them with 50% caustic soda solution.

OH–
(i) C6H5CHO C6H5CH2OH Benzyl alcohol
+ H2O +
C6H5CHO C6H5COOH Benzoic acid
(simple)

(ii) C6H5CHO C6H5CH2OH Benzyl alcohol

+ H2O OH– +
HCHO HCOOH Formic acid
(crossed)

This reaction involves oxidation of one aldehyde molecule to acid, while

the other aldehyde molecule is reduced to alcohol.
In the crossed Cannizzaro reaction of benzaldehyde with formaldehyde,
it is the formaldehyde that is converted to the acid and benzaldehyde to
alcohol. Because formaldehyde can be more easily oxidised than
benzaldehyde.
4. Grignard’s synthesis
Since benzyl alcohol is a primary alcohol, it is prepared by the action of
phenyl magnesium bromide on formaldehyde.
H C6H5 H H3O+
ether
C6H5MgBr + C=O C
H H O MgBr

C6H5
CH2 – OH
Br
+ Mg
OH

180
16.6.2 Properties :
It is a colourless pleasant smelling liquid with b.p. 478 K. It is sparingly
soluble in water, because of the presence of hydrophobic phenyl group (larger
in size when compared to methyl or ethyl group). But it is soluble in organic
solvents like benzene and alcohol.
Chemically it resembles aliphatic primary alcohol.
1. It is not so acidic as to dissolve in sodium hydroxide but reacts with
sodium metal forming sodium benzylate or sodium benzoxide.
2C6H5CH2OH + 2Na 2C6H5CH2ONa + H2
Sodium benzoxide brings about nucleophilic substitution at methyl carbon
atom of the methyl iodide forming ethers.
C6H5CH2O Na
+ C6H5CH2– O – CH3 + NaI
CH3 I
2. Reagents like PCl5, SOCl2 and HCl readily forms benzyl chloride
with benzyl alcohol.
C6H5 – CH2 – O – H
C6H5 – CH2Cl + POCl3 + HCl
Cl – PCl3 – Cl

C6H5 – CH2 – O – H
C6H5 CH2 Cl + SO2 + HCl
Cl – SO – Cl
4. On heating with phosphorous and hydriodic acid, it is reduced to
Toluene. Benzyl iodide is the intermediate in this reaction.
C6H5CH2 – OH C6H5 – CH2 – I
–H2O
I – H H–I C6H5CH3 + I2
Iodine is removed by phosphorous.
Hydrogen in presence of Palladium is the other reagent that can reduce
benzyl alcohol to Toluene.

181
 5. Benzyl alcohol forms esters with carboxylic acids in presence of
conc. sulphuric acid, and also with acid chlorides and acid anhydrides.

H+
C6H5CH2 OH + H OCOCH3 C6H5CH2OCOCH3
–H2O benzyl acetate

C6H5CH2 – O – H – HCl
+ C6H5CH2OCOCH3
CH3CO – Cl
Acetylchloride
CO – CH3
C6H5CH2 – O – H + O C6H5CH2OCOCH3
CO – CH3 + CH3COOH
Acetic anhydride
6. Oxidation :
(i) With mild oxidising agents like copper nitrate or lead nitrate, benzyl
alcohol is converted to benzaldehyde.
Pb(NO3)2
C6H5CH2OH C6H5CHO + H2O
or Cu(NO3)2
Decomposition of the metallic nitrate provide the source for the above
oxidation.
(ii) In the oxidation with acidified potassium dichromate or alkaline
potassium permanganate, benzaldehyde is first formed which undergoes
further oxidation to benzoic acid.
Na2Cr2O7/H+ or

C6H5CH2OH C6H5CHO C6H5COOH

Na2CO3/KMnO4 Benzaldehyde Benzoic acid

7. In addition to the above reactions, it undergoes reactions characteristic

of the benzene ring-namely electrophilic substitution reactions like
halogenation, nitration, sulphonation etc. In all these cases substitution takes
place in the benzene ring. Like CH3– and CH2Cl– groups, CH2OH– is also
ortho, para directing group. Hence ortho or para substituted products are
formed.

182
 CH2OH CH2OH CH2OH CH2OH CH2OH
Cl SO3H
Cl2 Conc.
+ +
H2SO4
Cl SO3H
o- and p- chloro o- and p-
substituted compounds sulphonic acid derivatives

16.6.3 Uses
(i) Used as a local anaesthetic in intravenus subcutaneous injections.
(ii) as an antiseptic in ointments.
(iii) as esters in perfumery. (Benzyl acetate has fragrance of Jasmine)
(iv) as benzyl benzoate in the treatment of asthma and whooping cough.
(v) in the manufacture of synthetic resins.

16.7 PHENOLS
Phenols : These form a class of compounds in which one or more
hydrogen atom of the benzene nucleus are replaced by hydroxyl group. The
simplest members are phenol [C6H5OH] and cresols [CH3–C6H4–OH].
Classification and Nomenclature
1. Phenols may be classified as monohydric, dihydric and trihydric
according to the number of hydroxyl groups.
(i) Monohydric phenols :
CH3
CH3 CH3
OH OH

OH
OH
Hydroxy benzene o-hydroxy toluene m-hydroxy toluene p-hydroxy toluene
(Phenol) (o-cresol) (m-cresol) (p-cresol)

(ii) Subsituted phenols :

These are named as derivatives of phenol or as hydroxy compounds.

183
 CHO OH COOH
OH OH O2N NO2

NH2
NO2 OH
o-aminophenol o-hydroxy 2,4,6-trinitro p-hydroxy
benzaldehyde phenol benzoic acid

(iii) Dihydric phenols :

OH OH CH3
OH

OH OH HO OH
OH
1,2-dihydroxybenzene 1,3-dihydroxybenzene 1,4-dihydroxybenzene 3,5-dihydroxytoluene
or or or or
ortho dihydroxy meta dihydroxy p-dihydroxy Orcinol
benzene benzene benzene
or or or
Catechol Resorcinol p-quinol

(iv) Trihydric phenols :

OH OH
OH
OH OH

OH HO OH
OH
1,2,3-trihydroxybenzene 1,2,4-trihydroxybenzene 1,3,5-trihydroxybenzene
(Pyrogallol) (Hydroxy quinol) (Phluroglucinol)

Occurence :
Coal tar is the most important source of phenols like phenol, cresol etc.,
from which they are obtained industrially. Some substituted phenols occur
in essential oil of plants like eugenol in clove oil, thymol in mint oil.

184
16.7.1 Preparation
1. From aryl halides : Phenols can be prepared by heating aryl halide,
with caustic soda at high temperature and pressure.

623K
Ar-Cl + NaOH ArOH + NaCl
300 atm.

623K
C6H5 Cl + NaOH C6H5OH + NaCl
Chloro benzene 300 atm. phenol

This reaction is an example of aromatic nucleophilic substitution.

The replacement of nuclear halogen is difficult because of the stronger C–Cl
bond compared to that in alkyl halides. Yet, this reaction is used for the large
scale preparation and is known as Dow’s process.
2. Phenol is also manufactured by heating chlorobenzene with steam
in presence of silica as catalyst.

SiO2
C6H5Cl + H2O C6H5OH + HCl
3. From sulphonic acids
Sodium salt of sulphonic acids when fused with sodium hydroxide yield
phenoxides. These on treatment with dil. hydrochloric acid give phenols.
ArSO3H + NaOH ArSO3Na + H2O

573 K
ArSO3Na + 2NaOH Ar – ONa + Na2SO3
Sodium phenoxide

ArONa + HCl ArOH + NaCl

4. By boiling weakly acidic aqueous solution of diazonium chloride,
phenol is formed.
H+
C6H5N2Cl + H2O C6H5OH + HCl + N2
Benzene diazonium
chloride

185
 This method is useful for the preparation of phenols which cannot be
prepared by other methods.
5. By the decarboxylation of phenolic acids. This is carried out by
heating sodium salt of phenolic acids with sodalime.

OH OH
NaOH / CaO
+ Na2CO3
COONa
∆
Sodium salicylate Phenol

6. Industrially phenol is prepared from cumene. Cumene is prepared

from benzene and propylene in presence of Lewis acid like anhydrous
aluminium chloride.
CH3
CH
AlCl3 CH3
+ CH3CH=CH2

Cumene
This is oxidised to hydro peroxide by oxygen of the air.
CH3
CH(CH3)2 |
O2 H3C – C–O–O–H

Cumene hydro peroxide

This is cleaved to phenol and acetone by aqueous hydrochloric acid.

CH3
| OH
H3C – C–O–O–H
H+
CH3
H2O
+ O=C
CH3
Phenol Acetone

186
16.7.2 Properties
1. Pure phenols are colourless liquids or crystalline solids. They turn
pink or red on exposure to air and light due to oxidation.
2. Lower phenols have characteristic ‘Carbolic acid’ - odour.
3. They are insoluble or sparingly soluble in water but dissolve readily in
alcohol and ether. Relatively high boiling point of phenols and solubility
in alcohols can be explained by intermolecular hydrogen bonding.
Insolubility in water is explained by the presence of hydrophobic phenyl
group.
16.7.3 General chemical properties
Phenols exhibit reactions of both the hydroxyl group and aromatic ring.
They differ from alcohols in having weakly acid character and in not
undergoing elimination and substitution reactions.
Reactions of hydroxyl group
In some reactions phenols resemble alcohols. In many others they differ
from alcohols.
Reactions different from alcohols
1. They form water soluble coloured complexes with neutral ferric
chloride. The colour of the complex vary from violet, red, blue or
green. Since different phenols give different colours.
Phenol itself gives violet colour. It is a characteristic test for phenol.
2. Acidic character
Phenols are weakly acidic. These are stronger acids than alcohols but
weaker than all mineral acids, carboxylic acids and even carbonic acid.
Hence phenols dissolve in sodium hydroxide (a strong base) but not in
sodium bicarbonate (weaker base). This property is used in the
separation of phenols from carboxylic acids.
C6H5OH + NaOH C6H5ONa + H2O
Sodium phenoxide

Similarly phenols evolve hydrogen on reaction with electropositive metals

like sodium.

187
 2C6H5OH + 2Na 2C6H5ONa + H2 ↑
16.7.4 Acidic nature of phenols
Factors that enhance the stability of the anion of acid and that increase
the ease of release of proton, enhance the strength of an acid.
Thus in the case of phenol, the phenolateion is more stabilised by
resonance than phenol itself.
OH O–
H2O

+ H3O+

Phenol Phenolate ion

Resonance in phenolate ion

O– O O O
(–) (–)

(–)

In the case of alcohols there is no stabilisation of the anion.

RCH2–OH RCH2–O(–)
Presence of –I, –M groups in benzene ring enhances its acid strength.
OH OH OH OH

> > >

NO2 Cl CHO CH3
At para position the resonance effect effectively operates.
OH OH

>

NO2
188
 Resonance in p-nitrophenol and its anion
+
:OH OH

etc.

N N+
O O(–) (–)O O(–)

O– O

etc.

N+ N+
O O(–) (–)O O(–)

Phenolate ion has no +ve charge on oxygen and hence is more stabilised
by resonance than phenol itself.
Consequence of this Resonance
1. Phenols are stronger acid than alcohols (because the RO–-alkoxide
ions are not stabilised by resonance).
2. The electron density is increased in the benzene ring and hence the
benzene ring is activated towards electrophilic substitution reaction.
3. Ortho and para positions are more electron dense, and the electrophilic
substitution takes place at ortho and para positions.
4. Oxygen is strongly bound to the nucleus hence it is not easily removed.
The acid strength of phenols depend on the nature of the substituent
present in the benzene ring. Electron withdrawng groups like -Nitro, cyano
groups increase the acid strength. Electron donating substituents like –NH2,
CH3- groups decrease the acid strength. (e.g.,) strength of phenol varies in
the order.

189
 OH OH OH OH OH

> > > >

NO2 C≡N CHO CH3

Reaction with zinc dust

Phenols on distillation with zinc dust give aromatic hydrocarbons.
ArOH + Zn ArH + ZnO
C6H5OH + Zn C6H6 + ZnO
This reaction is useful in the identification of aromatic ring present in a
natural product.
1) Reactions similar to alcohols
The hydrogen of the –OH group of phenol can be replaced by acyl
group forming esters.
Direct esterification of phenol using carboxylic acid in presence of
dehydrating agent like con. sulphuric acid forms phenol esters but the reaction
does not go to completion.
H+
C6H5OH + CH3COOH C6H5COOCH3 + H2O
Phenyl acetate

Acid chlorides and acid anhydrides react with phenols giving esters more
easily, especially in presence of a base.

C6H5 – OH + CH3 – COCl OH– C6H5OCOCH3 + HCl

OH–
C6H5 – OH + CH3COOCOCH3 C6H5OCOCH3 + CH3COOH
The reaction of phenols with benzoyl chloride in presence of sodium
hydroxide to form benzoates is known as Schotten-Baumann reaction.

190
 NaOH
C6H5OH + C6H5COCl C6H5OCOC6H5 + HCl
Phenyl benzoate
2) Etherification
Phenols react with alkyl halides or alkyl sulphates in presence of alkali
to form phenolic ethers. Aryl halides do not react with phenols. This alkylation
of phenol is a nucleophilic substitution reaction. This reaction is known as
Williamsons synthesis.
NaOH
ArOH ArO(–) + Na+

ArO(–) + R – X Ar–O–R + X–

NaOH
C6H5OH + (CH3)2 SO4 C6H5OCH3 + CH3OSO2OH
Dimethyl sulphate Anisole Methyl hydrogen sulphate

OH–
C6H5OH + C2H5Br C6H5O C2H5 + HBr
Phenetole or
ethoxy benzene

3) Reaction with phosphorous halide

The oxygen of the hydroxyl group in phenol is strongly bound to the
benzene ring hence it cannot be easily replaced. Though phenols react with
PCl5 to give chloro benzene, other reagents like HCl, PCl3, do not give
chloro benzene.

C6H5 – O – H C6H5Cl + POCl3 + HCl

Cl – PCl3 – Cl

The yield of chloro benzene is very small and the main product is triphenyl
phosphate (C6H5O)3PO. (Compare this reaction with alcohol)

191
4) Diazomethane directly converts phenol to anisole in alkaline medium.

OH–
C6H5OH + CH2N2 C6H5OCH3 + N2
diazomethane Anisole

5) Reaction with Ammonia

When heated with NH3 under pressure in presence of catalysts like
anhydrous zinc chloride or calcium chloride, hydroxyl groups of phenols are
replaced by amino groups.
ZnCl2/473 K
ArOH + NH3 ArNH2 + H2O

ZnCl2/473 K
C6H5OH + NH3 C6H5NH2 + H2O
Phenol Aniline

Reactions characteristic of the benzene ring

The phenolic –OH group increases the reactivity of benzene especially
with respect to electrophilic substitution reaction. Also it is ortho and para
directing group. But due to greater reactivity, phenols undergo poly
substitution and oxidation. Hence only under milder conditions mono
substitution is expected.

1. HALOGENATION
Halogens directly react with phenols, substituting the hydrogen at ortho
and para positions. When phenol is treated with bromine water the colour of
bromine disappears with the formation of white precipitate. The white
precipitate consists of 2, 4, 6-tribromo phenol.
OH OH
3 Br2 Br Br
+ 3 HBr
H2O

Br
2, 4, 6-tribromo phenol.

This is one of the tests for phenols.

192
 Mono bromoderivative can be prepared at lower temperature and in the
presence of non polar solvents like CCl4 and CS2.

OH OH OH
2 Br2 Br
+ + 2HBr
CCl4

Br
ortho bromo phenol para bromo phenol

2. NITRATION
Reaction with nitrating mixture - con. H2SO4 acid and con. Nitric acid
mixture-gives picric acid.

OH OH
O2N NO2
298 K
+ 3 H2O
H2SO4/HNO3

NO2
2, 4, 6-trinitro phenol (Picric acid)

With dilute nitric acid, a mixture of ortho and para nitro phenols are
formed.
OH OH OH
NO2
HNO3
+

NO2

ortho nitro phenol para nitro phenol

NO2+ (nitronium ion) is the electrophile in the reaction.

193
SULPHONATION
Reaction with con. H2SO4. It forms a mixture of ortho and para phenol
sulphonic acid.

OH OH OH
SO3H
293 K
+
Conc. H2SO4

SO3H
Ortho hydroxy benzene Para hydroxy benzene
Sulphonic acid Sulphonic acid

NITROSATION
It reacts with nitrous acid (a mixture of sodium nitrite and sulphuric
acid) to give p-nitrosophenol.

OH OH
200 K

HNO2

NO
para nitroso phenol

This reaction involves electrophilic attack by NO + (nitrosonium ion).

Coupling with diazonium chloride :
Phenol couples with benzene diazonium chloride in alkaline medium to
form p-hydroxy azobenzene. Diazonium ion C6H5N = N+ is the electrophile
in this reaction.

OH–
N=N–Cl + H OH N=N OH
273 K
(Benzene diazonium chloride) (p-hydroxy azobenzene-
a red orange dye)

This is also called dye test, which is Characteristic of phenol.

194
Kolbe schmidt or Kolbe’s reaction
When sodium phenoxide is heated with carbon dioxide at 400 K under
pressure, sodium salicylate is formed. This is decomposed by dilute
hydrochloric acid, when salicylic acid is formed. CO2 is the electrophile in
this reaction.

ONa OH OH
CO2 HCl
+ NaCl
400 K
COONa COOH
4 - 7 atm

Riemer-Tiemann reaction
This reaction is an example of formylation reaction. When phenol is
refluxed with chloroform and sodium hydroxide, a formyl group –CHO is
introduced at the ortho or para position to –OH group.

OH OH OH
CHCl3
+
NaOH CHO
OHC
Ortho Para
(Hydroxy benzaldehyde)

Similarly with CCl4 and NaOH, hydroxy benzoic acid is formed.

OH CCl4 OH OH
+
NaOH
COOH
HOOC
Ortho Para
(Hydroxy benzoic acid)

Phthalein fusion
Phenols are heated with phthalic anhydride and con. H2SO4 to give
Phenolphthalein. This can be tested by the formation of pink colour when it
is treated with sodium hydroxide.

195
 O O O O
H OH OH
C C
C=O C

H OH OH

Phenolphthalein

Oxidations
Phenol undergoes oxidation to quinone on treatment with chromyl
chloride (CrO2Cl2).

CrO2Cl2
OH + 2 ( O) O O

Catalytic hydrogenation
Phenol on hydrogenation in presence of nickel forms cyclohexanol.
OH
OH
Ni
+ 3 H2
443 K

(Cyclohexanol)
Condensation :
Phenol, when treated with formaldehyde and sodium hydroxide,
undergoes condensation reaction.

HO NaOH HO
+ HCHO

CH2OH
p-hydroxy phenyl methanol

This is called ‘Lederer-Manasse reaction’.

196
 In presence of excess of formaldehyde, three dimensional polymer called
‘Bakelite’ is formed.
OH OH
------H2C CH2 CH2-------

CH2 CH2
| |
Bakelite
16.7.4 Uses
Phenol is of much industrial importance. It is used in the manufacture of
dyes, drugs, plastics, explosives, pesticides etc. Phenol is an antiseptic and
germicide. It is used in some soaps and lotions.

SELF EVALUATION
(A) Choose the correct answer :
1. Which has the highest boiling point ?
(a) CH3CH3 (b) CH3OH (c) C2H5OH (d) C3H8
2. Which is soluble in H2O ?
(a) Phenol (b) Alkanes (c) Alcohols (d) Alkenes
3. Order of reactivity of alcohol towards sodium metal is
(a) primary < secondary > tertiary
(b) primary > secondary > tertiary
(c) primary < secondary < tertiary
(d) primary > secondary < tertiary
4. The boiling point of ethyl alcohol should be less than that of
(a) propane (b) formic acid
(c) dimethyl ether (d) None of the above
5. Ethyl alcohol cannot be used as a solvent for CH3MgI because
(a) CH3MgI reacts with alcohol giving methane
(b) The reaction between them is explosive in nature
(c) CH3MgI is converted to C2H5MgI
(d) Alcohol is immicible with CH3MgI

197
6. When alcohols are converted to alkyl chlorides by thionyl chloride in
presence of pyridine the intermediate formed is
(a) sulphonium ion (b) chlorosulphonic acid
(c) alkyl chlorosulphite (d) chlorosulphite
7. On oxidation of an alcohol gives an aldehyde having the same number of
carbon atoms as that of alcohol. The alcohol is
(a) 1o alcohol (b) 2o alcohol (c) 3o alcohol (d) None
8. A compound that gives a positive iodoform test is
(a) 1-pentanol (b) 2-pentanone (c) 3-pentanone (d) pentanal
9. The compound that reacts fastest with Lucas reagent is
(a) butan-1-ol (b) butan-2-ol
(c) 2-methyl propan-1-ol (d) 2-methyl propan-2-ol
10. The ionization constant of phenol is higher than that of ethanol because
(a) phenoxide ion is bulkier than ethoxide
(b) phenoxide ion is stronger base than ethoxide
(c) phenoxide ion is stablized through delocalisation
(d) phenoxide ion is less stable than ethoxide ion
11. Among the following compounds strongest acid is
(a) HC ≡ CH (c) C6H6 (c) C2H6 (d) CH3OH
12. The most unlikely representation of resonance structures of
p-nitrophenoxide ion is
O– O

(a) (b)

N N
+
(–)O O(–)
O O(–)

O– O

(c) (d) –

N N
+ +
O O O– O

198
13. p-nitrophenol is having lower pKa value than phenol because
(a) phenol is more acidic than p-nitro phenol
(b) anion of p-nitrophenol is more stabilised by resonance than that of
phenol
(c) degree of ionisation of p-nitro phenol is less than that of phenol
(d) anion of p-nitrophenol is less stable than that of phenol
14. The reaction of Lucas reagent is fast with
(a) (CH3)3COH (b) (CH3)2CHOH
(c) CH3(CH2)2OH (d) CH3CH2OH
15. When phenol is distilled with Zn dust it gives
(a) benzaldehyde (b) benzoic acid
(c) toluene (d) benzene
16. A compound that undergoes bromination easily is
(a) benzoic acid (b) benzene
(c) phenol (d) toluene
17. Isomerism exhibited by ethylene glycol is
(a) position isomerism (b) chain isomerism
(c) functional isomerism (d) both (a) and (c)
18. Ethylene diamine is converted to ethylene glycol using
(a) Na2CO3 solution (b) nitrous acid
(c) NaHCO3 (aqueous) (d) Baeyer’s reagent
19. Ethylene glycol forms terylene with
(a) adipic acid (b) phthalic anhydride
(c) terephthalic acid (d) oxalic acid
20. 1-propanol and 2-propanol can be best distinghished by
(a) oxidation with KMnO4 followed by reaction with Fehling solution
(b) oxidation with acidic dichromate followed by reaction with
Fehling solution
(c) oxidation by heating with copper followed by reaction with
Fehling solution
(d) oxidation with concentrated H2SO4 followed by reaction with
Fehling solution
199
21. Glycerol is used
(a) as a sweeteing agent
(b) in the manufacture of good quality soap
(c) in the manufacture of nitro glycerin
(d) in all the above
22. The alcohol obtained by the hydrolysis of oils and fats is
(a) pentanol (b) propanol (c) glycerol (d) glycol
23. The number of secondary alcoholic group in glycerol is
(a) 1 (b) 2 (c) 3 (d) 0
24. The active component of dynamite is
(a) Keiselghur (b) Nitro glycerine
(c) Nitro benzene (d) Trinitro toluene
25. The reaction of ethylene glycol with PI3 gives
(a) ICH2CH2I (b) CH2 = CH2
(c) CH2 = CHI (d) ICH = CHI
(B) Pick Out the incorrect statements :
1. (a) Secondary alcohol with heated copper at 570 K gives ketone
(b) Isobutyl alcohol in Victor Meyer’s test gives blue colour.
(c) Methyl alcohol is more toxic than ethyl alcohol
(d) Methyl alcohol is used in alcoholic beverages
2. (a) The intermediate compound in the preparation of ethylene from
ethyl alcohol and con.H2SO4 is C2H5.HSO4.
(b) An organic acid reacts with alcohol to form an ester.
(c) The acidity of phenol is due to the presence of benzene ring
(d) Tertiary alcohols can not be easily oxidised
3. (a) Benzyl alcohol and phenol can be distinguished by using Br2/H2O
reagent.
(b) Formation of phenol from chlorobenzene is an example of
electrophilic aromatic substitution.
(c) The IUPAC name of ethylene glycol is ethane 1,2-diol
(d) when ethylene glycol is heated to 773 K dehydration reaction
takes place.

200
4. (a) Ethylene glycol reacts with con.H2SO4 to form ethylene oxide.
(b) When acidified potassium permanganate reacts with ethylene glycol
C–C bond cleavage takesplace.
(c) Glycerol on dehydration forms CH2=CH–CHO
(d) Ethylene decolourises bromine water.
(C) Answer not exceeding sixty words :
1. What are alcohols ? How do they differ from inorganic hydroxides ?
2. Account for the following :
(a) lower members of alcohols are soluble in water but higher members
are not
(b) Alcohols cannot be used as solvent for grignard reagent.
3. Give reason.
Methanol is miscible with water while iodo methane is not.
4. Give chemical test to distinguish between ethanol and methanol.
5. Compare the acid strength in 1o, 2o and 3o alcohol giving reason.
6. Write the mechanism briefly when alcohols are treated with anhydrous
zinc chloride and HCl.
7. Why is that tertiary alcohols show greater reactivity towards hydrogen
halides than secondary and primary alcohols ?
8. How do primary, secondary and tertiary alcohols differ in terms of their
oxidation ?
9. How will you convert C2H5OH to C2H5OC2H5 ?
10. Complete the reaction and write the names of products.
Al2O3
C2H5OH + NH3
360oC

11. Explain the mechanism of acid catalysed dehydration of ethanol at high

temperature.
12. How do primary, secondary and tertiary alcohols differ in terms of their
dehydrogenation ?

201
13. Give chemical tests to distinguish between propan-2-ol and 2-methyl-
propan-2-ol.
14. Explain ‘esterification’ reaction with an example.
15. Why is glycol more viscous than ethanol ?
16. What happens when ethylene reacts with alkaline KMnO4 solution ?
17. Explain oxidation reactions of ethylene glycol.
18. How is terylene prepared from glycol ?
19. Write the conversion of ethylene glycol to 1,4-dioxan ?
20. How is glycerol obtained commercially ? State its two uses.
21. How does glycerol react with (i) PCl5 (ii) KHSO4.
22. Give a brief account of the following reaction. (i) esterification, (ii) Riemer
Tiemann reaction.
23. Explain Kolbe’s reaction.
24. Account for the following :
(i) Phenol has a smaller dipole moment than methanol.
(ii) Phenols do not give protonation reaction readily.
25. Explain why phenol does not undergo substitution of the –OH group
like alcohol.
26. Complete the following reaction giving names of products.
con.H2SO4
OH + HNO3 ?
excess

27. Give chemical test to distinguish between methanol and phenol.

28. Give a brief account of coupling reaction.
29. What happens when phenol is treated with diazonium chloride in presence
of NaOH ?
30. Explain Dow’s process.

202
31. Identify the product A and B.
OH
CHCl3 Ag+
A B
NaOH

CH3

Ans.
OH OH
CHO COOH

A= B=

CH3 CH3

32. Identify C and D.

ONa
CO2 dil. HCl
C D
403 K
6 atm

Ans.
OH OH
COONa COOH

C= D=

33. Identify the product. A and B

CH3
[O] [O]
CHOH A B
prolonged
CH3
Ans. A = CH3 – C – CH3 [O]
CH3 COOH
|| B
O
203
34. What are monohydric alcohols ? How are they classified ? Give any
three methods of preparing ethyl alcohol.
35. How will you distinguish the primary, secondary and tertiary alcohols by
Victor Meyer’s method ?
36. Write equation for the following conversions.
(a) Ethyl alcohol ethylene
(b) Ethyl alcohol diethyl ether
(c) Ethyl alcohol ethyl amine
37. Explain the mechanism of esterification.
38. Give short notes on the following :
(a) Kolbe’s reaction
(b) Riemer Tiemann reaction
(c) Coupling reaction
39. Explain the action of glycerol with
(i) oxalic acid at 383 K
(ii) oxalic acid at 530 K
(iii) concentrated HNO3 and H2SO4.
40. What are the oxidation products of glycerol ?
41. How is ethylene glycol prepared ? Give three methods.
42. Starting from phenol how would you obtain the following compounds ?
(a) p-quinone, (b) picric acid and (c) Anisole.
43. How would you distinguish between
(i) methyl alcohol and ethyl alcohol
(ii) benzyl alcohol and phenol
(iii) ethyl alcohol and benzyl alcohol
44. Give any four methods of preparing benzyl alcohol.
45. Write a note on the ‘Acidic nature of phenol’.

204
Problem.
1. How is the following conversion effected ?
Ethyl alcohol Ethylene glycol
Ans. Al2O3 cold alkaline
CH3CH2OH CH2 = CH2
620K KMnO4
(Baeyer’s reagent)

CH2 – CH2
| |
OH OH
2. Give the IUPAC names of
(i) CH3CH(OH)CH2OH
(ii) HO–CH2–CH2–OH
(iii) CH3–CH–COOH
|
OH
Ans. (i) propane-1, 2-diol
(ii) ethane-1,2-diol
(iii) 2-hydroxy propanoic acid
3. Identify the isomerism in each of the following pairs.
(i) CH3OCH2OCH3 and CH3OC2CH2OH
(ii) CH3CH(OH)CH2OH and CH2OHCH2CH2OH
(iii) CH3–CH–CH2–OH and CH3–CH2–CH2–CH2OH
|
CH3
Ans. (i) functional isomerism
(a) dimethoxy methane
(b) 2-methoxy ethanol

205
 (ii) position isomerism -diol position is changed
(a) propane-1,2-diol
(b) propane-1,3-diol
(iii) chain isomerism - carbon chain is changed.
(a) isobutyl alcohol
(b) n-butyl alcohol
4. Complete the following equations by writing the missing A, B, C, D etc.

dil.H2SO4 [O] SOCl2

(i) CH ≡ CH A B C
HgSO4

Ans. A = CH3CHO
B = CH3COOH
C = CH3COCl

PCl5 KCN H2O/H+ sodalime

(ii) C2H5OH A B C D
∆
Ans. A = C2H5Cl
B = C2H5CN
C = C2H5COOH
D = C2H6

5. Why alcohols cannot be used as solvents with (a) Grignard reagent

and (b) LiAlH4.
Ans. Alcohols are sufficiently acidic to react with strong bases R– :
and H– :
H
|
CH3OH + H – C – MgX CH4 + (CH3O) – MgX
|
H

4CH3OH + LiAlH4 4H2 + LiAl(OCH3)4

206
6. When tertiary butyl alcohol and 1-butanol are separately treated with a
few drops of KMnO4, in one case only the purple colour disappears and
a brown precipitate is formed. Which of the two alcohols gives the above
reaction and what is that brown precipitate.

Ans. 1-butanol, being primary alcohol gets oxidised by dilute KMnO4.

The brown precipitate is due to the formation of manganese dioxide.

2KMnO4 + H2O 3KOH + 2MnO2 + 3 (O)

manganese dioxide
(brown precipitate)

2(O)
CH3–CH2–CH2–CH2 –OH + CH3 CH2 CH2 COOH + H2O
room temp.
1-butanol butanoic acid
7. Write the conversion of acetic acid to t-butyl alcohol.
Ca(OH)2 ∆
CH3COOH (CH3COO)2Ca CH3COCH3
calcium acetate acetone

CH3MgBr

CH3
|
CH3 – C – OH
|
CH3
Tert. butyl alcohol

8. Compound (A) C6H12O2 on reduction with LiAlH4 yields two compounds

B and C. The compound (B) on oxidation gave (D) which on treatment
with aqueous alkali and subsequent heating furnished E. The latter on
catalytic hydrogenation gave (C). Compound (D) on oxidation gave
monobasic acid (molecular formula weight = 60). Deduce the structure
of (A), (B), (C), (D) and (E).
Ans. E is monobasic acid (RCOOH) having molecular weight 60 and it
is formed from D on oxidation. So E must be acetic acid and D must be
acetaldehyde. (B) on oxidation gives CH3CHO. So (B) must be alcohol
(CH3CH2OH).

207
 Acetaldehyde (D) on treating with aqueous alkali (NaOH) gives aldol
which on heating gives 2-butenal (E).

NaOH heat
CH3CHO CH3CHOHCH2CHO
–H2O
(D) aldol

CH3 – CH = CH CHO
2-butenal (E)
Compound E on catalytic hydrogenation gives butyl alcohol.
H2
CH3 – CH = CHCHO CH3 CH2 – CH2 – CH2 OH
1-butanol (C)

Hence compound (A) must be an ester. Ester (A) on reduction with

LiAlH4 yields two alcohols (B) and (C).
A is ethyl butyrate

LiAlH4
CH3CH2CH2COOCH2CH3 CH3CH2OH + CH3CH2CH2 CH2OH
ethyl alcohol butyl alcohol
(B) (C)

‘A’ can also be CH3CO-O-CH2CH2CH2CH3. This structure will be

answering all the above reactions.

PRACTICE
1. Write the IUPAC names of (i) CH3OCH2CH2OH (ii) CH3OCH2OCH3
CH2OH
and (iii)

Ans. (i) 2-methoxy ethanol ; (ii) dimethoxy methane and

(iii) phenyl methanol
2. Why sodium metal cannot be used to dry alcohols but it can be used to
dry ethers ?
Ans. Alcohols are acidic enough to react with sodium but ethers are
inert.

208
3. An organic compound has the formula C4H10O. It reacts with metallic
sodium liberating hydrogen.
(i) Write down the formula of three possible isomers of the compound
which are similar and react with sodium.
(ii) What will be the product if any one of the isomers reacts with acetic
acid ?
Ans. The three isomers are
(i) CH3CH2CH2CH2OH
CH3CH(OH)CH2CH3
CH3 – CH – CH2OH
|
CH3
(ii) CH3CH2CH2CH2OH + CH3COOH CH3CH2CH2CH2OOCCH3

PRACTICE QUESTIONS.
1. Give the IUPAC names of each of the following and classify them as 1o,
2o and 3o.
(a) CH3(CH2)3CHOHCH(CH3)2 (b) (CH3)3C–CH2OH
(c) (CH3)2 C – OH (d) BrCH2CH2 – CH – C (CH3)3
| |
C6H5 OH
(e) CH2 = CH–CHOHCH3 (f) PhCH2OH
(g) HOCH2CH2CH2CH2C6H5 (h) (C2H5)3COH
2. Give all the isomers of alcohols differing only in the position of –OH
with molecular formula C5H10O.
3. Give the structure of all primary alcohols with molecular formula C5H10O.
4. Give the Grignard reagent and carbonyl compound that can be used to
prepare
(a) CH3CH2CH2OH (b) (CH3)2C(OH)CH2CH2CH3

209
 (c) C6H5 CH2CH(OH)CH3 (d) C6H5
|
CH3CH2 – C – CH3
|
C6H5
5. Why dry ether is to be used as a solvent for Grignard reagent ?
6. Which of the following does not give Iodoform reaction ?
CH3CH2OH, CH3CH(OH)CH2CH3, CH3CH(OH)CH3, (CH3)3COH
7. How can ethyl alcohol be converted to isopropyl alcohol ?
8. How can isobutyl alcohol be converted to t-butyl alcohol ?
9. How can 1-butanol be converted to 2-butene ?
10. An organic compound C3H8O3 yields on acetylation with acetic anhydride
C9H14O6. How many –OH groups are present in the substance ? What is
the possible structure ?
11. Assign δ+and δ– to each atom joined by the covalent bond shown in the
following structures.
(a) CH3 – Br, (b) CH3OCH3, (c) CH3NH2, (d) CH3 – O – SO2 – OCH3
12. Predict the species produced during heterolytic fission of the following:
(a) (CH3)2CHOH (b) (CH3)3CBr
(c) CH3CH2Li (d) (CH3)3C – O+ – CH3
|
H
13. Which member of the following pairs would you expect to be more water
soluble ?
(a) CH3 CH2 OH or CH3 CH2 OCH3
(b) CH3 COOH or HCOOCH3

14. Which member of the following pairs would you expect to have higher
boiling point ?
CH3 O CH2 CH2 O CH3 or CH2 OH CH2 CH2 CH2 OH
Cl CH2 CH2 OH or CH2 OH – CH2 OH
210
GLYCOLS & GLYCEROLS
1. What happens when - give equation.
(i) ethylene + alkaline permanganate

KHSO4
(ii) glycerol
∆
KOH (aq)
(iii) Ethylene + chlorine product

2. How can the following conversion be effected ?

(i) glycerol acrolein
(ii) glycol dioxan
(iii) oxalic acid formic acid
3. What is the action of
(i) anhydrous ZnCl2 on glycol
(ii) Con.HI on glycerol
(iii) heat on a mixture of glycerol and oxalic acid (533 K)

4. Complete the following :

O2/Ag H2SO4/H2O
(i) C2H4 A B
523 K 473K

HNO3 HNO3
(ii) glycerol A B
(O) (O)

Na2CO3/H2O HOCl NaOH

(iii) Allyl chloride

5. Convert the following :

(i) glycol Formaldehyde
(ii) glycerol TNG
(iii) glycerol Glycerol Triacetate
211
Phenols
1. How can the following be obtained ?
(a) phenol from benzene diazonium chloride
(b) 2, 4, 6-tribromo phenol from phenol
2. How will you convert
(a) chloro benzene to phenol
(b) phenol to 2-acetoxybenzoic acid
3. How can the following conversion be effected ?
(a) phenol to phenolphthalein
(b) phenol to benzene
4. Write the reaction which takes place when
(i) Sodium phenoxide is treated with CO2 and the product is acidified
(ii) Phenol is heated with chloroform and NaOH
(iii) Phenol is reacted with dilute HNO3.
5. Account for the following :
(i) Phenol exhibits acidic character
(ii) Phenol does not get protonated readily
(iii) Phenol, Benzendiazonium chloride, NaOH solution gives red dye.
6. How are the following conversions done ?
(i) phenol to phenyl ethanoate
(ii) aniline to phenol and (iii) phenol to anisole
7. Arrange the following in the decreasing order of acid strength ?

OH , MeO OH , O2N OH , CH3 OH

8. Account for the following :

(i) phenol is soluble in NaOH and regenerated on adding HCl.
(ii) phenol is insoluble in NaHCO3 solution while acetic acid is soluble
(iii) Ethyl alcohol and phenol are miscible in all proportions

212
9. (i) What happens when phenol is warmed with CCl4 in presence of
NaOH ?
(ii) When phenol is treated with benzoyl chloride in presence of NaOH.
(iii) When phenol is treated with con. H2SO4.

10. Distinguish between

(a) Ethanal and phenol
(b) Phenol and acetic acid
(c) Phenol and aniline
(d) Phenol and anisole

SUMMARY :
Structure and isomerism of alcohols - chain isomerism, position
isomerism and functional isomerism.
Nomenclature - common system, carbinol system and IUPAC - system
of naming alcohols. Classification of hydroxy compounds - alkyl, aryl and
aralkyl hydroxy compounds. Classification as primary, secondary and tertiary
alcohols.
General methods of preparation - Hydration of olefins, hydrolysis of
alkyl halides, reduction of carbonyl compounds and use of Grignard reagents.
Properties : Hydrogen bonding and molecular association and abnormal
boiling point.
Chemical properties of alcohols - acidic property, elimination to form
olefins, substitution of hydroxy group, to form ethers, alkyl halides, esters
and oxidation to carbonyl compounds. Distinction between 1o, 2o and 3o
alcohols - uses of methyl alcohol and ethyl alcohol. Preparation and properties
of benzyl alcohol. Differences between aliphatic alcohol and benzyl alcohol.
Dihydric alcohol - ethylene glycol
Trihydric alcohol - glycerol - oil and fat - preparation - physical and
chemical properties. Special emphasis on oxidation reactions - reaction with
HI and dehydration - uses.
Phenols - Substituted phenols - structure and nomenclature - methods
of preparation - physical properties - presence of hydrogen bonding. Chemical
properties - Acidic property and resonance - properties of hydroxyl group.
Properties of benzene ring - activation of benzene ring towards electrophilic
substitution - formation of azo dyes and phenolpthalein.

213
REFERENCES :
1. Organic Chemistry - Graham Solomons, Craig Fryhle & Robert Johnson,
John Wiley & Sons - 7th edition.
2. Solutions Manuel - Graham Solomons, Craig Fryhle & Robert Johnson,
John Wiley & Sons - 7th edition.
3. Schaum’s Solved Problems Series in Organic Chemistry -
Tata McGraw-Hill Edition - 2003.
4. Problems in Organic Chemistry - Mrs. Rosenbe, Raja & Publication.
5. Keynotes in Organic Chemistry - Andrew. F. Pearson. Black Well
Publishers.
_____

214
 17. ETHERS
LEARNING OBJECTIVES
@ Ethers - structure, classification, isomerism and nomenclature.
@ General methods of preparation - properties - physical and chemical
properties - uses.
@ Aromatic ethers - nomenclature.
@ The methods of preparation of anisole - its physical and chemical
properties - uses.
17.1 ETHERS
These are compounds of the type R–O–R, where oxygen atom is linked
to both sides by either saturated, unsaturated or aromatic carbon. Their
general formula is R–O–R'.
CLASSIFICATION
Simple ethers :
If the two alkyl groups attached to the oxygen atom are the same
(R = R') then it is called a simple or symmetrical ether.
CH3 – O – CH3 C2H5 – O – C2H5
dimethyl ether diethyl ether

Mixed ethers :
If the two alkyl groups are different then they are called as mixed or
unsymmetrical ethers.
(e.g.,) CH3 – O – C2H5
ethyl methyl ether

If one or two aryl groups are attached to the oxygen atom then they are
called as aromatic ethers. For example
C6H5–O–CH3 C6H5–O–C6H5
anisole diphenyl ether
Nomenclature :
Common system - Ethers are named by prefixing the names of alkyl
groups attached to the oxygen atom before the word ‘ether’. Thus
CH3–O–CH3 is dimethyl ether CH3–O–C2H5 is ethyl methyl ether.

215
 IUPAC name - Here ethers are named as alkoxy derivatives of alkanes.
Formula IUPAC name Common name
CH3 – O – CH3 Methoxy methane Dimethyl ether
CH3 – O – C2H5 Methoxy ethane Ethyl methyl ether
CH3 – O – CH2–CH2 – CH3 1-methoxy propane methyl n-propyl ether
CH3– O – CH – CH3 2-methoxy propane methyl iso propyl ether
|
CH3

Isomerism :
Ethers are functional isomers of alcohols as both have the same general
formula CnH2n+2O.
The C2H6O stands for both CH3CH2OH and CH3– O – CH3.
Functional Isomerism
Molecular formula Ethers Alcohols

C3H8O CH3–O–CH2–CH3 CH3CH2CH2OH

ethyl methyl ether n-propyl alcohol

CH3 – CH – CH3
|
OH
isopropyl alcohol

C4H10O CH3CH2–O–CH2CH3 CH3–CH2–CH2–CH2–OH

diethyl ether n-butyl alcohol

CH3–O–CH2–CH2–CH3 CH3–CH–CH2OH
methyl-n-propyl ether |
CH3
isobutyl alcohol

CH3–O–CH–CH3 CH3–CH2–CH–CH3
| |
CH3 OH
methyl isopropyl ether sec.butyl alcohol
CH3
|
CH3–C–OH
|
CH3
tert. butyl alcohol

216
Metamerism :
It is a special isomerism in which molecules with same formula, same
functional group, differing only in the nature of the alkyl group attached to
oxygen.
CH3
|
CH3 – O – CH2CH2CH3 CH3–CH2–O–CH2CH3 CH3–O–CH–CH3
methyl-n-propyl ether diethyl ether methyl isopropyl ether

17.2 GENERAL METHODS OF PREPARATION

1. Intermolecular dehydration of alcohol. When excess of alcohol is
heated with con. H2SO4 or H3PO4, two molecules condense losing a
molecule of water forming ether.
H2SO4
R–OH + H – OR R – O – R + H2O

413K
C2H5 – O – H + H – O – C2H5 C2H5 – O – C2H5
con. H2SO4

This reaction proceeds by a nucleophilic substitution mechanism. The

nucleophile alcohol, brings about nucleophilic attack on protonated alcohol.
C2H5 C2H5
| |
O: O+ – H C2H5 – O – C2H5 + H+ + H2O
| |
H H

Dehydration can also be brought about by passing vapours of alcohol

over heated Alumina or Thoria.

250oC
2C2H5OH C2H5 – O – C2H5 + H2O
Al2O3

2. Williamson’s synthesis
This is the most important method. It consists of heating alkyl halides
with sodium or potassium alkoxide.
217
 RX + NaOR' R–O–R' + NaX

C2H5Br + NaOC2H5 C2H5 – O – C2H5 + NaBr

CH3Br + NaOC2H5 CH3 – O – C2H5 + NaBr

methyl bromide sodium ethoxide ethyl methyl ether

This involves nucleophilic attack by RO– on the carbon atom attached

to the halogen.
–
R – O + R' – Br R – O – R' + Br–

This method is suitable to prepare all kinds of ethers - simple and mixed
ethers.
3. From alkyl halides
By heating alkyl halides with dry silver oxide, ethers may be prepared.
∆
R–X + Ag2O + X–R R–O–R + 2AgX

∆
C2H5 – I + Ag2O + I – C2H5 C2H5 – O – C2H5 + 2AgI
Mixed ethers can be prepared by taking different alkyl halide with dry
silver oxide.
CH3I + Ag2O + I – C2H5 CH3 – O – C2H5 + 2AgI
methyl iodide ethyl iodide ethyl methyl ether

R – O – Ag Silver alkoxide may be an intermediate.

4. Using Grignard reagent.

Using Grignard reagent lower halogenated ether may be converted to
higher ethers.
R – O – CH2 X + X – Mg R' R – O – CH2R' + MgX2
Br
CH3–O–CH2Cl + BrMgCH3 CH3–O–CH2CH3 + Mg
monochloro dimethyl ether ethyl methyl ether Cl

218
17.2.1 Properties
(i) Lower members are gases, higher members are pleasant smelling volatile
liquids.
(ii) insoluble in water, soluble in organic solvents. These can be explained
on the basis of the absence of hydrogen bonding.
(iii) Ethers are lighter than water. Lower members are inflammable.
(iv) Lower ethers act as anaesthetics.

Chemical Properties :
These are chemically almost inert and do not react with acids, alkalies,
electro positive metals like sodium.
(i) Reaction of the alkyl radicals (substitution reactions)
(ii) Ether oxygen-capable of donating a pair of non bonding electrons.
(iii) The C–O bond which is not as stable as C–C bond, is cleaved.
Reaction of alkyl groups :
1. Halogenation
Ethers undergo substitution at the alkyl group when treated with chlorine
or bromine in absence of sunlight. Usually α-hydrogen is substituted more
readily.
Cl
α β |
Cl2
R – O – CH2 CH3 R – O – CH – CH3
α-chloro ether

Cl2 Cl2
C2H5 – O – C2H5 CH3 – CHCl – O – CH2CH3
dark α-chloro diethyl ether

CH3CHCl – O – CHCl – CH3

α, α'-dichloro diethyl ether

In sunlight, substitution is complete. Thus diethyl ether forms perchloro

diethyl ether.

219
 light
C2H5 – O – C2H5 + 10Cl2 C2Cl5 – O – C2Cl5

2. Reaction of ether oxygen :

(i) Formation of peroxide :
Ether oxygen is capable of forming a coordinate covalent bond with
electron deficient species. Thus it forms peroxide by the action of air or
oxygen.
.. .. ..
R–O–R+O: R–O
.. – R or R–O–R
.. ..

:O
.. : O

Ether forms Diethyl peroxide

(O)
C2H5 – O – C2H5 (C2H5)2O2
diethyl peroxide

These peroxides are unstable and decomposes violently with explosion

on heating. Hence ether should not be evaporated to dryness.

(ii) Formation of oxonium salt.

Strong mineral acids protonate the ethereal oxygen forming oxonium
salts. In this reaction diethyl ether acts as Lewis base.

H
.. |
R–O–R+HX R – O – R X–
+

.. +
C2H5 – O – C2H5 + HCl C2H5 – O – C2H5 Cl–
diethyl ether |
H
diethyl oxonium chloride

220
 H
|
R – O – R + H2SO4 (R – O – R) HSO4–
+
dialkyl oxonium hydrogen sulphate

H
|
C2H5 – O – C2H5 + H2SO4 (C2H5 – O – C2H5) HSO4–
+
diethyl oxonium hydrogen sulphate

(iii) Reaction with Lewis acids.

Similarly with Lewis acids like BF3, AlCl3.
.. R
R – O – R + BF3 O → BF3
R
(Boron trifluoride etherate)

C2H5
C2H5 – O – C2H5 + BF3 O : → BF3
diethyl ether
C2H5
(iv) With Grignard reagent
An ether solution of Grignard reagent contains the following complex
of ether. Thus the Grignard reagent is stabilised in dry ether.
R OR2
2R2O + R'MgX Mg
R2O X

CH3 O(C2H5)2
2 C2H5–O–C2H5 + CH3MgI Mg
diethyl ether methyl magnesium
O(C2H5)2 I
iodide

221
 Hence ether is used as a solvent for Grignard’s reagent.

3. Reaction involving C–O bond : Hydrolysis

(i) Ethers on boiling with water in presence dilute acids are hydrolysed to
form alcohols.
H+
R–O–R + H–O–H 2R – OH

H2SO4
C2H5 – O – C2H5 + H – O – H 2C2H5OH
This reaction proceeds with protonation of ether oxygen.
.. +
R2O + H+ R2 OH

OH2
R – O+– R' R – OH + R' – OH + H+
|
H
(ii) Reaction with HX
On treating with HBr or HI ether gets cleaved to form alcohol and alkyl
halide.
H
.. |
R – O – R + HI R – O+– R RI + HOR
I–
Halogen prefers to attack the carbon atom of the smaller alkyl group.
HI
C2H5 – O – CH3 C2H5OH + CH3I
(iii) With excess hot concentrated hydroidic acid, alkyl iodides are formed.

2HI
CH3 – O – C2H5 CH3I + C2H5I + H2O
This reaction also follows the mechanism mentioned in the previous
reaction.

222
 This reaction is used in the Zeisel’s method of detection and estimation
of alkoxy (especially methoxy) group in natural products like alkaloids.
4. With PCl5
Phosphorous pentachloride cleaves the ether into alkyl chlorides.
R – O – R' RCl + R'Cl + POCl3
Cl – PCl3 – Cl

C2H5–O–C2H5+ PCl5 2C2H5Cl + POCl3

17.2.2 Uses of diethyl ether

Diethyl ether is used as a refrigerant, as an anaesthetic, as a medium
for the preparation of Grignard reagent, as a solvent for the extraction of
organic compounds, mixed with ethanol as substitute for petrol.

17.3 AROMATIC ETHERS

Aromatic ethers or phenolic ethers are a class of compounds obtained
by the replacement of the phenolic hydrogen by an alkyl or aryl group. The
general formula can be Ar–O–R or Ar–O–Ar.
Nomenclature :

Formula Name in common Name in IUPAC

system system

C6H5OCH3 methyl phenyl ether methoxy benzene

(or)
anisole

C6H5OC2H5 ethyl phenyl ether ethoxy benzene

(or)
phenetole

C6H5 – O – C6H5 diphenyl ether phenoxy benzene

223
17.3.1 Preparation
1. Williamsons synthesis :
By heating sodium phenoxide with methyl iodide. This reaction
follows SN2 pathway. The nucleophile is C6H5O– (phenoxide ion) and the
substrate is methyl iodide.

C6H5O– Na+ + CH3 – I C6H5 – O – CH3 (Anisole) + I– + Na+

C6H5O– + C2H5I C6H5 – O – C2H5 + I–

(phenetole)
In this preparation Iodobenzene as a substrate and sodium ethoxide as
the reagent cannot be used to prepare anisole. Iodine is strongly bonded
to carbon atom of benzene hence it cannot be easily replaced.
2. Using diazomethane :
Phenolic –OH has acidic hydrogen atom hence diazomethane could
convert this to methyl group.
C6H5 – O . . – H + CH2 – N2 C6H5 – O – CH3 + N2
diazomethane

3. Manufacture of ether :
Large scale methylation of phenol is carried out using dimethyl
sulphate in presence of sodium hydroxide.
NaOH
C6H5OH + (CH3)2SO4 C6H5OCH3 + CH3.HSO4

– –
C6H5O + CH3 – O – SO2 – OCH3 C6H5–OCH3 + O–SO2–OCH3

This reaction involves nucleophilic attack by the phenoxide ion on

dimethyl sulphate.

17.3.2 Properties
It is a pleasant smelling liquid insoluble in water, soluble in organic
solvents, it gives general reaction of ether though differing in a few reaction.
It is not as reactive as phenol or methyl alcohol.

224
Chemical Properties
1. It forms oxonium compounds with Lewis acids
–AlCl
3
.. AlCl3 |
C6H5OCH3 C6H5 – O – CH3
+

–BF
3
.. BF3
|
C6H5–O–CH3 C6H5 – O – CH3
+
2. Heating with hydroiodic acid cleaves the ether linkage.
Anisole reacts with hydroiodic acid to give phenol and methyl iodide.
C6H5 – O – CH3
C6H5 OH + CH3I
H–I
anisole

I– + CH3 – O+ – C6H5 I – CH3 + HOC6H5

| phenol
H
(protonated ether

Here iodide is the nucleophile and the leaving group is ‘phenol’.

Because of the strong C–O bond in anisole, cleavage of the C–O bond
does not occur and iodobenzene, methyl alcohol are never formed.
3. Reaction due to the benzene ring :
Similar to –OH group, –OMe, group increase the reactivity of the
benzene ring with respect to electrophilic attack and is ortho, para -
directing. With a mixture of con.HNO3 and con. H2SO4 it gives a mixture
of ortho and para nitro anisole. OCH
OCH3 3
OCH3
NO2
con. HNO3
+
con.H2SO4

NO2
225
 Bromination yields ortho bromo anisole and p-bromo anisole.
OCH3 OCH3 OCH3
Br2 Br
+

Br
17.3.3 Uses of anisole
It is used in perfumery.
It is used as a starting material in organic synthesis.

Distinction between Aromatic and aliphatic ethers.

Aromatic ethers Aliphatic ethers

(Anisole) (Diethyl ether)
1. Comparatively high boiling Volatile liquid
liquid.
2. Used in perfumery. Used as anaesthetic.
3. Not used as solvent. Used as a solvent.
4. Can not be used as Mixed with alcohol, used as
a substitute for petrol. a substitute for petrol.
5. On heating with HI It forms C2H5OH, and C2H5I.
forms phenol and CH3I only.
6. With nitrating mixture Nitration does not take place.
forms nitro anisoles.
7. Does not form peroxide Forms peroxide in air.
easily.

226
 SELF EVALUATION
(A) Choose the correct answer :
1. The isomerism exhibited by C2H5OC2H5 and CH3 – O – CH – CH3 is
|
CH3
(a) Functional (b) metamerism
(c) position (d) chain
2. Which one of the following is simple ether ?
(a) CH3 – O – C2H5 (b) C2H5 – O – CH3
(c) C2H5 – O – C2H5 (d) C3H7 – O – C2H5
3. Diethyl ether can be decomposed with
(a) HI (b) KMnO4 (c) NaOH (d) H2O
4. Oxygen atom of ether is
(a) very active (b) Replacable
(c) oxidising (d) Comparatively inert
5. According to Lewis concept of acids and bases, ethers are
(a) Neutral (b) Acidic (c) Basic (d) Amphoteric
6. Intermolecular hydrogen bonds are not present in
(a) CH3COOH (b) C2H5OC2H5
(c) CH3CH2OH (d) C2H5NH2
7. When ethyl Iodide is treated with dry silver oxide it forms
(a) Ethyl alcohol (b) diethylether
(c) silver ethoxide (d) ethylmethyl ether
8. Williamson's synthesis is an example of
(a) nucleophilic addition (b) electrophilic addition
(c) electrophilic substitution (d) Nucleophilic substitution reaction
9. When ether is exposed to air for sometime an explosive substance
produced is
(a) peroxide (b) oxide (c) TNT (d) superoxide
10. Ether is formed when alkylhalide is treated with sodium alkoxide. This
method is known as
(a) Hoffmann reaction (b) Williamson's synthesis
(c) Wurtz synthesis (d) Kolbe's reaction

227
(B) Pickout the incorrect statement :
1. (a) An example of unsymmetrical ether is CH3OC2H5
(b) Ethers exhibit functional isomerism with alcohols
(c) Halogenated ether on treating with alcohols forms higher ether
(d) Ether is lighter than water
2. (a) Diethylether with chlorine in presence of sunlight forms (C2Cl5)2O.
(b) The formula of diethyl oxonium chloride is (C2H5)2–O+Cl-
(c) In anisole oxygen is strongly bonded to benzene ring.
(d) Ether is used as solvent for Grignard reagent.

3. (a) CH3OCH3 dry HI CH3I + CH3OH

(b) Ether is used as substitute for petrol
(c) In Williamson synthesis, ether is formed using alkoxide and alcohol
(d) Ethers act as Lewis base due to the presence of non-bonding electrons
on oxygen.
(C) Answer in one or two sentences :
1. Write the IUPAC names of
(a) C2H5OCH3 (b) C6H5OC2H5
2. Ethers should not be heated to dryness. Why ?
3. Ethers are the best solvents of Grignard reagents- Account for this
statement.
4. Write a note on williamson synthesis.
5. Complete and balance

250oC
C2H5OH ?
Al2O3
6. Why are ethers not soluble in water ?
7. Mention the uses of diethyl ether.
8. What happens when anisole is treated with Lewis acid ?
9. What happens when anisole is nitrated ?
10. Write equation for the conversion of phenol to anisole

228
(D) Answer not exceeding sixty words :
1. Write all possible isomers with the molecular formula C4H10O and name
them.
2. Give any three methods of preparing diethyl ether.
3. Mention the methods of preparation of anisole.
4. How does diethyl ether react with the following reagents ?
(a) O2 / long contact (b) HI in excess
(c) PCl5 (d) dilute H2SO4
5. Give any two chemical differences between anisole and an aliphatic ether.
6. Illustrate electrophilic substitution reactions of anisole.
7. Explain the formation of CH3 I and phenol when anisole is heated with
HI.
8. Diethyl ether forms peroxide easily while anisole does not form peroxide
easily - Explain.
SUMMARY :
Ethers - aliphatic and aromatic ethers.
Structure - nomenclature - common and IUPAC system.
Preparation - From alcohol, alkoxide and alkyl halide.
Properties - absence of hydrogen bonding - inert nature - formation of
oxonium salt - cleavage of ether linkage.
Diethyl ether and anisole - Distinction.
Uses.

REFERENCE :
1. Text Book of Organic Chemistry - P.L. Soni.

__________

229
 18. CARBONYL COMPOUNDS
ALDEHYDES AND KETONES

@ Introduction

@ Structure and classification

@ Nomenclature and isomers

@ General methods of preparation

@ Properties - physical and chemical related to structure

@ Knowledge of Carbanion addition reactions.

@ Learn about Condensation reactions.
@ Distinction between aldehydes and ketones.

@ Uses.

@ General methods of preparation of aromatic aldehydes and aromatic

ketones.

@ Properties - Physical and Chemical - related to structure.

@ Distinction between aliphatic aldehyde and aromatic aldehyde.

@ Distinction between aliphatic ketones and aromatic ketones.

@ Uses of aromatic aledhydes and ketones.

230
 Aldehydes and ketones are compounds with the oxidation state of
carbon lying in between –2 in alcohol and +2 in carboxylic acid. Hence they
are chemically and even biochemically an important class of compounds.
Because they can either be oxidised or reduced.
H H O
Reduction Oxidation
||
H3C – OH C H – C – OH
(Oxidation state || (Oxidation state
–2 in alcohol) O +2 in carboxylic acid)
(Oxidation state
is zero in aldehyde)

Thus ‘‘Pyridoxal’’ an aldehyde derived from the vitamin B6 (pyridoxine)

functions as a coenzyme, because of the dual nature.
Aldehydes and ketones come under the class of compounds called
‘‘carbonyl compounds’’. They have the carbonyl group.

C=O

Aldehydes differ from ketones in the presence of a hydrogen atom directly

bonded to the carbonyl group.

Aldehydes Ketones

C=O C=O
H

Example
CH3 CH3
C=O C=O
H H3C
(Acetaldehyde) (Acetone)

231
 The general formula can be
R R
C=O C=O
H R'
When R = R' = H that represents formaldehyde, the simplest member of
this series. R and R' can be alkyl or aryl.
If R is an aralkyl group we have an aralkyl aldehyde (e.g.,) phenyl
acetaldehyde
C6H5CH2
C=O
H

18.1 NOMENCLATURE
Common names of aldehydes are derived from the common names of
carboxylic acid or by adding the suffix “aldehyde” to the prefix that indicates
the chain length.
CH3COOH CH3CHO C4H9CHO
Acetic acid Acetaldehyde Pentanalehyde

In the IUPAC system, the prefix indicating the length of the carbon
chain is followed by the suffix al in place of ‘e’.

CH3CH2CH2CHO
Butane + al = butanal

Since the aldehyde group is always present in the end it is not shown by
any number.

Common name for ketones is arrived at by adding the suffix ‘‘ketone’’

to the name of alkyl groups present

CH3COCH2CH3
Ethyl methyl ketone

232
 A ketone is named by adding the suffix ‘one’ in place of ‘e’ in the name
of the parent hydrocarbon.

CH3CH2COCH2CH3 3-pentanone

The number of carbon forming the keto group should be mentioned.

For example, ethyl methyl ketone is named as 2-butanone in the IUPAC

name.

Formula Common name IUPAC name

HCHO Formaldehyde Methanal

CH3CHO Acetaldehyde Ethanal

CH3
|
CH3 –CHCHO Isobutyraldehyde 2-methyl propanal

CH2 = CH–CHO Acrolin or acraldehyde 2-propenal

CH3 CH = CH CHO Crotonaldehyde 2-butenal

C6H5CHO Benzaldehyde Phenyl methanal

C6H5CH = CH–CHO Cinnamaldehyde 3-phenyl-2-propenal

CH3CHOH – CH2 CHO aldol 3-hydroxy butanal

233
KETONES
Formula Common name IUPAC name
CH3COCH3 Acetone Propanone
CH3COCH2CH3 Ethyl methyl ketone 2-butanone
CH3CH2COCH2CH3 Diethyl ketone 3-pentanone
CH3 COCH2CH2CH3 methyl, n-propyl ketone 2-pentanone
O
||
CH3 – CCH2 CH = CH2 Allyl methyl ketone 4-pentene-2-one

ISOMERISM
Aldehydes exhibit (i) chain isomerism and (ii) functional isomerism.
Chain Isomerism arises due to changes in carbon chain.
(i) CH3 – CH2 – CH2 – CHO and CH3
butanal |
CH3 – CH – CHO
2-methyl propanal

(ii) CH3 CH2 CH2 CH2 CHO CH3

Pentanal |
H3C – C – CHO
|
CH3
2,2-dimethyl propanal
Functional isomerism :
Aldehydes are functional isomers of ketones and unsaturated alcohols.
O
CH3 CH2 CHO || CH2 = CH – CH2OH
propanaldehyde CH3 – C – CH3 unsaturated alcohol
acetone 2-propen-1-ol
Ketones exhibit chain isomerism and metamerism.
Chain isomerism :
O O
|| ||
CH3 CH2 CH2 C – CH3 CH3 – CH – C – CH3
|
2-pentanone
CH3 3-methyl-2-butanone
234
Positional Isomerism :
The carbonyl group may occupy different positions in the carbon chain
to give Positional Isomers.
O O
|| ||
CH3 – CH2 – C – CH2 – CH3 CH3 CH2 CH2 – C – CH3
3-pentanone 2-pentanone

18.3 GENERAL METHODS OF PREPARATION

1. (a) Oxidation of alcohols with acid dichromate :
Primary alcohols give aldehydes
Secondary alcohols give ketones.

K2Cr2O7/H+
CH3 – CH –O CH3 CH = O + H2O
| | + acetaldehyde
H H (O)
primary alcohol
ethyl alcohol

(CH3)2 C – O + K2Cr2O7/H+
| | (CH3)2 C = O + H2O
H H (O) acetone

secondary alcohol (isopropyl alcohol)

(b) Catalytic oxidation : By passing a mixture of alcohol vapours and

air over silver catalyst at 520 K aldehyde or ketone is formed.
O2/Ag
CH3 CH2 OH CH3CHO
520K acetaldehyde

O2/Ag
(CH3)2 CHOH (CH3)2 CO
520K
acetone

235
 (c) By the catalytic dehydrogenation of alcohols. The vapours of alcohol
are passed over heated copper at 573 K gives aldehyde or ketone.

573 K
RCH – O RCH = O + H2
Cu
| | aldehyde
H H
1o alcohol

573K
CH3 – CHOH CH3 – CHO + H2
Cu
| acetaldehyde
H
Ethyl alcohol

R2 C – O
573 K
| | R2C = O + H2
Cu
H H ketone

2o alcohol

CH3 573K
CH3
C –O C = O + H2
Cu
CH3 | | CH3
H H
Isopropyl alcohol acetone

2. Dry Distillation. By the distillation of calcium salt of fatty acids with

calcium formate - aldehyde is formed.
CH3COO OCOH CH3
∆ |
Ca + Ca
2 HC=O + 2CaCO3
CH3COO OCOH
Calcium acetate Calcium formate Acetaldehyde

236
 By the distillation of calcium salt of fatty acid, ketone is formed.
CH3COO CH3
∆
Ca | + CaCO3
CH3COO CH3 – C = O

calcium acetate acetone

3. Use of acid chloride :

(i) Rosenmund Reduction. Acid chlorides are reduced to aldehydes
by hydrogen in presence of palladium suspended in barium sulphate as
catalyst.
R– C=O R–C=O + HCl
Pd
| |
Cl + H–H BaSO4 H

Pd
CH3 – C = O + H2 CH3 – C = O + HCl
BaSO4
| |
Cl H
acetyl chloride acetaldehyde

As formyl chloride is unstable at room temperature, formaldehyde cannot

be prepared by this method.
This is called Rosenmund’s reduction. BaSO4 is used as a catalytic
poison, to stop the reduction at the stage of aldehyde. Otherwise, the
aldehyde formed will be further reduced to primary alcohol.
(ii) Using Dialkyl cadmium. Ketones can be prepared by the action of
organometallic reagent on acid chlorides. (e.g.,) Dialkyl cadmium is the
reagent of choice.

R–C=O O=C–R 2R – C = O + CdCl2

| Cd | |
Cl Cl R'
R' R'

237
4. By the hydrolysis of gem dihalides
(i) A gem dihalide is a compound in which two halogen atoms are
attached to the same carbon. Aldehydes are prepared by hydrolysis of gem
dihalides in which two halogen atoms are attached to the terminal carbon
atom using alkali.
Cl OH –H O
2
CH3– CH + 2 NaOH CH3CH CH3CHO
Cl OH
ethylidene chloride acetaldehyde

(ii) Ketones are prepared by hydrolysis of a gemdihalides in which two

halogens are attached to non terminal carbon atom.
CH3 Cl CH3 OH CH3
HOH –H2O
C + 2 NaOH C C=O
CH3 Cl CH3 OH CH3
2,2-dichloro propane acetone

5. By ozonolysis :
Ozone forms addition product with olefin called ozonide, which on
reductive cleavage gives aldehyde or ketone.
O
Zn/HCl
RCH = CHR' + O3 RCH CHR' RCH + R' CH
|| || + H2O
O O O O
(Ozonide) (Aldehyde)

O
Zn/HCl
R2C = CR'2 + O3 R2C CR'2 R2C + R'2 C + H2O
|| ||
O O
O O (ketone)
(ozonide)

238
 Thus if formaldehyde is obtained, that indicates the presence of double
bond at the terminal carbon. Hence to locate the position of double bond,
ozonolysis is helpful.
6. By the oxidative cleavage of 1, 2-diols using periodic acid.
C–C bond in 1,2-diols is cleaved by periodic acid.
R-CHOH HIO4 RCHO + R'CHO
...................
| Aldehydes
R'-CHOH
CH3 – CHOH HIO4
...................
| 2CH3CHO
CH3 – CHOH acetaldehyde

butane-2,3-diol

R2 –C OH HIO4
...................
| R2CO + R'2CO
R'2–C OH (ketone)

(CH3)2 – C – OH HIO4
...................
| 2CH3 COCH3
(CH3)2 – C – OH acetone

butane-2,3-dimethyl-2,3-diol

7. Hydration of Alkynes
By the hydration of alkynes in 42% sulphuric acid containing HgSO4 as
a catalyst. Acetaldehyde is obtained when acetylene is used. Acetone is
obtained using propyne.
(Acetylene) CH ≡ CH H+
CH3CHO (acetaldehyde)
Hg2+
H2 – O

(Propyne) CH3C ≡ CH
H+
CH3COCH3 (acetone)
O – H2 Hg2+

239
8. Stephen’s reaction :
Aldehyde can be prepared by Stephen’s reaction, by the reduction of
alkyl cyanide dissolved in ether with Stannous chloride and hydrochloric
acid.
CH3 – C ≡ N SnCl2
CH3 CH = NH.HCl
HCl Iminimum hydro chloride
H–H
methyl cyanide

O – H2
Hydrolysis
CH3 CH = NH.HCl CH3CHO + NH4Cl
acetaldehyde

18.3.1 PROPERTIES
Physical properties
Except formaldehyde (a gas) the other lower members of aldehydes and
ketones are volatile liquids and the higher members are waxy solids. Ketones
have pleasant odour. They have boiling points higher than hydrocarbons
(polar nature of carbonyl group) and lower than alcohols (absence of –OH
group). Solubility of carbonyl compounds decreases with the increase in
their molecular masses. Because with the increase in the length of carbon
chain the capacity of the carbonyl group to form hydrogen bonds with water
decreases.
Chemical Characteristics
Aldehydes and ketones contain the carbonyl group >C = O. Oxygen
being more electro negative, the >C = O bond is polarised so that oxygen
becomes negatively charged and carbon positively charged.

C=O C+ – O–
1. Therefore the nucleophilic reagents attack the electron deficient carbonyl
carbon.
C=O C – O–
– |
Nu Nu
240
 Both charged and uncharged nucleophiles can attack the carbonyl carbon
to form addition products. This is the most common reaction for aldehydes
and ketones.
2. Another kind of reaction of aldehydes and ketones which contain atleast
one α-hydrogen atom.
–
H –– CH2 CH2
α B–
C=O C=O + BH
R R
(Deprotonation of α-hydrogen forming carbanion)
α-hydrogen is the hydrogen attached to the α-carbon of the carbonyl
group. This hydrogen is acidic, hence a strong base (NaOH, C2H5ONa) can
remove this hydrogen as a proton, generating a carbanion of the aldehyde or
ketone. The carbanion being nucleophile brings forth nucleophilic attack on
any electron deficient carbon, normally carbonyl carbon leading to
condensation reaction.
Reactivity :

Aldehydes are more reactive than ketones for both steric and electronic
reasons.
The presence of alkyl group increases the crowding near carbonyl group
and also increases the electron density at the carbonyl carbon by Inductive
effect. (+I effect)
H R R
C=O C=O C=O
H H R
Most reactive less least

Reactions common to aldehydes and ketones.

(a) Reactions of alkyl group. (b) Reaction of carbonyl group.
(a) Reactions of alkyl group :
In aldehydes the α-hydrogen atoms are more easily replaced than in
ketones.
241
 CH3CHO + 3Cl2 CCl3 CHO + 3HCl
(Acetaldehyde) (Trichloro acetaldehyde)
CH3COCH3 + 3Cl2 CCl3 COCH3 + 3HCl
(Acetone) (Trichloro acetone)
This reaction proceeds with the formation of carbanion.
Cl
–
CH3 CH2 |
–H+ Cl – Cl
C=O C=O CH2
C = O + Cl–
R
R R
(ketone) (carbanion) (α-chloroketone)
(b) Addition reactions.
The carbon of the carbonyl group is the site of nucleophilic attack. (X–
is a nucleophile).
C =O H –– X C – OH
|
X
The negative part of the addendum adds to the carbon and the positive
part to the oxygen.
In the addition of sodium bisulphite to give bisulphite compound
– OSO2Na anion is the nucleophile.
OH
C = O + H OSOONa C
OSO2Na

CH3CHO + HOSO2Na CH3 OH

C
H OSO2Na
acetaldehyde bisulphite compound
CH3
C = O + HOSO2Na CH3 OH
H3C C
H3C OSO2Na
acetone bisulphite
242
Aldol Condensation :
This reaction is catalysed by base. The carbanion generated is nucleophilic
in nature. Hence it can bring about nucleophilic attack on carbonyl group.
Step 1 :
The carbanion is formed as the α-hydrogen atom is removed as a proton
by the base.

–
OH–
CH3 – C = O CH2 – C = O + H2O
| |
H H
Step 2 :
The carbanion attacks the carbonyl carbon of another unionised aldehyde
molecule.
H H
| | –
CH3 – C = O CH3– C – O
–
|
CH2 – CHO CH2 – CHO
alkoxide ion
Step 3 :
The alkoxide ion formed is protonated by water to give ‘aldol’.
H H
| – | –
H – OH
CH3 – C – O CH3 – C – OH + OH
| |
CH2CHO CH2CHO
Aldol
Acetone also undergoes this type of condensation as shown.
–
CH3 – C = O – CH2 – C = O + H2O
OH
| |
CH3 CH3
Acetone Carbanion

243
 –
CH3 – C = O CH3 – C – O
|
CH3 CH3
–
CH2 COCH3 CH2COCH3
(Nucleophilic attack)

–
CH3 – C – O CH3 OH
H2O
Protonation
CH3 C
CH2COCH3 CH2COCH3 CH3
When an aldehyde and a ketone react in the same way it is called ‘crossed
aldol condensation’.

– –
CH3 – C = O OH CH2 – C = O + H2O
| |
H H
H3C CH3
–
C = O C –– O
–
H3C CH2 – CHO H3C CH2CHO
–
CH3 O CH3 OH
H2O
C C
H3C CH2CHO H3C CH2CHO
Characteristics of Aldol condensation :
(i) It is an irreversible change.
(ii) It is an addition reaction with or without elimination of water.
(iii) A new carbon to carbon linkage is set up.
(iv) The aldols formed easily eliminate water to form unsaturated
244
compounds. For example aldol on heating gives crotonaldehyde.
CH3 – CH – CH.CHO CH3 – CH = CH – CHO
∆
| | Crotonaldehyde
–H2O
OH H
(v) This reaction is characteristic of carbonyl compounds having α-
hydrogen atom. If there is no α-hydrogen atom in the carbonyl compound,
aldol condensation does not take place.
HCHO, C6H5CHO, C6H5COC6H5.
Formaldehyde, Benzaldehyde Benzophenone

(ii) Addition of hydrogen cyanide

Aldehydes and ketones react with hydrogen cyanide to form cyanohydrin.
The reaction is carried out in the presence of base as a catalyst.
R R OH
C=O + HCN C
R' R' CN
Cyano hydrin

Mechanism : The mechanism involves the following steps :

Step 1 : The base removes a proton from hydrogen cyanide to produce
cyanide ion.
– –
HCN + OH H2O + CN
Nucleophile

Step 2 : The cyanide ion attacks the carbonyl carbon to form an anion.
–
O
–
C = O + CN C
CN

245
 Step 3 : The proton from the solvent combines with the anion to give
cyanohydrin.
O– OH
C + H+ C
CN CN
Cyano hydrin
Like other nitriles cyanohydrin can be hydrolysed to give carboxylic
acid.
H+/H2O
CH3 – CH – CN CH3 – CH – COOH
∆
| |
OH OH
Acetaldehyde cyanohydrin Lactic acid

This is a very efficient method of preparing lactic acid and other

α-hydroxy acids like Mandelic acid (C6H5CHOH COOH).
Grignard addition

Grignard addition to aldehydes and ketones are nucleophilic addition.

The addition product formed is hydrolysed to alcohols.
R R X
H3O+
C = O + R MgX C C + Mg
OMgX OH OH

Formaldehyde gives primary alcohol and other aldehydes give secondary

alcohol with Grignard reagent. Ketones give tertiary alcohol.

CH3 CH3
| |
HO
(i) H – C = O + CH3 – MgI H – C – OMgI 2 H – C – OH
| | |
H H H
formaldehyde primary alcohol
(ethyl alcohol)

246
(ii) CH3 CH3
| |
H2O
CH3 – C = O + CH3–MgI CH3 – C – OMgI CH3 – C – OH
| | |
H H H
acetaldehyde Secondary alcohol
Iso propyl alcohol

CH3 CH3
(iii) | |
H2O
CH3 – C = O + CH3 – MgI CH3 – C – OMgI CH3 – C – OH
| | |
CH3 CH3 CH3
acetone tertiary butyl alcohol
Addition of ammonia
Formaldehyde and ketones do not form addition compounds with
ammonia. They yield complex condensation products. Other aldehydes form
addition product with complex structure.
Examples : Acetaldehyde forms simple product while others form
products with complex structure with ammonia.
CH3 CH3 OH –H2O
C= O + HNH2 C CH3CH = NH
H H NH2 Aldimine
Acetaldehyde ammonia
Formaldehyde forms hexamethylene tetramine with NH 3.
6CH2O + 4NH3 (CH2)6 N4 + 6H2O
hexa methylene tetramine
This is used as Urinary antiseptic in medicine, in the name of ‘Urotropine’.
N
|
H2C CH2 CH2
|
N
CH2 CH2
N N
CH2
247
 Benzaldehyde undergoes condensation reaction with ammonia to form
hydrobenzamide.
C6H5 CH = O H2 N – H

+ + O = CHC6H5 C6H5CH= N
C6H5CH = O H2 N – H CHC6H5
C6H5CH= N
Hydro benzamide

Acetone with ammonia forms acetone ammonia initially at room

temperature. On heating it forms diacetone amine.
CH3 CH3
| |
CH3 – C = O + HNH2 CH3 – C – OH
|
NH2
acetone ammonia

CH3 CH3
| high temp
|
CH3 – C – OH + CH3 – C – CH3 CH3 – C – CH2 – C – CH3
–H2O
| || | ||
NH2 O NH2 O
diacetone amine
1. Reaction with hydroxylamine : Aldehydes and ketones react with
hydroxylamine to form oximes.
OH
(a) CH3 CH = O + HNH
.. OH CH3 – CH
NHOH

acetaldehyde hydroxylamine –H2O

CH3–CH = NOH
acetaldehyde oxime

248
 (b) OH
–H2O
..
C6H5CHO + HNHOH C6H5 – CH C6H5–CH = NOH
benzaldehyde NHOH Benzaldoxime

CH3 CH3 OH H3C

–H2O
..
C = O + HNHOH C C = NOH

CH3 CH3 NHOH H3C

Acetone oxime

2. Reaction with hydrazine (NH2–NH2)

Aldehydes and ketones react with hydrazine to form hydrazones.
CH3 CH3 OH CH3
–H2O
C = O + NHNH2 C C = NNH2
H H NHNH2 H
acetaldehyde acetaldehyde hydrazone

CH3 CH3 OH CH3

–H2O
C = O + H – NHNH2 C C = NNH2
CH3 CH3 NHNH2 CH3
Acetone Acetone hydrazone
3. Reaction with phenyl hydrazine C6H5NHNH2
Aldehydes and ketones react with phenyl hydrazine to form phenyl
hydrazones.
C6H5 C6H5 OH C6H5
–H2O
C = O + HNHNHC6H5 C C = NNHC6H5
(a)
H H NHNHC6H5 H
benzaldehyde benzaldehyde
phenyl hydrazone
CH3 CH3 OH CH3
–H2O
C = O + HNHNHC6H5 C C = NNHC6H5
CH3 CH3 NHNHC6H5 CH3
(b) acetone phenyl
acetone
hydrazone
249
4. Reaction with semicarbazide NH2NHCONH2
Aldehydes and ketones react with semicarbazide to form semicarbazone.
(a) CH3 CH3 OH
C = O + HNHNHCONH2 C
H H NHNHCONH2
acetaldehyde
–H2O
CH3
C = N–NHCONH2
H
acetaldehyde semicarbazone

(b) C6H5 C6H5 OH

C = O + HNHNHCONH2 C
H H NHNHCONH2
Benzaldehyde

–H2O

C6H5
C = NNHCONH2
H
benzaledehyde semicarbazone
Reduction of aldehydes and ketones
The products of reduction depends upon the reagents used and the
conditions of reactions. Hence a variety of reagents are used for reduction.
(i) Catalytic reduction : Aldehydes are reduced to primary alcohols by
hydrogen gas in presence of platinum metal as a catalyst.
R R
H2/Pt
C=O CHOH
H H

250
 Ketone on catalytic reduction gives secondary alcohol.
R
Pt
C=O R2CHOH
R H –– H
CH3 CH3
C=O Pt CH–OH
H2
CH3 H––H CH3
Isopropyl alcohol
It is an example of heterogeneous reaction.
Reduction using metal hydrides :
Metal hydrides like Lithium aluminium Hydride (LiAlH4) Sodium
borohydride (NaBH4) reduce them to alcohols.

These are ‘Hydride ion’ (H–) donors. Hydride ion is a nucleophile.

Hence it is nucleophilic addition reaction.
CH3 NaBH4
CH3 CH3 OH
H+
C=O C – O– C
H H– H H H H
Acetaldehyde Ethanol

(b) Reduction of carbonyl compounds to hydrocarbons.

(i) Clemmension Reduction :

Aldehydes and ketones can be reduced to hydrocarbons by zinc amalgam
and con.HCl.
CH3 Zn/Hg
CH3
C = O + 4 (H) CH2 + H2O
HCl
H3C CH3
(Propane)

This reaction proceeds by electron addition to carbonyl carbon followed

by protonation. Zinc metal is the electron source.

251
 In the absence of mercury, hydrogen gas will be evolved and the reduction
is incomplete. This reduction is called Clemmenson reduction.
(ii) Reduction under strongly basic condition :
Wolff-Kishner Reduction
Aldehydes and ketones are reduced to hydrocarbons by heating with
hydrazine and sodium ethoxide.
CH3 N2H4
CH3
C=O CH2 + N2 + H2O
C2H5ONa
H H
Hydrazones are formed as intermediates. The base removes the –NH2
hydrogen atoms as protons generating carbanion. Proton addition to
carbanion gives alkanes.
CH3
C = NNH2
H
Hydrazone
This is called Wolff-Kishner reduction.
Oxidation : –C=O
Aldehydes have | bond which is responsible for their reducing
H
properties. Ketones do not have such a structure and are not reducing agents.
All the oxidising agents like acidified potassium dichromate or acidified
or alkaline potassium permanganate (powerful oxidising agents) and even milder
oxidising agents like ‘Tollen’s reagent’ and ‘Fehling’s solution’ oxidise
aldehydes to monocarboxylic acids having the same number of carbon atoms.
(O)
RCHO RCOOH
Aldehyde Acid

Ketones are oxidised only by the strong oxidising agents (acidified

potassium dichromate or permanganate) to mono carboxylic acids having
lesser number of carbon atoms.
CH3COCH3 CH3COOH
(3c) (2c)

252
Popott’s Rule :
During oxidation of unsymmetric ketones with oxidising agent which
brings about the cleavage of C–C bond, the smaller alkyl group goes
preferentially with the carbonyl group resulting in the carboxylic acids.
a O b
: || :
: C ––: CH – CH – CH
CH3 ––
: : 2 2 3
: :

‘a’ cleavage ‘b’ cleavage

HCOOH CH3–CH2–CH2–COOH CH3COOH CH3CH2COOH

acetic acid propionic acid
CO2 + H2O n-butyric acid

minor products major produts

Because aldehydes are easily oxidised, they are reducing agents. They
reduce ammonical silver nitrate (Tollen’s reagent) to metallic silver and
Fehling’s solution (copper sulphate, sodium potassium tartrate) to red cuprous
oxide.
CH3CHO + 2Ag+ + 3OH– CH3COO– + 2Ag + 2H2O
Acetaldehyde Acetate ion (silver mirror)

CH3CHO + 2Cu2+ + 5OH– CH3COO– + Cu2O + 3H2O

(blue) (red precipitate)
cupric ion cuprous ion

Aliphatic aldehydes restore the original colour (red-pink) of the Schiff's

reagent. (when SO2 is passed through intensely pink coloured Schiff’s reagent
in water. It forms a colourless solution. This colourless solution is used for
this test). This is characteristic test for aldehydes. Ketones do not restore
this colour.
Polymerisation :

(i) When aqueous solution of formaldehyde is evaporated to dryness it

forms a white crystalline polymer called paraformaldehyde.

253
 H H
| |
n C=O – C–O–
| |
H H n
(ii) Acetaldehyde polymerises to a cyclic structure called paraldehyde
when a drop of concentrated sulphuric acid is added to it.
CH3
con.H2SO4
|
3CH3CHO CH

O O

CH3CH CH–CH3

O
Paraldehyde

Benzaldehyde does not undergo polymerisation.

18.3.2 Uses of Aldehydes :

(a) 40% aqueous solution of formaldehyde is known as formalin and is used

as a preservative for biological specimens and in leather tanning.
(b) A condensation product with ammonia, known as ‘urotropine’ is used
in medicine for urinary infection.
(c) In the process of ‘Vat dyeing’ to decolourise vat dyes by reduction.
(d) In the manufacture of polymeric resin called Bakelite (a condensation
polymer with phenol).
Acetaldehyde :

(i) For silvering of mirror.

(ii) Its trimer ‘paraldehyde’ is hypnotic.
(iii)In the preparation of large number of organic compounds such as
chloroform, acetic acid, ethanol, lactic acid etc.

254
Questions.
1. Which among the following reduces (a) Tollen’s reagent only
(b) Tollen’s and Fehling solution (c) None
C6H5CHO, CH3CHO, CH3COCH3, HCHO
Answers. (a) C6H5CHO (b) CH3 CHO, HCHO (c) CH3COCH3
2. How can the following be prepared ? Give equations.
2-butenal from acetaldehyde.
Clue :
OH– ∆
CH3CHO CH3CHOH CH2CHO CH3CH = CHCHO
H2O

18.4 AROMATIC ALDEHYDES

In aromatic aldehydes, the aldehyde group is directly attached to benzene
ring.
Names of Aromatic aldehydes
Formula Common Name IUPAC name
C6H5CHO Benzaldehyde Phenyl methanal
C6H5CH2CHO Phenyl acetaldehyde Phenyl ethanal
CHO
Salicylaldehyde 2-hydroxy
benzaldehyde
OH
C6H5CH = CH–CHO Cinnamaldehyde 3-phenyl prop-2-enal

CHO
Benzaldehyde : Phenyl methanal (IUPAC)

18.5 PREPARATION
1. Toluene is oxidised by chromium trioxide and acetic anhydride or
chromyl chloride or air in presence of V2O5 at 773 K.
(O)
C6H5CH3 C6H5CHO + H2O
Toluene air/V2O5 Benzaldehyde
773K

255
 2. Benzyl chloride is oxidised by aqueous lead nitrate.

H2O
Pb(NO3)2 HNO3

HNO3
C6H5CH2Cl C6H5CHO
Benzyl chloride Benzaldehyde

3. By the hydrolysis of benzal chloride. (gem dihalides)

OH
2H2O –H2O
C6H5CHCl2 C6H5CH C6H5CHO
OH
(unstable)

Distillation of calcium benzoate with calcium formate gives benzaldehyde.

C6H5COO OCOH
∆
Ca + Ca 2C6H5CHO + 2CaCO3
C6H5COO OCOH
Calcium benzoate (calcium formate)

18.5.1 Properties :

Colourless liquid with boiling point 452 K. It has the smell of bitter
almond and known as oil of bitter almonds.
Chemical Properties :
C6H5
C=O
H
It resembles aliphatic aldehydes in many properties.
Because of the presence of benzene ring the reactivity towards
nucleophilic attack on carbonyl carbon is decreased.
Absence of α-hydrogen atom indicates that a carbanion cannot be
generated at the α-carbon. So aldol type of condensation cannot be
expected.
256
 Presence of benzene ring makes possible the aromatic electrophilic
substitution reaction.
1. It is oxidised to benzoic acid by alkaline permanganate.
[O]
C6H5CHO C6H5COOH

It does not reduce Fehling’s solution, though it reduces Tollens reagent.

Because Ag+ is more easily reduced to Ag than Cu2+ to Cu+
2. It is reduced to benzyl alcohol by NaBH4 or LiAlH4.
[H–]
C6H5CHO C6H5CH2OH

3. It can be reduced to toluene by Clemmenson or Wolff Kishner procedure.

Zn/Hg/HCl
C6H5CHO C6H5CH3
or
N2H4 / KOH

4. It condenses with ammonia forming hydrobenzamide.

5. It undergoes addition and addition elimination reactions with HCN,
NaHSO3, RMgX and with NH2OH, C6H5NHNH2, NH2CONHNH2.
6. Benzaldehyde reacts with primary amines to form ‘‘aldimine’’ type of
compound called Schiffs base.
OH
[–H2O]
C6H5CH=O + RNH2 C6H5CH C6H5CH=NR
NHR
OH
[–H2O]
C6H5CH=O + C6H5NH2 C6H5CH C6H5CH=NC6H5
NHC6H5

Recognise the nucleophilic addition followed by elimination - pathway

in this reaction.
7. In the absence of catalyst, chlorine displaces aldehydic hydrogen forming
benzoyl chloride.
257
 C6H5 – C = O C6H5 – C = O + HCl
| |
H Cl – Cl Cl
8. Cannizaro reaction : Benzaldehyde undergoes Cannizaro reaction
because of the absence α-hydrogen. It involves self oxidation and
reduction of benzaldehyde when heated with concentrated NaOH.
NaOH
C6H5CHO + C6H5CHO C6H5COONa + C6H5CH2OH
Benzaldehyde Benzaldehyde Sodium benzoate Benzyl alcohol

The mechanism involves the transfer of hydride ion from one molecule
of benzaldehyde to the other molecule.
I step.
H H
| |
C6H5 – C = O C6H5 – C – O–
– |
OH OH
–
Nucleophilic attack by OH ion on carbonyl carbon.
II step.

.H|. H
|
C6H5 – C – O– + C6H5 – C = O C6H5 – C = O + C6H5 – C – O–
| | | |
OH H OH H

Transfer of hydride ion from the anion to carbonyl carbon of another

molecule.
III step.

H H
| |
C6H5 – C = O + C6H5 – C – O– C6H5 – C = O + C6H5 – C – OH
| | | |
O–H H O H
The benzyloxide ion picks up the acidic proton from benzoic acid to
give benzyl alcohol.

258
9. Claisen or Claisen Schmidt reaction
It reacts with aliphatic aldehydes or ketones in presence of NaOH forming
α, β unsaturated aldehyde or ketone.
NaOH
–
CH3CHO CH2CHO (Carbanion)
NaOH H+
C6H5CH = O C6H5 CH–O– C6H5CHOH
| |
(–)CH
2CHO CH2CHO CH2CHO
(Nucleophilic attack)

C6H5 – CH– OH C6H5 – CH

| β-elimination ||
CH – H CH – CHO
| –H2O
CHO (Cinnamaldehyde)

Similarly,
NaOH
C6H5CHO + CH3COCH3 C6H5CH = CHCOCH3

The carbanion formed from acetaldehyde or acetone brings forth a

nucleophilic attack on the carbonyl carbon of benzaldehyde. The aldol type
of product undergoes β-elimination (of water). This reaction is known as
Claisen Schmidt reaction.
10. Benzoin Condensation :

This is another reaction, which is characteristic of aromatic aldehydes.

When benzaldehyde is refluxed with aqueous alcoholic potassium cyanide -
α-hydroxy ketone called benzoin is formed. Cyanide ion (CN–) is the specific
catalyst in this reaction.
Benzoin can be considered as dimer of benzaldehyde.
O O
|| alc ||
C6H5CH = O + H – C – C6H5 C6H5CHOH – C – C6H5
KCN (Benzoin)

259
 In presence of cyanide ion, one molecule of benzaldehyde behaves as a
carbanion. That brings forth nucleophilic attack on the carbonyl group of
another molecule of benzaldehyde. This results to Benzoin.
11. Perkins reaction :

When benzaldehyde is heated with sodium salt of acetic acid in presence

of acetic anhydride, it forms cinnamic acid.
CH3COONa
C6H5CH = O + CH 3–CO–O–COCH3 C6H5CH = CH–COOH
∆
Acetic anhydride Cinnamic acid
+
CH3COOH
Sodium acetate is the base that generates a carbanion at the α-carbon in
the acetic anhydride. This brings forth nucleophilic attack on the carbonyl
carbon forming β -hydroxy acid, water gets removed from this by
β-elimination.
12. Knoevenagal reaction :

Benzaldehyde condenses with malonic acid in presence of pyridine

forming cinnamic acid, pyridine is the basic catalyst here. This mechanism is
quite similar to the previous reaction, involving carbanion, from the malonic
acid.
Pyridine
C6H5CH = O + H2C(COOH)2 C6H5CH = C(COOH)2
Malonic acid
CO2
C6H5CH=CHCOOH
∆
(Cinnamic acid)

Reactions of the benzene ring :

The reaction characteristic of benzene ring is electrophilic substitution.

The aldehyde group (CHO) reduces the activity of benzene with respect to
the attack by an electrophile. It is a meta-directing group. Hence meta
substituted products are formed.

260
Nitration :
CHO CHO

Conc. HNO3
Conc. H2SO4
NO2
(The electrophile being NO2+)

Sulphonation :

CHO CHO

Conc. H2SO4

SO3H
+
(The electrophile SO3H) (m-benzaldehyde sulphonic acid)

In presence of con. H2SO4 benzaldehyde condenses with two molecules

of N,N-dimethyl aniline forming triphenyl methane dye called Malachite
green.

H N(CH3)2
N(CH3)2
Conc. H2SO4
CH=O CH
N(CH3)2
H N(CH3)2

Triphenyl methane dye

Halogenation :
CHO CHO

Cl2
FeCl3
Cl
(FeCl3 is the Lewis acid catalyst that forms the electrophile Cl+)

261
Comparison of Formaldehyde and Acetaldehyde

Reactions HCHO CH3CHO

1. Iodoform test does not undergo gives iodoform
2. With Ammonia forms ‘urotropine’ gives simple
a condensation product addition product.
3. With alkaline undergoes Cannizzaro undergoes aldol
solution reaction condensation.
4. With phenol forms thermosetting does not form
plastic-bakelite resin.
5. With RMgX forms RCH2OH R–CH–OH is formed.
|
CH3

Comparison of Aliphatic aldehyde and aromatic aldehyde

Reactions CH3CHO C6H5CHO

1. Heating with gives a red precipitate no reaction.
Fehling’s solution.
2. With ammonia forms simple addition forms complex
product. condensation
product.
3. With caustic undergoes Aldol undergoes Cannizzaro
soda condensation reaction.
4. With primary does not forms Schiff’s base.
amines form Schiff’s base
5. With chlorine does not forms benzoyl
form acetyl chloride chloride.
6. Polymerisation undergoes does not polymerise.
polymerisation.
7. Electrophilic does not undergoes at the
substitution. undergo. meta position.
8. With Schiff’s gives pink colour gives pink colour.
reagent. in cold.

262
Uses

Benzaldehyde is used
(a) In the preparation of cinnamaldehyde, cinnamic acid and mandelic acid.
(b) Benzoin prepared from benzaldehyde is used as ‘tincture benzoin’ in
medicine for throat infection.
(c) With phenols and aromatic tertiary amines, it forms triphenyl methane
dyes.
(d) In perfumery, as a flavouring agent.
Questions.

1. What happens when the following is heated with 50% NaOH ?

(a) HCHO (b) C6H5CHO (c) a mixture of (a) and (b)
Ans. (a) CH3OH + HCOOH
(b) C6H5CH2OH + C6H5COOH
(c) C6H5CH2OH + HCOOH (HCHO is more easily oxidised
than benzaldehyde) Crossed Cannizzaro reaction.
18.6 KETONES

Preparation of ketones - Acetone

1. By the oxidation of isopropyl alcohol with acid dichromate acetone is
formed.
(CH3)2 C – O
| | (O)
H H (CH3)2C = O
K2Cr2O7/H+

2. Dry distillation of calcium acetate.

CH3 COO ∆
CH3
Ca C = O + CaCO3
CH3COO Distillation H3C
(Calcium acetate) (Acetone)

263
3. Passing the vapours of isopropyl alcohol over heated copper - catalytic
dehydrogenation takes place.
(CH3 )2 – C – O 573 K
| | (CH3 )2 C = O + H2
H H Cu Acetone
(Isopropyl alcohol)

4. By the hydrolysis of isopropylidene chloride.

CH3 Cl 2 NaOH CH3 OH –H2O CH3

C C C=O
CH3 Cl CH3 OH CH3

(Isopropyl alcohol) (Unstable) Acetone

18.6.1 Properties :

Colourless, volatile liquid, soluble in water and solubility is explained

by its polar nature.
Chemical properties :

It resembles acetaldehyde in many reactions - especially reactions due

to CH3 – C = O group.
|
1. It is not easily oxidised - hence it does not reduce Tollen’s reagent and
Fehling’s solution. It does not restore the colour of Schiff’s reagent.
2. Strong oxidising agents (H2SO4 + K2Cr2O7) oxidise acetone to acetic
acid.
(O)
CH3COCH3 CH3COOH

3. It can be reduced to isopropyl alcohol by sodium amalgam and water or

Lithium Aluminium Hydride.
H3C LiAlH4
H3C
C=O CHOH
H3C H3C

264
 H3C LiAlH4
H3C H2O
H3C
C=O C–O– C–OH
H3C H3C | H3C |
H(–) H H
alkoxideion isopropyl alcohol

Lithium aluminium hydride donates hydride ion (a nucleophile).

4. Clemmenson reduction or Wolff-kishner reduction converts acetone
to propane.

H3C Zn/Hg/HCl (or)

H3C
C=O CH2
H3C N2H4/NaOC2H5 H3C

(Acetone) (Propane)

5. Haloform reaction
The compounds having CH3CHOH– or CH3CO– group undergoes
haloform reaction.
It undergoes halogenation at α-carbon atom.
CH3–CO–CH3 + 3 Cl2 CCl3 – CO – CH3 + 3 HCl
In the presence of NaOH, chloroform is formed.

6. It undergoes addition reaction with HCN, NaHSO3 , RMgX and

condensation (addition followed by elimination) with NH 2 OH,
NH2–NH2, C6H5NHNH2, NH2 NHCONH2.

7. With ammonia its forms an addition product.

–H2O
NH2
CH3–C = O + H–NH2 (Ammonia) CH3–C–CH2 COCH3
| |
CH3 H–CH2COCH3 CH3
(Diacetone amine)

265
8. With chloroform acetone forms an addition products.
CH3 CH3
| KOH |
CH3 – C + H–CCl3 CH3 – C – CCl3 (Chloretone)
|| |
O OH
9. With dry hydrogen chloride first it forms mesityl oxide and then phorone.
This reaction follows aldol type condensation followed by dehydration.

H3C Dry. HCl H3C

C = O + H2CHCOCH3 C = CH–COCH3
H3C –H2O H3C Mesityl oxide
4-methyl pent-3-ene-2-one

H3C CH3 H3C CH3

C = CH–COCH3 + O = C C=CH.COCH=C
H3C CH3 –H2O H3C CH3
Phorone
2,6-dimethyl hept-2,5-diene-4-one

In presence of con. H2SO4 three molecules of acetone condense to give

mesitylene (1, 3, 5 trimethyl benzene)
CH3
Conc. H2SO4
3CH3–CO–CH3 + 3 H2O

CH3 CH3
18.6.2 Uses.
1. A very good laboratory and industrial solvent.
2. In the preparation of Tranquilizers like sulphonal, in medicine.
3. In the manufacture of cordite.

266
Comparison of Aldehyde and Ketone.

Reactions CH3CHO CH3COCH3

1. With Fehling’s gives a red does not react.
solution. precipitate
2. With Tollen’s gives silver mirror. no silver mirror.
reagent.
3. Oxidation gives acetic acid gives acetic acid
with loss of one
carbon atom.
4. Reduction with ethanol (primary isopropyl alcohol
NaBH4 alcohol) (secondary alcohol)
5. With NH3 simple addition forms complex
product is formed. ketonic amine.
6. Iodoform forms iodoform forms iodoform
reaction and formic acid. and acetic acid.
7. Polymerisation forms paraldehyde forms condensation
products.
8. With Schiff’s reagent. pink colour no pink colour in
appears in cold. cold.
9. Warming with a brown resinons no resinous mass.
NaOH mass.

18.7 AROMATIC KETONES

IUPAC name of acetophenone and benzophenone

Formula Common name IUPAC name

CH3COC6H5 methyl phenyl ketone acetophenone
C6H5COC6H5 diphenyl ketone benzophenone
Methyl phenyl ketone: CH3COC6H5
IUPAC name : Acetophenone
267
18.7.1 ACETOPHENONE
Preparation

1. Friedel Crafts acetylation of benzene with CH3COCl / AlCl3.

H COCH3
+ ClCOCH3 AlCl3 + HCl
Acetyl chloride
Benzene Acetophenone
+
This is an electrophilic substitution reaction. The electrophile CH3CO
is generated by the Lewis acid AlCl3 from acetyl chloride.

2. Dry distillation of calcium benzoate with calcium acetate.

C6H5COO COOCH3 ∆
Ca + Ca CaCO3+ C6H5COCH3
C6H5COO COOCH3 Acetophenone
(Calcium acetate) (Calcium acetate)

18.7.2 Properties

Colourless liquid, sparingly soluble in water readily soluble in ethanol

and ether.
Chemical properties :
1. Oxidation :
Acid permanganate oxidises aceto phenone to benzoic acid.
(O)
C6H5COCH3 C6H5COCOOH C6H5COOH+CO2
(Acetophenone) Phenyl glyoxalic acid benzoic acid

2. Reduction : Reagents like sodium and ethanol, sodium borohydride,

lithium aluminium hydride reduce acetophenone to phenyl methyl carbinol.
2(H)
(a) C6H5COCH3 C6H5CHOHCH3
(b) Clemmenson reduction or Wolff-kishner reduction converts aceto
phenone to ethyl benzene.
4(H)
C6H5COCH3 C6H5CH2CH3 + H2O

268
Halogenation :

At 273 K bromine in ether reacts with acetophenone to form phenacyl

bromide.
One α-hydrogen is removed as a proton to the remaining carbanion,
bromine addition takes place.

C6H5COCH2–H + Br – Br C6H5COCH2 Br + HBr

Phenaceylbromide

A small amount of anhydrous aluminium chloride catalyses this reaction.

Haloform reaction :

Because of the presence of CH3CO- group it undergoes haloform

reaction.
Cl2
CH3COC6H5 CHCl3 + C6H5COONa
NaOH

Electrophilic substitution :

Acetyl group deactivates the benzene ring and is meta directing group.
Nitration : COCH3
COCH3
HNO3

H2SO4 NO2
m-nitroacetophenone

18.7.3 Uses

1. Used as a hypnotic (sleep inducing) by name hypnone

2. In perfumary.
18.8 Benzophenone :

Diphenyl ketone O
||
C6H5 – C– C6H5

269
1. By Friedel Crafts reaction : Benzoylation of benzene takes place in
presence of anhydrous aluminium chloride as a catalyst. Benzoyl cation
(C6H5CO+) is the electrophile.
COC6H5
anhyd.
+ ClCOC6H5 AlCl3 + HCl

2. By the reaction of excess of benzene with carbonyl chloride (phosgene)

in presence of anhydrous aluminium chloride as a catalyst, Benzoyl
chloride may be formed initially.
4(H)
C6H6 + Cl – CO – Cl + C6H6 C6H5COC6H5
Benzene + Phosgene + Benzene Benzophenone

Thus involves two Friedel craft’s acylation reactions.

3. By the dry distillation of calcium benzoate.
C6H5COO ∆
Ca C6H5COC6H5 + CaCO3
Benzophenone
C6H5COO Distillation
(Calcium Benzoate)

18.8.1 Properties

1. It is a colourless, sweet smelling solid (m.pt. 323 K).

2. It is insoluble in water but soluble in alcohol and ether.
3. Though it gives all reactions of carbonyl compound, it does not form
addition product with sodium bisulphite because of steric hindrance and
lowered reactivity due to the presence of two phenyl groups.
4. Oxidation with K2Cr2O7 and con. H2SO4, it gives benzoic acid.

(O)
C6H5COC6H5 C6H5COOH
Benzophenone Benzoic acid

270
5. Reduction with sodium amalgam and water or lithium aluminium hydride,
diphenyl carbinol is formed.

2(H)
C6H5COC6H5 C6H5CHOHC6H5
Benzophenone diphenyl carbinol

Diphenyl carbinol is also called ‘benzhydrol’. Reduction wtih zinc

amalgam and con. HCl gives Diphenyl methane.
4(H)
C6H5COC6H5 C6H5CH2C6H5
Benzophenone diphenyl methane

6. On fusion with potassium hydroxide, it undergoes disproportionation

reaction.
O
||
C6H5 – C + O – K C6H5 COOK + C6H6
| | Potasium benzoate Benzene
C6H5 H

18.8.2 Uses :
Benzophenone is used in perfumery and in the preparation of benzhydrol
drop and diphenyl methane.

SELF EVALUATION
(A) Choose the correct answer :
1. The chain isomer of 2-methyl propanal is
(a) 2-butanone (b) butanal
(c) 2-methyl propanol (d) but-3-ene-2-ol
2. Schiffs reagent gives pink colour with
(a) acetone (b) acetaldehyde
(c) ethyl alcohol (d) methyl acetate

271
3. Isopropyl alcohol vapours with air over silver catalyst at 520 K give
(a) tert.butyl alcohol (b) acetaldehyde
(c) acetone (d) 2-propanol
4. Methyl ketones are usually characterised by
(a) the Fehling’s solution (b) the iodoform test
(c) the Schiff’s test (d) the Tollen’s reagent
5. Which of the following compounds is oxidised to give ethyl methyl
ketone ?
(a) 2-propanol (b) 2-pentanone
(c) 1-butanol (d) 2-butanol
6. Formaldehyde polymerises to give
(a) paraldehyde (b) paraformaldehyde
(c) formalin (d) formic acid
7. Tollen’s reagent is
(a) ammoniacal cuprous chloride (b) ammoniacal cuprous oxide
(c) ammoniacal silver nitrate (d) ammoniacal silver chloride
8. When acetaldehyde is heated with Fehling solution, it gives a precipitate of
(a) Cu2O (b) CuO (c) CuO + Cu2O (d) Cu
9. The compound that does not undergo Cannizzaro reaction is
(a) formaldehyde (b) acetaldehyde
(c) benzaldehyde (d) trimethyl acetaldehyde
10. The formation of cyanohydrin from a ketone is an example of
(a) electrophilic addition (b) nucleophilic addition
(c) nucleophilic substitution (d) electrophilic substitution
11. Hydrogenation of benzoyl chloride in the presence of Pd on BaSO4
gives
(a) phenol (b) benzoic acid
(c) benzyl alcohol (d) benzaldehyde
12. From which of the following, tertiary butyl alcohol is obtained by the
action of methyl magnesium iodide ?
(a) HCHO (b) CH3CHO (c) CH3COCH3 (d) CO2

272
13. During reduction of aldehydes with hydrazine and C2H5ONa the product
formed is
(a) R–CH = N–NH2 (b) R–C ≡ N
(c) R – C – NH2 (d) R–CH3
||
O
14. Aldol is
(a) 2-hydroxy butanol (b) 3-hydroxy butanol
(c) 3-hydroxy butanal (d) 2-hydroxy butanal
15. In the reduction of acetaldehyde using LiAlH4 the hydride ion acts as
(a) electrophile (b) nucleophile
(c) both (a) and (b) (d) a free radical
16. Which of the following statement is wrong ?
(a) 2-pentanone and 3-pentanone are position isomers
(b) aqueous solution of formaldehyde is known as formalin
(c) aldehydes and ketones undergo nucleophilic substitution
(d) aldehydes act as reducing agents
17. A cyanohydrin of a compound X on hydrolysis gives lactic acid. The X
is
(a) HCHO (b) CH3CHO (c) (CH3)2 CO (d) C6H5CH2CHO

18. The IUPAC name of CH3 – C = CH – C – CH3 is

| ||
CH3 O
(a) 4-methylpent-3-en-2-one (b) 2-methylpent-3-en-2-one
(c) 3-methyl pent-2-en-1-one (d) None of these
19. Which of the following does not give iodoform test ?
(a) aceto phenone (b) benzophenone
(c) CH3 – CHOH (d) CH3 – CH – CH2 CH2 – CH3
| |
CH3 OH
20. The compound which does not reduce Fehling solution is
(a) formaldehyde (b) acetaldehyde
(c) benzaldehyde (d) propionaldehyde
273
 Conc. H2SO4
21. CH3COCH3 The product is
(a) mesitylene (b) mesityl oxide
(c) phorone (d) paraldehyde
22. Which compound on strong oxidation gives propionic acid ?
(a) CH3 – CH – CH3 (b) CH3 – CO – CH3
|
OH

(c) CH3 (d) CH3 CH2 CH2 OH

|
CH3 – C – OH
|
CH3

23. The compound used in the preparation of the tranquilizer, sulphonal is

(a) acetone (b) acetophenone
(c) isopropyl alcohol (d) glycol
distillation
24. Calcium acetate + calcium benzoate gives
(a) benzophenone (b) benzaldehyde
(c) acetophenone (d) phenyl benzoate
25. Bakelite is a product of reaction between
(a) formaldehyde and NaOH (b) phenol and methanal
(c) aniline and NaOH (d) phenol and chloroform
(B) Answer in one or two sentences :
1. Give the structural formulae of
(a) mesitylene (b) phorone and (c) mesityl oxide
2. What is Rosenmund’s reduction ? What is the purpose of adding BaSO4
in it ?
3. Name one reagent used to distinguish acetaldehyde and acetone.
4. Give four examples of carbonyl compounds ?

274
5. Does formaldehyde undergo aldol condensation ? Justify your answer.
6. What type of aldehydes undergo Cannizzaro reaction ?
7. What is urotropine ? Give its use.
8. What happens when calcium acetate is dry distilled ?
9. What is formalin - write its use.
10. Ethanal is more reactive towards nucleophilic addition reaction than
propanone. Why ?
11. How is acetophenone prepared by Friedel-Crafts method ?
12. Write a note on haloform reaction.
13. How will you convert acetophenone to phenacyl bromide ?
14. Though benzophenone gives all reactions of carbonyl compounds, it does
not form addition product with NaHSO3 - give reasons.
15. Arrange the following in increasing order of reactivity towards
nucleophilic addition. HCHO ; CH3CHO and CH3COCH3
16. Predict the formulae of the products in the following reactions.
(i) CH3COCH3 + HCN
(ii) C6H5COCH3 + NH2OH
17. Formaldehyde and benzaldehyde give Cannizzaro reaction but
acetaldehyde does not - Account for this
18. Give two tests for aldehydes.
19. Mention the industrial uses of formaldehyde.
20. How will you distinguish between formaldehyde and acetaldehyde.
(C) Answer not exceeding sixty words :
1. Write any three methods of preparing formaldehyde from alcohol.
2. How does formaldehyde react with (i) NH3, (ii) CH3MgI followed by
hydrolysis and (iii) NaOH.
3. Illustrate the reducing property of acetaldehyde with examples.

275
4. How is acetone converted to
(i) mesitylene (b) mesityl oxide, (iii) phorone and (iv) isopropyl alcohol.
5. Write giving chemical equations, a brief account of the following :
(i) Rosenmund Reduction, (ii) Cannizzaro reaction
(iii) Clemmenson reduction, and (iv) Aldol condensation
6. Give nucleophilic addition reaction of acetaldehyde with (a) NaHSO3,
and (b) LiAlH4.
7. Discuss aldol condensation.
8. How are the following conversions carried out ?
(i) benzaldehyde from Toluene, (ii) acetophenone from benzene, and
(iii) benzoin from benzaldehyde.
9. Distinguish acetaldehyde from acetone.
10. Write a note on (i) Perkins reaction, and (ii) Knoevenagal reaction.
11. How will you distinguish between formaldehyde and acetaldehyde.
12. Write the differences between acetophenone and benzophenone.
13. Identify (B), (C) and (D)
O
|| LiAlH4 SOCl2 alc.KOH
CH3 – C – CH3 (A) (B) (C) (D)
Acetone

Answers (B) OH
|
CH3 – CH – CH3 : Isopropyl alcohol
Cl
|
(C) CH3 – CH – CH3 : Isopropyl chloride

(D) CH3 – CH = CH2 : propylene

14. How will you synthesise acetaldehyde from formaldehyde ?

276
Answers : O CH3MgBr K2Cr2O7
|| CH3CH2OH CH3CHO
H2O/H+ H2SO4
H– C–H ethyl alcohol acetaldehyde
formaldehyde

15. How will you distinguish between 2-pentanone and 3-pentanone.

O
||
Answers : Since 2-pentanone contains methyl ketone
(CH3– C –)
it undergoes iodoform test with an alkaline solution of iodine and forms
yellow precipitate of iodoform But-3-pentanone does not give this test.
O O
|| ||
CH3 – CH2 – CH2 – C – CH3 + 4 NaOH + 3 I2 CH3 CH2 – CH2 – C – ONa
2-pentanone + CHI3 + 3H2O + 3NaI
Iodoform
(yellow precipitate)

16. How will you synthesise acetone from acetaldehyde ?

Answers: O OH O
|| CH3MgI
| K2Cr2O7
||
CH3– C – H CH3 – CH – CH3 CH3 – C – CH3
acetaldehyde isopropyl H2SO4 acetone
alcohol

17. Give the IUPAC names of

(i) CH3 – CH – C – CH – OCH2 CH3

| || | and
OCH3 O CH3
(ii) CH3 – CO – CH – CH2 – CH2 – Cl
|
C2H5
Answers :
(i) 2-ethoxy-4-methoxy-3-pentanone and
(ii) 3-ethyl-5-chloro-2-pentanone.

277
18. An organic compound, C2H4O gives a red precipitate when warmed
with Fehling’s solution. It also undergoes aldol condensation in presence
of alkali.

(i) Write IUPAC name of the compound.

(ii) What is the hybridization of carbon atoms in the compound ?
(iii) Write equation for the reaction.
Answers : (i) Ethanal
(ii) sp2 and
(iii) CH3CHO + 2Cu2+ + 3OH– CH3COO– + 2Cu+ + 2H2O

NaOH H
CH3CHO + CH3CHO |
H3C – C– CH2–CHO
|
OH
aldol
19. Write the structural formula of the main product formed when ; (i) The
compound obtained by hydration of ethyne is treated with dilute alkali.
(ii) Methanal reacts with ammonia.

Hg2+ OH–
Answers: (i) HC≡CH + H2O CH3CHO CH3– CH – CH2 – CHO
Ethyne Ethanal |
OH
aldol

(ii) 6CH2O + 4NH3 (CH2)6 N4 + 6H2O

20. How will you synthesise 2-butanone from ethyl alcohol ?
Clue : Steps are (i) SOCl2 (ii) Mg/ether (iii) CH3CHO, (iv) H2O/H+
and (v) Na2Cr2O7 / H2SO4.
21. What happens when the following alcohol vapours are passed over heated
copper ? (a) n-butyl alcohol, (b) isobutyl alcohol, (c) 2-butanol and
(d) 2-methyl-2-propanol.

278
22. How can the following conversions be effected ?
(a) CH3COCl CH3CHO
(b) CH3COCl CH3COCH3
(c) CH3CN CH3CHO
(d) CH3CN CH3CH2OH
23. Which compounds on Clemmenson reduction give (a) 2-methyl propane,
(b) ethyl benzene, (c) propane and (d) diphenyl methane.

24. What happens when the following compounds are treated with dilute
NaOH solution in cold ?

(a) propanal, (b) (CH3)3C-CHO, (c) mixture of (CH3)3 CCHO and

acetone.

25. Identify the atoms that has undergone change in hybridisation in the
following reactions.

(a) CH3 CHO + HCN CH3COOH

(b) CH3C ≡ N CH3CH2CH3
(c) CH3COCH3 CH3CH2CH3
(d) CH ≡ CH CH2 = CH2
26. Draw resonance structures for the following :
(a) CH3COO–, (b) CH3CONH2, (c) C6H5CHO, (d) C6H5COO–
27. Which of the following pairs is more resonance stabilised ?
(a) C6H5CHO and C6H13CHO
(b) CH3COCH3 and CH3 COC6H5,
(c) p-hydroxy benzaldehyde and m-hydroxy benzaldehyde,
(d) C6H5CH2OH and CH3–C6H4–OH (para)

279
SUMMARY :
Functional group of aldehyde and ketone.
Structure, isomerism involved and nomenclature - common name and
IUPAC name.
Preparation - by the oxidation or dehydrogenation of alcohols ozonolysis
of olefins, hydration of alkynes, catalytic reduction of acid chloride, distillation
of calcium salt of fatty acid and hydrolysis of gem dihalide.
Properties - Higher boiling point of polar molecules than hydro carbons
- carbon of the carbonyl group is the site of nucleophilic attack - Most of the
addition reactions - nucleophilic - addition product eliminates water forming
condensation product. Reactions with NaHSO3, HCN, NH3 , RMgX,
NH2OH, C6H5NHNH2, NH2NHCONH2, reductions with NaBH4, LiAlH4,
also nucleophilic in nature, that give alcohols.
Some reductions - Zn/Hg/HCl or heating with N2H4/NaOC2H5 - gives
hydrocarbon.
Mild oxidising agents like Fehling’s solution, Tollen’s reagent - oxidise
aldehydes to mono carboxylic acids. Ketones require more powerful oxidising
agents like acidified K2Cr2O7 or KMnO4 in which carbon-carbon bond is
cleaved to give carboxylic acids having lesser number of carbon atoms.
Aldehydes and ketones having α-hydrogen atom form carbanions in
presence of base. These take part in condensation reactions with other
carbonyl compounds. Aldehydes and ketones having CH3CO- group undergo
haloform reaction.
Formaldehyde undergoes condensation with Ammonia to form
urotropine and phenol to form Bakelite.
Acetone and acetaldehyde undergo aldol condensation while
formaldehyde undergoes Cannizaro reaction.
Distinction between formaldehyde and acetaldehyde and acetaldehyde
and acetone.
Structure and nomenclature of aromatic aldehydes - preparation and
properties - Reactivity of carbonyl group - decreased by benzene ring.

280
Absence of α-hydrogen - cannot form carbanion. But carbanion formed
from other carbonyl compounds attack the carbonyl group of benzaldehyde.
Hence it takes part in all the nucleophilic addition reactions and condensation
reactions.
In addition it undergoes aromatic electrophilic substitution reactions.
The benzene ring - deactivated and meta-products formed.
Distinction between aliphatic and aromatic aldehydes.
Aromatic ketones - acetophenone and benzophenone, preparation -
Friedel Crafts acylation.
Properties - Resemblance of acetophenone with acetone. Benzophenone
- least reactive - absence of α-hydrogen - uses.
Name reactions
Rosenmund reduction
Clemmenson reduction
Wolff-kishner reduction
Aldol condensation
Cannizaro reaction
Fehling’s test
Tollen’s test
Claisen condensation
Perkins reaction
Knoevenagel reaction
Benzoin condensation
Friedel Crafts acylation

REFERENCES :
1. Organic Chemistry by Finar (Vol. I)
2. Text book of Organic Chemistry by P.L. Soni.
3. Text book of Organic Chemistry by Cram, Hammond & Hendrickson
______

281
 19. CARBOXYLIC ACIDS
LEARNING OBJECTIVES
@ To know about carboxylic acids and their derivatives.

19.1 CARBOXYLIC ACIDS O

Organic compounds containing the carboxyl group, —C are
OH
called carboxylic acids. The acid may be monocarboxylic acid, if it contains
one –COOH group ; a dicarboxylic acid if it contains two –COOH groups ;
a tricarboxylic acid if it contains three –COOH groups etc.
The aliphatic mono carboxylic acids are called fatty acids and the higher
members like Stearic acid (C17H35COOH), palmitic acid (C15H31COOH),
oleic acid (C16H33COOH) etc., occur as glycerides in oils and fats.

Nomenclature :

(a) Trivial system :

The names of lower members are derived from the source of individual
acids.
Formula Source Trivial name
HCOOH Red ant (formica) formic acid
CH3COOH Vinegar (acetum) acetic acid
C3H7COOH Butter (Butyrum) butyric acid
C4H9COOH Root of valarion plant valeric acid
C11H23COOH Laurel oil lauric acid
In case of substituted acids the position of the substituent is represented
by α, β, γ, δ etc. Thus
γ β α
CH3 – CH – CH2 – COOH
|
CH3 β-methyl butyric acid

282
Derived names :
Sometimes fatty acids are named as alkyl derivatives of acetic acid.
(e.g.,) MeCH2COOH Methyl acetic acid
Me2CHCOOH Dimethyl acetic acid
Me2CH.CH2COOH Isopropyl acetic acid

IUPAC names :
Acids are named after the alkane by replacing the ending ‘e’ by ‘oic’
acid.
HCOOH Methanoic acid
CH3COOH Ethanoic acid
CH3CH2COOH Propanoic acid
CH3CH2CH2COOH Butanoic acid
CH3CH2CH2CH2COOH Pentanoic acid

In case of substituted acid the longest carbon chain including the carboxyl
group is taken as the parent chain.
Position of the substituent is indicated by either 1, 2, 3, etc., (or) α, β,
γ, ...
When it is done by numbers the carbon of the carboxyl group is numbered
as (1) when it is done by Greek letters the carbon next to the –COOH group
is designated as ‘α α’.
CH3
4 3 | 21
CH3 – CH2 – CH – COOH
γ β α

2-methyl butanoic acid (IUPAC)

α-methyl butyric acid (Common)

283
Isomerism :

1. Chain isomerism :
This arises due to the difference in the carbon chain of alkyl group
attached to carboxyl group.
CH3
|
CH3 CH2 CH2 CH2 COOH CH3 – CH – CH2 COOH
(pentanoic acid) (3-methyl butanoic acid)

2. Functional isomerism :
Carboxylic acids may be functional isomers of esters.
CH3 CH2 COOH and CH3 COOCH3 HCOOC2H5
propanoic acid methyl acetate ethyl formate

19.2 Preparation of monocarboxylic acids :

1. Oxidation : Carboxylic acids are prepared by the oxidation of alcohols,
aldehydes or ketones with K2Cr2O7 and H2SO4. Primary alcohol is first
oxidised to aldehyde and then to carboxylic acid. On the otherhand
secondary alcohols are first oxidised to ketone and then to acid with
lesser number of carbon atoms.
(O) (O)
RCH2OH RCHO RCOOH

R (O)
R (O)
CHOH C=O RCOOH
R R

(O) (O)
(i) CH3CH2OH CH3CHO CH3COOH
ethyl alcohol acetaldehyde acetic acid

(ii) CH3 (O)

CH3 (O)
CHOH C=O CH3COOH + CO2
CH3 CH3 acetic acid
Isopropyl alcohol acetone

284
2. Hydrolysis methods :
(a) Hydrolysis of cyanides, amides and esters : Alkyl cyanides, amides,
esters are hydrolysed with aqueous acid or alkali to give carboxylic acid.
(i) R–C≡N R – C – NH2 H2O
|| RCOOH
O – H2 O
alkyl cyanide amide

CH3 – C ≡ N CH3 – C – NH2

H2O H2O
methyl cyanide || CH3COOH + NH3
O
acetamide

H2O H2O
H–C≡N H–C=O H – C – OH + NH3
Hydrogen cyanide | ||
NH2 O
Formamide
(ii) O
|| H2O
R – C – NH2 RCOOH + NH3
HO – H
Example,
O O
|| H2O ||
CH3 – C – NH2 CH3 – C – OH + NH3
acetamide

(iii) O O
|| H+ or OH–
||
R – C – OCH3 R – C – OH + CH3OH
ester +
HO – H
Example,
O O
|| HOH
||
CH3 – C – OCH3 CH3 – C – OH + CH3OH
methyl acetate H+ or OH– acetic acid
(acid or alkaline hydrolysis)
285
 (b) Hydrolysis of trihalides : By the hydrolysis of trihalides containing
three halogen atoms attached to the same carbon atom, carboxylic acids are
formed.
X OH –H2O
3KOH
R–C– X R – C – OH R–C=O
X OH |
unstable OH

3KOH
OH –H2O
CH3 – CCl3 CH3 – C – OH CH3 – C = O
trichloro ethane OH |
OH
3. From Grignard reagent :
O O
|| +H2O
|| OH
RMgI + CO2 R – C – OMgI R–C–OH + Mg
I
Methyl magnesium iodide with carbondioxide gives acetic acid.
O O
|| H2O || OH
CH3MgI + CO2 CH3 – C – OMgI CH3 – C – OH + Mg
I
Formic acid cannot be prepared by Grignard reagent since the acid
contains only one carbon atom.

Preparation of formic acid

4. From CH3OH or HCHO

By the oxidation of methyl alcohol or formaldehyde with K2Cr2O7/H2SO4.
3(O)
CH3OH HCOOH

(O)
HCHO HCOOH

286
5. From glycerol
By heating glycerol with oxalic acid at 373 K – 383 K
CH2 – OH
| + HO – C = O CH2 – O – CO –COOH
∆ |
CHOH | –CO2
| COOH 383 K CHOH
CH2OH |
O CH2OH
||
CH2 – O – C–H
| H2O CH2OH
CHOH |
| CHOH + HCOOH
CH2OH | formic acid
CH2OH
glycerol monoformate

19.2.1 Properties
1. Lower members are pleasant smelling liquids with higher boiling points.
The higher members are waxy solids. The higher boiling points are
explained on the basis of association by hydrogen bonding.
O H–O
R–C C–R
O–H O

2. The first few members are highly soluble in water and higher members
are insoluble. This can also be explained on the basis of hydrogen bonding
between acids and water. With higher members the size of the alkyl group
is increased which repels the hydrophilic groups.
Chemical Properties :
1. Fatty acids react with alkalies to form salt and water and liberates CO2
with carbonates (stronger than carbonic acid).
CH3COOH + NaOH CH3COONa + H2O
(sodium acetate salt)

287
 2 HCOOH + 2Na2CO3 2 HCOONa + H2O + CO2
(sodium formate)

2. They liberate hydrogen, when react with electropositive metals like zinc
or magnesium.
2CH3COOH + Zn (CH3COO)2 Zn + H2
(zinc acetate)

2HCOOH + Mg (HCOO)2 Mg + H2
(magnesium formate)

3. Reaction involving - hydroxyl group : carboxylic acid reacts with

alcohols in presence of mineral acid as catalyst and forms esters. This
reaction is called esterification.
H+
CH3COOH + C2H5OH CH3COOC2H5 + H2O
(ethyl acetate)

H+
HCOOH + CH3OH HCOOCH3 + H2O
(methyl formate)

Mechanism of esterification
Protonation of the –OH group of the acid, enhances the nucleophilic
attack by alcohol to give the ester.

Step 1. Protonation of carboxylic acid

H+ +
H
CH3 – CO – OH CH3 CO – O
H

288
Step 2. Attack by nucleophile.
H
H |+
+ .. O – C2H5
CH3 – CO – O C2H5 OH | + H
CH3 – C – O
H |
O H

–H+ / –H2O
OC2H5
|
CH3 – C
||
O
4. Dehydration
Except formic acid others undergo intermolecular dehydration on heating
with P2O5 forming anhydride.
CH3 – CO – O H P2O5 CH3 – CO
+ O
∆
CH3 CO OH CH3 – CO
(Acetic anhydride)

HCOOH on dehydration forms carbon monoxide.

H Con. H2SO4
C=O H2O + CO
HO
5. With phosphorous pentachloride or thionyl chloride.
(i) Acid chloride is formed.
O O
|| ||
CH3 – C – O – H CH3 – C + POCl3 + HCl
|
Cl – PCl3 – Cl Cl
acetic acid (acetyl chloride)

289
 (ii) Formic acid forms formyl chloride.

Formyl chloride being unstable decomposes to carbon monoxide and

hydrogen chloride.

O
||
H–C–O–H H–C=O + POCl3 + HCl
|
Cl – PCl3 – Cl Cl
formyl chloride

H–C=O HCl + CO
Cl
The carboxyl group is involved in resonance.
O O(–)
–C –C
O O
(–)

>
Hence reactions characteristic of C=O is almost absent with acids.
They do not form addition product with HCN, N2H4 etc.

6. Reduction
(i) Carboxylic acid group is not reduced easily. But it is reduced to primary
alcoholic group by LiAlH4 or H2/Ru under pressure. This reaction works
under higher pressure.

H2/Ru-pressure
R – C – OH R – CH2 – OH
or
||
LiAlH4
O
(ii) Heating with HI/P converts the carboxylic acid to alkane.

HI/P
CH3COOH CH3 – CH3
∆

290
7. Decarboxylation : When anhydrous sodium salt of carboxylic acids are
heated with sodalime, carboxyl group is removed with the formation of
hydrocarbon containing one carbon atom less.

NaOH/CaO
RCOONa RH + Na2CO3
∆
(Hydrocarbon)

NaOH/CaO
CH3COONa CH4 + Na2CO3
sodium acetate methane

Formic acid gets decarboxylated on heating.

H 160oC
C=O H2 + CO2
HO

H+ R O(–)
C RH + CO2
alkane
O
Carboxylate anion

8. Halogenation :
(i) Fatty acids having α-hydrogen atoms, can be converted to α-halo acids
by halogen in presence of halogen carrier like red phosphorous.
Br2/P
CH3CH2COOH CH3CHBr COOH CH3CBr2COOH
propionic acid α-bromo propionic acid α, α, di bromopropionic acid

(ii) HVZ - reaction : When the halogenation is carried out with halogen
and phosphorous trihalide, this reaction is known as Hell-Volhard
Zelinsky reaction. (HVZ-reaction).
Br2/PBr3 H2O
RCH2COOH RCH2COBr RCHBrCOBr RCHBrCOOH

9. Reactions with ammonia : Carboxylic acid reacts with NH3 to form

291
 ammonium salt which on heating undergoes dehydration to amides,
ultimately alkyl cyanide results.

–H2O P2O5
RCOOH + NH3 RCOONH4 RCONH2 RCN
(Ammonium Salt) ∆ (Amide) –H2O (Cyanide)

∆
HCOOH + NH3 HCOONH4 HCONH2
(Ammonium formate) –H2O (Formamide)

10. Kolbe’s electrolytic reaction : Electrolysis of concentrated aqueous

solution of sodium salt of acids gives hydrocarbon.
Electrolysis
CH3 – COO – Na CH3
| + 2CO2 + 2Na
CH3 – COO – Na CH3 sodium
ethane
Under this condition Formic acid gives hydrogen.
11. Dry distillation of calcium salt of fatty acids.
Calcium acetate on dry distillation gives acetone.
CH3 – COO
Ca CH3COCH3 + CaCO3
∆
CH3 – COO acetone
Calcium acetate

12. Reducing property

Formic acid is unique because it contains both an aldehyde group and
carboxyl group also. Hence it can act as a reducing agent. It reduces
Fehling’s solution, Tollens reagent and decolourises pink coloured KMnO4
solution.
O O
|| ||
H – C – OH H – C – OH
In all cases formic acid is oxidised to CO2 and water.
H
C = O + (O) H2O + CO2
HO
292
(a) Formic acid reduces ammoniacal silver nitrate solution (Tollen’s reagent)
to metallic silver.
HCOOH + Ag2O H2O + CO2 + 2Ag↓ (metallic silver)
(b) Formic acid reduces Fehling’s solution. It reduces blue coloured cupric
ions to red coloured cuprous ions.
HCOO– + 2Cu2+ + 5OH– CO32– + Cu2O + 3H2O
(blue) (red)

(c) On the otherhand when sodium formate is heated to 360oC it decomposes

to hydrogen and sodium oxalate.

360oC
H – COONa H2 + COONa
∆ |
H – COONa COONa
Sodium formate Sodium oxalate

Problems for Practice

Formic acid gives a red precipitate when heated with Fehling solution
but acetic acid does not - reason out.
Answer.
H
Formic acid has C = O group an aldehyde group but acetic acid

has no aldehydic group. Hence formic acid reduces - Fehling’s solution.

19.2.2 Uses of formic acid

(a) In Textile Industry for preparing ‘‘mordants’’.
(b) In leather tanning for removing lime from the hides.
(c) In coagulating rubber latex.
(d) Nickel formate as hydrogenation catalyst.
(e) As a stimulant for the growth of yeast.
(f) As an antiseptic and in preservation of fruits.
(g) In the treatment of gout.

293
19.2.3 Tests for carboxylic acid
1. Aqueous solution of carboxylic acids turn blue litmus into red colour.
2. Carboxylic acids give brisk effervescence with sodium bi-carbonate due
to the evolution of carbon-di-oxide.
3. On warming carboxylic acids with alcohol and concentrated sulphuric
acid it forms ester which is identified from its fruity odour.

19.3 Monohydroxy carboxylic acids

CH3CH(OH) COOH CH2(OH)CH2COOH
α-hydroxy propionic acid β-hydroxy propionic acid
(or) lactic acid

19.3.1 Lactic acid

Lactic acid is the main constituent of milk that has gone sour.
Natural Source : Pyruvic acid is the precursor in organism. It is also
present in gastric juice, cucumbers, or opium.

19.3.2 Manufacture
Industrially it is made by the Fermentation of solution of cane sugar (or)
glucose.
(a) To a dilute solution of cane sugar (or) glucose (or) maltose a little of
sour milk (or) decayed cheese is added. Temperature is maintained at
40 – 45o C for six days. The Bacillus acidi lacti brings forth fermentation.
Methyl glyoxal forms as intermediate compound. Acid is removed by the
addition of CaCO3 which precipitates calcium lactate. It is filtered and
decomposed with dilute sulphuric acid. The filterate is distilled under reduced
pressure.
H2O
C12H22O11 C6H12O6 + C6H12O6
cane sugar (glucose) (fructose)

BAL
C6H12O6 2CH3COCHO 2CH3CHOHCOOH
Methyl glyoxal Lactic acid

294
(b) Synthesis from acetylene
Acetylene is prepared by striking an electric arc using carbon electrodes
in an atomsphere of hydrogen. This is passed through dilute sulphuric acid
containing mercuric ion catalyst. Acetaldehyde is formed. It is converted to
cyanohydrin on treatment with HCN, which is then hydrolysed to get lactic
acid.

electric dil. H2SO4 HCN

2C + H2 CH≡CH CH3CHO
Arc 1%Hg
80

dil. HCl
CH3CH(OH)CN CH3CH(OH)COOH
(acetaldehyde cyano hydrin) lactic acid

(c) From propene :

Propene is treated with chlorine to get 1,2-dichloropropane. This on
treatment with aqueous alkali solution gives propane 1,2-diol. This on
oxidation with mild oxidising agent, gives lactic acid.
Cl2 dil/NaOH
CH3CH = CH2 CH3CHCl – CH2Cl CH3CH(OH)CH2OH
propylene 1,2-dichloro propane propane 1,2-diol

(O)
CH3CH(OH)COOH
lactic acid

(d) Hydrolysis of α-bromo propionic acid :

Hydrolysis of α-bromo propionic acid using moist Ag2O gives lactic
acid.
Ag2O
2CH3CH(Br)COOH 2CH3CH(OH)COOH
α-bromo propionic acid H2O lactice acid

Properties :
Colourless syrupy liquid, hygroscopic and extremely soluble in water.
Chemical properties :
Reactions characteristic of both –OH and –COOH group.

295
1. Oxidation :
(i) Mild oxidising agent like Fenton’s reagent Fe2+/H2O2 forms pyruvic
acid with lactic acid
(O)
CH3CH(OH)COOH CH3COCOOH
Lactic acid H2O2/Fe2+ Pyruvic acid
(ii) With dilute acidified permanganate it decomposes forming acetaldehyde.
CH3CH(OH)COOH + (O) CH3CHO + H2O +CO2
2. With dilute H2SO4 :
With dil. H2SO4 acid it dissociates to acetaldehyde and formic acid.
dil. H2SO4
CH3CH(OH)COOH CH3CHO + HCOOH
3. Haloform reaction :
It undergoes haloform reaction with I2 and caustic soda.
(O) I2
CH3CH(OH)COOH CH3COCOOH CI3COCOOH
pyruvic acid tri iodo pyruvic acid
NaOH
CHI3 + (COONa)2
iodoform sodium oxalate
4. With PCl5
With PCl5 it forms lactyl chloride.
CH3CH(OH)COOH + PCl5 CH3 – CH – COCl
|
Cl
lactyl chloride
5. Formation of cyclic ester :
Formation of cyclic diester - by heating in presence of catalytic amount
of con. H2SO4.
O
CH3 CH3
CHO H HO – C = O H+ CH C=O
+2H2O
+
O=C HC – CH3 O=C CH–CH3
OH H O O
lactide

296
Uses of lactic acid :
1. In tanning industry.
2. In soft drinks.
3. In the treatment of digestive disorder in children.
4. Preparation of lactates, ethyl lactate as a solvent.
5. Silver lactate as an antiseptic and astringent.

19.4 Dicarboxylic acids

They contain two carboxyl groups, one at each end of a saturated
hydrocarbon chain. Their general formula is
HOOC – (CH2)n – COOH where n = 0, 1, 2, 3, etc.
Dicarboxylic acids are named as Alkane dioic acid in IUPAC system.
Most simple dicarboxylic acids have common names.
Formula Common name IUPAC name
HOOC – COOH Oxalic acid Ethane dioic acid
HOOC – CH2 – COOH Malonic acid Propane dioic acid
HOOC–(CH2)2–COOH Succinic acid Butane dioic acid
HOOC (CH2)4 COOH Adipic acid Hexane dioic acid

19.4.1 Methods of preparation

Oxalic acid : ethane dioic acid, HOOC – COOH
1. Laboratory method. Oxalic acid is made by oxidation of sucrose or
molasses with concentrated nitric acid in the presence of vanadium
pentoxide as catalyst.

HNO3
C12H22O11 + 18 [O] COOH + 5H2O
V2O5 6 |
COOH
The –CHOH–CHOH - units present in sucrose molecule are split and
oxidised to oxalic acid.

297
2. Manufacture : Oxalic acid is made industrially by heating sodium formate
to 673 K.

673 K
2HCOONa NaOOC – COONa + H2
sodium formate sodium oxalate
The sodium oxalate thus formed is dissolved in water and calcium
hydroxide added to precipitate calcium oxalate. The solution is filtered and
the precipitate is treated with calculated quantity of dilute sulphuric acid to
liberate the oxalic acid.
COONa COO
| + Ca(OH)2 | Ca + 2 NaOH
COONa COO
sodium oxalate calcium oxalate

COO COOH
| Ca + H2SO4 | + CaSO4 ↓
COO COOH
oxalic acid

Calcium sulphate precipitates and oxalic acid is crystallised as the hydrate

(COOH)2.2H2O.
3. From glycol :
It is prepared by oxidising glycol with con.HNO3.
CH2OH [O] COOH
| |
CH2OH COOH
glycol

4. From Cyanogen :
By passing cyanogen through an aqueous solution of acid or alkali.
C≡N 2H2O CONH2 2H2O COOH
| | |
C≡N CONH2 COOH
cyanogen oxamide

298
Succinic acid, Butanedioic acid HOOC–CH2–CH2–COOH
Preparation : Succinic acid is prepared from ethylene dibromide by
treating with sodium cyanide and subsequent hydrolysis of ethylene dicyanide.
CH2Br 2NaCN
CH2CN H2O
CH2COOH
| | |
CH2Br CH2CN HCl CH2COOH
Ethylene ethylene succinic acid
di bromide dicyanide

19.4.2 Properties
Oxalic acid occurs as potassium hydrogen oxalate in the wood sorrel,
and tomatoes. The insoluble calcium oxalate is found in some stony deposits
in kidneys and bladder in human body. Oxalic acid is an active poison
depressing the central nervous system.

Chemical Properties
Dicarboxylic acid gives all the usual reactions of COOH group twice.
1. With alkali : With NaOH it gives two kinds of salts.
(e.g.,)
(i) COOH COONa NaOH COONa
| + NaOH | |
COOH COOH COONa
oxalic acid mono sodium disodium
oxalate oxalate

(ii) CH2COOH CH2COONa NaOH CH2COONa

| + NaOH | |
CH2COOH CH2COOH CH2COONa
Succinic acid mono sodium disodium succinate
succinate

2. With ammonia : Dicarboxylic acid gives ammonium salts first which

then loses water molecule to give amide.

299
 COOH COONH4 CONH2
∆
| + 2NH3 | | + 2H2O
COOH COONH4 CONH2
ammonium oxamide
oxalate

Succinic acid forms its ammonium salt. On strong heating it forms

succinimide.
CH2–COOH CH2COONH4 CH2CO
∆
| + 2NH3 | | NH
CH2–COOH CH2COONH4 CH2CO
Succinic acid Ammonium succinate Succinimide

3. With PCl5 :
With PCl5, these form the acid chlorides.
(i) COOH COCl
| + PCl5 | + POCl3 + H2O
COOH COCl phosphorous
oxalic acid oxalylchloride oxy chloride

CH2–COOH CH2COCl
| + PCl5 | + POCl3 + H2O
CH2–COOH CH2COCl
succinoyl chloride

4. Action of heat :
(i) Oxalic acid on heating at 373 K – 378 K loses water of hydration. On
further heating it decomposes to formic acid and carbon dioxide.
COOH 473K
| HCOOH + CO2
COOH formic acid

(ii) Succinic acid on heating to 300oC loses a molecule of water to form

anhydride.
CH2 – COOH 300oC
CH2 – CO
| | O + H2O
CH2 – COOH CH2 – CO
succinic anhydride (a cyclic compound)

300
5. Oxidation : On warming oxalic acid with acidified potassium
permanganate, it is oxidised to carbon dioxide.
COOH
| + [O] 2CO2 + H2O
COOH
Uses :
Oxalic acid is used
1. for removing ink stains and iron stains.
2. as mordant in dyeing and calico printing.
3. in manufacture of ink and metal polishes.
4. Redox titration

Succinic acid is used :

1. in the manufacture of lacquers and dyes.
2. It is a very important laboratory reagent.

19.5 STRENGTH OF CARBOXYLIC ACIDS

An acid is a proton donor. The base with which a proton can be released
determines the strength of an acid. Organic acids are weak acids. Greater
the stability of the anion of the acid, higher is its strength. Thus, for a
carboxylic acid, say acetic acid.
H H H
| O | O | O–
H – C–C H – C–C H – C–C
| O–H | O– | O
H H H
Acid Anion
+ H3O+
When the bonding pair of electrons between oxygen and hydrogen in
–O–H group, is shifted towards oxygen, easier the hydrogen is released as a
proton.
Thus when chloroacetic acid is taken, the (–I) effect of chlorine increases
its strength.

301
 H O
|
Cl C C
|
H O H
Thus the strength of the chloro acetic acids varies.
O O O
Cl3C – C >> Cl2CH–C > ClH2–C
OH O–H O–H
Trichloro acetic acid Dichloro acetic acid Monochloro acetic acid

On the other hand comparing the strength of carboxylic acids they vary
as follows :
CH3CH2 COOH < CH3COOH < HCOOH
propionic acid acetic acid formic acid

Since alkyl groups are +I groups, they increase the strength of the
–O–H bond making the release of hydrogen difficult. (i.e.,) it becomes a
weak acid.
In the case of aromatic acids, presence of chlorine, nitro group, carbonyl
group especially at ortho position increases its strength due to –I effect.

COOH COOH COOH

O2N Cl OHC

> >

Presence of –OH, Cl – at para positions decreases the strength by

resonance effect. (+M effect).

19.6 AROMATIC ACIDS :

When a carboxylic acid group is directly linked to the benzene ring
they are called aromatic carboxylic acids.

302
 CH3 OH NH2
COOH
COOH COOH COOH

Benzoic acid o-toluic acid salicylic acid anthranilic acid

(o-hydroxy benzoic (o-amino benzoic
acid) acid)

Benzoic acid is the simplest of aromatic acids.

19.6.1 Preparation

By oxidation
By the oxidation of ‘side chain’ of benzene derivatives (side chain - any
aliphatic portion linked to benzene ring) The side chain oxidation can
be carried out by acid dichromate or permanganate or alkaline
permanganate etc.

CH3 CH2CH3 CH2Cl CH2OH CHO

Toluene Ethyl Benzyl Benzyl Benzaldehyde

benzene chloride alcohol

The underlined portion indicates the side chain.

Toluene is oxidised by acidified KMnO4.
H+/KMnO4
(i) C6H5CH3 C6H5COOH Benzoic acid

NaOH
(O)
(ii) C6H5CH2Cl C6H5CH2OH C6H5COOH
KMnO4

H+/KMnO4
(iii) C6H5CHO C6H5COOH

303
2. Hydrolysis of phenyl cyanide :
H+ H+
C6H5CN (C6H5CONH2) C6H5COOH
H2O Benzamide H2O

3. Carbonation of Grignard reagent followed by hydrolysis.

C6H5 H2O Br
C6H5MgBr + O = C = O C=O C6H5C = O + Mg
| OH
BrMgO
OH

19.6.2 Properties

Physical properties
White crystalline solid-soluble in hot water, alcohol and ether and slightly
soluble in cold water.

Chemical Properties
Reactions of both –COOH group and benzene ring.

1. Acidic properties :
(a) Benzoic acid dissolves in NaOH and NH4OH forming salts.
C6H5COOH + NaOH C6H5COONa + H2O
(sodium benzoate)

–H2O
C6H5COOH + NH4OH C6H5COONH4 C6H5CONH2
∆
(Ammonium benzoate)

(b) It forms esters with alcohol in presence of catalytic amount of

Con. H2SO4.

H+
C6H5COOH + C2H5OH C6H5COOC2H5 + H2O
(ethyl benzoate)

304
2. Replacement of OH group.
By the action of phosphorous pentachloride or thionyl chloride, benzoyl
chloride is formed.
C6H5COOH + PCl5 C6H5COCl + POCl3 + HCl
C6H5COOH + SOCl2 C6H5COCl + SO2 + HCl
Thionyl chloride

3. Decarboxylation :
Heating with sodalime gives benzene.

NaOH
C6H5COOH C6H6 + CO2
CaO ∆
soda lime

4. Reduction :
Lithium Aluminium hydride reduces Benzoic acid to Benzyl alcohol.
O LiAlH4 LiAlH4
C6H5C [C6H5CHO] C6H5CH2OH
OH Benzyl alcohol
Benzoic acid

5. Reaction of benzene ring :

Benzoic acid undergoes electrophilic substitution. The –COOH group
decreases the activity of benzene ring with respect to electrophilic substitution
and is meta directing group.

Nitration :
COOH COOH
HNO3

H2SO4
NO2
m-nitro benzoic acid

305
6. Chlorination :
COOH COOH
Cl2

FeCl3

Cl
m-chloro benzoic acid

Anhydrous ferric chloride is a Lewis acid - a catalyst in this reaction.

7.Sulphonation :
COOH Fuming COOH
H2SO4

SO3H

m-sulphonyl benzoic acid

19.6.3 Uses of benzoic acid :

1. Benzoic acid is used as an urinary antiseptic
2. Sodium benzoate is used as food preservative
3. Benzoic acid vapours are used to disinfect bronchial tube.
4. It is used for the manufacture of dyes.
19.7 SALICYLIC ACID
It is o-hydroxy benzoic acid, and isomeric with meta and para hydroxy
benzoic acids. OH
OH OH
COOH

COOH COOH
(o-hydroxy benzoic acid) (m-hydroxy benzoic acid) (p-hydroxy benzoic acid)

19.7.1 Preparation :
Salicylic acid can be prepared by heating phenol with NaOH to get
sodium phenoxide.

306
 OH NaOH ONa
∆

This is heated with carbondioxide at 403K under pressure to form sodium

salicylate.

ONa CO2 OH

403K/pressure
COONa
Mechanism :
–O O OH O–
O
|| H
C
C O–
|| O
C
O
O
This reaction is called ‘Kolbe’s reaction’. The sodium salt on treatment
with dilute hydrochloric acid gives salicylic acid.
OH OH
COONa HCl COOH
+ NaCl

(Salicylic acid)

19.7.2 Properties

Physical Properties
It is a white crystalline solid - soluble in hot water, ethanol and ether.
Test for salicylic acid :
1. An aqueous solution of salicylic acid gives violet colour with neutral
ferric chloride.
2. It gives effervescence with the sodium bicarbonate.
3. It is soluble in sodium hydroxide and reprecipitated on acidification.

307
4. With Bromine water the colour is discharged with the formation of white
precipitate.

Mechanism :
Reaction of bromine with salicylic acid.

OH O +OH O
C C
+ Br–
O– O–
Br – Br Br

O OH
+OH
Br
C
O–
+ CO2
Br

OH OH
Br Br Br
2Br2

Br
Chemical Properties :
Properties of phenolic function.
1. Salicylic acid undergoes acetylation by heating with acetic anhydride to
form aspirin which is used as an analgesic and antipyretic.

OH OCOCH3
(CH3CO)2O
COOH COOH

Acetyl salicylic acid or Aspirin

308
 Instead of acetic anhydride, acetyl chloride can also be used.
2. Reaction with bromine water gives a white precipitate of tribromo phenol.
This reaction involves bromination with decarboxylation.
OH
OH OH Br
Br2 Br2 Br
COOH
–CO2

Br
(2,4,6 Tribromo phenol)

Reaction due to –COOH group.

1. With NaHCO3
It gives brisk effervescence with a solution of sodium bicarbonate or
sodium carbonate and dissolves forming sodium salicylate.
OH OH
+ NaHCO3 + CO2 + H2O
COOH COONa
(sodium salicylate)

The solution on treatment with HCl gives salicylic acid.

OH OH
HCl

COONa COOH
2. With CH3OH
On heating with methyl alcohol in presence of con. H2SO4 a pleasant
smelling liquid-methyl salicylate is formed.

OH OH
CH3OH + H2O
COOH H2SO4 COOCH3
(Methyl salicylate)

309
 Methyl salicylate is present in the oil of winter green and other essential
oils.

19.7.3 Uses
Salicylic acid is used (i) It is an antiseptic and disinfectant (ii) as a food
preservative (iii) as a medicine for rheumatic pain, (iv) in the manufacture of
aspirin, salol, methyl salicylate, (v) in the preparation of azo dyes.

19.8 FUNCTIONAL DERIVATIVES OF CARBOXYLIC ACID :

O
The general formula is ||
R–C–Y

Y Functional group Example

– OH Carboxylic acid CH3COOH acetic acid

– halogen acid halide CH3COCl acetyl chloride

– OCOR acid anhydride CH3COOCOCH3 acetic anhydride

– OR ester CH3COOC2H5 ethyl acetate

– NH2 amide CH3CONH2 acetamide

These compounds generally undergo nucleophilic substitution reactions

in which a nucleophile replaces the electro negative group (Y) to form
carboxyl derivatives. Relative reactivity of carboxylic acid derivatives is as
follows.
Acid chloride > acid anhydride > carboxylic acid > ester > amide.
19.8.1 Acetyl chloride : CH3COCl
Preparation of CH3COCl
It is prepared easily by the action of PCl5, PCl3 or SOCl2 on acetic acid.
(i) CH3COOH + PCl5 CH3COCl + POCl3 + HCl
(ii) 3CH3COOH + PCl3 3CH3COCl + H3PO3
Phosphorus acid

310
 (iii) CH3COOH + SOCl2 CH3COCl + SO2 + HCl

19.8.2 Physical Properties

Acetyl chloride is volatile, pungent smelling liquid, this cannot form
hydrogen bond. Hence its low boiling point and insolubility in water is
explained. It fumes in moist air due to hydrolysis producing hydrogen chloride
gas.

O
CH3— C O
Cl CH3 — C + HCl
O (gas)
OH
H H

Chemical Properties :
1. It is a powerful acetylating agent, a reagent that introduces CH3CO -
group, especially with compounds containing –OH group or –NH group.
O O
|| ||
(i) H – O – H + Cl – C – CH3 H – O – C – CH3 + HCl
.. acetic acid

O O
|| ||
(ii) C2H5–O–H + Cl – C – CH3 C2H5–O–C–CH3 + HCl
..
ethyl acetate

CH3
..
(iii) C6H5 OH + C=O CH3COOC6H5
Cl Phenyl acetate

2. Friedel Craft’s Acetylation :

In presence of anhydrous Aluminium chloride acetylation of benzene
takes place with the formation of acetophenone.

311
 COCH3
anhy. AlCl3
+ CH3COCl + HCl

It is an aromatic electrophilic substitution reaction.

The Lewis acid AlCl3 generates the electrophile from acetyl chloride.
The electrophile is the acetyl cation CH3–C+ = O.

19.8.3 Uses of acetylchloride

(a) As an acetylating agent.
(b) An important organic reagent.
(c) In the preparation of acetic anhydride.
(d) In the detection and estimation of alcoholic and amino groups.
19.9 Acetic anhydride : CH3COOCOCH3
Preparation :
1. From CH3COCl
By distilling a mixture of anhydrous sodium acetate and acetyl chloride.
CH3COCl + CH3COONa CH3COOCOCH3 + NaCl
∆
(Acetyl chloride) (Sodium acetate) (Acetic anhydride)
2. From acetic acid
By the action of dehydrating agent on acetic acid.
CH3CO OH P2O5 CH3CO
∆ O + H2O
CH3COO H
CH3CO
(Acetic anhydride)
19.9.1 Physical Properties
Acetic anhydride is a colourless, pungent smelling liquid, insoluble in
water. It is not as reactive as acetyl chloride and does not fume in moist air.

Chemical Properties :
Like acetyl chloride, it reacts with alcohol, phenol and amine, though
less reactive, normally acetylation using acetic anhydride is carried out in
presence of sodium acetate or concentrated sulphuric acid as catalyst.
312
1.
CH3CO
O CH3–CO–NH2+ CH3COOH (Ammonolysis)
(Acetamide)
CH3CO
.. +
H 2N – H
ammonia

CH3CO
2. O + H – Cl CH3COOH + CH3COCl
acetyl chloride
CH3CO (with dry hydrogen
chloride)

Cl
CH3CO |
O PCl3 2CH3COCl + POCl3
| acetylchloride
CH3CO
Cl
19.9.2 Uses of acetic anhydride
1. As an acetylating agent for the manufacture of dyes, cellulose acetate
etc.
2. In the manufacture of aspirin and some drugs.

19.10 Methyl acetate

Preparation
1. By esterification : When acetic acid is refluxed with methyl alcohol in
presence of a small amount of con. H2SO4, methyl acetate is formed.

H2SO4
CH3COOH + CH3OH CH3COOCH3 + H2O
Methyl acetate

2. By the action of acetyl chloride or acetic anhydride on methyl alcohol,

methyl acetate is formed.

313
 CH3COCl + CH3OH CH3COOCH3 + HCl

CH3COOCOCH3 + CH3OH CH3COOCH3 + CH3COOH

19.10.1 Physical Properties

It is a pleasant smelling volatile liquid, fairly soluble in water, no hydrogen
bonding and less polar than alcohols.

Chemical Properties
1. Hydrolysis : Esters are hydrolysed by warming with dil. acids or alkali.

H+/H2O
CH3COOCH3 CH3COOH + CH3OH
CH3COOCH3 + NaOH CH3COONa + CH3OH
sodium acetate
(Saponification)
2. Alcoholysis : In presence of a little acid, methyl acetate is cleaved by
ethyl alcohol to form ethyl acetate.
H+
CH3COOCH3 + C2H5OH CH3COOC2H5 + CH3OH
This is called ‘trans esterification’.
3. Ammonolysis : Reacts with ammonia on heating to form amide.
∆
CH3COOCH3 + NH3 CH3CONH2 + CH3OH
4. Claisen ester condensation : In presence of strong bases like sodium
ethoxide, it undergoes condensation forming aceto acetic ester.

C2H5ONa –
CH3COOCH3 CH2COOCH3 + H+

CH3 CH3 –
C=O C=O + OCH3
CH3O CH2COOCH3
Methyl acetoacetate
–
CH2COOCH3

314
19.10.2 Uses of methyl acetate
It is a very good laboratory and industrial solvent. Used for the
preparation of acetoaceticester a compound of synthetic importance.

19.11 Amides
CH3CONH2 Acetamide

Preparation of acetamide
1. By heating ammonium acetate

∆
CH3COONH4 CH3CONH2 + H2O

2. Ammonolysis of acetyl chloride, acetic anhydride or esters.

(i) CH3COCl + NH3 CH3CONH2 + HCl
(ii) CH3COOCOCH3 + NH3 CH3CONH2 + CH3COOH
Acetic anhydride

(iii) CH3COOCH3 + NH3 CH3CONH2 + CH3OH

Methyl acetate

3. Partial hydrolysis of methyl cyanide with alkaline hydrogen peroxide.

H2O2
CH3C≡N CH3CONH2
NaOH

19.11.1 Physical Properties

It exists as a dimer due to hydrogen bonding.
H
|
O HN
CH3 – C C – CH3

N–H O
|
H

315
 Colourless crystalline solid, soluble in water and alcohol.
It is the least reactive among acid derivative.
19.11.2 Chemical Properties
1. Hydrolysis :
Catalysed by acid or alkali, it is hydrolysed to acid.
H+
(a) CH3CONH2 CH3COOH + NH3
H2O (acetic acid)

NaOH
(b) CH3CONH2 CH3COONa + NH3
(Sodium acetate)

2. With HCl
It is feebly basic, forms unstable salt with strong inorganic acid.
CH3CONH2 + HCl CH3CONH2 . HCl
(amide hydrochloride)

3. On dehydration by heating with P2O5 it forms methyl cyanide.

P2O5
CH3CONH2 CH3C≡N
– H2O

4. It undergoes Hoff mann’s reaction with Br2/NaOH forming methyl

amine.
Br2
CH3CONH2 CH3NH2 + CO2
NaOH

19.11.3 Uses of acetamide

1. For the preparation of methyl cyanide.
2. In leather tanning.
3. As soldering flux.
4. As a plasticiser in cloth.

316
 SELF EVALUATION
(A) Choose the correct answer :
1. Which of the following is least acidic
(a) C2H5OH (b) CH3COOH
(c) C6H5OH (d) ClCH2COOH
2. Weakest acid among the following is
(a) Acetic acid (b) Phenol
(c) Water (d) Acetylene
3. Ester formation involves the reaction of
(a) an aldehyde and a ketone
(b) An alcohol with RMgX
(c) Two molecules of an acid with dehydrating agent
(d) An acylhalide with an alcohol
4. Heating a mixture of sodium acetate and soda lime gives
(a) methane (b) ethane
(c) aceticacid (d) benzene
5. The acid which reduces Tollen's reagent is
(a) acetic acid (b) benzoic acid
(c) formicacid (d) oxalic acid
CH3
|
6. The IUPAC name of CH3 – CH2 – CH – COOH is
(a) α-methyl butric acid (b) 3-methyl butanoic acid
(c) 2-methyl butanoic acid (d) Iso pentanoic acid
7. The Isomerism exhibited by CH3CH2COOH and CH3COOCH3 is
(a) metamerism (b) position
(c) chain (d) functional
8. The acid that cannot be prepared by Grignard reagent
(a) acetic acid (b) formic acid
(c) butyric acid (d) benzoic acid

317
9. Which order of arrangement is correct interms of the strength of the acid
(a) CH3–CH2COOH > CH3COOH < HCOOH < ClCH2COOH
(b) ClCH2COOH < HCOOH < CH3COOH < CH3CH2COOH
(c) CH3–CH2COOH < CH3COOH < HCOOH < ClCH2COOH
(d) HCOOH > CH3CH2COOH < CH3COOH > ClCH2COOH
10. The compound which undergoes intramolecular dehydration with P2O5
is
(a) acetic acid (b) formic acid
(c) propionic acid (d) Butyric acid
H o
11. C = O 160 C ? The product is
HO
(a) CO + H2O (b) HCOOH
(c) H2 + CO2 (d) HCHO + O2
12. When chlorine is passed through acetic acid in presence of red P, it forms.
(a) acetyl chloride (b) Trichloro acetaldehyde
(c) Trichloro acetic acid (d) Methyl chloride
13. Which of the following compounds will react with NaHCO3 solution to
give sodium salt and CO2 ?
(a) acetic acid (b) n-hexanol
(c) phenol (d) both (a) and (c)
14. When propanoic acid is treated with aqueous sodium - bicarbonatate,
CO2 is liberated. The "C" of CO2 comes from
(a) methyl group (b) carboxylic acid group
(c) methylene group (d) bicarbonate
15. Carboxylic acids are more acidic than phenol and alcohol because of
(a) inter molecular hydrogen bonding
(b) formation of dimers
(c) highly acidic hydrogen
(d) greater resonance stabilisation of their conjugate base
16. Among the following the strongest acid is
(a) ClCH2COOH (b) Cl3CCOOH
(c) CH3COOH (d) Cl2CHCOOH

318
17. Which of the following compound is optically active ?
(a) CH3CH2COOH (b) HOOC–CH2–COOH
(c) CH3CH(OH)COOH (d) Cl2CHCOOH
18. CH3CH(OH)COOH ? The product is
H2O2/Fe2+

(a) CH3COCOOH (b) CH3CH2COOH

(c) CH3CHOHCHO (d) COOHCH2COOH
19. The compound found in some stony deposit in kidneys is
(a) potassium oxalate (b) oxalic acid
(c) potassium succinate (d) calcium oxalate
20. Ethylene cyanide on hydrolysis using acid gives
(a) oxalic acid (b) succinic acid
(c) adipic acid (d) propionic acid
(B) Answer in one or two sentences :
1. What are carboxylic acids ?
2. Give the source and trivial names of
(i) C3H7COOH and (ii) HCOOH.
3. How is the conversion of acetonitrile to acetic acid effected ?
4. Boling point of carboxylic acids are higher than those of alcohols of
same molecular mass - reason out.
5. Formic acid reduces Tollen's reagent, but acetic acid does not-Give
reasons.
6. Write two tests of carboxylic acid.
7. Give the resonance structure of carboxylate anion.
8. Mention the inductive effect in monochloro acetic acid.
9. Write a note on esterification reaction with an example.
10. What happens when calcium salt of acetic acid is distilled.
11. Mention the uses of oxalic acid.
12. What is the action of dilute sulphuric acid with lactic acid ?
13. Give the structure of lactyl chloride and lactide.

319
(C) Answer not exceeding sixty words :
1. How is oxalic acid manufactured from sodium formate ?
2. Explain the isomerism exhibited by carboxylic acids.
3. Write a note on the acidic nature of acetic acid.
4. Give the mechanism involved in the esterification of a carboxylic acid
with alcohol.
5. Explain why carboxylic acids behave as acids. Discuss briefly the effect
of electron withdrawing and donating substituents on acid strength of
carboxylic acids.
6. Account for reducing nature of Formic acid.
7. Explain the following :
(i) Choloro acetic acid is stronger acid than acetic acid.
(ii) Fluoro acetic acid is stronger acid than chloro acetic acid.
(iii) Formic acid is stronger acid than acetic acid.
8. How is benzoic acid obtained from
CH2CH3

(a) (b) phenyl cyanide (c) carbon dioxide

9. How do you distinguish formic acid from acetic acid ?

10. Write the products in each of the following.
COOH glycerol
(i) |
COOH 383 K

COOH NH3
(ii) |
COOH

(iii) CH2 COOH NH3

|
CH2COOH

320
11. How are the follwing conversions carried out ?
(i) Salicylic acid aspirin
(ii) Salicylic acid methyl salicylate
(iii) Lactic acid lactide
12. What happens when lactic acid is
(i) treated with dilute H2SO4
(ii) heated alone
(iii) oxidised with alkaline KMnO4
13. Give the uses of (a) oxalic acid and (b) salicylic acid.
14. Outline the mechanism of (a) formation of ethylacetate from acetic acid
and ethyl alcohol. (b) Hydrolysis of ethyl cyanide to propionic acid.
15. Explain the order of strength of the following acids.
(a) CCl3COOH > CHCl2COOH > CH2ClCOOH > CH3COOH
(b) p-nitrophenol > m-nitro phenol > phenol > cresol.
SUMMARY :
Aliphatic mono carboxylic acids, hydroxy acids, dicarboxylic acid,
aromatic monocarboxylicacid, aromatic hydroxy acid, aromatic dicarboxylic
acid - structure and nomenclature - common name and IUPAC names - long
chain fatty acid - by the saponification of fats and oils.
General methods of preparation - Oxidation of alcohols aldehydes,
hydrolysis of cyanides, esters and using Grignard's reagent.
Properties - Hydrogen bonding - dimeric - higher boiling points - solubility
in water.
Acidic property explained by resonance stabilisation of the carboxylate
anion - Formation of salt, esters and amide. Esterification, anhydride
formation, decarboxylation - α-halogenation - formation of acid chloride.
Formic acid, differ from other carboxylic acid because of the presence
of aldyhydic (H – C = O) group. Hence it reduces Fehling's solution, Tollens
reagent and alkaline permanganate.

321
 Aromatic acids - Benzoic acid, salicylic acid, phthalicacid - preparation
- by oxidation, hydrolysis, Grignard reagent and Kolbe's synthesis. Properties
- Formation of salt, esters, acid chlorides, amides and electro philic
substitution at benzene ring and uses.
Derivatives of acids - like esters, acid chloride, acid anhydride, amide -
structure and nomonclature -preparation and properties - relative reaction -
hydrolysis to acids - reduction - uses.

REFERENCES :
1. Text Book of Organic Chemistry - Bahl and Arun Bahl.
2. A guide book to Mechanism in organic chemistry. - Peters Sykes -
Pearson Education Ltd.
_______

322
 20. ORGANIC NITROGEN COMPOUNDS
LEARNING OBJECTIVES
@ Nitro alkanes - Structure, isomerism, tautomerism - Nomenclature -
primary, secondary and tertiary nitro compounds.

@ Learning - the methods of preparation, properties, uses of nitroalkanes.

@ Recognising the presence of α-hydrogen - removed by base to generate

carbanion.

@ Aromatic nitro compounds - structure and nomenclature, preparation -

Nitration of benzene - mechanism - properties - reduction under different
conditions - Distinction between aromatic and aliphatic nitro compounds.

@ Aliphatic amines - structure, classification, isomerism, nomenclature -

primary, secondary and tertiary amines.

@ Learning general methods of preparation, properties - Distinction

between 1o, 2o, 3o - amines.

@ Aromatic amines - aralkyl amine - preparation, properties of

benzylamine.

@ Aniline - preparation, properties, - basic strength and resonance - uses.

@ Distinction between aliphatic amine and aniline, - ethylamine and

aniline, benzyl amine and aniline.

@ Aliphatic nitriles - structure - nomenclature.

@ Benzene diazonium chloride - preparation - properties related to its

synthetic importance.

323
20.1 ORGANIC NITROGEN COMPOUNDS
Aliphatic Nitro Compounds
Nitro alkanes are nitro derivatives of paraffins obtained by the
replacement of a hydrogen atom by a nitro group.
Nomenclature : R–NO2
Nitro alkanes are named by prefixing ‘nitro’ to the name of parent
hydrocarbon.
C2H5NO2 C3H7NO2
Nitro ethane Nitro propane
They may be primary, secondary and tertiary depending on whether the
nitrogroup is attached to a primary, secondary and tertiary carbon atom.
R R
RCH2NO2 CHNO2 R C – NO2
R R
1o 2o 3o
In the IUPAC system the position of the nitrogroup is indicated by
number.
NO2
|
CH3 – CH – CH3 2-nitro propane
CH3CH2CH2 – NO2 1-Nitro propane
CH3 – CH – CH2 – NO2 1-Nitro-2-methyl propane
|
CH3
CH3 1-Nitro-2,2-dimethyl propane
|
CH3 – C – CH2 – NO2
|
CH3

CH3
|
CH3 – C – CH3 2-nitro, 2-methyl propane
|
NO2
324
Isomerism :
Besides chain and position isomerism Nitroalkene shows functional
isomerism.

Isomerism :
Nitro compounds exhibit the following three types of isomerism.
1. Chain isomerism arises due to the difference in the arrangement of
carbon atoms.
CH3 – CH2 – CH2 – CH2– NO2 (linear chain)
1-nitro butane

CH3 – CH – CH2 – NO2 (branched chain)

|
CH3
1-nitro-2-methyl propane

2. Position isomerism arises due to the difference in the position of

nitro group.
CH3 – CH2 – CH2 – NO2
1-nitro propane

CH3 – CH – CH3
|
NO2
2-nitro propane

3. Functional isomerism is due to the difference in the nature of

functional group. Nitro alkanes are functional isomers of alkyl nitrites.
O
CH3 – N CH3 – O – N = O
O
Nitro methane Methyl nitrite

4. Tauto merism : Nitromethane exhibits tautomerism, a special type

of isomerism.
O O
CH3 – N (nitroform) and CH2 = N (acinitroform)
O OH

325
 These two functional isomers exist in equilibrium.

O O
CH3 – N CH2 = N
O OH
Nitro Acinitro

This is said to exhibit (‘‘Nitro-acinitro’’) tautomerism.

Both primary and secondary nitro compounds exhibit these kinds of
tautomerism.

20.1.1 Preparation of nitroalkanes

1. They are prepared by heating an alkyl halide with aqueous ethanolic
silver nitrate.
1. R––X + AgNO2 AgX + R –– NO2
CH3CH2Cl + AgNO2 AgCl + CH3CH2 NO2
2. By direct nitration of alkanes : Hexane and other higher alkanes
can be nitrated readily with fuming nitric acid or with oxides of nitrogen.
However the lower hydrocarbons can be nitrated only in the vapour phase
at higher temperature. (623 – 773 K).
C6H14 + HONO2 C6H13NO2 + H2O
400oC
CH4 + HONO2 CH3NO2 + H2O
methane nitric acid nitro methane

20.1.2 Properties
Nitro alkanes are colourless pleasant smelling liquids. Nitromethane is
soluble in water, higher members are sparingly soluble in water but readily
soluble in organic solvents.
They are highly polar compounds. Hence they are high boiling than the
alkyl halides and alkanes. Nitro methane is slightly acidic.
– O–
+ O +
H – CH2 – N CH2 = N (Nitrolic acid)
O OH
(Nitroform) (Tautomerism) (Aci form)

326
 The aciform contains replaceable hydrogen atom. Hence it dissolves in
alkali solution forming salt like compounds.

+ O– +
CH2 = N + NaOH CH2 = N – O– + H2O
O–H O– Na+
This anion exhibits resonance.
O– O– O
+ – + – +
CH2 = N CH2 – N CH2 – N
O– O O–
Only primary and secondary nitro compounds behave as acids in presence
of strong alkali.
This anion of the nitrolic acid is involved in many of the properties of
nitro alkanes. (Nitro methane)

1. Halogenation
Nitro alkanes are readily halogenated in α-position in presence of alkali.
O Br O Br O
Br2 | Br2 |
CH3CH2–N CH3– CH – N CH3 – C – N
NaOH NaOH |
O O Br O
Mono bromo di bromo
nitro ethane nitro ethane

Nitromethane reacts with halogen in presence of alkali to form trihalogen

derivative. (e.g.,) with chlorine it forms chloropicrin, CCl3NO2 which is
used as soil sterilizing agent.
NaOH
CH3NO2 + 3Cl2 CCl3 NO2 + 3HCl
Chloro picrin
(trichloro nitro methane)
2. Reaction with aldehydes and ketones
Condensation with aldehydes and ketones in presence of alkali solution
to give Nitroalcohols.
327
 dil. NaOH
HCHO + CH3NO2 CH2OH–CH2NO2
2-nitro ethanol

dil. NaOH
CH3CHO + CH3NO2 CH3CHOH–CH2NO2
1-nitro-2-propanol

dil. NaOH
CH3COCH3 + CH3NO2 (CH3)2COH–CH2NO2
1-nitro-2-methyl-2-propanol

3. Reduction : (i) Sn/HCl or Fe/HCl or H2/Raney nickel reduces nitro

alkanes to alkyl amines.
Sn/HCl
R – NO2 + 6 [H] RNH2 + 2H2O

Sn/HCl
CH3 – NO2 + 6 [H] CH3NH2 + 2H2O
Methylamine

(ii) Reduction under neutral conditions using Zn/NH 4Cl or Zn/CaCl2-

hydroxyl amines are formed.

Zn/NH4Cl
R–NO2 + 4 (H) RNHOH + H2O
Hydroxyl amine

Zn/NH4Cl
CH3 – CH2NO2 + 4 [H] CH3CH2NHOH + H2O
(Nitro ethane) ethyl hydroxylamine

4. Hydrolysis :
When boiled with mineral acids primary nitro alkane, undergoes
disproportionation reaction to form carboxylic acid and hydroxylamine.

HCl
CH3CH2NO2 + H2O CH3COOH + NH2OH
acetic acid hydroxylamine

328
20.1.3 Uses of nitro alkanes :
1. They are good solvents for a large number of organic compounds
including vinyl polymers, cellulose esters, synthetic rubbers, oils, fats, waxes
and dyes.
2. Used in organic synthesis.
Account for the following :
(a) Nitro ethane is soluble in NaOH solution.
(b) Nitro ethane reacts with nitrous acid.
(c) 2-methyl-2-nitro propane is neither soluble in NaOH nor reacts with
nitrous acid.
Answers.
(a) exhibits tautomerism of nitroform and aciform. Aciform is acidic
and soluble in NaOH.
(b) CH3CH2NO2 has two α-hydrogen and that reacts with HNO2.

(c) CH3
|
CH3 – C – CH3
|
NO2

has no α-hydrogen. Hence it does not have the above properties.

2. Predict the product.

NaOH
CH3NO2 + Cl2 ?

Answer : CCl3NO2 (chloro picrin)

3. What happens when nitro ethane is boiled with HCl ?

Answer : CH3COOH + NH2OH

329
20.2 AROMATIC NITRO COMPOUNDS
These are the substitution products of aromatic hydrocarbons like
benzene. One or more hydrogen atoms of the aromatic ring are replaced by
nitro group.
CH3
NO2 CH3 NO2 O2N NO2

NO2 NO2
NO2
Nitrobenzene p-nitro toluene m-dinitro benzene 2,4,6-trinitro toluene
There are some aromatic compounds which do not have nitro group
directly linked to the aromatic nucleus. The Nitro group is present in the
side chain. CH3
|
CH2NO2 CH–NO2

Phenyl nitro methane 1-nitro,1-phenyl ethane

Nitro benzene, the simplest of aromatic nitro compounds, is called ‘oil

of mirbane’.
20.2.1 Preparation of nitro benzene
It is prepared by the action of a mixture of con. HNO3 and con. H2SO4
(nitrating mixture) on benzene maintaining the temperature below 333 K.
Conc. Conc. NO2
H2SO4
+ HNO3 + H2O
330K

Sulphuric acid generates the electrophile –NO2+, nitronium ion-from

nitric acid. This is an example of aromatic electrophilic substitution reaction.

H NO2
+
NO2 NO2
+

330
 The generation of nitronium ion.
H
|
H2SO4 + HONO2 H – O – NO2 + HSO4–
+

H
| +
H – O – NO2 H2O + NO2
+

To the nitronium ion (being an electron deficient specie) the π bond of

benzene, donates a pair of electrons forming a δ-bond. A specie with a + ve
charge is formed as an intermediate. This is called ‘arenium ion’ and is
stabilised by Resonance.
H

+
NO2
H

In the last step, the hydrogen atom attached to the carbon carrying the
nitro group is pulled out as a proton, by the Lewis base HSO4–, so that
stable aromatic system is formed.

H
NO2
–
+ NO2 + HSO4 + H2SO4
H

20.2.2 Physical Properties

Aromatic nitro componds are yellow coloured liquid (nitro benzene) or
solids (other members). Nitro benzene has the smell of ‘bitter almonds’
and is called ‘the oil of Mirbane’. They are insoluble in water but soluble in
organic solvents such as benzene, ethanol and ether. They have high boiling
and melting points which is explained by highly polar nature of –NO2 group.

331
 Nitro group contains nitrogen in +3 oxidation state (as nitrogen itself an
electronegative element, existing in a +3 oxidation state). Hence reduction
of nitro group is the important chemical reaction.

Depending on the nature of the reducing agent and pH of the reducing

medium - reduction proceeds to different extents and hence different products
are formed.

1. Reduction of nitrobenzene

(a) Strongly acidic medium

When reduced with tin and hydrochloric acid, aromatic nitro

compounds are converted to aryl amines.

Sn/con.HCl
C6H5NO2 + 6 [H] C6H5NH2 + 2H2O
or
Fe/con.HCl Aniline

(b) Neutral medium

When reduced with a neutral, reducing agents like zinc dust and aqueous
ammonium chloride, aromatic nitro compounds form aryl hydroxylamines.

Zn/NH4Cl
C6H5NO2 + 4 [H] C6H5NHOH + H2O
Phenyl hydroxylamine

(c) Alkaline medium

In alkaline medium, Nitro benzene on reduction forms the intermediate
products nitrosobenzene (C 6 H 5 NO) and phenyl hydroxylamine
(C6H5NHOH). These undergo bimolecular condensation reaction. According
to the appropriate reducing agent in alkaline medium different products are
obtained.

332
 Na3AsO3/NaOH
C6H5 – N = N – C6H5
or glucose + NaOH ↓
O
SnCl2 + NaOH azoxy benzene
C6H5NO2 C6H5 – N = N – C6H5
azo benzene
Zn/NaOH
C6H5 – NH – NH – C6H5
hydrazo benzene or
(N, N' - diphenyl hydrazine)

(d) Catalytic reduction

Lithium Aluminium hydride is a powerful hydride ion donor. So it reduces
nitro benzene to Aniline. This reduction can also be carried out by H2/Ni.

LiAlH4
C6H5NO2 C6H5NH2 [Aniline]

H2/Ni
C6H5NO2 C6H5NH2
Catalytic
hydrogenation

(e) Electrolytic Reduction :

When nitro benzene is reduced electrolytically in presence of
concentrated sulphuric acid, phenyl hydroxylamine is first produced which
rearranges to give p-amino phenol.

Reactions due to the benzene ring :

Benzene ring can take part in electrophilic substitution reaction. The
presence of nitro group makes the ring less reactive [deactivate] towards
electrophilic substitution reaction. Nitro group is metadirecting group.
Hence in these reactions m-substituted products are formed.

1. Nitration
Nitro benzene can be nitrated with the mixture of concentrated nitric
acid and sulphuric acid at 100o C to give m-dinitro benzene. Using fuming
333
nitric acid and con. sulphuric acid and when the temperature is increased to
433 K nitro benzene gives 1,3,5-trinitro benzene.
NO2 NO2
Con.HNO3

Con. H2SO4/373 K

NO2
m-dinitrobenzene

NO2
NO2
Fuming HNO3

con.H2SO4/433 K O2N NO2

1,3,5-Trinitro benzene

2. Chlorination
Chlorine in presence of anhydrous ferric chloride generates positively
charged species. Chlorination takes place at meta position.
NO2 Cl

Cl2/FeCl3

NO2
3-chloro nitro benzene

Ferric chloride is the Lewis acid catalyst.

3. Sulphonation
When warmed with con. H2SO4, 3-Nitro benzene sulphonic acid is
obtained.
NO2 NO2
con.H2SO4

∆
SO3H
m-nitro benzene sulphonic acid

334
Uses of nitro benzene
1. Aromatic nitro compounds are used to form corresponding amino
compounds.
2. They are used to prepare explosives like TNT, 1,3,5-trinitro benzene.
3. Used in making dye stuffs and pharmaceuticals.

SUMMARY OF NITRO COMPOUNDS

Organic nitrogen compounds - structure nomenclature - isomerism -
nitro-acinitro tautomerism.
Preparation - direct nitration of hydrocarbons, nucleophilic substitution
with alkyl halide.
Properties : Polar compounds - high boiling when compared to
hydrocarbons or alkyl halides. α-hydrogen can be removed as a proton by a
base forming carbanion - This undergoes condensation with aldehydes and
ketones - Reduction in acid, neutral medium - Importance of Victor Meyer
Test.
Aromatic nitro compound - aromatic electrophilic substitution - nitrating
mixture - aromatic nitro compounds - yellow oils or solids - Reduction under
various conditions - acidic, neutral, alkaline mediums and electrolytic
reduction.
Polynitro compounds - explosives.

20.3 AMINES
Amines are compounds derived from ammonia by replacing one or more
hydrogen atoms by alkyl or aryl group.

.. .. ..
H–N–H CH3– N–H C6H5 – N – H
| | |
H H H
Ammonia Aliphatic amine Aromatic amine

335
 Amines are basic in nature. They accept protons forming alkyl or aryl
ammonium ions.

.. +
H+ + RNH2 R – NH2
|
Proton Alkyl amine H alkyl ammonium ion
20.3.1 Classification of amines
Amines are classified as primary, secondary and tertiary amines. When
one of the hydrogen atoms in ammonia is replaced by alkyl or aryl group, it
is primary amine.
CH3CH2NH2 C6H5NH2
ethylamine aniline
If two hydrogen atoms of amino group are replaced by alkyl or aryl
groups, it is a secondary amine.
(CH3)2 NH - dimethyl amine
If three hydrogen atoms are replaced by alkyl or aryl groups, it is tertiary
amine.
(CH3)3 N - Trimethyl amine
H R R
| | |
R – N – H R –N – H R– N – R
Primary Secondary Tertiary
1o 2o 3o
Primary amine has NH2 group (two hydrogen atoms
bonded to nitrogen)
Secondary amine has NH group (only one hydrogen bonded
to nitrogen)
Tertiary amine has – N group (No hydrogen atom bonded
to nitrogen)
Generally the strength of the base is in the order.
3o amine > 2o amine > 1o amine

336
 But because of steric effect the order of the basic strength is
2o amine > 1o amine > 3o amine

Nomenclature of Aliphatic amines

IUPAC system is similar to that of alkyl halides.

Molecular structure IUPAC name Common name

CH3 – NH2 amino methane methyl amine

CH3 – CH – CH3 2-amino propane isopropyl amine

|
NH2

CH3CH2CH2NH2 1-amino propane n-propyl amine

CH3 – CH – CH2 – NH2 1-amino-2-methyl isobutyl amine
| propane
CH3

CH3
|
CH3 – CH – CH – CH3 2-amino-3-methyl isopentyl amine
| butane
NH2

CH3NH CH2 CH3 (N-methyl amino) ethyl methyl

ethane amine

CH3NH – CH – CH3 2-(N-methyl amino) methyl isopropyl

| propane amine
CH3

CH3 – N – CH – CH2 CH3 2-(N,N-dimethyl dimethyl sec.butyl

| | amino) butane amine
CH3 CH3

337
20.3.2 General methods of preparation of amines
Reduction of compounds containing carbon-nitrogen bonds.
1. Catalytic or chemical reduction of nitro alkane. Primary amines
can be obtained by reduction of nitro alkanes with H2 / Pt (or Ni) or lithium
aluminium hydride.

3H2/Ni or Pt
(a) CH3 CH2 NO2 CH3CH2NH2 + 2H2O
Nitro ethane Ethylamine

Sn (or) Zn/HCl
(b) CH3 CH2 NO2 CH3CH2 NH2 + 2H2O

LiAlH4
(c) CH3NO2 CH3NH2
Nitro methane Methyl amine

2. Reduction of amides : Amines can be obtained by reduction of amides

with lithium aluminium hydride or sodium and alcohol.

Na/C2H5OH
(a) CH3CONH2 + 4 [H] CH3CH2NH2 + H2O
(Acetamide) Ethylamine

LiAlH4
(b) CH3CONHCH3 CH3CH2NHCH3
(N-methyl acetamide) (Secondary amine)
methylethylamine
3. Reduction of cyanides :
Primary amines can be prepared by reduction of alkyl cyanides (nitriles)
with H2/Ni or lithium aluminium hydride.
Na/C2H5OH
(a) CH3C ≡ N + 4 [H] CH3CH2NH2

LiAlH4
(b) CH3C ≡ N CH3CH2NH2
Ether

H2/Ni
(c) CH3C ≡ N CH3CH2NH2

338
4. Reduction of alkyl isocyanides :
Secondary amine can be prepared by the catalytic reduction or reduction
by lithium aluminium hydride of alkyl iso cyanide.

H2/Pt
CH3 – N ≡ C CH3NHCH3
Methyl isocyanide Dimethylamine

LiAlH4
CH3 – N ≡ C CH3NH CH3
ether
5. From amides
By elimination reaction - primary amine is prepared.

Hoffman’s hypobromite reaction or Hoffman’s bromamide reaction

Br2/KOH
CH3CONH2 CH3NH2 + CO2
This reaction involves the formation of
(i) Bromamide by substitution of –NH2 hydrogen. CH3CONHBr.
(ii) In presence of KOH [base], salt of bromamide is formed.
–
CH3CO – N – Br + K+
..

(iii) Bromine leaves as bromide ion forming nitrene.

.. ..
CH3CO – N – Br CH3 – CO – N + Br–
.. ..
Nitrene - an electron
deficient specie.

(iv) Migration of CH3- to electron deficient nitrogen forms methyl

isocyanate.
O
|| ..
CH3 –.. C – N O = C = N – CH3
..

339
 (v) In aqueous alkaline medium, isocyanate gets cleaved to give primary
amine and carbondioxide.
CH3 – N = C = O CH3NH2 + CO2
H2– O methylamine
methyl isocyanate

6. From ammonia :
By heating an alkyl halide with alcoholic ammonia in a sealed tube, a
mixture of primary, secondary, tertiary amines and quarternary ammonium
salt are obtained.
Nucleophilic substitution of alkyl halide or alcohol by Ammonolysis.
(Ammonia is the nucleophile in this reaction).
(a) CH3Br + NH3 CH3NH2 + HBr
CH3Br + CH3NH2 (CH3)2 NH + HBr
CH3Br + (CH3)2 NH (CH3)3 N + HBr
CH3Br + (CH3)3 N (CH3)4 N+ Br–
Tetramethyl ammonium bromide (a quarternary ammonium salt)
(b) Amines can be prepared by passing the vapours of alcohol and
ammonia over heated alumina at 673 K. A mixture of primary secondary
and tertiary amines are produced.

Al2O3
CH3CH2OH + NH3 (CH3CH2) NH2 + H2O
723K
1o amine

Al2O3
CH3CH2OH + (CH3CH2)2 NH (CH3CH2)2NH + H2O
2oamine
diethyl amine
Al2O3
CH3CH2OH + (CH3CH2)2NH (CH3CH2)3 N + H2O
3o amine
triethylamine

340
 In both of the above methods, pure amines cannot be prepared. Only
mixture of amines are obtained.
7. Gabriel’s phthalimide synthesis of primary amine.

CO CO CO
KOH RX
NH NK N–R
CO CO CO
phthalimide potassium phthalimide N-alkyl phthalimide

aqueous KOH

COOK
+ RNH2
alkylamine
COOK
potassium phthalate
This involves the treatment of phthalimide with potassium hydroxide to
form potassium salt. The salt is then heated with an alkyl halide to give
N-alkyl phthalimide, which in turn reacts with potassium hydroxide to form
a potassium phthalate salt and a pure primary amine.

20.3.3 Properties
1. Amines are polar molecules, capable of forming strong
intermolecular hydrogen bonds.
R R R
| | |
...... N – H | | | | | | N – H ..... N–H
| | |
H H H
This explains higher boiling points (compared to hydrocarbons) and
solubility in water and alcohol. Higher members are less soluble in water.
2. Generally amines have fishy odour.
3. The strength of hydrogen bonds and hence the boiling points of amines
are in the order.
Secondary amine > Primary amine > Tertiary amine

341
 Three alkyl groups hinder the formation of hydrogen bonds or accepting
of protons.
Chemical properties :
1. Basic properties :
(a) Basic nature of amines
The nitrogen in amines possess an unshared pair of electrons (lone
pair). The lone pair of electrons is available for the formation of a new bond
with a proton or Lewis acids. Thus amines are basic in nature and they react
with acids to form salts.
Amines are weak bases and they produce small amount of ions in aqueous
solutions. The extent of ion formation is described by an equilibrium constant
Kb. This basicity constant explains the relative strength of a weak base.
Stronger bases will have higher numerical values of (Kb) this constant.

Relative basic strength

The greater is the number of electron releasing alkyl groups, the greater
the availability of nitrogen’s lone pair and stronger the base.
CH3
.. .. |
NH3 < CH3NH2 < CH3 – NH
..

But in trimethyl amine bonding by proton is relatively difficult due to

steric crowding of methyl groups.
Amines react with water forming alkyl ammonium hydroxide.
.. +
CH3 – NH2 + H2O CH3NH3 OH–
methyl ammonium hydroxide

(b) Salt formation :

Amines are basic compounds. They react with acids to form alkyl
ammonium salts.
..
CH3NH2 + HCl CH3NH3+ Cl–
methyl ammonium chloride

342
2. Alkylation of amine :
When an amine is treated with alkyl halide, hydrogen atoms attached to
the nitrogen atom are successively replaced by alkyl groups. In the final
step, the tertiary amine adds one molecule of the alkyl halide to yield a
quaternary ammonium salt.

CH3Br CH3Br CH3Br

CH3NH2 CH3NHCH3 (CH3)2 NCH3 (CH3)4 N+Br–
1o amine 2o amine 3o amine Quarternary salts

These reactions involve SN2 mechanism.

3. Acylation of amine :
On treatment with acetyl chloride or on heating with acetic anhydride,
N-alkyl acetamide is formed.
CH3COCl
Acetyl chloride

CH3NH2 CH3NHCOCH3
Methyl amine N-methyl acetamide

CH3COOCOCH3
Acetic anhydride

Both the above reactions involve nucleophilic substitution reaction -

the nucleophile being alkyl amine and the leaving group the halide ion or
acetate ion.

4. Reaction with Nitrous acid :

(a) Primary amines react with nitrous acid to form alcohols and nitrogen
gas.
CH3NH2 + O = N – OH [CH3–N=N – OH] CH3OH + N2
primary amine unstable

Aliphatic diazonium compound is unstable because of absence of

resonance stabilisation.

343
 (b) Secondary amines react with nitrous acid to form N-nitroso amines
which are water insoluble yellow oils.
(CH3)2 N H + HO – N = O (CH3)2 N – N = O
Secondary amine N-nitroso dimethyl amine - yellow oil
(insoluble in water)
(c) Tertiary amines react with nitrous acid to form trialkyl ammonium
nitrite salts which are soluble in water.
(CH3)3 N + HONO (CH3)3 NH+ NO2–
Tertiary amine trimethyl ammonium nitrite
(salt soluble in water)

5. Carbylamine reaction :
Primary amines on heating with chloroform and alcoholic potash forms
a foul smelling substance called carbylamine or alkyl isocyanide.
CH3NH2 + CHCl3 + 3KOH CH3NC + 3KCl + 3H2O
Chloroform Methyl isocyanide

This reaction is characteristic of primary amines. Secondary and

tertiary amines do not undergo this reaction.

6. Mustard oil reaction :

This is also a reaction characteristic of primary amine. When primary
amines are warmed with carbondisulphide and mercuric chloride, alkyl
isothiocyanate, having a pungent mustard like odour is obtained.
CH3NH2 + S=C=S CH3 – N = C = S + H2S
Carbondisulphide methyl isothiocyanate

7. Formation of Schiff’s base

Primary amines condense with aromatic aldehydes forming Schiff’s
bases.
C6H5CHO + H2N CH3 C6H5CH = NCH3
Schiff’s base
(benzal-N-methyl amine)

344
20.3.4 Distinction between primary, secondary and tertiary amines

Primary amine Secondary amine Tertiary amine

RNH2 R2NH R3N

1. With HNO2 forms forms N-nitroso forms salt.

alcohol. amine.
2. With CHCl3/KOH No reaction. No reaction
forms carbylamine
3. With acetyl chloride form N,N-dialkyl No reaction
forms N-alkyl acetamide.
acetamide.
4. With CS2 and HgCl2 No reaction No reaction
alkyl isothiocyanate
is formed.
5. With Diethyl oxalate Forms N,N-dialkyl No reaction
COOC2H5 CONHR oxamic ester, a liquid.
| 2RNH2 | CONR2
COOC2H5 CONHR |
COOC2H5
dialkyl oxamide, a
solid at room
temperature is
formed.
6. With three molar With two molar With only one
proportion of alkyl proportion of molar proportion
halide, quarternary alkyl halide, of alkyl halide
ammonium salt- quaternary quarternary
crystalline ammonium salt ammonium salt
compound is formed. is formed.
is formed.
3RX + RNH 2 R4N+X– R2NH + 2RH R4N+ X – R3N + RX R4N+ X–

20.4 Aromatic amines

Amines containing phenyl group are known as aromatic amines. These
aromatic amines are of two types.
(i) Amines in which the amino group is directly attached to the benzene
ring.

345
 NH2

(ii) Amines in which the amino group is attached to the side chain of
benzene ring. CH NH 2 2

benzyl amine
Aralkyl amines :
These are amines having aromatic system such as benzene ring but the
amino group is present in the side chain.

CH2NH2 CH2NH2

Benzyl amine H3C p-Tolyl amino methane

[IUPAC : phenyl amino methane]

20.4.1 Preparation of benzyl amine

1. Reduction of benzonitriles or benzamides
By the reduction of benzonitrile or benzamide catalytically or with
Lithium Aluminium Hydride.
H2/Ni
C6H5C ≡ N C6H5CH2NH2
Benzonitrile
LiAlH4

H2/Pd
C6H5CONH2
Benzamide
C6H5CH2NH2
LiAlH4

346
2. From benzylbromide
By the action of alcoholic ammonia on benzyl bromide.

C6H5CH2 – Br + H–NH2 C6H5CH2NH2 + HBr

20.4.2 Physical Properties

Colourless liquid, sparingly soluble in water. It is a weaker base than
methylamine.
Chemical Properties
1. Basic properties :
It reacts with acids to form salt.
C6H5CH2NH2 + HCl C6H5CH2NH3 Cl–
benzylamine +
benzyl ammonium chloride
2. Substitution at Nitrogen
N-alkylation : With alkyl halide it forms secondary amine, tertiary amine
and finally quaternary ammonium salt.
CH3Br CH3Br
C6H5CH2NH2 C6H5CH2NHCH3 C6H5CH2 N (CH3)2

+ CH3Br
C6H5CH2 N (CH3)3 Br–

N-Acetylation :
With acetyl chloride or heating with acetic anhydride N-benzyl acetamide
is formed.
C6H5CH2 – NH2 + ClCOCH3 C6H5CH2NHCOCH3 + HCl
N-benzyl acetamide

C6H5CH2 NH2 + (CH3CO)2O C6H5CH2NHCOCH3 + CH3COOH

N-benzyl acetamide
3. With nitrous acid
With nitrous acid it forms benzyl alcohol.
C6H5CH2NH2 + O = N – OH C6H5CH2OH + N2

347
4. Oxidation
On oxidation with permanganate the side chain with the amino group is
oxidised to give benzoic acid.
CH2NH2 KMnO4 COOH

[O]
Benzylamine Benzoic acid

20.4.3 Aromatic amines :

These are compounds in which amino group is directly bonded to a
carbon atom forming the benzene or any aromatic ring.
NH2 NH2

CH3
Aniline o-Toluidine

Aniline or amino benzene, O-Toluidine or orthoamino toluene. These

are also called nuclear substituted amines.
20.4.4 Aniline
Preparation :
Manufacture :
1. By the catalytic reduction of nitro benzene.
Vapourised nitro benzene with hydrogen is passed over copper supported
on silica at 543 K and aniline is obtained.
NO2 H2/Cu/SiO2
NH2

543 K

2. By the chemical reduction of nitrobenzene under strongly acidic

condition such as Sn/HCl or with Hydride donors like LiAlH4.
NO2 NH2
Sn/HCl
+ 2H2O
(H)

348
 Reduction with Fe/con. HCl is used for the large scale preparation of
aniline.
3. By the ammonolysis of chloro benzene at high temperature and
pressure in presence of copper salts, aniline is prepared.

CuCl2
C6H5Cl + 2NH3 C6H5NH2 + NH4Cl
ammonium chloride

4. Hoffmann reaction : Using benzamide.

When an amide is treated with bromine and alkali, the amide is converted
into primary amine containing one carbon less than that of amide.
Br2
C6H5CONH2 C6H5NH2 + CO2
KOH

20.4.5 Properties
A colourless oily liquid sparingly soluble in water. Soluble in organic
solvent. It has higher boiling point than benzene, because of intermolecular
hydrogen bonding. This liquid turns brown on exposure to air due to
oxidation.
Basic nature of Aromatic amines :
Aniline is less basic than aliphatic amines. This is because, the lone pair
of electrons on the nitrogen atom is involved in resonance and is not easily
available for donation to protons. Because of positive charge on nitrogen
protonation becomes difficult.
H2N: H2N+ H2N+ H2N+

(–) (–)

(–)

Consequence of the resonance shown above :

1. Weaker base than aliphatic amine.
2. The electron density is increased in the benzene ring and hence the
benzene ring is activated towards electrophilic substitution reaction.

349
 3. Ortho and para positions are more electron dense hence electrophilic
substitution takes place at ortho and para positions.
4. Nitrogen is strongly bound to the nucleus hence is not easily removed.
(partial C-N double bond character)

1. Basic property :
These form crystalline salts with strong mineral acids such as HCl or
H2SO4.
+
C6H5NH2 + HCl C6H5NH3 Cl–
aniline hydrochloride or phenyl
ammonium chloride
2. Substitution of nitrogen :
(a) Alkylation with alkyl halides it forms 2o, 3o amines and finally
quaternary ammonium salt.
CH3I
C6H5NH2 + CH3I C6H5NHCH3 C6H5N (CH3)2
2o amine 3o amine
(N-methyl aniline) (N, N-dimethyl aniline)

CH3I +
C6H5N (CH3)2 C6H5N (CH3)3 I–
Phenyl trimethyl ammonium iodide

(b) Aniline reacts with acetyl chloride and acetic anhydride to form
corresponding amides called anilides.
C6H5NH2 + ClCOCH3 C6H5NHCOCH3 + HCl
Acetyl chloride N-phenyl acetamide

C6H5NH2 + CH3COOCOCH3 C6H5NHCOCH3 + CH3COOH

Acetic anhydride Acetanilide

(c) With Benzoyl chloride. In presence of sodium hydroxide, benzanilide

is formed.
NaOH
C6H5NH2 + ClCOC6H5 C6H5NHCOC6H5
benzoyl chloride benzanilide
This reaction is an example of Schotten-Baumann reaction.

350
3. Formation of Schiffs base
Aniline is Primary aromatic amine. It reacts with aldehydes to form
aldimines or Schiff’s base.
C6H5NH2 + O = CHR C6H5N = CHR
(Aldimine or Schiff’s base)

In all the above reactions the initial stage is the nucleophilic attack.
The nucleophile is the amine and the site of attack is either halogen carrying
carbon or carbonyl carbon. This is an addition - elimination reaction.

4. Reaction with nitrous acid :

3. A cold solution of sodium nitrite reacts with aniline dissolved in
hydrochloric acid, a clear solution is obtained. This solution contains
‘benzene diazonium chloride’. This reaction is known as ‘diazotisation’.

HCl
C6H5N H2 + O=N–OH C6H5 – N = N – Cl
(Benzene diazonium chloride)

5. Carbylamine reaction :
Aniline reacts with chloroform and alcoholic KOH to give an offensive
smelling liquid, phenyl isocyanide.

∆
C6H5NH2 + CHCl3 + 3KOH C6H5NC + 3KCl + 3H2O
(phenyl isocyanide)

6. Oxidation :
Aromatic amines are readily oxidised by dichromate and sulphuric acid
to p-benzoquinone.
O
NH2
K2Cr2O7/H+

351
7. Reaction with carbonyl chloride :
Carbonyl chloride form S-diphenyl urea with aniline. In the first step
phenyl isocyanate is formed. (C6H5N = C = O).
2C6H5NH2 + COCl2 C6H5NH
Carbonyl chloride C=O + 2HCl
C6H5NH
S-diphenyl urea

(‘S’ stands for symmetric)

8. With carbondisulphide, S-diphenyl thiourea is formed. Phenyl
isothiocyanate is formed in the first step. (C6H5–N=C=S)

2C6H5NH2 + CS2 C6H5NH

carbondi C=S + H 2 S
sulphide C6H5NH
S-diphenyl
thiourea

(‘S’ stands for symmetric)

9. Electrophilic substitution reaction

Because of the presence of - activated benzene ring in aniline, electrophilic
substitution reaction proceed under milder conditions.
(a) Halogenation :
Aniline decolourises bromine water with the formation of white
precipitate, which is 2,4,6-tribromoaniline.
NH2 NH2

+ 3Br2 /H2O Br Br + 3HBr

Br

2,4,6-nitro bromoaniline

352
(b) Sulphonation :
Heating with fuming sulphuric acid, p-amino benzene sulphonic acid is
formed. NH2 NH 2

353K
+ H2SO4 + H2O

SO3H

Ortho amino benzene sulphonic acid is sterically less favoured.

(c) Nitration : Nitration is accompanied by oxidation
But a mixture of con.HNO3 and con. H2SO4 gives m-nitroaniline also.
This can be explained as follows.
Nitric acid is a strong acid. It protonates aniline forming aniliniun ion.
C6H5NH3+. Because of positive charge on nitrogen it is meta directing.
+
NH2 NH3 NH3+ NH2

HNO3 NO2+ NaOH

H2SO4 (HNO3 + H 2SO4)

NO2 NO2
(m-nitroaniline)

p-nitro aniline is prepared in the following three stages.

NH2 NHCOCH3 NHCOCH3 NH2

CH3COCl HNO3/H2SO4 H3O+

+ CH3COOH

2 NO NO2
20.4.6 Uses of aniline
1. For preparing dyes and dye intermediates.
2. For the manufacture of anti oxidants in Rubber industry.
3. For preparing drugs (e.g.,) sulpha drugs.
4. For making isocyanates required for polyurethane plastics.

353
SUMMARY
AMINO COMPOUNDS
Structure, nomenclature, classification and isomerism including
metamerism - of aliphatic amines.
Preparation - Reduction of nitro compounds, amides, cyanides -
phthalimide synthesis - nucleophilic substitution - Ammonolysis.
Properties - hydrogen bonding and polar - higher boiling points - basic
and nucleophilic character.
Classification - primary, secondary and tertiary amine - Basic strength
of amines - N-alkylation, N-acylation, carbylamine reaction - quaternary
ammonium salt.
Uses - Distinction between primary, secondary and tertiary amines.
Aralkyl amine - Benzyl amine - preparation - reduction of amides,
cyanides - properties. Weaker a base than aliphatic amines - gives reactions
of aliphatic primary amine - oxidation of side chain to give benzoic acid.
Aromatic amines - aniline and toluidines - structure, nomenclature and
isomerism - preparation - reduction of nitro benzene - chemical and catalytic
- chloro benzene and ammonia, Hoffmann reaction.
Properties - inter molecular hydrogen bonding - higher boiling point -
less basic than aliphatic amines - resonance in aniline - N-alkylation, N-
acylation, formation of Schiff’s base, carbylamine reaction, reaction with
phosgene, carbondisulphide - Formation of phenol - diazotisation and
formation of azo dyes - electrophilic substitution in the benzene ring -
bromination, sulphonation and nitration - uses.

20.5 ALIPHATIC NITRILES

Alkyl cyanides :
These are compounds in which one hydrogen atom is replaced from a
hydrocarbon by a ‘cyanide’ group.
HCN R – CN R–H

354
 They can also be considered as being derived from hydrocyanic acid.
Nomenclature :
Common system : By addng ‘cyanide’ to the name of the alkyl group.
CH3 – CN
Methyl cyanide

‘Acid nitrile’ system :

In this system, they are named on the basis of the acid they produce on
hydrolysis.
CH3 – C ≡ N – Hydrolysis CH3COOH
Acetic acid

Hence it is called ‘Acetonitrile’.

C6H5 – C ≡ N – Hydrolysis C6H5COOH
Benzoic acid

Hence it is called ‘benzonitrile’.

IUPAC system :
They are named by suffixing ‘nitrile’ to the name of the parent
hydrocarbon.
Formula As cyanide As acid nitrile IUPAC name
HCN Hydrogen cyanide Formonitrile Methane nitrile

CH3CN Methyl cyanide Acetonitrile Ethane nitrile

CH3CH2CN Ethyl cyanide Propionitrile Propane nitrile

(or)
propiononitrile
3 2
CH3–CH–CH3 isopropyl isobutyronitrile 2-methyl-propane
| cyanide nitrile
CN (or)
2-cyano propane
(as a substituent)

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20.5.1 Uses of Nitriles
It is an important synthetic reagent to prepare, aldehydes, acids, amides,
esters, amines alcohols etc.
Acrylo nitrile (CH2=CH–CN) is used in the manufacture of synthetic
polymers like PAN.
Acetonitrile (CH3CN) is used as a solvent for extraction, crystallisation
and as reaction medium.

20.6 Benzene Diazonium Chloride : C6H5N2+Cl–

Aryl diazonium salts form an important class of compounds, characterised
by the presence of the functional group –N+ ≡ N (diazonium ion) directly
bonded to an aryl group –Ar.
The aryl diazonium ion Ar-N+ ≡ N forms salts with anions such as Cl–,
Br–, NO2–, HSO4–, BF4– etc., These are collectively called aryl diazonium
salts.

Nomenclature :
By adding ‘diazonium’ to the name of the parent aromatic compound
followed by the name of the anion.
Thus, C6H5N2+ Cl– is called benzene diazonium chloride.
Structure : The electronic structure
+ .. +
[ Ar – N ≡ N : Ar – N = N : ] X–

Resonance stabilised diazonium ion is further stabilised by the

involvement of the benzene ring, in benzene diazonium ion.

N+≡N N+=N– N+–N– N+–N–

+ (+)

(+)

356
 C–N bond in aryl diazonium salt is stronger than that in aliphatic
diazonium salt.
20.6.1 Preparation
Benzene diazonium chloride is prepared by the action of nitrous acid on
aniline at 273 – 278 K. Nitrous acid is formed by mixing aqueous solutions
of sodium nitrite and mineral acid like HCl or H2SO4.
NaNO2 + HCl HNO2 + NaCl
273 – 278 K
C6H5NH2 + HNO2 + HCl C6H5N2+Cl– + 2H2O
This is stable only under ice cold condition. In the dry condition it is
quite unstable and decomposes violently.
20.6.2 Properties
Colourless crystalline solids turning brown on exposure to air. Only
diazonium [ArN2+ BF4–] fluro borate can be dried without decomposition,
soluble in water and alcohol and insoluble in ether.
Chemical properties :
They are highly reactive compounds. They undergo reaction in which
(1) –N2 group is retained or (2) eliminated. In both cases useful compounds
can be prepared. They are as useful as Grignard reagent for synthesis.

1. Reactions in which –N2+ X– is replaced.

(a) Reduction to arenes :
Benzene diazonium chloride with Hypophosphorous acid, is reduced to
benzene.

H3PO2
C6H5 N2 Cl C6H6 + N2 + HCl
Cu+
H H
Cuprous salts catalyse this reaction.

(b) Replacement by –OH

When the aqueous solution is boiled, phenol is obtained.

357
 C6H5 N2 Cl C6H5OH + N2 + HCl
HO H
This is an example of SN1 reaction in which C6H5N2Cl initially gives
C6H5+ and water is the nucleophile.

(c) Replacement of RO– (or) RCOO– groups :

Similarly –N2Cl can be replaced by alkoxy group by warming with alcohol
or by acyloxy group by boiling with carboxylic acids.

C6H5 N2 Cl C6H5OCH3 + N2 + HCl

CH3O H Aromatic ethers
[Alcohol is the nucleophile] (anisole)

C6H5 N2 Cl C6H5OCOCH3 + N2 + HCl

CH3COO H Phenyl acetate
[Carboxylate ion is the (ester)
nucleophile]
(d) Replacement by Iodine :
Aqueous solution of diazonium salt reacts with potassium iodide solution
to form Iodobenzene.
C6H5 N2 Cl C6H5 I + N2 + KCl
I K [Iodide anion is the nucleophile]

(e) Replacement by Nitro group :

Diazonium salt when treated with sodium nitrite in the presence of
cuprous ion as a catalyst forms Nitro compounds.
NaNO2
C6H5N2Cl C6H5NO2
Cu+

2. Replacement by chlorine or bromine :

(a) Sand Meyer Reaction :

When aqueous solution of diazonium chloride is warmed with Cu2Cl2
or Cu2Br2 in halogen acid, halogenated benzene is formed.
358
 HCl
C6H5N2Cl C6H5 – Cl + N2
Cu2Cl2

HBr
C6H5N2Cl C6H5Br + N2
Cu2Br2

(b) Gattermann reaction :

When the diazonium chloride solution is warmed with copper powder
and the hydrogen halide, the corresponding halobenzene is obtained. Iodo
benzene cannot be prepared by this procedure.

Cu
C6H5N2Cl C6H5Cl + N2
HCl

Cu
C6H5N2Cl C6H5Br + N2
HBr

3. Replacement by cyanide group :

The diazonium salt solution when treated with cuprous cyanide /
potassium cyanide mixture, phenyl cyanide is formed.

Cu2(CN)2
C6H5 N2 Cl C6H5CN + N2 + HCl
NC K
Treatment of diazonium chloride with KCN solution in presence of
copper, also gives phenyl cyanide.

Cu
C6H5N2Cl + KCN C6H5CN + N2 + KCl

4. Replacement by an aryl group : (Gomberg Bachmann Reaction)

Decomposition of diazonium salts in presence of sodium hydroxide and
benzene, results in the formation of Biphenyl.

359
 NaOH
C6H5N2Cl + C6H6 C6H5 – C6H5 + N2 + HCl
Biphenyl

This reaction is known as ‘Gomberg’ or ‘Gomberg Bachmann’

reaction.
The above reactions do not follow strictly SN mechanism. Instead free
radicals are formed as intermediates.
5. Reduction :
Diazonium chloride is reduced to phenyl hydrazine on treatment with
SnCl2/HCl or Zn/HCl or NaHSO3.
4[H]
C6H5N2Cl C6H5NHNH2 + HCl
6. Diazonium coupling reaction :
Diazonium salt reacts with aromatic amine and phenols to give azo
compounds of the general formula.
Ar – N = N – Ar '
This reaction is known as Coupling reaction since all these compounds
are intensely coloured and used as dyes, thousands of azo dyes have been
synthesised by this procedure.

C6H5N2Cl + OH C6H5–N = N OH
[p-hydroxy azo benzene]
Red dye

The aromatic compound with which it couples should have any one of
the groups like –OH, –NH2, –OR, –NHR, –NR2 etc. coupling usually occurs
at para position.

ALL THE COUPLING REACTIONS INVOLVE

I. Formation of diazonium ion C6H5N2+ (an electrophile)
II. Electrophilic substitution on electron rich aromatic compounds like
phenols, amines etc., at para-position.

360
III. Diazo coupling reaction takes place in ice cold condition.

C6H5N2
+
C6H5N2+ + OH OH
H

C6H5N2
+
OH OH + H+
H C6H5N=N

N2Cl + N(CH3)2 N=N N(CH3)2

N, N - dimethyl aniline p-dimethyl amino azo benzene

Reaction with primary amine takes place in a different way :

(I)
N2Cl + H2N N=N–NH

Diazoaminobenzene
(Substitution at Nitrogen)
(II)
∆
N=N–NH N=N NH2
HCl

[Rearrangement] p-amino azo benzene

(Substitution at carbon)

Uses of diazonium salts :

It is a very valuable intermediate in the preparation of many class of
compounds like phenols, halides, cyanides etc.
Valuable laboratory reagents like phenyl hydrazine can be prepared.
Very useful in the manufacture of azo dyes.

361
SUMMARY
Benzene Diazonium chloride - structure - diazotisation of aniline -
properties - stable at low temperature - hydrogenolysis to benzene, hydrolysis
to phenol, formation of halo benzene, cyano benzene, nitrobenzene, anisole
- reduction to phenyl hydrazine - diazo coupling with aromatic amines and
phenols - formation of dyes.
Name reactions
1. Sandmeyer reaction 2. Gattermann reaction
3. Gomberg reaction 4. Diazo coupling reaction
Alkyl cyanides - nomenclature as Nitriles.

SELF EVALUATION
(A) Choose the correct answer :
1. Bromo ethane reacts with silver nitrite to give
(a) C2H5NO2 (b) C2H5–O–NO
(c) C2H5Ag + NaBr (d) C2H5NC
O
2. The isomerism exhibited by CH3 – CH2 – N and CH3 CH2 – O – N = O is
O
(a) position (b) chain (c) functional (d) tautomerism
3. In nitro alkanes –NO2 group is converted to –NH2 group by the reaction
with
(a) Sn/HCl (b) Zn dust (c) Zn/NH4Cl (d) Zn/NaOH
4. When nitromethane is reduced with Zn dust + NH4Cl in neutral medium,
we get
(a) CH3NH2 (b) C2H5NH2 (c) CH3NHOH (d) C2H5COOH
5. The compound that is most reactive towards electrophilic nitration is
(a) Toluene (b) benzene (c) benzoic acid (d) nitrobenzene
6. Nitromethane condenses with acetaldehyde to give
(a) nitro propane (b) 1-nitro-2-propanol
(c) 2-nitro-1-propanol (d) 3-nitro propanol
7. Which of the following compounds has the smell of bitter almonds ?
(a) aniline (b) nitro methane
(c) benzene sulphonic acid (d) nitrobenzene

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8. Nitration of nitrobenzene results in
(a) o-dinitro benzene (b) 1,3,5-trinitro benzene
(c) p-dinitro benzene (d) m-dinitro benzene
9. Nitrobenzene on electrolytic reduction in con. sulphuric acid, the
intermediate formed is
(a) C6H5NH – NHC6H5 (b) C6H5 – NHOH
(c) C6H5 – N = N – C6H5 (d) C6H5.HSO4
10. Electrophile used in the nitration of benzene is
(a) hydronium ion (b) sulphonic acid
(c) nitronium ion (d) bromide ion
11. The reduction of CH3 – CH2 – C ≡ N with sodium and alcohol results in
the formation of
(a) CH3 – CH– CH3 (b) CH3 – CH2 – CH2 – OH + N2
|
NH2
(c) CH3 – CH2 – CH2 – NH2 (d) CH3 – CH2 – NH2

12. The basic character of amines is due to the

(a) tetrahedral structure (b) presence of nitrogen atom
(c) lone pair of electrons on nitrogen atom
(d) high electronegativity of nitrogen
13. The organic compound that undergoes carbylamine reaction is
(a) (C2H5)2NH (b) C2H5NH2 (c) (C2H5)3N (d) (C2H5)4 N+ I–
14. Primary amine acts as
(a) Electrophile (b) Lewis base (c) Lewis acid (d) Free radical
15. Oxidation of aniline with acidified potassium dichromate gives
(a) p-benzo quinone (b) benzoic acid
(c) benzaldehyde (d) benzyl alcohol
16. Which one of the following is a secondary amine ?
(a) aniline (b) diphenyl amine (c) sec.butylamine (d) tert.butylamine
NaNO2/HCl
17. C6H5NH2 X. Identify X.
(a) C6H5Cl (b) C6H5NHOH
(c) C6H5N2Cl (d) C6H5OH

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18. Which of the following will not undergo diazotisation ?
(a) m-toluidine (b) aniline
(c) p-amino phenol (d) benzyl amine
19. Aniline differs from ethylamine by the reaction with
(a) metallic sodium (b) an alkyl halide
(c) chloroform and caustic potash (d) nitrous acid
20. When aqueous solution of benzene diazonium chloride is boiled the
product formed is
(a) benzyl alcohol (b) benzene + N2
(c) phenol (d) phenyl hydroxylamine
(B) Answer in one or two sentences :
1. How are nitro alkanes prepared ?
2. Write about the functional isomerism of nitro methane ?
3. Give the reduction of nitromethane in (a) acid medium, (b) neutral
medium.
4. Mention the uses of nitromethane.
5. How will you convert benzene to m-dinitro benzene ?
6. Explain the electrolytic reduction of nitro benzene ?
7. What are amines ? How are they classified ?
8. Give the structural formula of (i) 2-amino-2-methyl propane.
(ii) 2-(N, N-dimethyl) amino butane
9. What happens when acetonitrile is hydrolysed ?
10. Write the name and structure of four isomeric amines having the molecular
formula C3H9N.
11. How will you distinguish between ethylamine and diethylamine ?
12. Write a note on the basicity of amines ?
13. Explain why ethylamine is stronger than ammonia ?
14. What is Gabriel phthalimide synthesis ?
15. How is nitrobenzene converted to aniline ?
16. What happens when aniline is treated with bromine ?
17. What happens when aniline is treated with phosgene ?
18. How will you distinguish between aniline and ethylamine ?

364
19. Explain why aniline is less basic than methylamine ?
20. How is benzene diazonium chloride prepared ?
21. Write a note on Sandmeyer reaction.
22. How will you synthesise, benzylamine from aniline ?
NaNO2 CuCN LiAlH4
Ans : Aniline Benzene cyano benzene Benzyl amine
HCl, 0oC
diazonium chloride
23. What are the reagents that would convert the following into Ethyl amines ?
(a) CH3CONH2 (b) CH3CN (c) CH3CH2NO2 (d) CH3CH = NOH
24. Account for the following :
(a) (CH3)2NH is a stronger base than NH3
(b) CH3CH2NH2 is more basic than CH3CONH2
(c) Aniline is less basic than Ethyl amine
(d) On sulphonation of aniline, p-amino benzene sulphonic acid is formed.
25. What is the action of NaNO2/HCl (aq) at ice cold temperature on
(a) C2H5NH2 (b) C6H5NH2 (c) (CH3)2NH (d) (CH3)3N
26. What happens when ethylamine is treated with
(a) CHCl3/NaOH (b) CS2 (c) COCl2 (d) C6H5CHO
27. Justify :
(a) Diazo coupling reaction is an example of aromatic electrophilic
substitution reaction
(b) Formation of acetanilide from aniline and acetic anhydride is a
nucleophilic attack by aniline
(c) Formation of methylamine by ammonolysis of methyl iodide is an
example of SN2 reaction
(d) Addition of bromine water to aniline, gives a white precipitate.
This is an example of aromatic electrophilic substitution.
28. What is the action of
(a) Diethyl oxalate on Ethylamine
(b) Diethyl oxalate on Diethyl amine
(c) Nitrous acid on Diethyl amine
(d) Nitrous acid on Triethyl amine

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29. Account for
(a) Reduction of CH 3 CN gives CH3 CH 2NH 2 while CH 3NC gives
(CH3)2NH
(b) (CH3)2NH requires two molar proportion of CH3I to give the same
crystalline product formed by (CH3)3N with one mole of CH3I
(c) Nitration of aniline with con.HNO3 may end up with same meta nitro
product
(d) p-toluidine is a stronger base than p-nitroaniline.
30. Account for the following :
(a) Nitroethane is soluble in NaOH
(b) Nitro ethane reacts with nitrous acid
(c) 2-methyl-2-nitro propane has neither of the properties.
31. What happens when
(a) nitro ethane is boiled with HCl
(b) nitro benzene is treated with Lithium Aluminium Hydride
(c) When Toluene is treated with fuming nitric acid and sulphuric acid.
32. Account for
(a) Nitration of benzene is easier than nitration of nitrobenzene
(b) Benzaldehyde undergoes condensation with nitro methane in presence
of KOH
(c) Nitromethane gives trichloro nitro methane on treatment with
chlorine/NaOH while nitro ethane gives only dichloro ethane
33. How can the following conversions be effected ?
(a) Nitro benzene Nitrosobenzene
(b) Nitro benzene azoxy benzene
(c) Nitrobenzene Hydrazobenzene
34. Distinguish between
(a) Nitroethane and ethyl nitrite
(b) Nitro benzene and nitro phenol
(c) Nitro toluene and phenyl, nitromethane

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(C) Answer not exceeding sixty words :
1. Write the methods of preparation of nitro methane ?
2. Explain the reduction of nitro methane in different medium.
3. Write a note on the ‘reduction of nitro benzene under different conditions.
4. Explain the mechanism of nitration of nitro benzene.
5. Write the differences between nitro methane and nitro benzene.
6. Give three methods of preparing ethylamine from aceto nitrile ?
7. Distinguish between primary, secondary and tertiary amines.
8. Write the mechanism of ‘Hoffmann’s bromamide reaction’.
9. How do primary, secondary and tertiary amines react with nitrous acid ?
10. Write any three methods of preparing benzylamine ?
11. Comment on the ‘basic nature’ of aniline.
12. Write a note on
(i) Carbylamine reaction, (ii) Mustard oil reaction, (iii) Acetylation of
benzylamine, (iv) Formation of Schiff’s base, (v) Diazotisation reaction.
13. Distinguish between benzylamine and aniline.
14. How are the following compounds obtained from benzene diazonium
chloride ?
(i) phenol, (ii) ester, (iii) p-hydroxy azo benzene.
(D) Solve the problems :
1. Nitrobenzene does not undergo Friedel-Crafts alkylation. Give reasons.
Ans. Due to powerful electron withdrawing effect of the –NO2 group,
the benzene ring in C6H5NO2 is deactivated towards Friedel Craft’s alkylation
and hence it is used as a solvent in many Fridel-Craft’s reaction.
2. Boiling points of nitroalkanes are much higher than those of hydrocarbons
of comparable mass - give reasons.
Ans. Nitroalkanes are polar in nature (µ = 3 – 4D) and thus have greater
dipolar attraction than hydrocarbons. This results in higher values of b.p.
(µ = Dipole moment)

367
3. Explain why amines are more basic than amides.
Ans. In simple amines the lone pair of electrons is on nitrogen and hence
available for protonation. In amides, on the other hand, the electron pair on
nitrogen is delocalized to the carbonyl oxygen through resonance.
O O–
|| .. | +
R – C – NH2 R – C = NH2
amide
4. An organic compound (A) with molecular formula C6H7N gives (B)
with HNO2/HCl at 273 K. The aqueous solution of (B) on heating gives
compound (C) which gives violet colour with neutral FeCl3. Identify the
compounds A, B and C and write the equations.
Ans. (A) C6H5NH2 - aniline, (B) C6H5N2Cl - benzene diazonium
chloride, (C) Phenol
5. Outline the mechanism of
(a) Nitration of aniline
(b) Acetylation of aniline to form acetanilide
6. Outline the preparation of
(a) para nitroaniline from aniline
(b) tri bromo benzene from tribromo aniline
7. Indicate the mechanism of
(a) the formation of N-methyl aniline from aniline
(b) the formation of p–hydroxy azobenene from benzene diazonium
chloride
8. Explain the following order of strength of bases.
(a) (CH3)2 NH > CH3NH2 > NH3
(b) p-toluidine > Aniline > p-nitro aniline
Diazonium chloride
1. How are the following conversions effected ?
(a) C6H5NH2 C6H6
(b) C6H5NO2 C6H5OH

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 (c) C6H5NH2 C6H5I
(d) C6H5NH2 C6H5NO2
2. Starting from aniline how can the following be prepared ?
(a) Chloro benzene (b) p-hydroxy azobenzene
(c) Benzonitrile (d) p-amino azo benzene
3. How can the following conversion be effected ?
(a) Nitrobenzene to anisole
(b) Chloro benzene to phenyl hydrazine
(c) Aniline to benzoic acid
(d) Benzene diazonium chloride to Ethyl benzene
4. Identify the electrophile and nucleophile in the following reactions :
(a) C6H5N2Cl + KI C6H5I + KCl
(b) C6H5N2Cl + C6H5OH C6H5N=N–C6H4OH
(c) C6H5N2Cl + CH3OH C6H5OCH3
(d) C6H5N2Cl + H2O C6H5OH

KEY
HNO2 H3PO2
1. (a) C6H5NH2 C6H5N2Cl C6H6
HCl

(b) C6H5NO2 Sn/HCl HNO2 H2O

C6H5NH2 C6H5N2Cl C6H5OH

HNO2 KI
(c) C6H5NH2 C6H5N2Cl C6H5I
HCl

HNO2 NaNO2
(d) C6H5NH2 C6H5N2Cl C6H5NO2
HCl

HNO2 HCl
2. (a) C6H5NH2 C6H5N2Cl C6H5Cl
HCl Cu2Cl2

369
 HNO2 Phenol
(b) C6H5NH2 C5H5N2Cl C6H5–N = N–C6H4–OH
HCl

HNO2 KCN
(c) C6H5NH2 C6H5N2Cl C6H5CN
HCl Cu2(CN)2

Aniline
(d) C6H5NH2 HNO2 C6H5N2Cl C6H5N=N C6H4NH2
HCl

Sn/HCl HNO2 CH3OH

3. C6H5NO2 C6H5NH2 C6H5N2Cl C6H5OCH3
HCl

NH3 HNO2 Sn/HCl

C6H5Cl C6H5NH2 C6H5N2Cl C6H5NHNH2
HCl HCl

HNO2 KCN H3O+

C6H5NH2 C6H5N2Cl C6H5CN C6H5COOH
HCl Cu2(CN)2

HBr Na
C6H5N2Cl C6H5Br C6H5–C2H5
Cu2Br2 C2H5Br
dry ether

4. (a) I– - nucleophile
(b) C6H5N2+ - electrophile
(c) CH3OH - nucleophile
(d) H2O - nucleophile
REFERENCES :
1. Organic reactions, Conversions, Mechanism & Problems. - R.D. Madan,
S.Chand & Co. Ltd.
2. A guide book to Mechanism in organic chemistry. - Peters Sykes -
Pearson Education Ltd. _______

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 21. BIOMOLECULES
LEARNING OBJECTIVES
@ Recognises the importance of carbohydrates, proteins, amino acids and
lipids.
@ Classification of carbohydrates.
@ Structural elucidation of simple carbohydrates.
@ Proteins and amino acids.
@ Classification, structure and functions of lipids in biosystems.
A living organism is a collection of organic molecules which interact
with each other and with their environment in a very unique way. All living
organisms are made of one or more cells which are considered as the smallest
units of life. Cells are essentially packets of chemicals necessary for life. The
compounds present in cells are composed of carbon, hydrogen, oxygen,
nitrogen, phosphorus and sulphur. Nearly all the carbon compounds found
in living cells can be placed into one or another of the following four classes.
(i) Carbohydrates, (ii) Amino acids and proteins, (iii) Nucleic acids and
(iv) Lipids.

21.1 CARBOHYDRATES
Carbohydrates are polyhydroxy aldehydes or polyhydroxy ketones. They
are naturally occuring organic substances. They are present in both plants
and animals. Carbohydrates are formed in the plants by photosynthesis from
carbon dioxide and water in sunlight.
Classification :
Carbohydrates may be classified into two broad groups.
1. Sugars and 2. Non-sugars or polysaccharides.
1. Sugars : Sugars are sweet crystalline substances and soluble in water.
(i) Monosaccharides : The monosaccharides are polyhydroxy aldehydes
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or polyhydroxy ketones which cannot be hydrolysed into simpler sugars.
They may again be classified according to the nature of carbonyl group.

(a) Aldoses, which contain an aldehyde group O

||
( —C—H)

O
(b) Ketoses, which contain a keto group ||
( —C— )

The aldoses and ketoses are further divided into sub-groups on the basis
of the number of carbon atoms in their molecules, as trioses, tetroses,
pentoses, hexoses etc.
Thus monosaccharides are generally referred to as aldotrioses,
aldotetroses, aldopentoses, aldohexoses, ketohexoses etc.
The aldoses and ketoses may be represented by the following general
formulae.
H
C=O CH2OH
| |
(CHOH)n C=O
| |
CH2OH (CHOH)n
aldoses |
CH2OH
(n = 1, 2, 3, 4, 5) ketoses
(n = 0, 1, 2, 3, 4)
(ii) Oligosaccharides :
Oligosaccharides are sugars that yield two to ten monosaccharide
molecules on hydrolysis and are thus again classified into various groups
depending upon the number of monosaccharide units formed on hydrolysis.

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(a) Disaccharides : The disaccharides are sugars which on hydrolysis give
two molecules of the same or different monosaccharides.
C12H22O11 + H2O C6H12O6 + C6H12O6
Sucrose Glucose Fructose

(b) Trisaccharides : These give three molecules of monosaccharides on

hydrolysis.
C18H32O16 + 2H2O C6H12O6 + C6H12O6 + C6H12O6
Raffinose Galactose Glucose Fructose

2. Non-sugars (or) Polysaccharides

These are carbohydrates which involve a large number of monosaccharide
units linked to each other by oxide bridges. These linkages are called
glycosidic linkages. The common and widely distributed polysaccharides
correspond to the general formula (C6H10O5)n. They get hydrolysed to give
monosaccharides.
H+
(C6H10O5)n + n H2O n C6H12O6
Starch Glucose

Thus chemically, polysaccharides are long chain polymers of

monosaccharides. Starch, Cellulose and inulin are examples of polysaccharides.
Thus whole of the classification of the carbohydrates may be summarised
as below.
CARBOHYDRATES

Sugars Non-sugars
(Polysaccharides)
Monosaccharides oligosaccharides Homopoly- Heteropoly-
saccharides saccharides

Aldoses Ketoses

Disaccharides Trisaccharides Tetrasaccharides ... ... ...

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21.2 Preparation, structure and uses of Glucose and Fructose
Glucose : Glucose is a monosaccharide and belongs to aldohexose.
Glucose is known as dextrose because it occurs in nature as the optically
active dextro-rotatory isomer. It is also called grape sugar as it is found in
most sweet fruits especially grapes. It is present in honey also.
Preparation : It is prepared in laboratory by acid hydrolysis of cane
sugar in presence of alcohol.

H+
C12H22O11 + H2O C6H12O6 + C6H12O6
Cane sugar Glucose Fructose

Structure of Glucose :
The structure of glucose has been derived from the following facts.
1. Elemental analysis and molecular weight determination show that the
molecular formula of glucose is C6H12O6.
2. Complete reduction of glucose with concentrated hydriodic acid in the
presence of red phosphorous produces n-hexane as the major product.
This indicates that the six carbon atoms in the glucose molecule form an
unbranched chain of six carbon atoms.

HI/P
Glucose CH3 – CH2 – CH2 – CH2 – CH2 – CH3
Reduction
n-hexane
3. Glucose readily dissolves in water to give a neutral solution. This indicates
O
that the glucose molecule does not contain a carboxyl ||
group. ( — C – OH )

4. Glucose reacts with hydroxylamine to form a monoxime or adds only

one mole of HCN to give a cyanohydrin. This reaction indicates the
O
presence of either an aldehyde || or a ketone
( —C—H)
O
||
( — C — ) group.

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5. Mild oxidation of glucose with bromine water gives gluconic acid. This
indicates the presence of an aldehyde group since only the aldehyde
group can be oxidised to an acid, containing same number of carbon
atoms. Since the six carbon atoms in glucose form a consecutive
unbranched chain, the aldehyde group, must occupy one end of this chain.
6. Further oxidation of gluconic acid with nitric acid gives saccharic acid.
This indicates the presence of a primary alcoholic group.
COOH COOH
Br2/H2O
| HNO3
|
Glucose (CHO)4 (CHOH)4
Mild | Strong |
oxidation CH2OH oxidation COOH
gluconic acid saccharic acid

7. Glucose reduces an ammoniacal solution of silver nitrate (Tollen’s

reagent) to metallic silver or a basic solution of cupric ion (Fehling’s
solution) to red cuprous oxide. These reactions further confirm the
presence of a aldehyde group.
8. Glucose reacts with acetic anhydride in the presence of pyridine to form
a penta acetate. This reaction indicates the presence of five hydroxyl
groups in a glucose molecule.
From the above evidences we conclude that glucose is a penta hydroxy
hexanal (an aldohexose) and can be represented by the following structure.
H O
C
|
* CHOH
|
* CHOH
|
* CHOH
|
* CHOH
|
CH2OH *C = asymmetric carbon atom
Glucose
(2,3,4,5,6 penta hydroxy hexanal)

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FRUCTOSE :
Fructose is present in abundance in fruits and hence it is called as fruit
sugar. It is also present in cane sugar and honey alongwith glucose in
combined form. Since naturally occuring fructose is laevorotatory, it is also
known as laevolose. It is a ketohexose.
Preparation :
Fructose is obtained by hydrolysis, of cane sugar with sulphuric acid,
along with glucose.

dil.H2SO4
C12H22O11 + H2O C6H12O6 + C6H12O6
Cane sugar Glucose Fructose
The solution having equal molecules of D (+) glucose and D (–) fructose
is termed as invert sugar and the process is known as inversion of sucrose.
Structure :
The structure of fructose has been derived from the following facts.
1. Elemental analysis and molecular weight determination show that the
molecular formula of fructose is C6H12O6.
2. Complete reduction of fructose with concentrated hydriodic acid in the
presence of red phosphorous gives n-hexane as the major product. This
indicates that the six carbon atoms in the fructose molecule form a
consecutive unbranched chain.

HI/P
Fructose CH3 – CH2 – CH2 – CH2 – CH2 – CH3
Reduction n-hexane

3. Fructose readily dissolves in water to give a neutral solution. This indicates

O
that the fructose molecule does not contain a carboxyl ||
( — C – OH )
group.
4. Fructose reacts with acetic anhydride in the presence of pyridine to form
a penta acetate. This reaction indicates the presence of five hydroxyl
groups in a fructose molecule.
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5. Fructose reacts with hydroxylamine to form a monoxime, or adds only
one mole of HCN to give a cyanohydrin. This reaction indicate the
O
presence of either an aldehyde ||
( —C—H)
O
or a ketonic group. ||
( —C— )
6. Fructose is not oxidised by Bromine water indicating the absence of
aldehydic group.
Oxidation of fructose with concentrated nitric acid yields a mixture of
glycollic acid and tartaric acid. Since this oxidation occurs with the rupture
of the carbon chain, the carbonyl group must be present as a ketone
group.
COOH CH2OH
HNO3
| |
Fructose + 4 (O) (CHOH)2 + COOH + 3H2O
| glycollic acid
COOH
tartaric acid
7. Partial reduction of fructose with sodium amalgam and water produces
a mixture of two epimeric alcohols, sorbitol and mannitol, because a
new asymmetric centre is being created at C–2. This confirms the
presence of a ketonic group.
8. When fructose is treated with HCN, it forms an addition product which
upon hydrolysis and subsequent reduction with hydriodic acid and red
phosphorous gives 2-methyl-hexanoic acid. This indicates that the ketone
group is adjacent to one of the terminal carbon atoms.
CH2OH CH2OH CH3
HCN | CN Hydrolysis | COOH Reduction | COOH
Fructose C C C
| OH | OH | H
(CHOH)3 (CHOH)3 (CH2)3
| | |
CH2OH CH2OH CH3
2-methyl hexanoic acid

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 From the above evidences we conclude that fructose is a
pentahydroxyhexanone (a ketohexose) and can be represented by the
following structure.
CH2OH
|
C=O
|
* CHOH
|
* CHOH
| * C = asymmetric carbon atom
* CHOH
|
CH2OH
fructose
(1, 3, 4, 5, 6, pentahydroxy-2-hexanone)

21.3 DISACCHARIDES
Disaccharides are sweet tasting, crystalline, water-soluble substances,
easily hydrolysed by enzymes and dilute mineral acids to two monosaccharide
units.
C12H22O11 + H2O C6H12O6 + C6H12O6
disaccharide monosaccharide monosaccharide

The hydrolysis involves a cleavage of glycosidic linkage (i.e.,) in the

formation of disaccharide molecule atleast one monosaccharide unit is linked
to the other through the carbonyl carbon (C1 in glucose and C2 in fructose).

1. Disaccharides linked through the glycosidic carbon atoms of each

component (C 1 of glucose to C 2 of fructose) are non-reducing
disaccharides. (e.g.,) Sucrose.

2. Disaccharides linked through C1 of the first to C4 or C6 of the second

component. (Reducing disaccharides) (e.g.,) Lactose.

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 Sucrose : Sucrose is the commonest sugar known. The most important
sources are sugar cane and sugar beets.

It is a colourless, odourless crystalline compound. It is soluble in water.

It is dextrorotatory. It is a non-reducing sugar as it does not reduce Tollen’s
or Fehling’s reagent. Sucrose, on heating slowly and carefully, melts and
when allowed to cool, it solidifies to pale yellow glassy mass called ‘Barley
Sugar’.

When heated to 200oC, it loses water to form brown amorphous mass

called caramel. On strong heating, it chars to almost pure carbon giving the
smell of burnt sugar.

It is composed of α-D-glucose unit and β-D-fructose unit. These units

are joined by a-β-glycosidic linkage between C-1 of the glucose unit C-2 of
the fructose unit.

Structure :
H–C CH2OH
| |
H – C – OH O C
| |
HO – C – H HO – C – H
| O | O
H – C – OH H – C – OH
| |
H–C H–C
| |
CH2OH CH2OH
Polysaccharides
Polysaccharides are polymers of monosaccharides. The most important
polysaccharides are starch and cellulose. They have a general formula
(C6H10O5)n.
Starch : Starch is a white amorphous substance with no taste or smell.
Starch is present in wheat, corn, barley, rice, potatoes, nuts, etc.

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 When heated to a temperature between 200–250oC, it changes into
dextrin. At higher temperature charring occurs. When boiled with dilute
acid, starch ultimately yields glucose.
(C6H10O5)n (C6H10O5)n C12H22O11
Starch Dextrin Maltose

C6H12O6
Glucose

When treated with enzyme, diastase, it yields maltose.

2 (C6H10O5)n + nH2O nC12H22O11
Maltose

Starch solution gives a blue colour with a drop of iodine. The exact
chemical nature of starch varies from source to source. Even the starch
obtained from same source consists of two fractions (i) amylose and
(ii) amylopectin.
Cellulose : Cellulose is found in all plants and so is the most abundant
of all carbohydrates. It is the material used to form cell walls and other
structural features of the plants.
Cellulose is insoluble in water and in most of the organic solvents. When
it is boiled with dilute H2SO4, it is completely hydrolysed into D-glucose.
(C6H10O5)n + nH2O nC6H12O6
Cellulose Glucose

21.4 AMINO ACIDS

An amino acid is bifunctional organic molecule that contains both a
carboxyl group, –COOH as well as an amine group, –NH 2. Amino acids
derived from proteins have the amino group on the alpha (α) carbon, that is,
the carbon atom next to the carboxyl group. These α-amino acids may be
represented by the following general formula.

380
 H O
| ||
R– C – C – OH
|
NH2
α-carbon

The aminoacids differ in the nature of R-group bonded to α-carbon

atom. The nature of R-group determines the properties of proteins.
Nearly twenty five amino acids have been obtained from the hydrolysis
of proteins. The human body can synthesise some of the amino acids that it
needs for maintaining good health. Those amino acids that cannot be
synthesised by the body and must be supplied in the diet are called Essential
Amino acids. The amino acids that can be synthesised from other compounds
by the tissues of the body are called Non - essential Amino acids.
Except Glycine (NH2 – CH2 – COOH), all the α-amino acids have an
asymmetric carbon atom. Hence, each of these amino acids can exist as
optical isomers. Due to the presence of an acidic and a basic group in the
same molecule, amino acids exist in an ionic form called a Zwitter ion where
the proton of –COOH group is transferred to the –NH2 group.
NH2 +NH
3
| |
R – CH – COOH R – CH – COO–
Amino acid Zwitter ion

Depending on the pH of the solution, the amino acid can donate or

accept a proton.
H O H O H O
| || | || | ||
H+3N – C–C–OH H+ H+3N–C–C–O – OH
–
H2N–C–C–O–
| | |
R R R
+Low pH cation (Acidic solution) Zwitter ion High pH Anion
(II) (I) (Basic solution) (III)

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 When an ionised form of amino acid is placed in an electric field, it will
migrate towards the opposite electrode. In acidic solution (low pH), the
cation (II) move towards cathode. In basic solution (high pH), the anion
(III) move towards anode. The zwitter ion does not move towards any of
the electrodes. The pH at which the amino acid shows no tendency to
migrate when placed in an electric field is known as isoelectric point.
This is characteristic of a given amino acid.
Proteins are formed by joining the carboxyl group of one amino acid to
the α-amino group of another amino acid. The bond formed between two
amino acids by the elimination of a water molecule is called a peptide
linkage or bond.
– C– OH + H –N – – C – N – + H2O
|| | || |
O H O H
Carboxyl group Amine group of Peptide bond
of one amino acid other amino acid

The product formed by linking amino acid molecules through peptide

linkages, – CO – NH –, is called a peptide. Peptides are further designated
as di, tri, tetra or penta peptides accordingly as they contain two, three, four
or five amino acid molecules, same or different, joined together.

In peptide formation the two different amino acid molecules may react
in one of the two ways.
CH3 CH3
| |
(i) NH2 – CH2 – COOH + H2N – CH – COOH H2N–CH2–CO–NH–CH–COOH
Glycine Alanine Glycylalanine (a dipeptide)

CH3 CH3
| |
(ii) H2N – CH – COOH + H2N–CH2–COOH H2N–CH–CO–NH–CH2–COOH
Alanine Glycine Alanyl glycine (a dipeptide)

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21.5 LIPIDS
Lipids form a group of organic compounds which are widely distributed
in living system. Lipids are mainly divided into three types, namely simple,
compound and derived, depending on the basis of the nature of products
obtained on hydrolysis.
Functions of lipids in biosystems :
Fats and oils act as storage of energy in plants and animals. In the animal
body, fats are stored in fatty tissues, which are almost pure fat,. Fat give
about 2¼ times as much energy as carbohydrates or proteins. Thus, as far as
weight is concerned, storage of fat is the most economical way for the body
to maintain a reserve energy supply. Fat is a poor conductor of heat. Hence,
fat layer under skin serves to prevent losses of heat from the body.
Wax acts as a protective agent on the surfaces of animals and plants.
Waxy coating on the surface of plants and fruits protects them from excessive
loss of moisture and becoming infected with fungi and bacteria.
Phospholipids like lecithins, and cephalins play a greater role in biosystem.
The lecithins are required for normal transport and utilisation of other lipids,
especially in the liver. lecithin aids in the organisation of the cell structure.
Cephalins are found in the brain. Cephalins have been implicated in the
process of blood coagulation.
Galactolipids occur in considerable amount in the white matter of the
brain and of all nervous tissue. The presence of galactose in the glycolipids
suggests the importance of milk sugar in the diet of infants and children
during the development of the brain and nervous system.

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 SELF EVALUATION
(A) Choose the correct answer :

1. Which is a mono saccharide among the following :

(a) Sucrose (b) Cellulose (c) Maltose (d) Glucose
2. Identify the reducing sugar.
(a) Sucrose (b) Cellulose (c) Starch (d) Glucose
3. Sucrose is not
(a) a di saccharide (b) a non-reducing sugar.
(c) hydrolysed to only glucose (d) hydrolysed to glucose & fructose
4. Sucrose contains glucose and fructose linked by
(a) C1 – C1 (b) C1 – C2 (c) C1 – C4 (d) C1 – C6
5. Glucose is not oxidised to gluconic acid by
(a) Br2/H2O (b) Fehling solutions
(c) Tollen’s reagent (d) Conc. HNO 3
6. Inversion of sucrose refers to
(a) oxidation of sucrose (b) reduction of sucrose
(c) hydrolysis of sucrose to glucose and fructose
(d) polymerisation of sucrose.
7. Glucose forms___________ with acetic anhydride and sodium acetate.
(a) di acetate (b) tetra acetate
(c) penta acetate (d) hexa acetate
8. The amino acid without chiral carbon is
(a) Glysine (b) Alanine (c) Proline (d) Thyrosine
9. The building block of proteins are
(a) α-hydroxy acids (b) α-amino acids
(c) β-hydroxy acids (d) β-amino acids
10. Which is not true of amino acid ?
(a) amino acid forms Zwitter ion
(b) has isoelectric point
(c) dual behaviours
(d) amino acid is insoluble in NaOH solution
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11. Two amino acids say A, B- react to give
(a) two dipeptides (b) three dipeptides
(c) four dipeptides (d) only one
12. A di peptide does not have
(a) two peptide units (b) portions of two amino acids
(c) an amido group (d) salt like structure
13. Proteins are not sensitive to
(a) acids (b) bases
(c) elevated temperature (d) water
14. Denaturation does not involve
(a) breaking up of H– bonding in proteins
(b) the loss of biological action of enzyme
(c) the loss of secondary structure
(d) loss of primary structure of proteins
15. Specificity of enzyme is due to
(a) the sequence of amino acids
(b) secondary structure
(c) tertiary structure
(d) all of the above
16. Ultimate products of hydrolysis of proteins is
(a) aniline (b) aliphatic acid
(c) amino acid (d) aromatic acid
17. Proteins are
(a) polypeptides (b) poly acids
(c) poly phenols (d) poly esters
18. Which of the following contains a lipid ?
(a) starch (b) mineral oil
(c) edible oil (d) peptide
19. Which among the following contains triglyceride ?
(a) Wax (b) Cooking oil
(c) Essential oil (d) Albumin
20. Which contains a long chain ester ?
(a) wax (b) cooking oil
(c) turpentine oil (d) cellulose

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21. An example of a fatty acid obtained from a cooking oil is
(a) acetic acid (b) stearic acid
(c) benzoic acid (d) oxalic acid
22. Which is not a saturated fatty acid ?
(a) Palmitic acid (b) Stearic acid
(c) Oleic acid (d) Glyceric acid
23. Alkaline hydrolysis of cooking oil gives
(a) soap (b) glycerol
(c) fatty acid (d) both (a) and (b)
24. Hair and nail contains
(a) cellulose (b) fat
(c) keratin (d) lipid
25. Important constituent of cell wall is
(a) lipid (b) cellulose
(c) protein (d) vitamin
(B) Answer in one or two sentences :
1. What are carbohydrates ? Give two examples
2. Give the structure of sucrose.
3. What is starch ? What are the ultimate hydrolysis products ?
4. What is the action of con. HI on glucose ?
5. What is Saponification ?
(C) Answer not exceeding sixty words :
1. Outline the classification of carbohydrates giving example for each.
2. How can a reducing sugar differ from non-reducing sugar.
3. Distinguish glucose from fructose.
4. Show the formation of a peptide bond with an equation.
5. Mention the biological importance of lipids.
6. Write about the preparation and properties of glucose.
7. How is the structure of fructose determined ?
8. Write short notes on the manufacture of Soap and Wax ?

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SUMMARY :
The molecules, which form the basis of our life, are complex molecules
called biomolecules which in turn combine and form the living beings,
carbohydrates, proteins, nucleic acids and lipids are biomolecules.
Carbohydrates are polyhydroxy aldehydes or polyhydroxy ketones. They
are naturally occuring organic substances.
Proteins are complex polyamides formed from amino acids. They are
essential for proper growth and maintenance of body. They contain many
peptide –CO–NH– bonds. Therefore, proteins are long polymers of amino
acids linked by peptide bonds.
Amino acids are the compounds which contain carboxylic acid group
and amino group. Amino acids form proteins. Except glycine all the α-amino
acids are optically active. The dipolar form of aminoacid is called Zwitter
ion. The pH at which the amino acid shows no tendency to migrate when
placed in an electric field is known as isolectric point.

REFERENCES :
1. Organic Chemistry by Morrison and Boyd.

2. Chemistry of natural products by O.P. Agarwal Vol. I and II.

______

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 22. CHEMISTRY IN ACTION
LEARNING OBJECTIVES
@ To know the applications of chemistry for overcoming numerous problems
faced by the mankind in various fields.
@ To learn the uses of chemical compounds in the field of medicine as
anesthetics, analgesics, antipyretics, antiseptics and antimalarials, etc.
@ To study the nature of Dyes and their applications.
@ To know the applications of chemical compounds as food preservatives,
artificial sweetening agents, antioxidants.
@ To know about rocket propellants.
@ To learn about the modern chemical industry's chief product - polymers.
A detailed account of types, preparation and uses of polymers are given.

We find ourselves associated with hundreds of things which are either

chemical in nature themselves or have their origin in chemistry. Thus, the
proverb, ‘‘Chemistry is not for chemists alone’’ is true in its absolute term.
It has helped in overcoming a large number of problems faced by the mankind
in recent past, in the fields of food, shelter and disease.
To a common man, however, this contribution of chemistry remains
unknown though not unnoticed. Here, in this unit, a brief account of
‘‘chemistry in action’’ is presented.

22.1 MEDICINAL CHEMISTRY

The chemical compounds which exert, various physiological effects of
therapeutic value are called drugs. Drugs fall into two general categories :
(i) The drugs that are used in the treatment and cure of any specific
disease.
(ii) The drugs that have some characteristic effect on the animal organism,
but do not have any remedial effect for a particular disease. This class includes,
morphine, cocaine etc.

388
 The effects of the drugs belonging to the first category are described by
the term chemotherapy.
Treatment of certain diseases by destroying the invading organism
without damaging the cells of the host, by the use of certain organic
compounds in known as chemotherapy.

1. Anaesthetics
The drugs which produce loss of sensation are called anaesthetics. They
are classified into two types. (i) General anaesthetics are the agent, which
bring about loss of all modalities of sensation, particularly pain along with
‘reversible’ loss of conciousness. (ii) Local anaesthetics prevent the pain
sensation in localised areas without affecting the degree of conciousness.
(i) Nitrous oxide N2O : It is a colourless, inoragnic non-irritating gas.
It is the safest of the anaesthetic agents. This is used after mixing general
anaesthetics like ether.
(ii) Chloroform CHCl3 : Volatile liquid. It has pleasent smell and sweet
taste. With oxygen it forms a toxic carbonyl chloride. Hence it is not used
now.
(iii) Ether : The present form of C2H5–O–C2H5 is a volatile liquid. This
is mixed with stabilizer 0.002% propyl halide. After absorption by tissues it
attacks the central nervous system and makes unconcious.

2. Analgesics
Analgesics are the compounds which relieve all sorts of pains without
the loss of consciousness. These are also called as pain killer, or pain
relievers. These are effective in headaches, myalgia and arthalgia.
Examples : Aspirin, Novalgin are commonly used analgesics. Aspirin
acts both as antipyretic as well as analgesic. Certain narcotics (which produce
sleep and unconsciousness) are also used as analgesics.

3. Antipyretics
Antipyretics are the compounds which are used for the purpose of
reducing fever (lowering the body temperature to the normal). The most

389
common antipyretics are, aspirin, antipyrine, phenacetin, and paracetamol.
Their administration (taking these drugs) often leads to perspiration.
O
OC2H5 OH
||
O – C – CH3
COOH

NHCOCH3 NH–CO–CH3

acetyl salicylic acid phenacetin p-acetamidophenol

(aspirin) (paracetamol)

4. Antiseptic :
Antiseptic is a substance that rendors micro organisms innocuous by
killing them or preventing their growth. This term is used particularly for
preparations applied to living tissues.
(i) Iodoform, CHI3 is used as an antiseptic and its 1% solution is a
disinfectant.
(ii) 0.2 percent solution of phenol acts as an antiseptic and its 1% solution
is a disinfectant.

5. Antiprotozoals (Antimalarial)
Malaria causes shivering and fever. The body temperature rises to 103-
106oF. It causes physical weakness with the side-effects in lever and also
causes aneamia.
Extracts of certain plants, specially the roots and stems, are extensively
used as antimalarial. Cinchona bark which gives rise to quinine acts as
antimalarial. The last antimalarial discovered in 1961 is pyrimethamine.
However, quinine, primaquine and chloroquine are some of the best
antimalarials.
Chloroquine is used specially to control malarial parasite of the ovale
vivax etc. It is not used in curing the disease. It is used as a mixture with
other antimalarials.

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6. Antibiotics
Many microorganisms (bacteria, fungi and moulds) produce certain
chemicals which inhibit the growth or metabolism of some other
microorganism. Such chemical compounds are known as antibiotics. These
need be present only in low concentration to be effective in their antibiotic
action. The first antibiotic, discovered by Alexander Fleming in1929, from
mould Penicillium notatum, was penicillin.
There are three main sources of antibiotics.
(i) Bacteria (ii) Fungi and (iii) Actinomycetes

Penicillins
Penicillins is the name given to the mixture of natural compounds having
the molecular formula C9H11N2O4 S - R, and differing only in the nature of
R. Depending upon the nature of R, there are at least six natural penicillins.
Uses. Penicillin is extensively used for rheumatic fever, narrowing of
heart wall, bronchitis, and pneumonia etc.

7. Antacids
Quite often, after eating oily and spicy food, one may feel uncomfortable
due to some burning sensation in stomach/food pipe. This is due to the
imbalance in the acidity in the stomach.
Certain drug formulations provide relief from such burning sensation.
These are known as antacids.
Antacids are available in tablet as well as gel/syrup forms. These antacids
contain magnesium and aluminium hydroxides, in addition to flavouring
agents and colour.

8. Antispasmodics
There are a group of medicines that include natural bellodona alkaloids
(atropine, bellodona).

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 These medicines are used to relieve cramps, spasms of the stomach,
intestines and bladder. Some are used with antacid, or other medicine in the
treatment of peptic ulcer. These medicine prevent nausea, vomiting and
motion sickness. In certain surgical and emergency procedure, these are
used to help relax stomach and intestine for certain types of examination or
diagnosis.
Example : Anisotropine, Atropine, Dicyclomine, Cindinium cap

22.2 DYES
Since time immemorial, human beings have been fascinated by colour.
In the beginning, the colour materials were extracted from vegetable sources.
Now a days, such substances are synthesized in factories through simple
chemical reactions.
Dyes are coloured compounds used in imparting colour to textiles, food
stuffs etc. A dye should have the following characteristics.
(i) It should have a suitable colour.
(ii) It should be able to fix itself or be capable of being fixed to the fabric.
(iii)It should be fast to light.
(iv)It should be resistant to the action of water, dilute acids and alkalies
(all detergents and washing soaps are alkaline in nature).
Many natural dyes have been known for a long time. These were obtained
from vegetable sources. Now a days, practically all the dyes are synthetic,
and are prepared from aromatic compounds obtained from coal tar. Therefore,
such dyes are sometimes called as coal tar dyes.

22.3 Colour and Structure of Dyes

The relationship between the colour of a substance and its structure
was explained by a German scientist Otto Witt (1876) through the
chromophore and auxochrome theory. According to this theory,
(i) An organic compound appears coloured due to the presence of certain
unsaturated groups (the groups with multiple bonds) in it. Such groups with
multiple bonds are called chromophores.

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 Some typical chromophores are,
O |
Nitro –N Azoxy –N=N→O Carbonyl >C=O

O
Azo –N = N– Quininoid Polyene –(HC=CH)n–

(ii) The compounds containing the chromophore group is called

chromogen. The colour intensity increases with the number of chromophores
or the degree of conjugation. For example, ethene (CH2 = CH2) is colourless,
but the compound CH3 – (CH = CH)6 – CH3 is yellow in colour.
(iii) The presence of certain groups which are not chromophores
themselves, but deepen the colour of the chromogen. Such supporting groups
are called auxochromes. Auxochromes may be acidic (phenolic) or basic.
Some important auxochromes are –OH, –NH2, –NHR, NR2.
The presence of an auxochrome in the chromogen molecule is essential
to make it a dye. However, if an auxochrome is present in the meta position
to the chromophore, it does not affect the colour. For example, in the
compound p-hydroxyazobenzene (a bright red dye),

N=N OH

(a) azobenzene, N=N is the chromogen

(b) diazo group, –N=N– is the chromophore

(c) hydroxyl group, –OH is auxochrome

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22.4 CHEMICALS IN FOOD
Foods can also be preserved by using certain chemical substances which
can kill the food spoiling microorganisms. These chemical substances either
directly kill such organisms, or produce some other chemical substance in
the preserved food which then kills the food spoiling microorganisms. This
method of food preservation is called chemical preservation.
A chemical substance which prevents the spoilage of food material by
destroying the food-spoiling microorganisms in it is called a food
preservative.
Sodium benzoate, and potassium metabisulphite are used for food
preservation.
Sodium benzoate is used to preserve fruit juices and squash as sodium
benzoate is soluble in water. It kills the food spoiling microorganisms.
Potassium meta-bisulphite is used for preserving the colourless fruits
like apple, litchi, mango chutney and lemon squashes etc. Potassium
metabisulphite reacts with the acid of fruit/juice and produces SO2, which
kills the microorganisms.

22.4.1 Artificial Sweetening Agents

Mono and disaccharides are sweet in taste. Sweetness is commonly
associated with sugars. However, certain organic compounds which have
been synthesized in laboratories are known to be many times sweeter than
canesugar. Such compounds are called artificial sweetening agents or
artificial sweetners.
Some commonly used artificial sweetners are, (i) Saccharin, (ii) Dulcin,
(iii) Cyclamate, (iv) Nectarin and (v) Sucralose

22.4.2 Antioxidants
The substances that act against oxidants are called antioxidants.
Antioxidants thus minimise the damage caused by oxidants. Antioxidants
protect us against cardiovascular disease, cancer and cataract and they slow
down the effect of ageing. The most important antioxidants are vitamin C,
vitamin E and β-carotene.

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 Antioxidants act as radical inhibitors. These antioxidants can be used as
food preservatives. Vitamin E is a naturally occurring preservative found in
vegetable oil.

22.5 ROCKET PROPELLANTS

Rockets have been in use since early fifty’s. Russians used powerful
rockets to put their space vehicles in space. United States of America used
Saturn rockets for their Apollo space missions. India has recently launched
its satellite launch vehicle SLV-3 from Sriharikota.
Rocket motors are used both in space vehicles and in offensive weapons
such as missiles. The propulsion system in most space vehicles consists of
rocket engines powered by chemical propellants. These also called rocket
propellants.
Propellants are combustible compounds which on ignition undergo rapid
combustion to release large quantities of hot gases. A propellant is a
combination of an oxidiser and a fuel.
Working of a propellant. When a propellant is ignited, it burns to produce
a large quantity of hot gases. These gases then come out through the nozzle
of the rocket motor. The passage of gases through the nozzle of the rocket
motor, provides the necessary thrust for the rocket to move forward according
to the Newton’s Third law of Motion (to every action, there is an equal and
opposite reaction).
Some of the examples for propellents are Hydrazine, Liquid hydrogen,
Polyurethane, etc.
22.6 POLYMERS :
A polymer is a giant molecule obtained by intermolecular combination
of a large number of small molecules of the same or different type.

22.6.1 Polyalkenes
Polyalkenes are the polymers which are derived from unsaturated
hydrocarbons containing double bond. Important polymers of this class are :
(a) Polyethylene, (polyethene). It is obtained from ethylene (ethene).
Ethene polymerizes under high pressure and high temperature to give
polyethene (also called polyethylene). This polymerization is catalysed by
traces of oxygen or organic peroxides.

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 peroxide, high temp.
nCH2 = CH2 – (– CH2 – CH2 –)n
ethene high pressure polyethene

(b) Polystyrene. This polymer is obtained from the monomer styrene

(C6H5 – CH = CH2). The mechanism of polymerization is similar to that for
other alkene polymers.
nC6H5 – CH = CH2 – (– CH2 – CH –)n –
styrene |
C6H5
polystyrene

Properties and Uses : Polystyrene is good transparent polymer. It is

used for hot-drink cups, toys, household articles, etc.
(c) Synthetic rubbers. Synthetic rubbers obtained from butadiene are :
(i) Buna rubbers (ii) Butyl rubbers

Buna rubbers
Buna rubbers are obtained as a result of polymerisation / copolymerisation
of butadiene with acrylonitrile or styrene. There are two types of Buna-
rubbers.
Buna-S. It is obtained by the polymerization of butadiene and styrene
in presence of sodium metal.
Na
nCH2=CH–CH=CH2 + nCH = CH2 – (– CH2–CH=CH – CH2 – CH – CH2 – )n–
butadiene | |
C6H5 C6H5
styrene buna-S

In the name Buna-S, Bu stands for butadiene, na for sodium (acting as

polymerization initiator), and S- for styrene.
Buna-S is also called General Purpose Rubber Styrene (GRS). In actual
practice, it is obtained as a result of copolymerisation of three parts of
butadiene with one part of styrene.
Properties and Uses : Neoprene and Buna-S are extremely resistant
towards wear and tear and used for the manufacture of tyres, rubber tubes
and other mechanical rubber goods.

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 Buna-N. It is obtained as a result of copolymerisation of two parts of
butadiene with one part of acrylonitrile in the presence of sodium metal. The
reaction is,
Na
2CH2 = CH – CH = CH2 + CH2 = CH –(– (CH2 – CH – CH2 – CH – CH – CH2– )n–
| | | |
CN CH CH CN
|| ||
CH2 CH2
butadiene acrylonitrile Buna-N
Properties and Uses : Buna-N rubber is hard and extremely resistant
to the swelling action of oils (petrol), solvents, heat etc. Therefore, it is used
for the manufacture of storage tanks for the solvents.

22.6.2 CONDENSATION POLYMERS

Some important condensation polymers of commercial/industrial interest
are described below.

(i) Polyesters
The polymers having ester linkage are known as polyesters. Some
important polyesters are : Terylene (dacron) and glyptal.

(ii) Polyamides
The polymers having an amide linkage between their monomers are
called polyamides. Typical polyamide polymers are described below.

(a) Nylon-66. It is obtained by condensing adipic acid with

hexamethylenediamine with the elimination of water molecule. The chain
length depends upon the temperature and time for which the process is carried
out.
O O H H O O
|| || | | || ||
nH2N (CH2)6 NH2 + nHO–C–(CH2)4–C–OH – –N–(CH2)6–N–C–(CH2)4–C –n–

hexamethylenediamine adipic acid nylon-66

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 The polyamides are identified by numbers. These numbers refer to the
number of carbon atoms in diamine and in the dibasic acid. As in the above
case, the carbon atoms are 6 in each case, therefore, the product is described
as nylon-66.
Properties and Uses : Nylon-66 is a linear polymer, and has very high
tensile strength. It shows good resistance to abrasion. Nylon-66 is usually
fabricated into sheets, bristles for brushes and in textile. Crinkled nylon fibres
are used for making elastic hosiery.
22.6.3 Formaldehyde Resins
Formaldehyde resins are typical thermosetting plastics. This class of
plastics include phenol-formaldehyde, urea-formaldehyde and melamine-
formaldehyde resins. On heating, these resins become highly cross-linked
thereby forming infusible and insoluble product.
SELF EVALUATION
(A) Choose the correct answer :
1. The substance capable of absorbing blue light from the visible radiation
would appear
(a) yellow (b) yellow-green (c) red (d) blue
2. The unsaturated group(s) present in an organic compound is/are called
(a) chromogens (b) auxochromes
(c) no specific name (d) chromophores
3. If an auxochrome does not affect the colour of the chromogen, it should
be present in the ................ position relative to chromophore.
(a) para- (b) meta- (c) ortho- (d) same-
4. In the compound, O2N–C6H4–N=N–C6H4–N(CH3)2, the chromophore
is
(a) –NO2 (b) – N = N – (c) – NO2 and –N = N – (d) –N (CH3)2
5. Diazonium salts give coupling reactions with
(a) alcohol (b) aromatic amines (c) all amines (d) amines and phenols
6. Substances which bring the body temperature down to normal
temperature are known as
(a) antipyretics (b) analgesics (c) antibiotics (d) none
7. The compound which acts both as antipyretic as well as analgesic is
(a) phenacetin (b) sulpha drugs (c) paracetamol (d) aspirin
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8. A 1% solution of phenol is a
(a) antiseptic (b) disinfectant (c) antimalarial drug (d) antihistamine
9. The medicine used for curing rabies is called
(a) antibacterial (b) antiviral (c) antifungal (d) antibiotics
10. The substance that function as a moisture barrier between the skin and
the atmosphere is called
(a) preservative (b) emulsifier (c) anticaking agent (d) moisturizer
(B) Answer in one or two sentences :
1. Define chemotherapy.
2. What are anaesthetics ? Give one example.
3. In what way antipyretics are important.
4. Why Iodoform and phenolic solutions are called antiseptic ?
5. Give two examples of antimalarials.
6. What are antibiotics ?
7. In what way antacids are important ?
8. What are antipasmodics ?
9. Give any two characteristics of Dye.
10. What are chromophores ? Give two examples.
11. What are artificial sweetening agents ? Give two examples.
12. What is Buna-S ?
(C) Answer not exceeding sixty words :
1. Write briefly on antibiotics ? In what way antipasmodics are helpful ?
2. Explain briefly on characteristics of rocket propellants.
SUMMARY :
The chemicals which can cure several diseases are called drugs. Medicinal
chemistry deals with action of various chemical compounds which are used
as drug. Each drug is unique in character. Anaesthetics, analgesics,
antipyretics, antimalarials, antacids, antispasmodics are very important. The
nature of dyes and the relation between colour and structure of dyes.
Chemicals used in food, are also dealt with. Rocket propellants are discussed
briefly. A detailed account on polymers like, addition, condensation polymers,
discussed.
REFERENCES :
1. Biochemistry by Leninger.
2. Pharmaceutical Chemistry by Ghosh.
__________
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 GENERAL REFERENCES
TO ORGANIC CHEMISTRY
1. Organic Chemistry - Graham Solomons, Craig Fryhle & Robert Johnson,
John Wiley & Sons - 7th edition.

2. Solutions Manuel - Graham Solomons, Craig Fryhle & Robert Johnson,

John Wiley & Sons - 7th edition.

3. Schaum’s Solved Problems Series in Organic Chemistry -

Tata McGraw-Hill Edition - 2003.

4. Problems in Organic Chemistry - Mrs. Rosenbe, Raja & Publication.

5. Keynotes in Organic Chemistry - Andrew. F. Pearson. Black Well

Publishers.

6. Stereochemistry of Carbon Compounds - Ernest I. Eliel. Tata McGraw-

Hill Edition Publishing Co.

7. Organic reactions, Conversions, Mechanism & Problems. - R.D. Madan,

S.Chand & Co. Ltd.

8. A guide book to Mechanism in organic chemistry. - Peters Sykes -

Pearson Education Ltd.

9. Organic Chemistry - G. Mac Loudon - Oxford University Press - 2002.

10. Text Book of Organic Chemistry - P.L. Soni.

11. Text Book of Organic Chemistry - Bahl and Arun Bahl.

12. A Text Book of Pharmaceutical Chemistry - Jayashree Ghosh - S.Chand

& Co.

GGGGG

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