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Brilliant Preparatory

Section, Sitamarhi
XII Chemistry Advanced Study Material
Inorganic Chemistry
1 Atomic Structure II
2 Periodic Classification II
3 p Block Elements
4 d Block Elements
5 f Block Elements
6 Coordination Compounds and Bio-Coordination Compounds
7 Nuclear Chemistry
Physical Chemistry
8 Solid State II
9 Thermodynamics II
10 Chemical Equilibrium I
11 Chemical Kinetics II
12 Surface Chemistry
13 Electro Chemistry
Organic Chemistry
14 Isomerism in Organic Chemistry
15 Hydroxy Derivatives
16 Ethers
17 Carbonyl Compounds
18 Carboxylic Acids
19 Organic Nitrogen Compounds
20 Biomolecules
21 Chemistry in Action

Session : 2015-17

Office: Rajopatti, Dumra Road, Sitamarhi(Bihar), Pin-843301


Ph.06226-252314, Mobile: 9431636758, 9931610902

1. ATOMIC STRUCTURE - II
Learning Objectives
( To study the dual property of electron and understand the
property through experiments.
( To derive the de-broglie relation and learn its significance.
( To learn Heisenbergs uncertainty principle.
( To study Molecular Orbital Theory and its application to
Homodiatomic and Heterodiatomic molecules.
( To understand the concept of Hybridisation and Hybridisation of
s, p and d orbitals.

CHRONOLOGY OF ATOMIC STRUCTURE


1.

Dalton(1808)

: Discovery of atom

2.

Julius Plucker (1859)

: First discoverer of cathode rays

3.

Goldstein(1886)

: Discovered anode rays and proton

4.

Sir.J.J.Thomson(1897)

: Discovered electron and determined


charge/mass(e/m) ratio for electron

5.

Rutherford(1891)

: Discovered nucleus and proposed


atomic model

6.

MaxPlanck(1901)

: Proposed quantum theory of radiation

7.

RobertMillikan(1909)

: Determined charge of an electron

8.

H.G.J.Mosely(1913)

: Discovered atomic number

9.

Niels Bohr(1913)

: Proposed a new model of atom

10. Clark Maxwell(1921)

: Electromagnetic wave theory

11. de-Broglie(1923)

: Established wave nature of particles

12. Pauli(1927)

: Discovery of neutrino

13. Werner Heisenberg(1927) : Uncertainty Principle


14. James Chadwick(1932)

: Discovery of neutron

15. Anderson(1932)

: Discovery of positron

16. Fermi(1934)

: Discovered antineutrino

17. Hideki Yukawa(1935)

: Discovered mesons

18. Segre(1955)

: Discovered antiproton

19. Cork and Association(1956) : Discovered antineutron

Progress of Atomic Models

In 1803, John Dalton, proposed his atomic theory. He suggested that atoms
were indivisible solid spheres.

J.J.Thomson proposed that an atom was a solid sphere of positively charged


material and negatively charged particles, electrons were embedded in it
like the seeds in a guava fruit. But later this concept was proved wrong.

Rutherford suggested the planetary model, but this model was rejected.

In 1913, Neils Bohr proposed that electrons revolve around the nucleus in
a definite orbit with a particular energy. Based on the facts obtained from
spectra of hydrogen atom, he introduced the concept of energy levels of
atom.

In 1916 Sommerfeld modified Bohrs model by introducing elliptical orbits


for electron path. He defined sub energy levels for every major energy level
predicted by Bohr.

The concept of Quantum numbers was introduced to distinguish the orbital


on the basis of their size, shape and orientation in space by using principal,
azimuthal, magnetic and spin quantum numbers.

From the study of quantum numbers, various rules are put forward for
filling of electrons in various orbitals by following

Aufbau principle

Pauli exclusion principle and

Hunds rule of maximum multiplicity.

In 1921 Burry and Bohr gave a scheme for the arrangement of electrons in
an atom. Further the nature of electron (s) is studied.

1.1 DUAL PROPERTY OF AN ELECTRON


In case of light, some phenomena like interference, diffraction etc., can be
explained if light is supposed to have wave character. However certain other
phenomena such as black body radiation and photo electric effect can be explained
only if it is believed to be a stream of photons i.e., has particle character. Thus
light is said to have a dual character. Such studies on light were made by Einstein
in 1905.
Louis de Broglie, a French Physicist, in 1924, advanced the idea that like
photons, all material particles such as electron, proton, atom, molecule, a piece
of chalk, a piece of stone or iron ball possessed both wave character as well as
particle character. The wave associated with a particle is called a matter wave.
1.1.1

Difference between a particle and a wave

The concept of a particle and a wave can be understood by the different


points of distinction between them.
PARTICLE

WAVE

1. A particle occupies a well-defined 1. a wave is spread out in space e.g. on throwing


position in space i.e a particle is
a stone in a pond of water, the waves start
localized in space e.g. a grain of
moving out in the form of concentric circles.
sand, a cricket ball etc.
Similarly, the sound of the speaker reaches
everybody in the audience. Thus a wave is
delocalized in space.
2. When a particular space is occupied 2. Two or more waves can coexist in the same
by one particle, the same space
region of space and hence interfere.
cannot be occupied simultaneously
by any other particle. In other
words, particles do not interfere.
3. When a number of particles are 3. When a number of waves are present in a
present in a given region of space,
given region of space, due to interference, the
their total value is equal to their
resultant wave can be larger or smaller
sum i.e it is neither less nor more.
than the individual waves i.e. interference may
be constructive or destructive.
4

1.1.2 Experiments to prove particle and wave property of Electrons


a) Verification of Wave character
i) Davisson and Germers Experiment
In 1927 Davisson and Germer observed that, a beam of electrons obtained
from a heated tungsten filament is accelerated by using a high positive potential.
When this fine beam of accelerated electron is allowed to fall on a large single
crystal of nickel, the electrons are scattered from the crystal in different directions.
The diffraction pattern so obtained is similar to the diffraction pattern obtained
by Braggs experiment on diffraction of X-rays from a target in the same way
(Fig. 1.1).
D iffr action p attern
P h o to g ra p h ic
p la te
m
ea s
t b on
en ctr
c id le
In of e

Nickel crystal
Fig.1.1 Electron diffraction experiment by Davisson and Germer
Since X-rays have wave character, therefore, the electrons must also have
wave character associated with them. Moreover, the wave length of the electrons
as determined by the diffraction experiments were found to be in agreement with
the values calculated from de-Broglie equation.
From the above discussion, it is clear that an electron behaves as a wave.
ii)

Thomsons experiment

G.P. Thomson in 1928 performed experiments with thin foil of gold in place
of nickel crystal. He observed that if the beam of electrons after passing through
the thin foil of gold is received on the photographic plate placed perpendicular to
the direction of the beam, a diffraction pattern is observed as before (Fig. 1.2).
This again confirmed the wave nature of electrons.
5

Thin foil
of Gold

Fig. 1.2 Diffraction of electron beam by thin foil of gold (G.P. Thomson
experiment)
b)

Verification of the particle character

The particle character of the electron is proved by the following different


experiments:i)

When an electron strikes a zinc sulphide screen, a spot of light known as


scintillation is produced. A scintillation is localized on the zinc sulphide screen.
Therefore the striking electron which produces it, also must be localized
and is not spread out on the screen. But the localized character is possessed
by particles. Hence electron has particle character.

ii)

Experiments such as J.J.Thomsons experiment for determination of the ratio


of charge to mass (i.e. e/m) and Milliken oil drop experiment for
determination of charge on electron also show that electron has particle
character.

iii)

The phenomenon of Black body radiation and Photoelectric effect also prove
the particle nature of radiation.
6

1.2 de-Broglie Relation


The wavelength of the wave associated with any material particle was
calculated by analogy with photon as follows :In case of a photon, if it is assumed to have wave character, its energy is
given by
E = h (according to the Plancks quantum theory)

...(i)

where is the frequency of the wave and h is Plancks constant.


If the photon is supposed to have particle character, its energy is given by
E = mc2 (according to Einstein equation)

...(ii)

where m is the mass of photon and c is the velocity of light.


From equations (i) and (ii), we get
But

or

h.c/

=
=
=
=

mc2
c/
mc2
h / mc

de Broglie pointed out that the above equation is applicable to any material
particle. The mass of the photon is replaced by the mass of the material particle
and the velocity c of the photon is replaced by the velocity v of the material
particle. Thus, for any material particle like electron, we may write
= h / mv or = h / p
where mv = p is the momentum of the particle.
The above equation is called de Broglie equation and is called de
Broglie wavelength.
Thus the significance of de Broglie equation lies in the fact that it relates the
particle character with the wave character of matter.
Louis de-Broglies concept of dual nature of matter finds application in the
construction of electron microscope and in the study of surface structure of solids
by electron diffraction. The de-Broglies concept can be applied not only to
electrons but also to other small particles like neutrons, protons, atoms, molecules
etc.,
7

Significance of de-Broglie waves


The wave nature of matter, however, has no significance for objects of
ordinary size because wavelength of the wave associated with them is too small
to be detected. This can be illustrated by the following examples.
i)

Suppose we consider an electron of mass 9.1 10-31 kg and moving with a


velocity of 107 ms-1. Its de-Broglie wavelength will be;
h
6.626 10-34 kg m2s-1
= __ = __________________
mv
9.1 10-31 kg 107 ms-1

= 0.727 10-10m = 7.27 10-11m

This value of can be measured by the method similar to that for the
determination of wave length of X-rays.
ii)

Let us now consider a ball of mass 10-2 kg moving with a velocity of


102 ms-1. Its de-Broglie wave length will be;
h
6.626 10-34 kg m2s-1
= __ = ________________ = 6.62 10-34m
mv
10-2 kg 102 ms-1

This wavelength is too small to be measured, and hence de-Broglie relation


has no significance for such a large object.
Thus, de-Broglie concept is significant only for sub-microscopic objects in
the range of atoms, molecules or smaller sub-atomic particles.
Problem 1
The kinetic energy of sub-atomic particle is 5.85 10-25J. Calculate the
frequency of the particle wave. (Plancks constant, h = 6.626 10-34 Js)
Solution
K.E. = mv2 = 5.85 10-25J
h
By de-Broglie equation, = ___
mv
But

v
= __

v
h
__ = ___

mv

mv2
or = ___
h

2 5.85 10-25 J
____________
6.626 10-34 JS

1.77 109 s-1

Problem 2
Calculate the de-Broglie wavelength of an electron that has been accelerated
from rest through a potential difference of 1 kV
Solution
Energy acquired by the electron (as kinetic energy) after being accelerated
by a potential difference of 1 kV (i.e 1000 volts)
= 1000 eV
= 1000 1.609 10-19 J, (1 eV) = 1.609 10-19 J)
(Energy in joules = Charge on the electron in coulombs Pot. diff. in volts)
= 1.609 10-16 J
i.e. Kinetic energy
1
2
16
mv = 1.609 10 J
2

or

1
9.110 31 v 2 = 1.609 10 16 J
2

or

v 2 = 3.5361014

or

v = 1.88 10 7 ms 1

h
6.626 10 34
=
mv 9.110 31 1.88 10 7
= 3.87 10-11 m
9

Problem 3
Calculate the wavelength associated with an electron (mass 9.1 10-31 kg)
moving with a velocity of 103m sec-1 (h=6.626 10-34 kg m2 sec-1).
Solution
Here we are given
m = 9.1 10-31 kg
v = 103 m sec-1
h = 6.626 10-34 kg m2 sec-1

h
6.626 1034
=
=
mv (9.11031 ) 103
= 7.25 10-7 m
Problem 4
A moving electron has 4.55 10-25 joules of kinetic energy. Calculate its
wavelength (mass = 9.1 10-31 kg and h = 6.626 10-34 kg m2 s-1).
Solution
Here we are given
Kinetic energy i.e.

1
mv 2 = 4.55 10 25 J
2

m = 9.1 10-31 kg
h = 6.626 10-34 kg m2 s-1

1
(9.110 31 )v 2 = 4.55 10 25
2

4.55 10 25 2
= 10 6
31
9.1 10

or

v2 =

or

v = 103 m sec1

10

h
6.626 1034
=
mv (9.11031 )103
= 7.25 10-7 m.

Problem 5
Calculate the kinetic energy of a moving electron which has a wavelength of
4.8 pm. [mass of electron = 9.11 10-31 kg, h = 6.626 10-34 Kg m2 s-1].
Solution
According to de-Broglie equation,

h
mv

v=

h
6.626 1034 kg m 2 s 1
=
= 1.516 108 ms 1
31
12
m 9.1110 kg 4.8 10 m

or

v=

h
m

1
1
Kinetic energy = mv2 = 9.111031 kg (1.516108 ms1 ) 2
2
2

= 10.47 10-15 kg m2 s-2 = 1.047 10-14 J


Problem 6
Two particles A and B are in motion. If the wavelength associated with the
particle A is 5 10-8m, calculate the wavelength of particle B, if its momentum
is half of A.
Solution
According to de-Broglie relation,
=

h
p

or

p =

h
For particle A, p A =
A

11

Here, pA and A are the momentum and wavelength of particle A.


h
For particle B, p B =
B
Here pB and B are the momentum and wavelength of particle B.
1
pA
2

But,

pB =

h 1 h
=
B 2 A
A
1
=
B
2

But

or

B = 2A

A = 5 10-8 m
B = 2A = 2 5 10-8 m = 10 10-8 m = 10-7 m.

Problem for practice


1.

Calculate the momentum of a particle which has a de-Broglie wavelength of


1A. [h = 6.626 10-34 kg m2 s-1]
[Ans. : 6.63 10-24 kg ms-1]

2.

What is the mass of a photon of sodium light with a wavelength of 5890 ?


[h= 6.626 10-34 Js]
[Ans. : 3.75 10-36 kg]

3.

Calculate the wavelength of 1000 kg rocket moving with a velocity of 300


km per hour.
[Ans.: 7.92 10-39 m]

4.

What must be the velocity of a beam of electrons if they are to display a deBroglie wavelength of 100?
[Ans. : 7.25 104 ms-1]

5.

The wavelength of a moving body of mass 0.1 mg is 3.31 x 10-29m. Calculate


its kinetic energy (h = 6.626 x 10-34 Js).
[Ans : 2 10-3 J]
12

6.

Calculate the wavelength of a particle of mass m = 6.62 10-27 kg moving


with kinetic energy 7.425 10-13 J (h = 6.626 10-34 kg m2 sec-1).
[Ans. : 6.657 10-15 m]

7.

Calculate the wavelength of an electron in a 10 MeV particle accelerator


(1 MeV = 106eV).
[Ans. : 0.39 pm]

8.

What will be the wavelength of oxygen molecule in picometers moving with


a velocity of 660 ms-1 (h = 6.626 10-34 kg m2 s-1).
[Ans. : 18.8 pm]

9.

A moving electron has 4.9 10-25 joules of kinetic energy. Find out its de Broglie wavelength (Given h = 6.626 10-34 Js; me = 9.1 10-31 kg).
[Ans. : 7 10-7 m]

1.3 THE UNCERTAINTY PRINCIPLE


The position and the velocity of the bodies which we come across in our
daily life can be determined accurately at a particular instant of time. Hence the
path or trajectories of such bodies can be predicted. However, Werner Heisenberg
in 1927 pointed out that we can never measure simultaneously and accurately
both the position and velocity (or momentum) of a microscopic particle as small
as an electron. Thus, it is not possible to talk of trajectory of an electron. This
principle, which is a direct consequence of the dual nature of matter and radiation,
states that, it is impossible to measure simultaneously both the position
and velocity (or momentum) of a microscopic particle with absolute
accuracy or certainty.
Mathematically, uncertainty principle can be put as follows.
x.p

h
4

where, x = uncertainity in the position of the particle and


p = uncertainity in the momentum of the particle.
The sign means that the product of x and p can be either greater than
or equal to h/4 but can never be less than h/4.

13

Example 1
Calculate the uncertainty in the velocity of a wagon of mass 3000kg
whose position is known to an accuracy of 10 pm (Plancks constant =
6.626 1034 Kg m2 s-1.
Solution : ere we are given
m

= 3000 kg

x = 10 pm
= 10 10-12 m = 10-11 m
y uncertainty principle,
v =

h
4 m x

6.626 10 34
=
22
4 3000 10 11
7
10-27ms-1
= 1.76
Example 2
Calculate the uncertainty in the position of an electron if the uncertainty in its
velocity is 5.7 105 m/sec (h = 6.626 10-34 kg m2 s-1, mass of the electron
= 9.1 1031 kg).
Solution:

Here we are given


v = 5.7 10 5 ms-1
m = 9.1 10 31 kg
h = 6.626 10 34 kg m2 s-1

Substituting these values in the equation for uncertainty principle


i.e. x (m v) =
we have x =

h
4

h
4 m

14

6.626 10 34

22
9.110 31 5.7 105
7
= 1.0 10-10 m
i.e Uncertainty in position = 10-10 m.
4

PROBLEMS FOR PRACTICE


1.

The approximate mass of an electron is 10-27 g. Calculate the uncertainty in


its velocity if the uncertainty in its position were of the order of 10-11 m .
[Ans: 5.25 x 106 m sec-1]

2.

Calculate the product of uncertainity in position and velocity for an electron


of mass 9.1 x 10-31 kg according to Heisenberg uncertainty principle.
[Ans: 5.77 x 10-5 m2 sec-1]

3.

Calculate the uncertainty in velocity (v ) of a cricket ball (mass = 0.15 kg)


if the uncertainty position (x ) is of the order of 1 (i.e. 10-10 m).
[Ans: 3.5x10-24 m sec-1]

4.

Using uncertainity principle,calculate the uncertainty in velocity of an electron


if the uncertainty in position is 10-4 m.
[Ans: 0.577 m sec-1]

5.

The uncertainity in the position of a moving bullet of mass 10 g is


10-5 m.Calculate the uncertainty in its velocity .
[Ans: 5.25 x 10-28 m sec-1]

1.4 THE WAVE NATURE OF ELECTRONS


It has been made clear that, if a substance is divided into finer and finer
pieces, we reach molecules and atoms, then we realize that the atoms consist of
electrons and nuclei. It has been clarified that matter is a collection of ultra
microscopic particles. Upto the 19th century, these particles were considered to
move obeying Newtonian mechanics and Maxwellian electromagnetism.
However, this view point has became doubtful after the proposal of the Bohr
model of the atomic structure (Bohrs quantum theory).
On the other hand, light had been considered to be electromagnetic waves.
However, after the discovery of light quanta (photons), it was clarified that
15

the light has wave nature at one time and particle nature at another time. Therefore,
light has a kind of duality.
The idea of deBroglie wave nature waves or deBroglie matter waves is
based on the fact that light has both wave and particle nature. Hence particle like
electron or proton can also be considered to be particle with wave nature.
Einsteins relations which connect the particle and wave aspects in light
quanta
h
(1)

would be satisfied for de Broglie matter waves as well. Therefore the relations,
Eq.(1), are often called Einstein-de Broglies relations.

E = h,

p=

If we apply these relations to the case of the Bohr model of the hydrogen
atom, we can well understand its possibility as follows. If we consider that the
electron in a hydrogen atom moves at constant speed along a circular orbit around
the nucleus (proton), the quantum condition in Bohrs quantum theory is written
as Eq(2). By using Einsteins relation p = h/ in this equation, the quantum
condition is written
2a = n,

(n = 1, 2, 3, ....)

(2)

This equation means that the circumference of the circular orbit of the electron
must be a integral multiple of the wavelength of de Broglie wave. In other word,
de-Broglie wave accompanying the motion of the electron should be continuous.
Therefore, we can easily understand the quantum condition that determines the
stationary states by considering the continuity of de Broglie waves (See the
following figure).
Bohrs quantum condition. The condition
for stationary states
The circumference of the circular orbit of
the electron should be an integral multiple of
the wavelength of de Broglie wave,
otherwise the wave cannot be smoothly
continuous.

16

Energy of electron in an atom. By applying Schrodinger wave equation


to hydrogen atom, the energy of electron (En) was found as :
2 2 me4
En = 2 2
(1)
n h
where n is the principal quantum number. This expression is same as Bohrs
equation for energy of electron in a hydrogen atom.
Substituting the values of m, e and h in relation (1), we get
1312
kJ mol 1
2
n
Significance of negative electronic energy
En =

(2)

The energy of an electron at infinity is arbitrarily assumed to be zero. This


state is called zero-energy state. When an electron moves and comes under the
influence of nucleus, it does some work and spends its energy in this process.
Thus, the energy of the electron decreases and it becomes less than zero ie., it
acquires a negative value.
Example 1
The ionization energy of hydrogen atom in the ground state is 1312 kJ mol-1.
Calculate the wavelength of radiation emitted when the electron in hydrogen
atom makes a transition from n = 2 state to n = 1 state (Plancks constant,
h = 6.626 10-34 Js; velocity of light, c = 3 108 m s-1; Avogadros constant,
NA = 6.0237 1023 mol-1).
Solution
I.E. of hydrogen atom in the ground state = 1312 kJ mol-1
Energy of hydrogen atom in the first orbit (E1) = -I.E = -1312 kJ mol-1
Energy of hydrogen atom in the nth orbit (En) =

- 1312
kJ mol 1
2
n

1312
= -328 kJ mol-1
22
E = E 2 E1 = [328 (1312)] kJ = 984 kJ mol1

Energy of hydrogen atom in the second orbit (E2) =

Energy released per atom =

E
N

=
17

984103 J/atom
6.02371023

E
c
= h = h ;
N

Nh1c
E

6.6261034 Js 3 108 ms1 6.0237 1023


=
= 1.2 10-7 m
984 103 J
Example 2
The electron energy of hydrogen atom in the ground state works out to be
2.18 10-18 J per atom. Calculate what will happen to the position of the
electron in this atom if an energy of 1.938 10-18 J is supplied to the each hydrogen
atom.
Solution
Energy of H atom in the ground state = -2.18 10-18 J atom-1
Energy added = 1.938 10-18 J atom-1
Energy of electron in the excited state = (-2.18 + 1.938) 10-18 J atom-1
= -0.242 10-18 J atom-1

2.181018 J atom1
0.24210 J atom =
n2
18

2.18 1018 J atom1


= 9,
n =
0. 242 1018 J atom1
Hence electron will get excited to third shell.
2

n=3

Example 3
Calculate the ionisation energy of hydrogen atom as well as energy needed
to promote its electron from first energy level to third energy level.
Solution
The energy of electron in hydrogen atom is given by the expression,
i)

Ionisation energy is the amount of energy required to remove an electron


from neutral gaseous atom i.e. to shift the electron from n = 1 to n =
When n = 1, E1 = -1312 kJ mol-1;

n = ,

E = 0

Ionisation energy = E - E1 = 0 - (-1312 kJ mol-1) = + 1312 kJ mol-1


18

ii)

Energies of electron when present in n = 1 and n = 3 are :


E1 =

1312
= 1312 kJ mol 1
12

E3 =

1312
= 146 kJ mol 1
32

Energy needed to promote an electron from


n = 1 to n = 3 is, E where E = E3 - E1 = [-146 - (-1312)] kJ mol-1
= 1166 kJ mol-1
Shapes of orbitals
An orbital is the region of space around the nucleus within which the
probability of finding an electron of given energy is maximum .The shape of this
region (electron cloud) gives the shape of the orbital. The plot of angular wave
functions or square of angular wave functions (probability functions) give us the
shapes of orbitals.These two plots differ only slightly. Let us consider the individual
shapes.
Shape of s-orbitals
For s-orbitals, when l = 0, the value of m is 0 i.e., there is only one possible
orientation. This means that the probability of finding an electron is the same in all
directions at a given distance from the nucleus. It should, therefore, be spherical
in shape. Hence all s- orbitals are non- directional and spherically symmetrical
about the nucleus.
The size of an s-orbital depends upon value of the principal quantum number
n. Greater the value of n larger is the size of the orbital.

Fig. 1.3 Shapes of 1s and 2s-orbitals


19

An important feature of the 2s-orbital is that there is a spherical shell within


this orbital where the probability of finding the electron is zero (nearly). This is
called a node or nodal surface. In 2s orbital there is one spherical node. The
number of nodal surfaces or nodes in s-orbital of any energy level is equal to
(n-1), where n is the principal quantum number.
Shape of p-orbitals
For p-subshell l = 1, there are three values of m namely -1, 0, +1. It
means that p orbitals can have three possible orientations. These three p-orbitals
are equal in energy (degenerate state) but differ in their orientations. Each
p-orbital consists of two lobes symmetrical about a particular axis. Depending
upon the orientation of the lobes, these are denoted as 2px , 2py and 2pz accordingly
as they are symmetrical about X,Y and Z - axis respectively.
The lines in the figure represents the cross-section of the three dimensional
boundary surface of p-orbitals. The boundary surface means the surface which
encloses 90 percent of the dots representing the electrons. Two lobes of each porbital are separated by a nodal plane (a plane having zero electron density). For
example, for 2px orbital, YZ plane is the nodal plane x .

Fig.1.4Shapes of 2px, 2py and


2pz orbitals

Fig. 1.5 Nodal plane for


2px orbital

Thus, p-orbitals have dumb-bell shape and have directional character. The
probability of finding the electron is equal in both the lobes. The p-orbitals of
higher energy levels have similar shapes although their size are bigger.
Shape of d-orbitals
For d-subshell, l = 2, there are five values of m namely -2, -1, 0, 1, 2. It
20

means d- orbitals can have five orientations. These are represented by dxy, dyz,
dzx, dx2-y2 and dz2; for example, 3dxy, 3dyz, 3dzx, 3dx2-y2 and 3dz2. The dxy, dyz and
dzx orbitals have same shape i.e., clover leaf shape but they lie in XY, YZ and ZXplanes respectively.The dz2 orbital is symmetrical about Z-axis and has a dumb bell shape with a doughnut shaped electron cloud in the centre. The
dx2-y2 orbital is also clovar leaf shaped but its leaves are directed along the X and
Y- axis.
The reason for the presence of four lobes in any nd orbital lies in the fact that
the d - orbitals have two nodes, and hence two changes in algebraic sign of ,
which lead to four lobes.
y

yx

d xy

d yz

d xz

d x 2 -y 2

d z2

Fig. 1.6 Shapes of d-orbitals


1.5 MOLECULAR ORBITAL THEORY
Molecular orbital theory was put forward by Hund and Mullikan in 1932.
This theory is modern and more rational. This theory assume that in molecules,
atomic orbitals lose their identity and the electrons in molecules are present in
new orbitals called molecular orbitals. A brief outline of this theory is given below:
(i) In a molecule, electrons are present in new orbitals called molecular orbitals.
(ii) Molecular orbitals are formed by combination of atomic orbitals of equal
energies (in case of homonuclear molecules) or of comparable energies (in
case of heteronuclear molecules).
(iii) The number of molecular orbitals formed is equal to the number of atomic
orbitals undergoing combination.
(iv) Two atomic orbitals can combine to form two molecular orbitals. One of
these two molecular orbitals one has a lower energy and the other has a
higher energy. The molecular orbital with lower energy is called bonding
molecular orbital and the other with higher energy is called anti bonding
molecular orbital.
21

(v) The shapes of molecular orbitals depend upon the shapes of combining
atomic orbitals.
(vi) The bonding molecular orbitals are represented by (sigma), (pi), (delta)
and the antibonding molecular orbitals are represented by , , *.
(vii) The molecular orbitals are filled in the increasing order of their energies,
starting with orbital of least energy. (Aufbau principle).
(viii) A molecular orbital can accommodate only two electrons and these two
electrons must have opposite spins. (Pauls exclusion principle).
(ix) While filling molecular orbitals of equal energy, pairing of electrons does
not take place until all such molecular orbitals are singly filled with electrons
having parallel spins. (Hunds rule).
1.5.1 Energy level diagram for molecular orbitals
In case of homonuclear diatomic molecules, combination of two 1s atomic
orbitals of participating atoms give rise to two new molecular orbitals designated
as 1s and *1s. In the same manner the 2s and three 2p-orbitals of each atom
i.e., eight atomic orbitals can give rise to eight new molecular orbitals viz.,
2s , *2s , 2p x , *2p x , 2p y , *2p y , 2p z , *2p z .
Atomic Structure and Chemical Bonding
Energy levels of these molecular orbitals have been determined
experimentally by spectroscopic studies.The order of increasing energy in case
of the diatomic homonuclear molecules of first and second period of the periodic
table is as given below:
1s < 1s* < 2s < *2s < 2p x = 2p y < 2p z < *2p x = *2p y < *2p z
This order of energies of various molecular orbitals is valid for molecules or
ions like, H2, H2+, He2+, He2 (hypothetical), Li2, Be2 (hypothetical), B2, C2 and
N2 molecules. This energy diagram for the molecular orbitals is shown in Fig.1.7a.
However, experimental evidence for oxygen and heavier diatomic molecules have
shown that above sequence of energy levels of MOs is not correct. In case of
these elements, the order of energy levels of 2p z , 2px and 2py is reversed i.e.,
2p z has lesser energy than 2p x or 2p y . Thus, the order of increasing energy of
MOs for these molecules is as follows.
1s < 1s* < 2s < *2s < 2p z < 2p x = 2p y < *2p x = *2p y < *2p z
22

This order of energies of various MOs is valid for molecules or ions like O2,
O (super oxide ion), O22- (peroxide ion), F2 and Ne2 (hypothetical). This energy
level diagram for MOs is shown in Fig.1.7(b).
2

Fig. 1.7a Molecular orbital energy


level diagram for diatomic homonuclear
molecules of first and second period
(except O2, F2 etc.)

Fig. 1.7b.Molecular orbital


energy level diagram for
homonuclear diatomic
molecules of O2 and other
heavier elements
1.5.2 Electronic configuration of a molecule and its correlation with
molecular behaviour
The distribution of electrons among various molecular orbitals is called
electronic configuration of a molecule. It can give us very important information
about the molecules as explained below.

1. Stability of a molecule in terms of a number of electrons in bonding


and antibonding molecular orbitals. From the electronic configuration it is
possible to find out the number of electrons in bonding molecular orbitals(Nb)
and number of electrons in antibonding molecular orbitals (Na).
(a) If Nb>Na, the molecule is stable : This is evident because in this case
the influence of bonding electrons will be more than the influence of antibonding
electrons, resulting in a net force of attraction.
(b) If Nb< Na, the molecule is unstable : This is again obvious because
in this case the influence of antibonding electrons will be more than the influence
23

of bonding electrons, resulting in a net force of repulsion.


(c) If Nb = Na, the molecule is unstable : This is because in this case the
influence of bonding electrons will be equal to the influence of antibonding electrons
resulting in no net force of attraction.
2. Bond order and stability of a molecule or an ion. The stability of a
molecule or an ion can also be determined from another parameter called bond
order. Bond order may be defined as half the difference between the number of
electrons in bonding molecular orbitals (Nb) and the number of electrons in
antibonding molecular orbitals (Na) i.e,
1
(N N a )
2 b
The resulting molecule or ion will be stable if Nb > Na i.e., if bond order is
positive. The resulting molecule or ion will be unstable if Nb Na i.e, if bond
order is negative or zero.

Bond Order =

3. Relative stability of molecules or ions in terms of bond order : The


stability of a molecule or an ion is directly proportional to bond order. Thus, a
molecule with bond order 3 (e.g., N2) is more stable (i.e., has a higher bond
dissociation energy) than a molecule with bond order 2 (e.g., O2) or 1 (e.g., Li2).
4. Nature of bond in terms of bond order : A chemical bond can be
single, double or triple but cannot be a fraction, on the otherhand bond order can
be a fraction.
5. Bond length in terms of bond order : Bond length is found to be
inversely proportional to bond order. Greater the bond order, shorter the bond
length and vice versa.
For example, the bond length in nitrogen molecule (bond order = 3) is
shorter than in oxygen molecule (bond order = 2), which in turn is shorter than in
hydrogen molecule (bond order = 1).

24

Table 1.

Bond order, Bond dissociation energy and bond length in N2,


O2 and Li2 molecules

Molecule

Bond order

Bond dissociation energy

Bond length

Nitrogen

945 kJ mol-1

110 pm

-1

121 pm

-1

267 pm

Oxygen
Lithium

495 kJ mol

110 kJ mol

6. Diamagnetic and paramagnetic nature of the molecule : If all the


electrons in the molecule are paired then the substance is diamagnetic in nature.
On the other hand, if the molecule has unpaired electron(s) it is paramagnetic in
nature.
1.5.3 Molecular orbital energy level diagrams of certain diatomic
homonuclear molecules and molecular ions
The filling of molecular orbitals is governed by the following principles.
(i) Aufbau principle (ii) Paulis exclusion principle and (iii) Hunds rule of maximum
multiplicity. Now, let us consider some examples of homonuclear diatomic
molecules.
1. Hydrogen molecule, H2. It is formed by the combination of two
hydrogen atoms. Each hydrogen atom in the ground state has one electron in 1s
orbital. Therefore, in all there are two electrons in hydrogen molecule which are
present in lower most 1s molecular orbital. According to Paulis exclusion
principle, these two electrons should have opposite spins.
The molecular orbital electronic configuration of hydrogen molecule is (1s)2.
The molecular orbital energy level diagram of H2 molecule is given in
Fig. 1.8.

Fig. 1.8 Molecular orbital energy level diagram of H2 molecule


The bond order of H2 molecule can be calculated as follows.
Here,

N b = 2 and Na = 0
25

Bond order =

Nb Na 2 0
=
= 1.
2
2

i)

Nature of bond : This means that the two hydrogen atoms in a molecule of
hydrogen are bonded by a single covalent bond.

ii)

Diamagnetic character : Since no unpaired electron is present in hydrogen


molecule, it is diamagnetic in nature.

2. Diatomic helium molecule, He2 (Hypothetical). The electronic


configuration of helium (Z = 2) in the ground state is 1s2. As each helium atom
contains two electrons, there will be four electrons in He2 molecule. Keeping in
view the Aufbau principle and Paulis exclusion principle its electronic configuration
would be as follows.
He2 : (1s)2 (*1s)2.
The molecular orbital energy level diagram of He2 (hypothetical) is given in
Fig. 1.9.

Fig. 1.9 Molecular orbital energy level diagram of He2 (hypothetical)


molecule
Here,

Nb = 2 and Na = 2

Nb Na 2 2
=
= 0.
2
2
As the bond order for He2 comes out to be zero, this molecule does not
exist.

Bond order =

3. Nitrogen molecule (N2). The electronic configuration of nitrogen (Z=7)


in the ground state is 1s 2 2s 2 2p1x 2p1y 2p1z . Therefore, the total number of electrons
present in nitrogen molecule (N2) is 14. These 14 electrons can be accommodated
in the various molecular orbitals in order of increasing energy.
26

N 2 : KK( 2s ) 2 (*2s ) 2 ( 2p x ) 2 ( 2p y ) 2 ( 2p z ) 2
Here (1s ) 2 (1s* ) 2 part of the configuration is abbreviated as KK, which
denotes the K shells of the two atoms. In calculating bond order, we can ignore
KK, as it includes two bonding and two antibonding electrons.
The molecular orbital energy level diagram of N2 is given in Fig. 1.10.

Fig. 1.10 Molecular orbital energy level diagram of N2


The bond order of N2 can be calculated as follows.
Here,
Nb = 8 and Na = 2
N Na 8 2

=
= 3.
Bond order = b
2
2
i) Nature of bond : A bond order of 3 means that a triple bond is present in
a molecule of nitrogen.
ii) Diamagnetic nature : Since all the electrons in nitrogen are paired, it is
diamagnetic in nature.
4. Oxygen molecule, O2. The electronic configuration of oxygen (Z = 8)
in the ground state is 1s22s22p4. Each oxygen atom has 8 electrons, hence, in O2
27

molecule there are 16 electrons. Therefore, the electronic configuration of O2 is


as follows.
O 2 : KK( 2s ) 2 (*2s ) 2 ( 2p z ) 2 ( 2p x ) 2 = ( 2p y ) 2 (*2p x )1 = (*2p y )1
Here (1s ) 2 (1s* ) 2 part of the configuration is abbreviated as KK.
The molecular orbital energy level diagram of O2 molecule is given in Fig.1.11.

Fig. 1.11 Molecular orbital energy level diagram of O2 molecule

1.6

Bond order =

Nb Na 8 4
=
= 2.
2
2

HYBRIDISATION

Hybridization is the concept of intermixing of the orbitals of an atom having


nearly the same energy to give exactly equivalent orbitals with same energy, identical
shapes and symmetrical orientations in space.
The new equivalent orbitals formed are known as the hybrid orbitals or
hybridized orbitals. Hybrid orbitals have properties entirely different from the
properties of the original orbitals from which they have been obtained.
28

Salient Features regarding Hybridisation


i)
ii)
iii)
iv)
v)
vi)
vii)
viii)

Orbitals involved in hybridization should have nearly the same energy.


The orbitals of one and the same atom participate in hybridization.
The number of hybrid orbitals formed is equal to the number of hybridizing
orbitals.
The hybrid orbitals are all equivalent in shape and energy.
A hybrid orbital which is taking part in bond formation must contain one
electron in it.
Due to the electronic repulsions between the hybrid orbitals, they tend to
remain at the maximum distance apart.
The head on overlap of atomic orbitals give sigma () bonds.
The sidewise or lateral overlap of atomic orbitals give pi () bonds.

1.6.1 Tips to Predict the Type of Hybridisation in a Molecule or Ion (Other


than Complex Ions)
Step 1 : Add the number of valence electrons of all the atoms present in the
given molecule/ion.
Step 2 : In case of a cation, subtract the number of electrons equal to the charge
on the cation and in case of an anion, add number of electrons equal to the
charge on the anion.
Step 3 : (i) If the result obtained in step 2 is less than 8, divide it by 2 and find the
sum of the quotient and remainder.
(ii) If the result obtained in step 2 lies between 9 and 56, divide it by 8 and
find the first quotient (Q1). Divide the remainder R1 (if any) by 2 and find the
second quotient (Q2). Add all the quotients and the final remainder (R2).
Let the final result obtained in (i) or (ii) be X. The type of hybridisation is
decided by the value of X as follows :
Value of X
Type of hybridisation

2
sp

3
sp2

4
sp3

5
6
3
sp d sp3d2

Example
i)

BeCl2
Total valence electrons = 2 + 7 2 = 16
16
= 2(Q1 ) + zero(R 1 ) ;
8
29

X=2

7
sp3d3

Hybridisation = sp
ii)

BF3
Total valence electrons = 3 + 7 3 = 24
24
= 3(Q1 ) + zero(R 1 ) ;
8
Hybridisation = sp2

iii)

X=3

NH3
Total valence electrons = 5 + 3 = 8 ;

X=

8
=4
2

X=

8
=4
2

Hybridisation = sp3
iv) H2O
Total valence electrons = 2 + 6 = 8 ;
Hybridisation = sp3
v)

PCl5
Total valence electrons = 5 + 7 5 = 40
40
= 5(Q1 ) + zero(R 1 ) ;
8
Hybridisation = sp3d

X=5

vi) SF6
Total valence electrons = 6 + 7 6 = 48
48
= 6(Q 1 ) + 0(R 1 ) ; X = 6
8
Hybridisation = sp3d2

vii) IF7
Total valence electrons = 7 + 7 7 = 56

56
= 7(Q1) + 0(R1) ;
8
Hybridisation = sp3d3

30

X=7

viii) NO2- ion


Total valence electrons = 5 + 2 6 = 17
Charge = -1. Total electrons = 17 + 1 = 18

18
2
= 2(Q1) + 2(R1) ;
= 1(Q2) + 0(R2) ; X = 2+1+0=3
8
2
Hybridisation = sp2
ix) NO3- ion
Total valence electrons = 5 + 3 6 = 23; Charge = -1
Total electrons = 23 + 1 = 24

x)

24
= 3(Q 1 ) + 0(R 1 ) ; X = 3
8
Hybridisation = sp2
CO32Total valence electrons = 4 + 3 6 = 22; Charge = -2
Total electrons = 22 + 2 = 24

24
= 3(Q 1 ) + 0(R 1 ) ; X = 3
8
Hybridisation = sp2
xi) SO42Total valence electrons = 6 + 4 6 = 30; Charge = -2
Total electrons = 30 + 2 = 32
32
= 4(Q 1 ) + 0(R 1 ) ; X = 4
8
Hybridisation = sp3

xii) ICl4Total valence electrons = 7 + 7 4 = 35; Charge = -1


Total electrons = 35 + 1 = 36
36
4
= 4(Q1 ) + 4(R 1 ) ; = 2(Q 2 ) + 0(R 2 ) ; X = 4 + 2 + 0 = 6
8
2

31

Hybridisation = sp3d2
xiii) NH4+
Total valence electrons = 5 + 4 = 9; Charge = +1
Total electrons in NH4+= 9 - 1 = 8
8
= 4(Q 1 ) + 0(R 1 ) ;
2
Hybridisation is sp3

X = 4

Hybridisation in some Typical Molecules and Ions


Hybridisation

Examples

sp

Be F2, BeCl2, C2H2, CO2

sp2

SO2, BH3, BF3, NO2-, NO3-, CO32-

sp3

NH3, H2O, CH4, CCl4, SiCl4, H3O+,NH4+, ClO2-,


ClO3-, ClO4-,NF3

sp3d

PCl5, ClF3, SF4, XeF2

sp3d2

SF6, XeF4, XeOF4, BrF5

sp3d3

IF7, XeF6

1.7 INTERMOLECULAR FORCES


The ionic, covalent and coordinate bond arises due to attractive forces
between atoms. Vander Waal (Dutch physicist, 1873) was the first to propose
the existence of attractive forces between the atoms of inert gases with fully filled
orbitals. These forces also exist between non-polar molecules as well as polar
molecules. The attractive interactions between the molecules are responsible for
bringing the molecules close together. The attractive interactions between the
different molecule of a substance are called intermolecular forces. The magnitude
of these forces is maximum in the solids and decreases on passing from solid to
liquids and from liquid to gaseous state. Vander Waal successfully explained the
liquefaction of gases on the basis of inter molecular forces. These forces are
purely electrostatic and thus physical in nature.

32

Hydrogen bonding. Hydrogen bonding comes into existence as a result of


dipole-dipole interactions between the molecule in which hydrogen atom is
covalently bonded to a highly electronegative atom. Therefore, the conditions for
the effective hydrogen bonding are :
i) high electronegativity of the atom bonded to hydrogen atom so that bond
is sufficiently polar.
ii) small size of the atom bonded to hydrogen so that it is able to attract the
bonding electron pair effectively.
If the atom bonded to hydrogen has low value of electronegativity and/or
large atomic size, dipole-dipole interactions are not strong enough to allow effective
hydrogen bonding.
Only nitrogen, oxygen and fluorine form strong hydrogen bonds because
they have high value of electronegativity and small atomic size.
Strength of H-bonds. It is a weak bond because it is merely an electrostatic
force and not a chemical bond. Its strength depends upon the electronegativity of
atom to which H atom is covalently bonded. Since electronegativity of F > O >
N, the strength of H- bond is in the order H - F ......... H > H-O.....H > HN.....H. Hydrogen bonds are much weaker than covalent bonds. The bond
strength of different bonds is in the order : Ionic bond > Covalent bond >
Hydrogen bond > dipole-dipole interactions, Vander Waals (London forces).
Types of Hydrogen bonds
There are two different types of hydrogen bonds as :
i) Intermolecular hydrogen bonding. This type of bond is formed
between the two molecules of the same or different compounds. Some examples
of the compounds exhibiting intermolecular hydrogen bonds are :
+ 1. Hydrogen fluoride, H - F. In the solid state, hydrogen fluoride consists
of long zig-zag chains of molecules associated by hydrogen bonds as shown
below :
F
F
F
H
H
H
H
Therefore, hydrogen fluoride is represented as (HF)n.
33

+
2
O H

2. Water H
. In water molecule, the electronegative oxygen atom
+

forms two polar covalent bonds with two hydrogen atoms. The oxygen atom
due to its higher electronegativity acquires partial negative charge and the two
hydrogen atoms acquire partial positive charge. The negatively charged oxygen
forms two hydrogen bonds with two positively charged hydrogen atoms of two
neighbouring molecules. Each oxygen atom is tetrahedrally surrounded by four
hydrogen atoms as shown below :

Hydrogen bonding in water results in a hydrogen bridge (H-O-H) network


extending in three dimensions and the associated water molecule may be expressed
as (H2O)n.
ii) Intramolecular hydrogen bonding. This type of bond is formed
between hydrogen atom and N, O or F atom of the same molecule. This type of
hydrogen bonding is commonly called chelation and is more frequently found in
organic compounds. Intramolecular hydrogen bonding is possible when a six or
five membered rings can be formed.
H
O

O
C

O
OH

O
C

O-Nitrophenol

Salicylic Acid
34

Salicylaldehyde

Intramolecular hydrogen bonding (chelation) decreases the boiling point of


the compound and also its solubility in water by restricting the possibility of intermolecular hydrogen bonding.
Importance of H-bonding
i)

Life would have been impossible without liquid water which is the result of
intermolecular H-bonding in it.
ii) Hydrogen bonding increase the rigidity and strength of wood fibres and
thus makes it an article of great utility to meet requirements of housing,
furniture, etc.
iii) The cotton, silk or synthetic fibres also own their rigidity and tensile strength
to hydrogen bonding.
iv) Most of our food materials such as carbohydrates and proteins also consist
of hydrogen bonding.
v) Hydrogen bonding also exists in various tissues, organs, skin, blood and
bones.
SELF EVALUATION
A. Choose the correct answer
1.

a)
2.

313.6
, If the value of Ei = -34.84 to which value n corresponds
n2
4
b)
3
c) 2
d) 1

En =

Dual character of an electron was explained by


a) Bohr

3.

c) de-Broglie

d) Pauli

de-Broglie equation is
a)

4.

b) Heisenberg

mv
h

b)

= hmv

c)

hv
m

d)

The value of Bohr radius for hydrogen atom is


a) 0.529 10-8 cm
c) 0.529 10-6 cm

b) 0.529 10-10 cm
d) 0.529 10-12 cm

35

h
mv

5.

Which of the following particle having same kinetic energy, would have the
maximum de-Broglie wave length
a) -particle

c) -particle

b) proton

d) neutron

6.

If the energy of an electron in the second Bohr orbit of H-atom is -E, what
is the energy of the electron in the Bohrs first orbit?
a) 2E
b) -4E
c)
-2E
d)
4E

7.

The energy of electron in an atom is given by En =


2 2 me 4
n 2h 2

d)

2 me4
n 2h 2

The bond order of oxygen molecule is


a) 2.5
b) 1
c)

d)

The hybridisation in SF6 molecule is


a) sp3
b) sp3d2

sp3d

d)

sp3d3

a)
8.
9.

4 2 me 4
n 2h 2

b)

2 2 me 2
n 2h 2

c)

c)

10. The intramolecular hydrogen bonding is present in


a) o-nitrophenol
b) m-nitro phenol c) p-nitrophenol d) None
B. Answer in one or two sentences
11. What do you understand by the dual character of matter?
12. State Heisenbergs uncertainty principle.
13. What is the significance of negative electronic energy?
14. Define an orbital.
15. What are molecular orbitals?
16. Why He2 is not formed?
17. What is bond order?
18. Define hybridisation.
C. Answer not exceeding 60 words
19. Discuss the Davisson and Germer experiment.
20. Derive de-Broglies equation. What is its significance?
36

21. Discuss the shapes of s, p and d orbitals.


22. Briefly explain Molecular Orbital Theory.
23. Explain the formation of O2 molecule by molecular orbital theory.
Summary
This chapter explains the dual nature of matter. de-Broglie equation is derived
and its significance is discussed. Heisenberg uncertainty principle is explained.
Schrodingers wave equation and wave functions are explained.
Molecular orbital theory and its application to certain homo diatomic and
hetero diatomic molecules are discussed. The concept of hybridisation of atomic
orbitals and its applications are discussed. Different types of forces exist between
molecules are explained.
References
1)

Theoretical principles of Inorganic Chemistry-G.S.Yanker, 9th Edn-1993.

2)

Selected topics in Inorganic Chemistry - V.Mallik, G.D.Tuli and R.D.Madan,


6th Ed. - 2002.

3)

Concise Inorganic Chemistry - J.D.Lec, 3rd Ed. - 1977 and 5th Ed. 2002.

37

2. PERIODIC CLASSIFICATION - II
Learning Objectives
( To recall the periodic properties Atomic/Ionic radii, Ionisation Energy,
Electron affinity and electronegativity.
( To learn the calculation of atomic and ionic radii using different
parameters.
( To study the methods of determination of ionisation potential and
differentiate I, II and III ionisation potential.
( To know how to explain the factors affecting ionisation potential with
specific examples.
( To understand the methods to determine the electron affinity and factors
affecting electron affinity.
( To analyse the various scales of electronegativity values using simple
relations.

38

2.1 REVIEW OF PERIODIC PROPERTIES


Repetition of properties of elements at regular intervals in the periodic table
is called periodicity in properties. The periodicity is mostly due to similar outermost
electronic configuration of the elements. Some of the properties are briefly
reviewed.
2.1.1 Atomic and Ionic radii
Atomic or Ionic radius is generally defined as the distance between the
centre of the nucleus and the outermost shell of electrons in an atom or ion.
As we move from left to right across a period, there is regular decrease in
atomic and ionic radii of the elements. This is due to the increase in the nuclear
charge and the additive electrons are added to the same electronic level. On
moving down a group both atomic and ionic radii increase with increasing atomic
number. The increase in size is due to introduction of extra energy shells which
outweigh the effect of increased nuclear charge.
2.1.2 Ionisation Energy (Ionisation Potential)
The energy required to remove the most loosely bound electron from an
isolated atom in the gaseous state in known as Ionisation Energy.

Atom(g) Energy
Positive Ion(g) + Electron
The ionisation energy of an atom depends on the following factors (i) size of
the atom (ii) charge on the nucleus (iii) screening effect of inner electrons (iv)
penetration effect of electrons (v) effect of half-filled and completely filled
sublevels.
In a period, the value of ionisation potential increases from left to right with
breaks where the atoms have somewhat stable configurations. In a group, the
ionisation potential decreases from top to bottom.
2.1.3 Electron affinity
Electron affinity or electron gain enthalpy is the amount of energy released
when an isolated gaseous atom accepts an electron to form a monovalent gaseous
anion.
Atom (g) + Electron Anion (g) + Energy
39

Electron gain enthalpies generally increase on moving from left to right in a


period. Electron gain enthalpies generally decrease on moving down the group.
2.1.4 Electronegativity
Electronegativity may be defined as the relative tendency of an atom in a
molecule to attract the shared pair of electrons towards itself.
In a period, electronegativity increases on moving from left to right. This is
due to the reason that the nuclear charge increases whereas atomic radius
decreases. In a group, electronegativity decreases on moving down the group.
This is due to the effect of the increased atomic radius.
2.1.5 Anomalous periodic properties
A few irregularities that are seen in the increasing values of ionisation potential
along a period can be explained on the basis of the concept of half-filled and
completely filled orbitals.
2.2 CALCULATION OF ATOMIC RADIUS (COVALENT RADIUS)
Atomic radius is the distance from the centre of the nucleus to the point
where the electron density is effectively zero.
a.

Homonuclear diatomic molecules

In case of homonuclear diatomic molecules of A2 type (e.g. F2, Cl2, Br2, I2


... etc.) the bond length, d(A-A) is given by
d(A A) =

r(A) + r(A)

d(A A) =

2 r(A)

r(A)

d(AA)
______
2

The above equation shows that in the case of homonuclear diatomic molecule
of A2 type, the covalent radius of an atom A, r(A) is equal to one half of the internuclear distance, d(A-A). Therefore, the covalent radius of an atom in a
homonuclear diatomic molecule can be obtained by dividing the internuclear
distance by two.

40

Example
1.

Cl2 molecule
The value of ClCl bond distance as found experimentally is 1.98. Thus
r(Cl) =

2.

d(Cl Cl) 1.98


=
= 0.99
2
2

Diamond

The value of d(CC) distance as found experimentally in a variety of saturated


hydrocarbons is 1.54.
r(C) =

Thus
b.

d(C C ) 1.54
=
= 0.77
2
2

Heteronuclear diatomic molecule

In case of heteronuclear diatomic molecule of AB type, bond length


d(A B) is given by
d(A B) = r(A) + r(B)
r(A) and r(B) are the covalent radii of A and B atoms.
Example
i)

CCl4 molecule
The experimental value of d(C Cl) is 1.76
Thus

d(CCl) = r(C) + r(Cl)


r(C) = d(C Cl) r(Cl)
= 1.76 r(Cl)

Thus the covalent radius of carbon atom can be calculated by subtracting


the covalent radius of Cl atom from d(CCl) bond length. The covalent radius of
Cl atom can also be obtained, provided that covalent radius of C atom is known.
ii)

SiC
The experimental value of d(Si-C) is 1.93 . Thus,
d(Si C) =

r(Si) + r(C)
41

r(Si)

=
=
=
=

d(Si C) r(C)
1.93 r(C)
1.93 0.77 [ r(C) = 0.77 ]
1.16

The experimental values of covalent bond length for some common


homonuclear diatomic molecules are given below.
Molecule
i)
ii)
iii)
iv)
v)

Bond

H2
F2
Cl2
Br2
H3C-CH3

Bond length ()

HH
FF
ClCl
BrBr
CC

0.74
1.44
1.98
2.28
1.54

2.2.1 Calculation of ionic radii


Paulings Method
Pauling has calculated the radii of the ions on the basis of the observed
internuclear distances in four crystals namely NaF, KCl, RbBr and CsI. In each
ionic crystal the cations and anions are isoelectronic with inert gas configuration.
NaF crystal

: Na+ - 2, 8
F - 2, 8

Ne type configuration

KCl crystal

: K+
Cl

Ar type configuration

- 2, 8, 8
- 2, 8, 8

Further the following two assumptions are made to assign the ionic radii.
i) The cations and anions of an ionic crystal are assumed to be in contact
with each other and hence the sum of their radii will be equal to the inter nuclear
distance between them.
r(C+) + r(A) = d (C+A)
where
r(C+)

- radius of cation, C+

r(A)

- radius of anion, A
42

(1)

d(C+A) - internuclear distance between C+ and A ions in C+A ionic


crystal
ii) For a given noble gas configuration, the radius of an ion is inversely
proportional to its effective nuclear charge. i.e.
r(C + )

1
Z (C + )

(2)

r(A )

1
Z (A )

(3)

where,
Z*(C+) & Z*(A) are the effective nuclear charges of cation (C+) and anion
(A-) respectively. On combining (2) & (3)

r(C+ )
r(A )

Z* (A )
Z* (C + )

(4)

Hence the above two equations (1) & (4) can be used to evaluate the
values of r(C+) and r(A) provided that the values of d(C+A), Z*(C+) and
Z*(A) are known.
Slater rules
The value of screening constant (S) and effective nuclear charge (Z*) can
be calculated by using Slaters rules. According to these rules the value of S
for a given electron is estimated as follows.
i) Write down the complete electronic configuration of the element and
divide the electrons into the following orbital groups starting from the inside of
the atom.
(1s) :

(2s, 2p) : (3s, 3p) : (3d) : (4s, 4p) :

(4d) :

(4f)

: (5s, 5p) : (6s, 6p) .......etc.

ii) Select the electron for which the value of S is to be calculated. For this
calculation add up the contributions to S for the other electrons according to the
following rules.

43

Contribution to S for each


electron of this type

Type of electron
i)

All electrons in groups outside


the electron chosen

ii)

All other electrons in the same


group as the chosen one (n)

0.35
(or 0.30 for 1s electron)

iii)

All electrons in shell immediately inside (n1)

iv) All electrons further inside

0.85
1.00

Calculation of effective nuclear charge (Z*)


Example 1
Calculate the effective nuclear charge experienced by the 4s electron in
potassium atom.
Solution
The electronic configuration of K atom is
K 19 = (1s2) (2s2 2p6) (3s2 3p6) 4s1
Effective nuclear charge (Z*) = Z S
Z* = 19
= 19

[(0.85 No. of electrons in (n 1)th shell) +


(1.00 total number of electrons in the inner shells)]
[0.85 (8) + (1.00 10)]

Z* = 2.20
Example 2
Calculate the effective nuclear charge of the last electron in an atom whose
configuration is 1s2 2s2 2p6 3s2 3p5
Z = 17
Z* = Z S
= 17 [(0.35 No. of other electrons in nth shell)
+ (0.85 No. of electrons in (n 1)th shell)
+ (1.00 total number of electrons in the inner shells)]
44

= 17 [(0.35 6) + (0.85 8) + (1 2)]


= 17 10.9 = 6.1
Calculation of ionic radii
Example
Calculate the ionic radii of K+ and Cl ions in KCl crystal. The internuclear
distance between K+ an Cl- ions are found to be 3.14.
Solution
r(K+) + r(Cl) = d(K+Cl) = 3.14

(1)

K+ and Cl ions have Ar (Z=18) type configuration. The effective nuclear charge
for K+ and Cl can be calculated as follows.
K+

(1s2)
innershell

Z*(K+)

ZS

19 [(0.35 7) + (0.85 8) + (1 2)]

19 11.25 = 7.75

17 [(0.35 7) + (0.85 8) + (1 2)]

17 11.25 = 5.75

Z*(Cl-)

(2s2 2p6)
(n-1)th shell

(3s2 3p6)
nth shell

r(K + ) Z* (Cl ) 5.75


=
=
=0.74
r(Cl ) Z* (K + ) 7.75
r(K+) = 0.74 r(Cl)

(2)

Substitute (2) in (1)


0.74 r(Cl-) + r(Cl) = 3.14
1.74 r(Cl) = 3.14
r(Cl)

3.14
= 1.81
1.74

45

(3)

From (2)
r(K+) = 0.74 r(Cl)
= 0.74 1.81
= 1.33
r(K+) = 1.33
r(Cl) = 1.81
Ionisation potential
Ionisation energy of an element is defined as the amount of energy required
to remove the most loosely bound electron from isolated neutral gaseous atom in
its lowest energy state. The process is represented as
M

(g)

+ Energy supplied

I
1 M

+
(g)

+ e

Ionisation energy is measured in electron volts per atom (eV/atom), kilo calories
per mole (kcal/mole) or kilo joules per mole (kJ/mole).
Successive ionisation potentials
In addition to first ionisation potential (I1) defined above, second, third. etc.
ionisation potentials are also known. Second ionisation potential (I2) is the energy
required to remove one more electron from the gaseous cation, M+(g) to get the
doubly positively charged gaseous cation, M2+(g), i.e.,
M + (g) + I 2 M 2 + (g) + e
Similarly, third ionisation potential (I3) is the energy required to remove still
one more electron from M2+(g) cation to get M3+(g) cation, i.e.
M 2 + (g) + I 3 M 3 + (g) + e

Similarly ionisation potentials of higher and higher grades are also known.
Each successive ionization potential or energy is greater than the previous
one, since the electron must be removed against the net positive charge on the
ion.

46

Factors governing ionization energy. The ionization energy depends upon


the following factors:
(a) Size of atom or ion. The ionization energy decreases with the increasing
size of atom. The larger the size of atom, lesser is the ionization energy. This is
due to the fact that electrons are tightly held in smaller atoms whereas in large
atoms, electrons are held quite loose, i.e., lesser energy is required for removal
of electrons from larger atoms than the smaller one. Hence ionization energy is
lower for larger atoms and higher for smaller atoms.
Example 1
The I.E of Be (At. No.4) is greater than that of Li (At. No.3) because the
nuclear charge of Be (Z=4) is greater than Li(Z=3). Higher the nuclear charge,
greater would be the force of attraction between nucleus and outermost electron.
Hence, the first I.E. of Be is than that of Li.
Example 2
The I.E. of Be is more than that of B though the nuclear charge of boron
atom (Z=5) is greater than that of beryllium atom (Z = 4). This can be explained
as follows:
Boron atom (Z = 5; 1s2 2s2 2px1 2py0 2pz0) is having one unpaired electron
in the 2p-subshell. Be-atom (Z = 4; 1s2 2s2) is having paired electrons in the 2ssubshell.
As the fully filled 2s-subshell in Be-atom is more stable than B-atom due to
symmetry, more energy would be needed to remove an electron from Be-atom.
Hence, Be has high I. E.
3. The I.E. of carbon (At. No.6) more than that of boron (At. No.5)
Reason: Carbon (Z = 6; 1s2 2s2 2px1 2py1 2pz0) is having more nuclear
charge than boron (Z = 5; 1s2 2s2 2px1 2py0 2pz0). In both the cases, one has to
remove electron from same 2p-subshell. Carbon is having more nuclear charge
than boron. Therefore the nucleus of carbon, attracts the outer 2p-electron more
firmly than does boron. Thus, first I.E. of carbon would be more than that of
boron.
(b) Magnitude of nuclear charge. The higher the nuclear charge of
protons in the nucleus, the higher is the ionization energy. Because of the higher
47

nuclear charge, the electrons are bound with more force and hence higher energy
will be required for their removal. For instance, magnesium has higher nuclear
charge (12 protons) as compared to sodium (11 protons). Hence ionization energy
in case of magnesium is higher as compared to sodium.
Similarly the I.E. of fluorine is more than that of oxygen. It can be explained
as follows.
(i) F (Z = 9; 1s2 2s2 2px2 2py2 2pz1) is having more nuclear charge than
oxygen (Z = 8; 1s2 2s2 2px2 2py1 2pz1). In both the cases, the electron has to be
removed from the same 2p-subshell. As fluorine is having more nuclear charge
than oxygen, it means that the nucleus of fluorine will attract the outer 2p-electrons
more firmly than oxygen. Hence, first I.E. of fluorine would be more than that of
oxygen.
(c) Effect of number of electrons in the inner shells. (Screening or
shielding effect). The attractive force exerted by the nucleus on the most loosely
bound electron is atleast partially counterbalanced by the repulsive forces exerted
by the electrons present in the inner shells. The electron to be removed is thus
shielded from the nucleus by the electrons in the inner shell. Thus, the electron in
the valence shell experiences less attraction from the nucleus. Hence the ionisation
energy will be low. This is another reason why ionization energy decreases in
moving down a group.
(d) Effect of shape of orbital. The shape of orbital also influences the
ionization potential. As s-electrons remain closer to the nucleus than p-,d-, and
f-electrons of the same valence shell, the ionization energy decreases in the order
given below:
s>p>d>f
For instance, the first ionization energy of aluminium is lower than that of magnesium.
The electronic configuration of magnesium is [Ne]3s2 and that of aluminium is
[Ne] 3s2 3p1. Thus, one has to remove 3p-electron in case of aluminium and 3s
electron in the case of magnesium. But it is easier to remove the p electron than
the s-electron. Thus, the first ionization energy of aluminium is lower than that of
magnesium.
(e) Effect of arrangement of electrons. The more stable the electronic
arrangement, the greater is the ionization energy. As the noble gases have the
stablest electronic arrangements, they show maximum ionization energy.
48

Example
The I.E of Ne is greater than that of F. It can be explained as follows:
The nuclear charge of Ne (Z = 10) is more than that of F (Z = 9). Greater
the nuclear charge, greater would be the force of attraction between nucleus and
outermost electron. Hence, the first I.E. of neon would be greater than that of
fluorine.
Electron Affinity or Electron gain enthalpy (E.A.)
The electron affinity of an element may be defined as amount of energy
which is released when an extra electron enters the valence orbital of an isolated
neutral atom to form a negative ion.
Atom(g) + Electron(g) Negative ion(g) + Energy
The greater the energy released in the process of taking up the extra electron,
the greater will be the electron affinity. Thus, ionisation potential measures the
tendency of an atom to change into a cation (M M+ + le-) whereas the electron
affinity measures the tendency of an atom to change into anion (X + e- X-).
Successive Electron Affinities. As more than one electron can be
introduced in an atom, it is called second electron affinity for the addition of two
electrons and so on. The first E. A. of active non metals is positive (exothermic)
while the second E. A. even for the formation of oxide or sulphide ion is negative
(endothermic). For example, the overall E.A. for the formation of oxide or sulphide
ions has been found to be endothermic to the extent of 640 and 390 kJ mol-1
respectively.
X-(g) + e- + energy X2-(g)
It is interesting to note that the electron affinity of elements having a d10 s2
configuration has been found to be negative. This is so due to the accommodation
of the electron in the higher p-orbital (Zn = -87 kJ mol-1, Cd = -56 kJ mol-1).
Elements of group 17 possess high electron affinity. The reason for this is
that by picking up an electron halogens attain the stable noble gas electronic
configuration.
The electron affinity is expressed in kJ mol-1.

49

Change of Electron Affinity along a Group. On moving down a group,


the size of atom increases significantly and hence, the effective nuclear attraction
for the electron decreases. Consequently the atom will possess less tendency to
attract additional electrons towards itself. It means that electron affinity would
decrease as we move down a group. In case of halogens the decrease in electron
affinity from chlorine to iodine is due to steady increase in atomic radii from
chlorine to iodine.
On moving down a group the electron affinity decreases. Thus, the electron
affinity of Cl should be less than F. But actually the electron affinity of
F (320 kJ mol-1) is less than Cl (348 kJ mol-1). The reason for this is probably
due to small size of fluorine atom. The addition of an extra electron produces
high electron density which increases strong electron-electron repulsion. The
repulsive forces between electrons results in low electron affinity.
Electron affinities of noble gases are zero. As these atoms possess ns2np6
configuration in their valence shells, these are stablest atoms and there are no
chances for the addition of an extra electron. Thus, the electron affinities of noble
gases are zero.
Electron affinities of beryllium and nitrogen are almost zero. This may be
due to the extra stability of the completed 2s-orbital in beryllium and of the exactly
half-filled p-orbital in nitrogen. As these are stable electronic configurations, they
do not have tendency to accept electrons and therefore, the electron affinities for
beryllium and nitrogen are zero.
Change of Electron Affinity along a Period. On moving across a period,
the size of atoms decreases and nuclear charge increases. Both these factors
favour an increase in force of attraction exerted by the nucleus on the electrons.
Consequently, the atom will possess a greater tendency to attract the additional
electron, i.e., its electronic affinity would increase as we move from left to right.
Due to this reason electron affinities of non-metals are high whereas those of
metals are low.
Of all the metals, the E.A. of gold is comparatively high (222.7 kJ mol-1).
This value may be attributed to the higher effective nuclear charge and poor
shielding of the nucleus by d electrons.

50

Factors affecting electron affinity


(1) Atomic size
Electron affinity

1
Size of atom

Smaller the size of an atom, greater is its electron affinity. As the size of
atom increases, the effective nuclear charge decreases or the nuclear attraction
for adding electron decreases. Consequently, atom will have less tendency to
attract additional electron towards itself. Therefore.
Electron affinity Effective nuclear charge.
In general, electron affinity decreases in going down the group and increases
in going from left to right across the period. On moving down the group atomic
size increases and on going from left to right in a period atomic size decreases.
(2) Shielding or Screening Effect
Electron affinity

1
Shielding effect

Electronic energy state, lying between nucleus and outermost state hinder
the nuclear attraction for incoming electron. Therefore, greater the number of
inner lying state, less will be the electron affinity.
(3) Electronic Configuration - The electronic configurations of elements
influence their electron affinities to a considerable extent.
Electron affinities of inert gases are zero. This is because their atoms have
stable ns2 np6 configuration in their valence shell and there is no possibility for
addition of an extra electron.
Electron affinity of beryllium, magnesium and calcium is practically zero.
This is attributed to extra stability of the fully completed s-orbitals in them. Thus,
if an atom has fully filled or half filled orbitals, its electron affinity will be low.
Example 1
The electron affinities of Be, Mg and N are almost zero because both
Be (Z = 4; 1s2 2s2) and Mg (Z = 12; 1s2 2s2 2p6 3s2) are having s orbital fully
51

filled in their valence shell. Fully filled orbitals are most stable due to symmetry.
Therefore, these elements would be having least tendency to accept electron.
Hence, Be and Mg would be having zero electron affinity.
N (Z = 7 ; 1s2 2s2 2px1 2py1 2pz1) is having half filled 2p-subshell. Half filled
sub shells are most stable due to symmetry (Hunds rule). Thus, nitrogen is having
least tendency to accept electron. Hence, nitrogen is having almost zero electron
affinity.
Example 2
Electron affinity of fluorine is less than that of chlorine. Although the
electron affinity of elements decreases down the group, yet fluorine is having less
electron affinity than chlorine because the size of F-atom (0.71 ) is very small
and has only two shells, i.e., n = 1, 2 (9F = 1s2 2s2 2px2 2py2 2pz1).
i) Because of small size of fluorine atom the 2p-subshell becomes compact.
There occurs repulsion among electrons of the valence shell and also with electron
to be added. This repulsion is responsible for less tendency of F-atom to accept
electron.
ii) Because of small size of fluorine there occurs large crowding of electrons
around the nucleus. This crowding is able to screen the nucleus. Because of this,
effective nuclear charge gets decreased. Thus, the electron is having less attraction
during addition. Hence electron affinity gets decreased.
2.5 ELECTRONEGATIVITY SCALES
Electronegativity scale is an arbitary scale. They are based on various types
of experimental data like bond energy, dipole moment, ionisation potential and
electron affinity. Most commonly used scales are
1. Paulings scale
2. Mullikens scale
3. Sandersons scale
4. Alfred and Rochows scale
Paulings scale (1932)
This scale is based on an empirical relation between the energy of a bond
and the electronegativities of bonded atoms.
52

Consider a bond A-B between two dissimilar atoms A and B of a molecule


AB. Let the bond energies of A-A, B-B and A-B bonds be represented as
EA-A, EB-B and EA-B respectively. It may be seen that the bond dissociation energy
of A-B is almost higher than the geometric mean of the bond dissociation energies
of A-A and B-B bonds i.e.,

E A B > E A A E B B
Their difference () is related to the difference in the electronegativities of
A and B according to the following equation

=
=
(or)

0.208

E A B E A A E B B
(X A X B ) 2
= XA XB

Here, XA and XB are the electronegativities of A and B respectively.


The factor 0.208 arises from the conversion of Kcals to electron volt.
Considering arbitarily the electronegativity of hydrogen to be 2.1, Pauling
calculated electronegativities of other elements with the help of this equation.
Disadvantage of Pauling scale
The disadvantage of Paulings scale is that bond energies are not known
with any degree of accuracy for many solid elements.
Problem
Calculate the electronegativity of chlorine from the following data
EH-H = 104 K cal mol-1 ; ECl-Cl = 36 K cal mol-1
EH-Cl = 134 K cal mol-1
According to Paulings equation

E HCl E H H E Cl Cl

=
=

134 104 36
134 61.18 =

72.82
53

0.208

X Cl X H

X Cl X H

=
=
=
=
=

0.208 72.82
1.77
1.77
1.77 + 2.1
3.87

XCl - 2.1
XCl
2.

[ XH = 2.1]

Mullikens Scale

In 1934, Mulliken suggested an alternative approach to electronegativity


based on ionization energy and electron affinity of an atom. According to this
method electronegativity could be regarded as the average of the ionization energy
and electron affinity of an atom
Electronegativity =

I.E. + E.A
2

Mulliken used ionisation energy and electron affinity values measured in


electron volts and values were found to be 2.8 times higher than Pauling values.
The values of ionisation energy and electron affinity are measured in
kJ mol-1 and 1eV =96.48 kJ mol-1.
Therefore the commonly accepted Pauling values are more nearly obtained
by
Electronegativity =

I.E. + E.A
I.E. + E.A
=
2 2.8 96.48
540

This method has an ordinary theoretical basis and also has advantage that
different values can be obtained for different oxidation states of the same element.
Disadvantage
Although Mullikens scale is less empirical than Pauling Scale, yet it suffers
from a serious disadvantage that electron affinities with the exception of a few
elements are not reliably known.

54

Problem
Calculate the electronegativity values of fluorine and chlorine on Mullikens
scale, given that (Ionisation potential) F = 17.4 eV/atom (Electron affinity) F =
3.62 ev/atom, (IP)Cl = 13.0 ev/atom and (EA)Cl = 4.0 ev
Electronegativity of fluorine

Electronegativity of chlorine

(IP) F + (EA) F
2 2.8

17.4 + 3.62
21.02
=
= 3.75
5 .6
5 .6

(IP) Cl + (EA) Cl
2 2.8

1 3 .0 + 4 .0
17
=
5 .6
5 .6
Applications of electronegativity
=

1)

= 3.03

Nature of bond

The concept of electronegativity can be used to predict whether the bond


between similar or dissimilar atoms is non-polar covalent bond, polar covalent
bond (or) ionic bond.
i)

When XA = XB, i.e. XA - XB = 0, then A-B bond is non polar covalent bond
or simply covalent bond and is represented as A-B. eg. H-H bond in H2
molecule is a covalent bond and is represented as H-H bond.

ii)

When XA is slightly greater than XB, i.e. XA - XB is small, the A-B bond is
polar covalent bond and is represented as A--B+ . e.g. The O-H bonds
in H2O molecule are polar covalent bonds and are represented as O--H+,
since XO > XH and XO - XH is small.

iii)

When XA >> XB, i.e., XA - XB is very large, A-B bond is more ionic or
polar bond and is represented as A--B+, Since XA >> XB. For example
Na-Cl bond in Na Cl molecule is an ionic bond and is represented as Na+Cl(Here Cl = A and Na = B).

55

2.

Percentage of ionic character in a polar covalent bond


Pauling estimated the percentage of ionic character in various A-B+ polar
covalent bonds from known (XAXB) values and has derived the following
conclusions :
(i) When (XAXB) = 1.7, the amount of ionic character in A-B+ bond is
50% and that of covalent character is also 50%. Thus A-B bond is 50%
ionic and 50% covalent.
(ii) When (XAXB) < 1.7, the amount of ionic character in A-B+ bond is less
than 50% and that of covalent character is more than 50%. Thus A-B+
bond is predominantly covalent and hence is represented as AB.
(iii) When (XAXB) > 1.7, the amount of ionic character in A-B+ bond is
more than 50% and that of covalent character is less than 50%. Hence
A-B+ bond is predominantly ionic and hence is represented as AB+.
SELF EVALUATION
A. Choose the correct answer
1.

2.
3.
4.

5.

6.

The value of C-C distance found experimentally in a saturated hydrocarbon


is
a) 1.34
b) 1.36
c) 1.54
d) 1.56
On moving down the group, the radius of an ion
a) Decreases
b) Increases
c) No change d)None of these
*
Effective nuclear charge (Z ) can be calculated by using the formula
a) Z* = Z S
b) Z* = Z + S
c) Z* = S Z d) Z = Z* S
Pick the correct statement
a) Carbon having more nuclear charge than boron
b) The size of carbon atoms is larger than boron
c) Carbon forms electron deficient compounds
d) Carbon forms ionic compounds
Comparing the ionisation energy of fluorine with carbon, fluorine has
a) higher ionisation energy
b) lower ionisation energy
c) same ionisation energy
c) none of these
Among the following which has the maximum ionisation energy
a) Alkali elements
b) Alkaline elements
c) Halogens
c) Noble gases
56

7.

8.
9.

10.
11.
12.
13.

14.
15.
B.
16.

17.

The electron affinity of an atom


a) directly proportional to its size b) inversely proportional to its size
c) is independent of its size
d) none of these
Among the following which has higher electron affinity value
a) Fluorine
b) Chlorine
c) Bromine
d) Iodine
The scale which is based on an empirical relation between the energy of a
bond and the electronegativities of bonded atoms is
a) Pauling scale
b) Mullikens scale
c) Sandersons scale
d) Alfred and Rochows scale
Electron affinity is expressed in
a) kJ
b) J
c) kJ mol
d) kJ mol-1
The bond length of Cl2 molecule is
a) 0.74
b) 1.44
c) 1.98
d) 2.28
The order of ionization energy
a) s < p < d < f
b) s > p > d > f c) s > d > p > f d) s<d<p<f
Across the period, electron affinity
a) decreases
b) increases
c) decrease and the increases
d) increase and then decreases
Noble gases have _____electron affinity
a) High
b) Low
c) Zero
d) Very low
When XA>>XB, AB bond is
a) polar covalent
b) non-polar covalent c) Ionic
d) metallic
Answer in one or two sentences
Arrange the following species in the increasing order of size
a) O2, F, Mg2+, Na+
b) F, F
c) N, O
d) Fe2+, Fe, Fe3+
e) Na+, Cl, Na, Cl
f) I, I+, I
Arrange the following elements in the increasing order of their first ionisation
potentials, give proper explanation for your answer.
a) Li, Be, B
b) N, O, F
c) C, N, O, F
57

18. Which element of the following has the highest ionisation potential?
Na, Cl, Si and Ar.
19. Describe with reasons which atom in each of the following pairs has higher
ionisation energy?
a) Mg and Al
b) B and Al
c) Al and Si
20. Which element of the following pairs of elements has higher ionisation energy?
Justify your answer
a) K or Ca b) Be or B c) I or Ba d) F or Cl
e) N or O
21. Which element of the following groups of elements has smallest ionisation
energy. Justify your answer.
a) Ca or Be
b) Ca or K
c) Cl or I
d) Be, B, C
22. Answer the following questions
a) Which element has the most positive value of electron affinity?
b) Which element has low electronegativity?
23. Mention the disadvantage of Pauling and Mulliken scale.
24. Why EA of fluorine is less than that of chlorine?
C. Answer not exceeding 60 words
25. How is atomic radii calculated from covalent bond length?
26. Explain Pauling method to determine ionic radii.
27. Explain the variation of IE along the group and period.
28. Explain the various factors that affect electron affinity.
29. How electronegativity values help to find out the nature of bonding between
atoms?
Summary
The periodicity in properties of elements are reviewed briefly. Atomic and
ionic radii of molecules are calculated by using simple examples. The factors
governing ionisation potential are explained with specific examples. The factors
affecting electron affinity are discussed briefly. The different scales of
electronegativity values are explained in detail.
References
1) Concise Inorganic Chemistry, J.D. Lee, 3rd Edition, 1977.
2) Selected Topics in Inorganic Chemistry, Wakid V.Malik, G.D.Tuli,
R.D.Madan 7th edition, 2001.
58

3. p - BLOCK ELEMENTS
Learning Objectives
( Understand the general trends in the chemistry of elements of groups
13,14,15,16,17 and 18.
( Understands the preparation, properties and the uses of potash alum.
( Knowledge about know about silicones.
( Understand the extraction of lead, properties and the uses of lead.
@ Understands the preparation, properties, uses and the structure of
halides, oxides, oxyacids and hydrides of phosphorus.
( Recognize the anomalous behavior of Fluorine.
( Understand about interhalogen compounds.
( Know about the isolation of noble gases.
( Recognises the preparation, properties and the structure of xenon
compounds.
( Appreciates the application of noble gases.

59

PERIODIC TABLE
18
n s 2 n p 1-5
He

Ne

Cl

Ar

As

Se

Br

Kr

Sn

Sb

Te

Xe

Pb

Bi

Po

At

Rn

13

14

15

16

17

12

Al

Si

Ga

Ge

In
Tl

ns2np1 n s 2 n p 2
13
14
15
16

B o ro n g ro u p
C a rb o n g ro u p
N itro g en g ro u p
O x y g en g ro u p

n s 2n p 3

17
18

n s 2n p 4

n s 2n p 5 n s 2 n p 6

H alo g en fam ily


N o b le g ase s

p-block elements grouped with s-block elements are called as main group
elements or representative elements. There are 44 main group elements. pblock
elements occupy groups 13-18 of the periodic table including inert gases.
p-block elements play dominant part in all natural processes. Aluminium plays
vital role in aircraft and as conductors. Carbon is the backbone of all organic
compounds. Silicon chips play a vital part in computers. Nitrogen acts as a building
block of life. Molecular oxygen is a cell fuel.
60

General characteristics of p-block elements


1.

The general electronic configuration of p-block elements is ns2 np1-6.

2.

These elements include metals and non-metals with a few semi metals
(Metalloids)

3.

Most of them form covalent compounds.

4.

These elements possess relatively higher ionisation energy and the value
tends to increase along the period but decrease down the group.

5.

Most of the elements show negative (except some metals) as well as positive
oxidation states (except Fluorine).

6.

One of the familiar characteristic of p-block elements is to show inert pair


effect i.e. the tendency of being less availability for ns electron in bonding.
The inert pair effect increases down the group with the increase in atomic
number.

Group 13 elements The Boron family


The group 13(IIIA) elements are Boron, aluminium, gallium, indium and
thallium.

Boron is a relatively rare element, accounting for only about 0.001% of the
earths crust by mass.

Aluminium is the most important of 13th group elements.

Gallium is remarkable for its unusually low melting point (29.7C) and
therefore generally exist as a liquid at room temperature. Its most important
use is in making gallium arsenide. This is a semi conductor material employed
in the manufacture of diode lasers for laser printers, compact disc players
and fibre optic communication devices.

Indium is also used in making semi conductor devices, such as transistors


and electrical resistance thermometers called thermistors.

Thallium is extremely toxic and has no commercial use.

61

3.1 GENERAL TRENDS


Electronic configurations: The general electronic configuration of the
various elements of this family is ns2 np1.
Table 3.1 Electronic configuration of group 13 elements
Atomic
Number

Electronic Configuration

Group
Number

Period
Periodic
Number
Number

Boron

[He] 2s2 2p1

13

Aluminium

13

[Ne] 3s2 3p1

13

Gallium

31

[Ar] 3d10 4s2 4p1

13

Indium

49

[Kr] 4d10 5s2 5p1

13

Thallium

81

[Xe] 4f14 5d10 6s2 6p1

13

Element

3.1.1 Potash Alum, K2 SO4. Al2 (SO4)3. 24 H2O


Potash Alum is manufactured from alunite or alum stone.
From Alunite: Alunite or alum stone is K2SO4. Al2(SO4)3. 4Al(OH)3. It is finely
powdered and boiled with dilute sulphuric acid, the aluminium hydroxide part
changes into aluminium sulphate. When a little more potassium sulphate in
calculated amount is added, the alum is crystallised.
Properties
1. Potash alum is a white crystalline solid.
2. It is soluble in water but insoluble in alcohol.
3. The aqueous solution is acidic due to the hydrolysis of Al2 (SO4)3.
4. When heated, it melts at 365K and on further heating loses the whole of its
water of crystallisation and swells up. The swollen mass so produced is
called burnt alum.
Uses
1.

It is used in purification of water, water proofing of textiles and in dyeing


and paper industry.

2.

It is also employed to arrest bleeding.


62

3.2 GROUP - 14 ELEMENTS - THE CARBON FAMILY


The group 14 (IVA) elements carbon, silicon, germanium, tin and lead are
especially important both in industry and in living organisms.

Carbon is an essential constituent of the molecules on which life is based.

Silicon is the second most abundant element in the earths crust.

Both silicon and germanium are used in making modern solid state electronic
devices.

Tin and lead have been known and used since ancient times.

General Trends
Electronic configuration: The elements of this group possess ns2 np2
electronic configuration.
Atomic
Number

Electronic Configuration

Group
Number

Period
Periodic
Number
Number

Carbon

[He] 2s2 2p2

14

Silicon

14

[Ne] 3s2 3p2

14

Germanium

32

[Ar] 3d10 4s2 4p2

14

Tin

50

[Kr] 4d10 5s2 5p2

14

Lead

82

[Xe] 4f14 5d10 6s2 6p2

14

Element

Table 3.2 Electronic Configuration of Group 14 elements

63

3.2.1 Silicones structure and uses


The silicones are a group of organosilicon polymers. They have a wide
variety of commercial uses.
The complete hydrolysis of SiCl4 yields silica SiO2, which has a very stable
three-dimensional structure. The fundamental research of F.S. Kipping on the
hydrolysis of alkyl-substituted chlorosilanes led, not to the expected silicon
compound analogous to a ketone, but to long-chain polymers called silicones.
R

Cl
Si

Si

OH
Si

Cl

R
HO

H 2O

Si = 0
OH

R
OH + HO

Si

OH

HO

Si

R
O

Si

OH

The starting materials for the manufacture of silicones are alkyl-substituted


chlorosilanes. Thus the hydrolysis of trialkylmonochlorosilane R3SiCl yields hexaalkylsiloxane.
R
R

Si

R
O

Si

R
R
The dialkyldichlorosilane R2SiCl2 on hydrolysis gives rise to straight chain
polymers and, since an active OH group is left at each end of the chain,
polymerisation continues and the chain increases in length.
R
HO

Si
R

R
O

Si

R
O

Si
R

64

R
O

Si
R

OH

The hydrolysis of alkyl tricholorosilane RSiCl3 gives a very complex crosslinked polymer.
|
|
O
O
R

Si

Si

O
R

Si

Si

Uses
1)

Silicones act as excellent insulators for electric motors and other appliances
as they can withstand high temperatures.

2)

Straight chain polymers of 20 to 500 units are used as silicone fluids. They
are water repellent because of the organic side group. These polymers are
used in waterproofing textiles, as lubricants and as polish.

3)

Silicone rubber retain their elasticity even at low temperatures and resist
chemical attack. They are mixed with paints to make them damp-resistant.

4)

Silicone resins, a cross-linked polymer used as non-stick coating for pans


and are used in paints and varnish.

5)

Silicone oils are highly stable and non-volatile even on heating. Hence used
for high temperature oil bath, high vacuum pump etc.

3.2.2 Metallurgy of Lead


Ores
1.
2.
3.
4.

Galena
PbS
Cerrusite PbCO3
Anglesite PbSO4
Lead ochre PbO

65

Extraction: Lead is mainly extracted from the sulphide ore galena. Galena
contains lead sulphide and small quantities of silver.
1.

Concentration: The ore is concentrated by froth floatation process.

2. Smelting in a Reverberatory furnace: The concentrated ore is roasted


in a reverberatory furnace at a moderate temperature. The temperature of furnace
is controlled by regulating the air supply. During roasting, galena is partly oxidized
to lead monoxide and partly to lead sulphate.

Fig. 3.1 A reverberatory furnace


2PbS + 3O2

PbS + 2O2

2 PbO + 2SO2
PbSO4

More of galena is then added. The temperature is raised and simultaneously


the air supply is reduced. Lead sulphide reacts with the two oxidised products
giving lead.
PbS+2PbO
PbS+PbSO4

3Pb+SO2
2Pb+2SO2

Thus in this process roasting and smelting are carried out in the same furnace,
at two different temperatures.
About 90% of lead is obtained as metal, the rest passes into slag. Lead is
recovered from the slag by heating with lime and powdered coke.

66

Powdered ore

Concentration

ore rich in PbS


roasting
ore rich in PbO, PbSO4, PbS

Pure lead metal

smelting
Impure Metal

Electrolytic
refining

Liquation
Desilverisation
Pb metal +Au, Sn

Pb +Sn, Ag, Au

Purification of Lead
Lead extracted by the above method contains impurities such as silver,
copper, tin, bismuth, gold and iron. It is refined by the following processes.
a.

Liquation

The impure metal is heated on a sloping hearth. Lead melts and flows down
the slope. The infusible impurities remain on the hearth.
b.

Desilverisation
Silver is removed by either Pattinsons process or Parks process.

c.

Electrolytic refining
Very pure lead is obtained by this process.
Anode Impure lead
Cathode Very pure lead
Electrolyte Lead fluosilicate + Hydrofluosilicic Acid
(H2SiF6)
(PbSiF6)

The metallic impurities which are more electropositive than lead, such as
iron and tin, go into the solution while the rest of the impurities are thrown
down as anode mud.

67

Physical properties
1.
2.
3.
4.

Lead is a bluish grey metal with a bright luster.


It is soft and can be cut with a knife and drawn into a wire and rolled into a
sheet.
It is not a good conductor of heat and electricity.
It marks paper.

Chemical properties
1.

Action of air

i)

It is unaffected by dry air but in moist air a layer of lead carbonate or lead
hydroxide is deposited on its surface which protects it from further action of
air.
When heated in air or oxygen, lead is oxidized to litharge (PbO) and red
lead (Pb3O4)

ii)

2Pb + O2 2PbO
3Pb + 2O2 Pb3O4
2.

Action of water

Lead is not attacked by pure water in the absence of air, but water containing
dissolved air has a solvent action on it due to the formation of lead hydroxide (a
poisonous substance). This phenomenon is called Plumbo solvency.
2Pb + O2 + 2H2O

2Pb(OH)2

3.

Action of acids

i)
ii)

Dilute H2SO4 and HCl have no action on lead.


Hot Conc. H2SO4 liberates SO2 but the reaction is retarded by the formation
of an insoluble layer of lead sulphate.
Pb + 2H2SO4 PbSO4 + 2H2O + SO2

iii)

Concentrated HCl evolves hydrogen and also forms Chloroplumbic acid


Pb + 2HCl
PbCl2 + 2HCl

PbCl2 +H2
H2PbCl4
chloroplumbic acid

68

Uses: Lead is used


1.
2.
3.
4.
5.
6.

For making lead pipes,


For making telegraph and telephone wires,
In making bullets and lead accumulators,
In lead chambers, for the manufacture of sulphuric acid,
For making alloys like solder, pewter and type metal,
For preparing tetraethyl lead (Pb(C2H5) 4) which is used as an additive to
petrol to prevent knocking.

Problem
An element A belongs to 14th group and occupies period number 6. A
reacts with conc. HCl. to give B an acid. A is used to prepare C which is used
as an antiknock in automobiles. Identify the element A and the compounds B
and C Write the reactions.
Solution
1.

As per the position in the periodic table, the element A is lead.

2.

Lead with Conc. HCl gives B


Pb + 4 HCl

H2PbCl4 + H2

Compound B is chloroplumbic acid.


3.

Compound C is tetraethyl lead.

3.3 GROUP 15 ELEMENTS THE NITROGEN FAMILY


The group 15 (VA) elements are nitrogen, phosphorus, arsenic, antimony
and bismuth.

Nitrogen is a gas. It makes up 78% of the earths atmosphere by volume.

Phosphorus is the most abundant element of 15th group, accounting for


0.10% of the mass of the earths crust.

Arsenic is also used to make pesticides and semi conductors, such as GeAs.

Bismuth is a silvery solid. Bismuth compounds are present in some


pharmaceuticals such as Peptobismol.

The natural abundance of As, Sb and Bi in the earths crust is relatively low.
69

General trends
Electronic configuration: All these elements have general electronic
configuration of ns2 np3.
Table 3.3 Electronic configuration of group 15 elements
Element

Atomic
Number

Electronic Configuration

Group
Number

Period
Periodic
Number
Number

Nitrogen

[He] 2s2 2p3

15

Phosphorus

15

[Ne] 3s2 3p3

15

Arsenic

33

[Ar] 3d10 4s2 4p3

15

Antimony

51

[Kr] 4d10 5s2 5p3

15

Bismuth

83

[Xe] 4f14 5d10 6s2 6p3

15

3.3.1 Compounds of Phosphorus


a)

Halides of Phosphorus

Phosphorus combines with all the halogens forming phosphorus halides which
are all covalent compounds. Phosphorus chlorides are more important. Tri and
pentachlorides of phosphorus are most common.
I.

Phosphorus Trichloride, PCl3

Preparation: PCl3 is prepared by heating white phosphorus in a current of dry


chlorine.
P4 + 6Cl2

4PCl3

Dry white phosphorus is placed in the retort and gently heated on a water bath.
A current of pure, dry chlorine is led over the phosphorus. The phosphorus
trichloride formed being volatile distils over and is collected in a water cooled
receiver.

70

D R Y C H L O R IN E

O
C aC l 2

W H IT E
P H O S PH O R U S

S A N D BATH
P C l3

Fig. 3.2 Laboratory Preparation of PCl3


The phosphorus trichloride obtained as above contains some PCl5 as impurity.
This is removed by distilling the PCl3 over white phosphorus.
Physical properties
1.
2.
3.

Colourless low boiling liquid


It fumes in moist air
It has pungent odour.

Chemical Properties
1. It is violently hydrolysed by water giving phosphorus acid and hydrochloric
acid gas.
PCl3 + 3 H2O 3HCl + H3PO3
In a similar manner it reacts with organic compounds containing hydroxyl (OH)
group, such as acids and alcohols.
PCl3 + 3CH3COOH
Acetic Acid
PCl3 + 3C2H5OH
Ethyl alcohol
2.

3CH3COCl + H3PO3
Acetyl Chloride
3 C2H5Cl + H3PO3
Ethyl Chloride

It reacts with chlorine or sulphuryl chloride forming phosphorus pentachloride.

71

PCl3 + Cl2

PCl5

PCl3 + SO2Cl2 PCl5 + SO2


3.

It readily combines with oxygen forming phosphorus oxychloride


2PCl3 + O2 2POCl3

4.

It reacts with SO3 to form phosphorus oxychloride and SO2


SO3 + PCl3 POCl3 + SO2

Structure: PCl3 molecule has a pyramidal shape, which arises from sp3
hybridisation of phosphorus atom. One of the tetrahedral positions is occupied
by a lone pair of electrons.

P
Cl
Cl

Cl

Cl

xx
x Px
x
Cl

Cl

x - E lectro n o f p
- E lectro n o f C l

II. Phosphorus pentachloride, PCl5


Preparation: Phosphorus pentachloride is usually prepared by the action of an
excess of chlorine on phosphorus trichloride.
PCl3 + Cl2 PCl 5
Physical properties
1.
2.

Phosphorus pentachloride is a yellowish white crystalline solid.


It sublimes on heating at 473 K and melts at 318 K under pressure.

Chemical properties
1.

Phosphorus pentachloride dissociates on heating into phosphorus trichloride


and chlorine.
PCl5

2.

PCl3 + Cl2

It is violently hydrolysed by water giving phosphorus oxychloride or


phosphoric acid depending upon the quantity of water.
72

insufficient water

PCl5 + H2O

POCl3 + 2HCl
Excess of water

PCl5 + 4H2O
3.

It reacts with compounds containing hydroxyl groups forming chloro


derivatives. In all these cases, the hydroxyl group is replaced by chlorine.
C2H5OH + PCl5
Ethyl Alcohol

4.

H3PO4 + 5HCl

C2 H5Cl + POCl3 + HCl


Ethyl Chloride

It reacts with metals on heating to give corresponding chlorides.


2Ag + PCl5 2 AgCl + PCl3

Structure
PCl5 molecule has trigonal bipyramidal shape in vapour state which arises
from sp3d hybridisation of phosphorus atom.
Cl

Cl
Cl

x
x

Cl

Cl
x
P
x

Cl

Cl

Cl

x - E lectro n o f p
- E lectro n o f C l

Cl
Cl

b)

Oxides of phosphorus

I.

Phosphorus trioxide P2O3 or P4O6


It is obtained by the combustion of phosphorus in a limited supply of air.
4P + 3O2 2P2O3

Physical properties
1. It is a white waxy substance
2. It has a garlic odour.
Chemical properties
1. It reacts with cold water, gives phosphorus acid.
P2O3 +3H2O 2H3PO3
73

2.

It reacts with hot water vigorously to form inflammable phosphine.


2P2O3 + 6H2O PH3 + 3H3 PO4

II. Phosphorus pentoxide P2O5 or P4O10


Phosphorus pentoxide can be prepared by burning phosphorus with sufficient
supply of air.
P4 + 5O2 P4 O10
Physical properties
It is a white solid and an acidic oxide.
Chemical properties
1.

It reacts with moisture to form metaphosphoric acid.


P4O10 + 2H2O 4HPO3

When the solution is boiled, the metaphosphoric acid is changed to


orthophosphoric acid.
HPO3 + H2O H3PO4
or
P4O10 + 6H2O 4H3 PO4
2. Phosphorus pentoxide extracts water from many inorganic compound
including sulphuric acid, nitric acid and several organic compounds. It is therefore,
used as a powerful dehydrating agent.
P4O10

H2SO4

SO3
- H2O
P4O10

2HNO3

N2O5
- H2O

P4O10

RCONH2
Amide

-H2O

RCN
Nitrile

Use: It is used as a dehydrating agent.


74

c)

Oxy-Acids of Phosphorus

I.

Phosphorus acid - H3PO3

It is prepared by the action of cold water on phosphorus (III) oxide or


phosphorus (III) chloride.
P2O3 + 3H2O 2H3PO3
PCl3 + 3H2O H3PO3 + 3HCl
Physical properties
It is a white crystalline solid with garlic taste.
Chemical Properties
1.

Acidic nature: It is a dibasic acid and gives salts of two types.


H3PO3 + NaOH
H3PO3 + 2NaOH

NaH2PO3 + H2O
Sodium dihydrogen Phosphite
Na2HPO3 + 2H2O
Disodium hydrogen Phosphite

2. When it is heated it undergoes auto-oxidation and reduction to form


phosphoric acid and phosphine.

4H3 PO3 3H3PO4 + PH3


3. It is a powerful reducing agent because it has P-H bond. It reduces silver
nitrate solution into silver.
2AgNO3 + H3PO3 + H2O 2Ag +H3PO4+2HNO3
Electronic structure
O

O
x x
H

P
x
H

x - E lectro n o f P
- E lectro n o f C l
- E lectro n o f H

HO

OH
H

Use: It is used as a reducing agent


75

II. Ortho phosphoric Acid, H3PO4


Preparation
1. It is prepared by dissolving phosphorus pentoxide in water and boiling the
solution.
P2O5 + 3H2O

2H3PO4
2. Laboratory preparation: In the laboratory orthophosphoric acid can be
prepared by boiling a mixture of red phosphorus with 50% nitric acid in a flask
fitted with a reflux condenser on a water bath till no more oxides of nitrogen are
liberated.
Iodine acts as a catalyst. The product is evaporated below 453 K and then
cooled in a vaccum desiccator surrounded by freezing mixture when crystals of
orthophosphoric acid are deposited.
P+5HNO3 H3PO4 +5NO2 +H2O
Physical properties
1. It is a deliquescent crystalline solid.
2. It is soluble in water.
Chemical properties
1. It is a tribasic acid. It combines with alkalies like NaOH to form three series
of salts.
H3PO4 +NaOH

NaH2PO4 + H2O
Sodium Di hydrogen Phosphate

H3PO4 +2NaOH

Na2HPO4
+ 2H2O
Disodium hydrogen Phosphate

H3PO4 + 3NaOH

Na3PO4
+ 3H2O
Sodium Phosphate

2. On heating it gives pyrophosphoric acid at 523 K and at 589 K gives


metaphosphoric acid
523K

H3PO4
3.

589K

H4 P2O7

2HPO3 + H2O

On reaction with silver nitrate, it gives yellow precipitate of silver phosphate.


H3PO4 + 3AgNO3 Ag3PO4+3HNO3
76

Uses
1.
2.
3.
4.

It is used in the preparation of HBr and HI as a substitute for sulphuric acid.


It is used as souring agent in the preparation of soft drinks.
It is used in the preparation of phosphate salts of sodium, potassium and
ammonium.
It is used in the manufacture of phosphatic fertilisers.

Structure
Being a tribasic acid, the structure of phosphoric acid is represented as
O

O
x x
O x P x O
x
O

x - E lectro n o f P
- E lectro n o f O
- E lectro n o f H

HO

OH
OH

III. B. Pyrophosphoric acid, H4 P2 O7


Preparation: Pyrophosphoric acid is prepared by heating orthophosphoric
acid to 523 K 533 K.
2H3PO4 H4P2O7 + H2O
Physical Properties
It is a colourless crystalline solid.
Chemical Properties
1.

It is reconverted to orthophosphoric acid on boiling with water


H4P2O7 + H2O 2H3PO4

2.

When heated strongly, it yields metaphosphoric acid


H4P2O7

2PO3 + H2O

77

Structure: The Structure of pyrophosphoric acid is represented as:


O
x x
H

x P
x
O

O
x x
x

O x

d)

P
x
O

HO

OH

OH

OH

Phosphine - PH3
Phosphine is the best known hydride of phosphorus.

Laboratory preparation: It is usually obtained by boiling white phosphorus


with 30-40% solution of caustic soda in an inert atmosphere of CO2.
4P + 3NaOH + 3H2O

PH3 + 3NaH2PO2
Sodium hypophosphite

Phosphine so obtained is impure. It is passed into an aqueous solution of


hydrogen iodide, PH4I is formed. PH4I is heated with KOH or NaOH, pure
phosphine is obtained.
PH3 + HI PH4I
PH4I + NaOH PH3 + NaI + H2O
Physical properties
Phosphine is colourless gas with rotten fish odour.
Chemical properties
1. Dissociation: Phosphine dissociates at about 723 K and gives red
phosphorus.
4PH3
2.

723 K

P4 + 6H2

Action of air: It burns with oxygen and produces phosphorus pentoxide.


4PH3 + 8O2

P4O10 + 6H2O
78

3. Action of chlorine: Phosphine burns in chlorine spontaneously forming


PCl3 and PCl5.
PH3 + 3Cl2

PCl3 + 3HCl

PH3 + 4Cl2

PCl5 + 3HCl

4. Reducing properties: PH3 is a powerful reducing agent. When it is passed


through the salt solutions, corresponding metal is formed.
PH3 + 6AgNO3+ 3H2O 6g + 6HNO3 + H3PO3
Uses
1.

Smoke screens

When PH3 burns it produces smoke which is dense enough to serve as


smoke screens.
2. Holmes signal : Containers which have a perforated bottom and a hole at
the top are filled with calcium phosphide and calcium carbide. These are thrown
into the sea. Water enters the container through the bottom and reacts with calcium
carbide and calcium phosphide to give acetylene and phosphine. Phosphine gets
ignited spontaneously as it comes in contact with air and also ignites acetylene.
Thus a bright red flame is produced which is accompanied by huge smoke due to
the burning of phosphine. This serves as a signal to the approaching ships.
Ca3P2 + 6H2O 2 PH3
CaC2

+ 3Ca(OH)2

+ 2H2O C2H2 + Ca(OH)2

Problem
An element A occupies group number 15 and period number 3 reacts
with chlorine to give B which further reacts with chlorine to give C at 273 K.
Both B and C are chlorinating agent for organic compounds. C is a better
chlorinating agent because it chlorinates metals also. B reacts with SO3 and
reduces it to SO2. B has a pyramidal shape. C has trigonal bipyramidal shape by
sp3d hybridisation. Identify the element A and the compounds B and C. Write
the reactions.
1.

The element which occupies group number 15 and period number 3 is


phosphorus. Therefore A is phosphorus. Phosphorus reacts with chlorine
79

to give PCl3. Therefore compound B is phosphorus trichloride and it has a


pyramidal shape.
P4 + 6Cl2

4PCl3
2.

PCl3 further reacts with Cl2 to give PCl5. Therefore, the compound C is
phosphorus pentachloride and it has a trigonal bipyramidal shape.
PCl3 + Cl2

3.

PCl5

PCl3 and PCl5 are chlorinating agents for organic compounds. So, both
reacts with C2H5OH gives C2H5Cl.
PCl3 + 3C2H5OH
PCl5 + C2H5OH

4.

PCl5 is a better chlorinating agent. So it chlorinates copper.


PCl5 + 2Cu

5.

3C2H5Cl+ H3PO3
C2H5Cl + POCl3 + HCl

2CuCl + PCl3

PCl3 reacts with SO3 and reduces it to SO2.


PCl3 + SO 3

POCl3 + SO2

3.4 Group 16 THE OXYGEN FAMILY


The group 16 (VI A) elements are oxygen, sulphur, selenium, tellurium and
polonium. The first four elements are collectively called CHALCOGENS or ore
forming elements, because many metal ores occur as oxides and sulphides.

Oxygen the most abundant element, is an important constituent of atmosphere


and ocean. It constitutes 46.6% earths crust.

Sulphur is less abundant and occurs in free and combined states. Sulphur is
also known as Brim stone.

Polonium, a radioactive element that occurs in trace amounts in uranium


ores. Its name from Poland, the home country of Marie Curie who discovered
the element in 1898.
General Trends
Electronic configuration
All of these elements have ns2np4 configuration, just two electrons short of
an octet configuration.
80

Table 3.4 Electronic configuration of Group 16 elements


Element

Atomic
Number

Electronic Configuration

Group
Number

Period
Periodic
Number
Numbe

Oxygen

[He] 2s22p4

16

Sulphur

16

[Ne] 3s23p4

16

Selenium

34

[Ar] 3d10 4s2 4p4

16

Tellurium

52

[Kr] 4d10 5s2 5p4

16

Polonium

84

[Xe] 4f14 5d10 6s2 6p4

16

3.5 GROUP 17 - THE HALOGEN FAMILY


Group 17 of the periodic table contains the elements fluorine, chlorine,
bromine, iodine and astatine. These are collectively known as HALOGENS. It
is derived from two Greek words Halo and Gens meaning Salt producer.
Because most of them exist in Sea water.
General Trends
Electronic Configuration: All these elements possess ns2np5 configuration.
Table 3.5 Electronic Configuration of group 17 elements
Element

Atomic
Number

Electronic Configuration

Group
Number

Period
Periodic
Number
Numbe

Fluorine

[He] 2s22p5

17

Chlorine

17

[Ne] 3s23p5

17

Bromine

35

[Ar] 3d10 4s2 4p5

17

Iodine

53

[Kr] 4d10 5s2 5p5

17

Astatine

85

[Xe] 4f14 5d10 6s2 6p5

17

81

Chemical Properties
1. Oxidising power: An important feature of the halogen is their oxidising
property which is due to high electron affinity of halogen atoms. The oxidising
power decreases from fluorine to iodine. Fluorine is the strongest oxidising agent.
It oxidises other halide ions to halogens in solution or when dry.
F + 2 X 2F + X (X = Cl , Br , I)
2

Halogen of low atomic number oxidises the halide ion of higher atomic number.
2. Solubility: Halogens, being non-polar molecules, do not dissolve to a
considerable extent in a polar solvent like water. However, fluorine reacts with
water readily forming a mixture of O2 and O3.
2F2 + 2H2O

4HF + O2

3F2 + 3H2O

6HF + O3

Chlorine, bromine and Iodine are more soluble in organic solvents such as
CCl4, CHCl3 and produce yellow, brown and violet colour.
3.

Hydrides of the Halogens (Hydrogen halides):

i)

All halogens react with hydrogen to form volatile covalent hydrides of formula
HX.

ii)

These hydrides are called hydracids.

iii)

The activity of halogens towards hydrogen decreases from fluorine to iodine.


Hydrogen combines explosively with fluorine even in dark. It combines
with chlorine in the presence of sunlight and with bromine on heating.
Hydrogen combines with iodine on heating and in presence of a catalyst.

iv) Hydracids are the reducing agents.


v)

Except HF, all hydrogen halides are gases. HF is a liquid because of inter
molecular hydrogen bonding.
H F ....... H F ....... HF ....... HF

vi) The acidic character of HX are in the following order.


HF < HCl < HBr < H.

82

Anamalous Nature of Fluorine


1.

Fluorine is the most reactive element among halogen. This is due to the
minimum value of FF bond dissociation energy.

2.

Fluorine decomposes cold dilute alkalies liberating OF2 and with conc. alkali,
O2 is liberated. Under similar conditions, the other halogens will give rise to
the hypohalites and halates respectively.

3.

It has the greatest affinity for hydrogen, forming HF which is associated


due to the hydrogen bonding. Hydrofluoric acid is a weak acid whereas the
other hydrohalic acids are strong acids.
...... H F...... H F..... HF.

4.

It differs markedly from the other halogens in that it can form two types of
salts with metals. NaF and NaHF2.

5.

The salts of HF differ from the corresponding salts of other hydracids. AgF
is soluble in water while the other AgX are insoluble.

6.

Being strongly electronegative it can have only a negative oxidation state


while the other halogens can have negative as well as positive oxidation
state.

7.

HF attacks glass while others do not.

8.

Fluorine, because of the absence of d-orbitals in its valence shell does not
form any polyhalides. Thus we have 3 , Br3, Cl3 ions but no F3 ion.
ETCHING ON GLASS

Etching glass
Industrially, hydrogen fluoride is obtained by heating fluorspar (CaF2) with
concentrated H2SO4 in a lead vessel.
CaF2 + H2SO4 CaSO4 + 2HF.
HF distils over and the vapours are condensed in water in a lead receiver.
Aqueous HF thus obtained is stored in wax bottles. It cannot be stored in glass
or silica bottles as it attacks silicates and silica.
Na2 SiO3 + 6HF Na2SiF6 + 3H2O
SiO2 + 4HF

SiF4 + 2H2O
83

The action of hydrofluoric acid on silica and silicates is used for etching
glass. The glass article is first covered with a film on wax. The design to be
etched is now drawn on the waxed surface and is then exposed to the action of
hydrofluoric acid. Now the glass can be very soon etched. The wax is finally
washed off with turpentine.
3.5.1 ISOLATION OF FLUORINE
Symbol - F Atomic number -9

Period Number

: 2

Valency 1

Group Number

: 17

Atomic mass19

Fluorine does not occur free in nature. It occurs in the combined form.
Dennis Method: This was devised by Dennis, Veeder and Rochow in 1931.
In this fluorine is prepared by the electrolysis of fused sodium or potassium
hydrogen fluoride (perfectly dry) Electrolysis is carried out between graphite
electrodes in a V-shaped electrically heated copper tube. The ends of the tube
are covered with copper caps into which the graphite electrodes are fixed with
bakelite cement. The copper tube is thickly lagged to prevent loss of heat.
KHF2

KF + HF

HF H+ + F
2H+ + 2e H 2
2F 2e F

(At cathode)
(At anode)

B A K E L IT E
ST O PP ER S

H2
N aF
E L EC T R IC
R E SISTA N C E
FU R N A C E

N aF

G R A PH IT E
E L EC T R O D E
C O PPE R U -T U B E S
FU SE D
KH F2

Fig. 3.3 Preparation of fluorine


84

Fluorine liberated at the anode is passed through the U-tube containing


sodium fluoride. This removes the hydrogen fluoride vapours coming with fluorine.
NaF +HF NaHF2
Physical Properties
1.
2.
3.

Fluorine is a gas and has pale greenish yellow colour.


It has extremely pungent and penetrating odour.
It is heavier than air.

Chemical Properties
Fluorine is the most active member of halogen family.
1. Action with Hydrogen: Hydrogen explodes violently in fluorine even in
the dark.
H2 + F2 2HF
2. Action with non-metals: Non-metals like carbon, silicon and phosphorus
burn in fluorine forming fluorides.
C + 2F2 CF4
Tetra fluoromethane
Si + 2F2 SiF4
Silicon tetrafluoride
2P + 5F2 2PF5
Phosphorus pentafluoride
3.

Action with metals: It reacts with metals forming corresponding fluorides.


2Ag + F2 2AgF
2Al + 3F2 2AlF3

4. Formation of Interhalogen compounds: It forms a variety of inter halogen


compounds with other halogens.
Br2 + 3F2 2Br F3
2 + 5F2 2 F5
85

Uses
1. Fluorine is used in the manufacture of a series of compounds known as
freons. These non-toxic, non-combustible and volatile liquids are used as
refrigerants in refrigerators, deep freezers and air conditioners. The most
common, freon is known as dichlorodifluoro methane CF2 Cl2.
2. CaF2 is used as flux in metallurgy.
3. NaF is used as a preservative to prevent fermentation and also for preventing
dental cavities.
4. SF6 is used as an insulating material in high voltage equipment.
5. Teflon is used as container to store hydrofluoric acid.
6. UF6 is used in the separation of U235 from U238.
INTERHALOGEN COMPOUNDS OR INTERHALOGENS
Each halogen combines with another halogen to form several compounds
known as interhalogen compounds. The less electronegative element is written
first. In naming also, the less electronegative element is mentioned first.
They are divided into four types.
AX

AX3

AX5

AX7

CIF
BrF
BrCl
ICl
IBr

ClF3
BrF3
ICl3

BrF5
IF5

IF7

They can all be prepared by direct combination or by the action of a halogen


on a lower interhalogen, the product formed depends on the conditions.
473K

Cl2+ F2 (equal volume)

2ClF (AX type)

2 + Cl2 liquid (equi molar) 2Cl (AX type)


Cl2 + 3F2 (excess)

573K

2 ClF3 (AX3 type)

Br2 + 3F2 (diluted with nitrogen) 2Br F3


Br2 + 5F2 (excess) 2Br F5 (AX5 Type)
86

2 + 5F2 (Excess) 2F5 (AX5 Type)


F5 + F2 (Excess)

573K

F7 (AX7 Type)

The bonds are essentially covalent because of the small electronegativity


difference, and the melting and boiling points increase as the difference in
electronegativity increases.
The interhalogens are generally more reactive than the halogens (except F)
because the A-X bond is weaker than the XX bond in the halogens. The reactions
are similar to those of the halogens. Hydrolysis gives halide and oxyhalide ions,
the oxyhalide ion being formed from the larger halogen present.
BrF5 + 3 OH

5F + BrO3 + 3 H+
Bromate

Cl + OH

Cl + O + H+
hypoiodite

Structures of interhalogen compounds


Interhalogen compounds are generally covalent compounds in which the
larger halogen forms the central atom.
1. Type AX. As excepted, the compounds of the type AX are linear. Thus
CF, BrF, BrCl, Br and CI are all linear in structure.
Electronic structure of Chlorine atom, in the ground state and hybridised
state is represented as in Fig. 3.4.

Linear Molecule
AX

Four sp3 hybrid orbitals


Figure 3.4 Linear structure of the interhalogen compounds
of the type AX
87

Although the spatial arrangement of the four electron pairs (bp = 1 and
lps = 3) round the central chlorine atom is tetrahedral, due to the presence of
three lone pairs of electrons in three hybrid orbitals, the shape of AX molecule
gets distorted and become linear.
2. Type AX3 Compounds of the type AX3 have trigonal bipyramidal structure,
Fig. 3.5 for the ClF3 molecule.
Bipyramidal structure arises out of sp3d hybridisation involved in the formation
of this compound, as illustrated in the Fig.3.6. The three dotted arrows indicate
electrons contributed by the three fluorine atoms (without lone pair it is T-shaped).

Fig. 3.5 Bi pyramidal structure of CIF3 molecule

Fig. 3.6 sp3d hybridisation involved in the formation of Cl F3 molecule


3. Type AX5 (F5, BrF5, etc.) These compounds are formed by sp3d2
hybridisation and hence have an octahedral structure, as shown in Fig. 3.7 for
the formation of F5 molecule (without lone pair it is square pyramidal).

88

Fig. 3.7 Structure of IF5


4. Type AX7 (F7). This compound has a pentagonalbipyramidal structure
since this is formed by sp3d3 hybridisation.
F
F

F
I

F
F

F
Fig. 3.8 Structure of IF7
Problem
An element A occupies group number 17 and period number 2, shows
anomalous behaviour. A reacts with water forms a mixture of B, C and acid D.
B and C are allotropes. A also reacts with hydrogen violently even in dark to
give an acid D. Identify A,B,C and D. write the reactions.
Solution
i) The element A that occupies group number 17 and period number 2 is
fluorine.
ii) Fluorine reacts with water and forms a mixture of B and C
2F2 + 2H2O 4HF + O2
89

3F2 + 3H2O

6HF + O3

Therefore, B is Oxygen and C is Ozone.


iii)

Fluorine reacts with hydrogen to give D.


F2 + H2 2HF
D is Hydrofluoric acid.

3.6 GROUP 18 NOBLE GASES OR INERT GASES


Group 18 of the periodic table consists of helium, neon, argon, krypton,
xenon and radon. All these are gases under ordinary conditions of temperature
and pressure. All of them (except Rn) are present in air in traces. Rn is obtained
from radio active distintegration of radium.
On account of their very minute quantities in atmosphere, they were named
as rare gases. Due to their chemical inactivity these were named as inert
gases. A number of xenon compounds and two krypton fluorides were prepared
and thus they were named as noble gases.
Electronic Configuration
All these elements possess ns2 np6 configuration. The differentiating electron
enters into p-sub shell and thus are included in p-block elements.
Table 3.6 Electronic Configuration of Group 18 elements
Element

Atomic
Number

Electronic Configuration

Group
Number

Period
Periodic
Number
Numbe

Helium

1s2

18

Neon

10

1s22s22p6

18

Argon

18

1s22s22p63s2 3p6

18

Krypton

36

1s22s22p63s23p63d104s2 4p6

18

Xenon

54

1s22s22p63s23p63d104s2
4p64d105s2 5p6

18

Radon

86

1s22s22p63s23p63d104s2 4p6
4d104f145s2 5p65d106s2 6p6

18

90

ISOLATION OF NOBLE GASES


The noble gases are isolated from air by removing oxygen and nitrogen
from air free from carbon-di-oxide, water vapour, dust particles, etc., This can
be accomplished by either chemical methods or physical methods. In the chemical
method, the unwanted gases are removed by means of compound formation
while in the physical method, these are removed by the fractional evaporation of
liquid air.
CHEMICAL METHOD
The first step in this method is to isolate the noble gases mixed together,
from the atmosphere by passing repeated electric sparks in air so as to remove
nitrogen and oxygen as nitrogen dioxide (N2 + 2O2 2NO2 ). The second step
is to separate the various constituents from one another taking advantage of the
fact that they can be adsorbed on activated charcoal at different temperatures.
Step 1 Removal of oxygen and nitrogen of the atmosphere as Nitrogen
dioxide
Ramsay - Raleighs method:- A mixture of air and oxygen is constantly
admitted into a glass globe of about 50 litres capacity. Two platinum electrodes
are introduced and a discharge from a transformer of about 6000 - 8000 volts is
passed by the action of which nitrogen and oxygen rapidly combine to form
oxides of nitrogen. The oxides are dissolved out in a solution of sodium hydroxide
continuously circulated through the flask.
N2+ O2

2 NO

2 NO + O2 2NO2
2NO2 + 2NaOH NaNO3 + NaNO2 + H2O
Oxygen if any is removed by introducing alkaline pyrogallol in the globe.
The supply of air and electric discharge is shut after some time and the remaining
mixture of noble gases is pumped out.

91

To Tr a n sfo rm e r

Soda out
G a se s in
S o d a in

Fig. 3.9 Chemical method for isolation of noble gases


Step 2 Separation of noble gases (DEWARS METHOD)
The mixture of noble gases obtained by the above method is separated into
individual constituents by the use of coconut charcoal which adsorbs different
gases at different temperatures.

Fig. 3.10 Separation of noble gases (Dewars method)


The mixture of noble gases is passed into a double-walled bulb containing
coconut charcoal and placed in a low temperature bath at 173K. It is allowed to
remain in contact with the charcoal for about half an hour. At 173K, only argon,
92

krypton and xenon are adsorbed by the charcoal while helium and neon remain
unadsorbed. These are pumped out and collected.
The mixture of helium and neon is kept in contact with coconut charcoal at
93K which completely adsorbs neon leaving free helium.
The charcoal at 173K containing argon, krypton and xenon is placed in
contact with another charcoal at the temperature of the liquid air when argon
diffuse into the other charcoal.
The temperature of the first charcoal (temp.173K) still containing krypton
and xenon is raised to 183K when krypton is set free while xenon remain adsorbed
in the charcoal. When it is heated, xenon is recovered.
XENON FLUORIDE COMPOUNDS
Xenon forms three binary Fluorides XeF2, XeF4, and XeF6 by the direct
union of elements under appropriate experimental conditions.
Xe+F2

673K

XeF2

673K

Xe + 2 F2

XeF4
573K

Xe+ 3 F2

XeF6

PROPERTIES: Xe F2, Xe F4 and Xe F6 are colourless crystalline solids subliming


readily at 298K. They are powerful fluorinating agents. They are readily
hydrolysed by even traces of water. For example.
2Xe F2 + 2 H2O 2Xe + 4HF + O2
Structure: The structure of the three xenon fluorides can be deduced from
VSEPR theory. XeF2 and XeF4 have the linear and square planar structure
respectively. XeF6, has 7 electron pairs (6 bonding and one lone pair) and thus
have a distorted octahedral structure in the gas phase.

93

USES OF NOBLE GAS


(A) HELIUM
1. Because of its lightness and non-inflammability helium is used to filling
balloons for meteorological observations.
2. Because of its lightness it is used in inflating aeroplane tyres.
3. Helium oxygen mixture is used by deep-sea divers in preference to nitrogen
oxygen mixtures. It is much less soluble in blood than N2. This prevents
bends which is the pain caused by formation of nitrogen bubbles in blood
veins when a diver comes to the surface.
4. A mixture of oxygen and helium is used in the treatment of asthma.
5. Liquid helium (b.pt 4.2K) is used as cryogenic agent for carrying out various
experiments at low temperatures.
6. It is used to produce and sustain powerful super conducting magnets which
form essential part of modern NMR Spectrometers and Magnetic Resonance
Imaging system (MRI) for clinical diagnosis.
(B) NEON
1. Neon is used in discharge tubes and fluorescent bulbs for advertisement
display purposes.
2. Mixed with helium it is used to protect electrical instruments from high
Voltages.
3. It is also used in beacon lights for safety of air navigation as the light possesses
fog and storm-penetrating power.
4. Neon light is used in botanical gardens as it stimulates growth and helps the
formation of chlorophyll.
(C) ARGON
1. Mixed with 26% percent nitrogen it is used in gas filled electric lamps.
2. It is also used in radio valves and tubes.
(D) KRYPTON AND XENON
1. Krypton and xenon are also used in filling incandescent metal filament electric
bulbs.
2. They are also used to a small extent in discharge tubes.
(E) RADON
1. It is used in radioactive research and in radiotherapy for treatment of cancer.
94

SELF EVALUATION
A. Choose the correct answer
1

Which of the following does not belong to group 13?


a) B

2.

b) Si

6.

c) P2 O3

d) SO3

b) P2O5

c) H3PO3

d) H3PO4

b) trigonal bipyramidal

c) linear

d) tetrahedral

The compound used as smoke screen


b) PCl5

c) PH3

d) H3PO3

Which shows only -1 oxidation state?


b) bromine

c) chlorine

d) iodine

One can draw the map of building on a glass plate by


a) HI

9.

b) NO2

a) pyramidal

a) fluorine
8.

d) Sn

The shape of PCl5 is

a) PCl3
7.

c) Ge

The compound with garlic odour is


a) P2 O3

5.

d) In

An element which was burnt in limited supply of air to give oxide A which
on treatment with water gives an acid. B. Acid B on heating gives acid C
which gives yellow precipitate with AgNO3 solution A is
a) SO2

4.

c) Ge

Which of the following is most abundant in earths crust?


a) C

3.

b) Al

b) HF

c) HBr

d) HCl

Among the halogen acid, the weakest acid is


a) HF

b) HCl

c) HBr

d) HI

10. Halogens belong to the group number


a) 14

b) 15

c) 17

95

d) 18

11. The noble gases are unreactive because they


a) have same number of electrons b) have an atomicity of one
c) are gases with low densities
d) have stable electronic configuration.
12. The shape of XeF4 is
a) tetrahedral b) octahedral c) square planar d) pyramidal
13. Which is not known?
a) XeF6

b) XeF4

c) XeO3

d) ArF6

14. The lightest gas which is non-inflammable is


a) He

b) H2

c) N2

d) Ar

15. Which of the following has highest first ionisation energy?


a) He

b) Ne

c) Ar

d) Kr.

B. Answer in one or two sentences


16. Write a note on plumbo solvency.
17. H3PO3 is diprotic. Why?
18. Draw the structure of a) PCl 5 b) H3PO3
19. Prove that P2O5 a powerful dehydrating agent.
20. Why H2O is a liquid while H2S is a gas?
21. Why the compounds of fluorine with oxygen are called fluorides of oxygen
and not oxides of fluorine?
22. Fluorine atom is more electronegative than iodine atom yet, HF has lower
acid strength than HI. Explain?
23. What are interhalogen compounds? How are they formed?
24. Discuss the oxidising power of fluorine.
25. How is XeF6 prepared?
26. Why do noble gases form compounds with fluorine and oxygen only?

96

27. Write the uses of Neon?


C. Answer not exceeding 60 words
28. What are silicones? How are they prepared? Mention its uses?
29. Give an account of manufacture of lead. Describe its important properties
and uses.
30. How are the following compounds prepared from phosphorus?
a) P2O3

b) P2O5

c) PCl3

d) PCl5 e) PH3

31. How fluorine is isolated from their fluorides? Describe its important properties
and uses.
32. Give a detailed account of the interhalogen compounds with special reference
to the compounds involving iodine. Draw their structures.
33. Describe in detail how noble gases are isolated from air?
34. Give an account of various types of compounds which are formed by xenon?
D. Practice Problems
1.

An element A belongs to 14th group is a metal, which can be cut with a


knife. It is not a good conductor of heat and electricity. A in pure state does
not react with water but air dissolved water forms hydroxide. Identify A.

2.

An element A occupies group number 15 and period number 3, exhibits


allotropy and it is tetra atomic. A reacts with caustic soda a to give B which
is having rotten fish odour. A reacts with chlorine to give C which has a
smell of garlic. Identity A, B and C. Write the reactions.

3.

An element A occupies group number 15 and period number 3, reacts with


chlorine to give compound B. The compound B on hydrolysis gives a dibasic
acid C. The compound C on heating undergoes auto oxidation and reduction
to give a tribasic acid D. Identify the element A, compound B, C and D.
Write the reactions.

4.

An element A occupies group number 17 and period number 2, is the most


electronegative element. Element A reacts with another element B, Which
occupies group number 17 and period number 4, to give a compound C.
97

Compound C undergoes sp3d2 hybridisation and has octahedral structure.


Identify the elements A and B and the compound C. Write the reactions.
SUMMARY

Groups 13-18 of the periodic table are known as p-block elements.

Group 13 is known as boron family. Potash alum is manufactured from


alunite.

Group 14 is known as carbon family. Silicones are organo silicon


polymers. Lead is extracted from galena.

Group 15 is known as nitrogen family. Phosphorus form oxides, halides,


oxyacids and hydrides.

Group 16 is known as oxygen family.

Group 17 is known as halogen family. Fluorine has different behaviour than


other halogens. Halogens are extremely reactive and as such they are found
in the combined state only. Fluorine is the most electronegative of all elements.
F2 is obtained by electrolysis of their halide salts.

Group 18 is known as rare gases or inert gases, with closed valence shell
electronic configuration exhibit low chemical reactivity. Xenon can form
compounds with fluorine.

References
1.

Inorganic Chemistry by P.L.Soni.

2.

Inorganic Chemistry by Puri and Sharma.

3.

Concise Inorganic Chemistry by J.D.Lee.

4.

Chemistry fourth edition by McMurry Fay.

98

4. d - BLOCK ELEMENTS
Learning Objectives
( To study the nature of four transition series and their general
characteristic properties of d-block elements.
(To learn the general methods of extraction of metals.
( To have an idea about the composition, properties and uses of alloys.
( To study about the methods of preparation of compounds, their
properties and uses.

There will come a time, when the world will be filled with one science, one
truth, one industry, one brotherhood, one friendship with nature... this is my
belief, it progresses, it grows stronger, this is worth living for, this is worth
waiting for.
Dimitry Mendeleyev, Russian Chemist in YA Urmantsev.

99

27
Co
40
Zr

46
Pd

110
Uun

The d-block elements are located in the middle of the periodic table and
consists of metals only. It consists of four series, each series consists of 10 elements.
In these elements, the last electron enters the d orbital of the penultimate
shell i.e. the last electron goes to (n-1) d orbital. Hence these elements are named
as d-block elements. These elements have partly filled d-subshells in their
elementary form or in their simple ions. The d-block elements are called transition
elements because these represent a transition from highly electropositive elements
(metals) of s-block to least electropositive elements (non-metals) of p-block.
Classification of d-block Elements
Based on whether the last electron goes to 3d,4d,5d or 6d orbital, d-block
elements are classified into four series. They are
i)

3d series or First transition series (21Sc to 30Zn)

ii) 4d series or Second transition series (39Y to 48Cd)


iii) 5d series or Third transition series (57La and 72Hf to 80Hg)
iv) 6d series or Fourth transition series (89Ac and 104Rf to 112) or Incomplete
series.

100

Electronic configuration of d-block Elements


In the transition elements, d-orbitals of penultimate shell are successively
filled. The first transition series involves the filling of 3d orbitals. It starts from
scandium (Z=21) and goes up to zinc (Z=30).
The second transition series involves the filling of 4d-orbitals and includes
10 elements from yttrium (Z=39) to cadmium (Z=48).
The third transition series involves filling of 5d-orbitals. The first element of
this series is lanthanum (Z=57). It is followed by fourteen elements called
lanthanides which involve the filling of 4f-orbitals. The next nine elements from
hafnium (Z=72) to mercury (Z=80) belong to third transition series.
The general electronic configuration of transition elements is
(n-1)d1-10 ns1-2.
4.1 General characteristics of d-block elements
4.1.1 Atomic and Ionic Radii
The atomic and ionic radii of transition elements are smaller than those of pblock elements and larger than those of s-block elements. The atomic and ionic
radii of first transition elements are given in the Table 4.1.
Table 4.1 Atomic radii of elements of first transition series
Ele me nt
Atomic
(pm) radii

Sc

Ti

Cr

Mn

Fe

Co

Ni

Cu

Zn

144

132

122

118

117

117

116

115

117

125

The atomic radii of first transition series decreases from Sc to Cr and


remains almost constant till Cu and then increases towards the end. This can
be explained based on two effects namely screening and the nuclear charge
effect. These two effects oppose each other resulting in increase in nuclear
charge. Hence very slight variation in the atomic radii from Cr to Cu is
observed.
It has been observed that Zirconium and Hafnium have almost equal
atomic radii. This is because of lanthanide contraction.
4.1.2 Metallic character
All the transition elements are metals, since the number of electrons in the
outermost shell is very small, being equal to 2. They are hard, malleable and
101

ductile. The presence of partially d-orbitals favours covalent bonding. These


metals are good conductors of heat and electricity.
4.1.3 Formation of coloured ions
Most of the transition metal compounds are coloured in their solid or solution
form. The colour of transition metal ions is due to the presence of unpaired
electrons in it and the energy gap between two energy levels in the same
d-subshell being small. Hence very small amount of energy is required for excitation
of electrons from one energy level to the other. The energy can be easily provided
by the visible light. The colour observed corresponds to the complementary colour
of the light absorbed.
The colour of some transition metal ions are given in the Table 4.2.

102

It may be noted that Zinc, Cadmium and Mercury salts do not form any
coloured compounds because of the absence of vacant d orbitals to which electrons
can be excited. Sc3+ ions are also colourless because of the absence of d-electrons.
4.1.4 Catalytic Properties
Most of the transition metals and their compounds are used as catalyst.
The catalytic activity of transition metals is due to the following reasons.
i)

They show a variety of oxidation states and thereby can form intermediate
products with various reactants.
ii) They are also capable of forming interstitial compounds which can adsorb
and activate the reacting species.
Some examples of catalyst are
i)

Iron / molybdenum act as catalyst in the synthesis of ammonia by Habers


Process.
ii) Vanadium pentoxide (V2O5) is used for catalytic oxidation of SO2 to SO3
iii) TiCl4 is employed as a catalyst in the manufacture of polythene.

4.1.5 Variable oxidation states


All transition elements exhibit variety of oxidation states (or) variable valencies
in their compounds. This property is due to the following reasons.
i)

These elements have several (n 1) d and ns electrons.

ii)

The energies of (n 1)d and ns orbitals are fairly close to each other.

Salient features of oxidation states of transition elements


1.

The elements which exhibit the maximum number of oxidation states occur
either in or near the middle of the series. For example , in the first transition
series manganese exhibits maximum number of oxidation states (+2 to +7).

2.

The elements in the beginning of the series exhibit fewer oxidation states
because they have less number of d-electrons which they can lose or
contribute for sharing. The elements at the end of the series exhibit fewer
oxidation states, because they have too many d electrons and hence fewer
vacant d-orbitals can be involved in bonding.

103

3.

The transition elements in lower oxidation states (+2 and +3) generally form
ionic bonds and in higher oxidation state form covalent bonds.

4.

The highest oxidation state shown by any transition metal is +8. For example,
ruthenium and osmium show highest oxidation states of +8 in some of their
compounds.

5.

Some transition metals show oxidation state of zero in their compounds.


Ni(CO)4 and Fe(CO)5 are common examples.

4.1.6 Magnetic Properties


The magnetic properties of a substance are determined by the number of
unpaired electrons in it. There are two main type of substances.
i)

Paramagnetic substances

The paramagnetic character arises because of the presence of unpaired


electrons. Paramagnetic substances are the substances which are attracted by
magnetic field.
ii)

Diamagnetic Substances

Diamagnetic character arises because of the absence of unpaired electrons.


Diamagnetic substance are the substances which are repelled by the magnetic
field.
Most of the transition elements and their compounds are paramagnetic and
are attracted by magnetic field. Greater the number of unpaired electrons in the
substance greater is the paramagnetic character, The magnetic character of a
substance is expressed in terms of magnetic moments. The magnetic moment
can be calculated using the relation

= n(n + 2) BM (Bohr Magneton)


n = number of unpaired electrons
Example
Ti3+ - The number of unpaired electrons is 1. Hence

= 1(1 + 2)BM =

3 = 1.732 B.M
104

Larger the value of magnetic moment, the greater is the paramagnetic character.
In addition to paramagnetic and diamagnetic substance, there are a few
substances such as iron which are highly magnetic as compared to ordinary metals.
These substances are called ferromagnetic substances
4.1.7 Complex formation
The cations of d-block elements have strong tendency to form complexes
with certain molecules (e.g. CO, NO, NH3....etc) or ions (e.g. F-, Cl-, CN....etc) called ligands. Their tendency to form complexes is due to two reasons.
i)

Small size and high positive charge density.

ii)

Presence of vacant (n-1)d orbitals which are of appropriate energy to accept


lone pair and unshared pair of electrons from the ligands for bonding with
them.
Examples of some complex compounds are,
[Cu(NH3)4]2+, [Ag(NH3)2]+, [Fe(CN)6]4-,....etc.

4.1.8 Formation of alloys


Transition metals form alloys with each other. This is because they have
almost similar size and the atoms of one metal can easily take up positions in the
crystal lattice of the other.
Eg. Alloys of Cr-Ni, Cr-Ni-Fe, Cr-V-Fe, Mn-Fe......etc.
4.2 FIRST TRANSITION SERIES
4.2.1 Occurrence and principles of extraction of copper
Atomic mass : 63.54
Valency : 1 and 2
Atomic number : 29
Symbol : Cu
Position in the periodic table : Period Number -4, Group Number -11.
Occurrence
Copper was known to the earliest races of mankind. It was named as cuprum
by the Romans because they used to get it from the island of Cyprus. Copper
is found in the native state as well as in the combined state. Native copper is
found in large quantities in Michigan (USA). In India, copper is mainly found in
Singhbhum (Bihar), Khetri and Darbia (Rajasthan) and in Tamilnadu.
105

Ores
i)
ii)
iii)

Copper pyrite, CuFeS2.


Cuprite or Ruby copper, Cu2O.
Copper glance, Cu2S.
The chief ore of copper is copper pyrite. It yields nearly 76% of the world
production of copper.
Extraction from copper pyrites
Extraction of copper from copper pyrites involves the following steps.
1.

Crushing and concentration


The ore is crushed and then concentrated by froth-floatation process.

2.

Roasting

The concentrated ore is heated strongly in the reverberatory furnace, in


excess of air. During roasting,
i)
ii)
iii)

Moisture is removed.
The volatile impurities are removed.
Sulphur, phosphorus, arsenic and antimony which are present as impurity
are removed as volatile oxides.

S + O2
P4 + 5O2
4As + 3O2

SO 2
2P 2O5
2As2O3

iv) The copper pyrite is partly converted into sulphides of copper and iron.

2CuFeS2 + O2
2FeS + 3O2
3.

Cu2S + 2FeS + SO2


2FeO + 2SO2

Smelting

The roasted ore is mixed with powdered coke and sand and is heated in a
blast furnace. It is made of steel plates lined inside with fire clay bricks. Hot air at
800C is introduced from the tuyers near the base of the furnace. As a result, the
following changes occur.
2FeS + 3O2

2FeO + 2SO2

106

FeO
2Cu2S
Cu2O
FeO

+
+
+
+

SiO2
3O2
FeS
SiO2

FeSiO3 (fusible slag)


2Cu2O + 2SO2
Cu2S + FeO
FeSiO3 (fusible slag)

As a result of smelting, two separate molten layers are formed at the bottom of
the furnace. The upper layer consists of slag and is removed as a waste while the
lower layer is called matte. It chiefly consists of cuprous sulphide and some
unchanged ferrous sulphide.
4.

Bessemerisation

The molten matte is transfered to a Bessemer converter as shown in the Fig.


4.2. The Bessemer is mounted on a horizontal axis and is fitted with small pipes
called tuyeres through which a blast of hot air and fine sand is admitted.
Any sulphur, arsenic and antimony still present escape as their respective
oxides. Ferrous sulphide present in matte is oxidised to ferrous oxide which
combines with silica to form slag
2FeS + 3O2
FeO + SiO2

2FeO + 2SO2
FeSiO3 (slag)

Some of the cuprous sulphide undergoes oxidation to form cuprous oxide


which then reacts with more cuprous sulphide to give copper metal. The impure
metal thus obtained is called blister copper and is about 98% pure.
2Cu2S + 3O2
2Cu2O + Cu2S
5.

2Cu2O
6Cu

+ 2SO 2
+ SO 2

Refining

Blister copper contains about 2% of impurities and it is purified by electrolytic


refining.
Electrolytic Refining
This method is used to get metal of high degree of purity. For electrolytic
refining of copper,
i)
ii)
iii)

A block of impure copper metal acts as anode


A thin plate of pure copper metal acts as cathode
Copper sulphate solution acidified with sulphuric acid is taken as electrolyte.
107

When electric current is passed through the electrolytic solution pure copper get
deposited on the cathode ,impurities settle near the anode in the form of sludge
called anode mud.
Properties
Physical properties
Copper is a reddish brown metal, with high lustre, high density and high
melting point 1356C.
Chemical Properties
i) Action of air and moisture
Copper gets covered with a green layer of basic copper carbonate, in the
presence of CO2 and moisture
2Cu + O2 + CO2 + H2O
ii)

Cu(OH)2 . CuCO3
(Green) Copper Carbonate

Action of Heat

Copper when heated to redness (below 1370K) in the presence of oxygen


or air, first it gets converted to black cupric oxide and further heating to above
1370K, it gets converted into red cuprous oxide.
2Cu + O2

1370 K
Below

1370 K
4Cu + O2 Above

2CuO
2Cu2O

iii) Action of acids


a)

With dil.HCl and H2SO4

Dilute acids such as HCl and H2SO4 have no action on these metals in the
absence of air or an oxidising agent. Copper dissolves in these acids in the
presence of air
2Cu + 4HCl + O2 (air)
b)

2CuCl2 + 2H2O

2Cu + 2H2SO4 + O2 (air) 2CuSO4 + 2H2O


With dil. HNO3
Copper reacts with dil.HNO3 with the liberation of NO gas.
3Cu + 8HNO3(dil) 3Cu(NO3)2 + 2NO + 4H2O
108

c)

With con.HNO3 and con. H2SO4

Copper reacts with con.HNO3 and con.H2SO4 with the liberation of


NO2 and SO2 respectively.
Cu + 4HNO3 (con)

Cu(NO3)2 + 2NO2 + 2H2O

Cu + 2H2SO4 (con)

CuSO4 + SO2 + 2H2O

iv) Action of chlorine


Chlorine reacts with copper, resulting in the formation of copper chloride.
Cu + Cl2
v)

CuCl2

Action of alkalis
Copper is not attacked by alkalies.

Uses
1.
2.
3.
4.

It is extensively used for making electric cables and other electric appliances.
It is used for making utensils, containers, calorimeters, coins, ...... etc.
It is used in electroplating.
It is alloyed with gold and silver for making coins and jewellery.

Alloys of Copper
Alloy

% composition

Uses

i)

Brass

Cu = 60-80, Zn = 20-40 For making utensils, condenser


tubes, wires, .....etc.

ii)

Bronze

Cu = 75-90, Sn = 10-25 For making cooking utensils,


statues, coins ...etc.

iii)

Gun metal Cu = 87, Sn = 10, Zn = 3 For making gun barrels, gears,


castings etc.

109

4.2.2 Occurrence and principles of extraction of chromium


Chromium
Atomic mass

: 51.99

Valency : 0,1,2,3,4,5,6

Atomic number : 24

Symbol : Cr

Position in the periodic table : Period Number -4, Group Number -6.
L.N. Vanquelin, a french chemist discovered a new element in 1797, while
examining a mineral found in Siberia. It was named chromium because it forms
coloured compounds [Greek word - chroma - colour]
Occurrence
Metallic chromium does not occur in the native state. In India chromite ore
occurs in Bihar, Mysore, Chennai and Bombay.
Ores
The important ore of chromium is
Chromite or chrome ore, FeO Cr2O3
The chief ore of chromium is chromite ore.
Extraction of chromium metal from chromite ore
The extraction of chromium metal from chromite ore consists of the following
steps.
1.

Concentration
The crushed ore is concentrated by gravity separation method.

2.

Conversion of the concentrated chromite ore into Na2CrO4

The concentrated ore is mixed with excess of Na2CO3 and a small amount
of lime and roasted in a reverberatory furnace at 900-1000C in the presence
of free supply of air. During this process, chromite ore is converted into soluble
sodium chromate.

110

4(FeO. Cr2O3) + 8Na2CO3 + 7O2 (from air)


900-1000C

Chromite ore

8Na2CrO4 +2Fe2O3 + 8CO2


Soluble
Insoluble
Conversion of Na2CrO4 into Na2Cr2O7
The solution containing Na2CrO4 is treated with a calculated quantity of
H2SO4, Na2CrO4 is converted into Na2Cr2O7.
2Na2CrO4 + H2SO4 Na2Cr2O7 + Na2SO4 + H2O
Conversion of Na2Cr2O7 into Cr2O3
Na2Cr2O7 is heated with carbon to get sodium chromite, Na2Cr2O4 which
on treatment with H2O, gives Cr2O3 precipitate.

Na2Cr2O4 + 3CO

Na2Cr2O4 + H2O

Cr2O3 + 2 NaOH

Na2Cr2O7 + 3C

Reduction of Cr2O3 to chromium metal


Aluminothermic process

Fig. 4.1 Aluminothermic process


1. BaO2 + Mg Powder 2. Fireclay crucible
4. Sand

3. Magnesium ribbon,

5. Cr2O3 + Al

Chromic oxide is mixed with powdered Aluminium in the ratio 3:1 and is
placed in a large fire clay crucible. A mixture of barium peroxide and Mg powder
is placed over this. The crucible is surrounded by sand which prevents loss of
heat by radiation. The mixture is ignited by a piece of Mg ribbon. During this
process a large amount of heat is liberated, in which Cr2O3 is reduced to chromium.
111

The molten chromium is collected in the crucible and aluminium oxide is removed
as slag.
Cr2O3 + 2Al 2Cr + Al2O3 + 468.6 kJ
Properties of Cr
Physical Properties
1.

The metal is silvery white and crystalline.

2.

It is very hard and brittle

3.

It melts at 2113K.

Chemical Properties
1.

Action of air : It is unaffected by air at ordinary temperatures.

When heated to very high temperature at about 2000C it is oxidised to


chromic oxide.
4Cr + 3O2 2Cr2O3
2. Action of Water : There is no action at ordinary temperatures. However it
decomposes steam at red heat to give chromic oxide and hydrogen.
2Cr + 3H2O Cr2O3 + 3H2
3. Action of Acids : It dissolves in dilute hydrochloric acid and sulphuric acid
to liberate hydrogen and forms chromous salts.
Cr + 2HCl CrCl2 + H2
Cr + H2SO4 CrSO4 + H2
4. With hot concentrated sulphuric acid it gives chromic sulphate and liberates
sulphur dioxide.
2Cr + 6H2SO4 Cr2(SO4)3 + 3SO2 + 6H2O
5. Dilute nitric acid does not attack the pure metal while concentrated acid
renders it inactive or passive i.e., it does not show its usual reactions.
6. Action with Halogens : Chromium combines directly with fluorine and dry
chlorine to give chromium (III) halides.
2Cr + 3F2 2CrF3
2Cr + 3Cl2 2CrCl3
112

Use : In chrome - plating.


1.

The articles to be plated with chromium are made the cathode in an electrolytic
bath consisting of chromic acid and sulphuric acid while the anode is made
of a plate of lead. During electrolysis chromium deposits on the article
(cathode). Generally the articles are first plated with nickel and then subjected
to chromium plating.

2.

In the manufacture of alloy steels (e.g.) chrome steel, chrome vanadium


steel, stainless steel and tungsten steel.

3.

Chrome nickel steel is used for armour plates.

4.

Chromium salts are used as mordants and in the manufacture of coloured


glass and pottery.

5.

Chromium compounds are used in dyeing as pigments and in tanning of


leather.

Alloys of chromium
Alloy

% composition

i)

Ferrochrome

Cr = 65% Fe = 35%

It is used in manufacture of
chrome steel, burglar proof safe

ii)

Stainless steel

Cr = 11-13%
C = 0.1 - 0.4%
Fe = 73% Ni = 8%

It is used for cutlery and house


hold wares.

iii)

Nichrome

Cr = 15%, Ni = 60%
Fe = 25%

It is used in resistance wires


for electrical heating

Cr = 20-35%
Co = 40-80%
Ni = 0.25%
C = 0.75 - 2.5%

It is used in cutlery, surgical


instruments,.....etc.

iv) Stellite

113

Uses

4.2.3 Occurrence and principles of extraction of zinc


Zinc
Atomic mass : 65.37
Valence : 2
Atomic number : 30
Symbol : Zn
Position in the periodic table : Period Number -4, Group Number -12.
The ancient used an alloy of Zn and Cu not very different from brass without
knowing its actual composition. Zinc has been known in our country for a long
time and has been mentioned in Ayurvedic treatises as yashda. It is commonly
called jast.
Occurrence
Zinc does not occur in the native form since it is a reactive metal. However,
in the combined state, zinc is widely distributed.
Ores
The important ores of zinc are
i)
ii)
iii)

Zinc blende, ZnS


Calamine, ZnCO3
Zincite, ZnO

The chief ore of Zinc is Zinc blende. In India large deposits of zinc blende occur
in Zawar mines near Udaipur in Rajasthan.
Extraction of Zinc from Zinc blende
The extraction of Zinc from Zinc blende involves the following steps.
1. Concentration
The ore is crushed and then concentrated by froth-floatation process.
2. Roasting
The concentrated ore is then roasted in the presence of excess of air at
about 1200 K.

2 ZnS + 3O2 2ZnO


3.

+ 2SO2

Reduction

Zinc oxide is mixed with powdered coke and heated to 1673 K in a fire
clay retort, in which ZnO is reduced to zinc metal.
114

ZnO + C 1673
K

Zn + CO

Purification
Zinc is purified by electrolytic refining. In this process, Impure Zinc is anode
and cathode is of pure thin sheet of Zinc. The electrolyte is ZnSO4 solution
containing a little of dil.H2SO4. On passing electric current, pure zinc get deposited
at the cathode.
Properties
Physical properties
i)
ii)
iii)

Zinc is a bluish white metal


It is good conductor of heat and electricity.
It is malleable and ductile.

Chemical properties
i)

Action of air

When heated in air at 773 K, it burns to form a white cloud of Zinc oxide
which settles to form a wooly flock called philosophers wool.
773 K
2Zn + O2
2ZnO

ii)

Action of water

Pure zinc does not react with water but impure zinc (Zn-Cu couple)
decomposes steam quite readily evolving H2 gas.
Zn + H2O (steam) ZnO + H2
iii) Action of dilute acids
Pure zinc is not attacked by dilute acids. However, impure zinc reacts with
dilute acids with the liberation of H2.
Zn + 2HCl

Zn + H2SO4

ZnCl2 + H2
ZnSO4 + H2

iv) Action of con.H2SO4


Zinc reacts with hot con.H2SO4 forming ZnSO4.
Zn + 2H2SO4

ZnSO4 + SO2 + 2H2O


115

v)

Action of HNO3

Zinc reacts with HNO3 at various concentrations and it gives different


products.
4 Zn + 10 HNO3 (dil) 4 Zn (NO3)2 + N2O + 5 H2O
Nitrous oxide
4 Zn + 10 HNO3 (very dilute) 4 Zn (NO3)2 + NH4NO3 + 3H2O
Ammonium nitrate
vi) Action of alkalies
Zinc dissolves in hot NaOH solution forming soluble zincate ion.
Zn + 2NaOH + 2H2O Na2ZnO2 + H2O
Sodium zincate
Uses of zinc
1.
2.
3.
4.

It is widely used for galvanizing iron sheets.


It is used in the extraction of gold and silver by the cyanide process.
Zinc plates and rods are used in batteries and dry cells.
Zinc dust and granulated zinc are used in laboratory as reducing agents.

4.3 SECOND TRANSITION SERIES


4.3.1 Occurrence and principles of extraction of silver
Silver
Atomic mass : 108
Valency : 1
Atomic number : 47
Symbol : Ag
Position in the periodic table : Period Number -5, Group Number -11.
Occurrence
Silver occurs both in the native as well as in the combined state.
Ores
The important ores of silver are
i) Argentite or silverglance, Ag2S
ii) Horn silver or chlorargyrite, AgCl
iii) Pyrargyrite or Ruby silver, Ag2S . Sb2 S3
The chief ore of silver is Argentite. The silver content in these ores is very small
116

(about 1%). Silver is obtained to a small extent from the gold ores in the kolar
fields in Karnataka and in the Anantapur mines.
Extraction of silver from the Argentite ore
Silver is extracted from the argentite ore by the Mac-Arthur and Forrests
cyanide process. The various steps involved in this process are as follows.
1.

Concentration
The crushed ore is concentrated by froth-floatation process.

2.

Treatment of the ore with NaCN

The concentrated ore is treated with 0.4-0.6% solution of sodium cyanide


for several hours. The mixture is continuously agitated by a current of air, so that
Ag present in the ore is converted into soluble sodium argento complex.
Ag2S + 4NaCN

3.

2Na [Ag(CN)2] + Na2S


Sodium argento cyanide (soluble)
Precipitation of silver

The solution containing sodium argento cyanide is filtered to remove insoluble


impurities and filtrate is treated with zinc dust, silver gets precipitated.
2Na [Ag(CN)2] + Zn Na2[Zn(CN)4] + 2Ag
4.

Electrolytic refining

The impure silver is further purified by electrolytic refining. The impure silver
is made the anode while a thin sheet of pure silver act as the cathode. The
electrolyte is silvernitrate acidified with 1% nitric acid. On passing electricity
pure silver gets deposited at the cathode.
5.

Extraction of silver from silver coins

Silver coins are Ag-Cu alloys. Ag can be obtained from such an allloy by
dissolving the alloy in concentrated HNO3, a solution containing mixture of AgNO3
and Cu(NO3)2 is obtained. The solution is boiled to expel excess of nitric acid,
then the solution is treated with con.HCl, silver is precipitated as AgCl. AgCl is
separated and converted to silver by fusing with excess Na2CO3.
4AgCl + 2Na2CO3 4Ag + 4NaCl + 2CO2 + O2

117

The silver thus obtained, is purified by fusion with borax and followed by
electrolytic purification.
Properties
Physical properties
i)
ii)

It is a white lustrous metal.


It melts at 1233C and boils at 2485C.

iii) Molten silver absorbs about twenty times its volume of oxygen which it
again expels on cooling. Globules of molten silver are thrown off. This is called
spitting of silver. This can be prevented by covering the molten metal with a
layer of charcoal.
Chemical properties
i)

With dilute HNO3


Dilute HNO3 reacts with silver liberating nitric oxide.
3Ag + 4HNO3 3AgNO3 + NO + 2H2O

ii)

With con.HNO3 or con.H2SO4

Hot con.HNO3 or con.H2SO4 react with silver liberating NO2 and SO2
respectively.
Ag + 2 HNO3 AgNO3 + NO2 + H2O
2Ag + 2H2SO4 Ag2SO4 + SO2 + 2H2O
iii) Action with chlorine
Chlorine attacks silver, forming silver chloride.
2Ag + Cl2 2AgCl
iv) Action of alkalies
Silver is not attacked by alkalies.
Uses of silver
i)
ii)
iii)

Silver salts are used in silvering of mirrors


AgBr is used in photography
Silver salts are used in silver plating.
118

iv) Silver is used in making electrodes.


v) Silver leaf is used in medicine, while silver amalgam is employed in dental
filling.
4.4 THIRD TRANSITION SERIES
4.4.1 Occurrence and principles of extraction of gold
Gold
Atomic mass : 196.97
Valency : 1 and 3
Atomic number : 79
Symbol : Au
Position in the periodic table : Period Number -6, Group Number -11.
Occurrence
Gold is mainly found in the native state either mixed with quartz in ancient
rocks (vein gold) or scattered in sand and gravel (placer gold) or in the alluvial
sand (alluvial gold).
Ores
The important ore of gold is
Alluvial sand or gravel
Nearly half of the total world production of gold comes from the mines in
South Africa. India occupies 8th position among the gold producing countries of
the world and account for about 2% of the total world production. The Kolar
mines in Karnataka produce about 99.97% of our gold output.
Extraction from Gold Ores - Mac Arthur Forrest Cyanide Process.
The extraction of gold from the sulphide or telluride ore involves the following
steps :
i)

Crushing, grinding and concentration

The gold ore is crushed and powdered, and then concentrated by frothfloatation process.
ii)

Roasting

The concentrated ore is roasted in excess of air or oxygen when impurities


of sulphur, arsenic and tellurium are oxidised and escape as their volatile oxides.

119

iii) Treatment with KCN


The finely powdered roasted ore is taken in large vats made up of cement
or iron and having false wooden bottoms with holes. It is then treated with a
dilute (0.5%) solution of KCN in presence of excess of air for 24 hours. As a
result, gold dissolves in KCN to form a soluble complex called potassium
aurocyanide.
4Au + 8KCN + 2H2O + O2 4K[Au(CN)2] + 4KOH
Pot. aurocyanide
iv) Precipitation of gold
The above solution containing potassium aurocyanide is filtered to remove
insoluble impurities and then treated with zinc dust. Gold being less electropositive
than zinc, it gets precipitated.
2K[Au(CN2] + Zn K2[Zn(CN)4] + 2 Au
The precipitated gold is recovered by filtration .It is further purified by electrorefining.
iv) Electrolytic refining
This method is used when very pure gold is required. The impure gold is
made the anode while a thin sheet of pure gold acts as the cathode. The electrolyte
consists of a solution of auric chloride (AuCl3) acidified with 10-12% HCl. On
passing current pure gold gets deposited on the cathode.
Properties
Physical properties
i)

Gold is a lustrous yellow metal which melts at 1063C to a green liquid and
boils at 2610C.

ii)

It is the most malleable and ductile of all metals.

iii)

It is a good conductor of heat and electricity.

Chemical properties
i)

Gold is unaffected by dry or moist air or oxygen.

ii)

Alkalies have no action on gold.


120

iii) With Aquaregia


Gold dissolves in aquaregia (3 parts of con.HCl + 1 part of con.HNO3) to
form auric chloride.
2Au + 9 HCl + 3HNO3 2AuCl3 + 6H2O + 3NOCl
Auric chloride
Nitrosyl chloride
iv) With chlorine
At 200C, gold is readily attacked by chlorine forming auric chloride.
2Au + 3Cl2 2AuCl3
Uses
i)
ii)
iii)

It is used in coinage, jewellery and ornamental vessels.


Gold leaf is used for decorations, lettering and in medicine as tonic.
Purple of cassius which is a combination of gold with colloidal stannic
hydroxide is used for making ruby red glass and high class pottery.

Fineness of gold
Gold content of an alloy of gold is termed its fineness and is generally
expressed in carats. Pure gold is 24 carats. Ornaments available these days are
made of 18 carat gold, which is an alloy containing 18 parts by weight of gold
alloyed with 6 parts by weight of another metal generally copper.
4.5 COMPOUNDS
4.5.1 Potassium dichromate (K2Cr2O7)
Preparation of potassium dichromate from chrome iron ore
The preparation of K2Cr2O7 from its ore involves the following steps
i)

Conversion of chrome iron ore to sodium chromate

The powdered ore is mixed with Na2CO3 and quick lime, then roasted in a
reverberatory furnace with free expose to air.
4FeO.Cr2O3 + 8Na2CO3 + 7O2 8Na2CrO4 + 2Fe2O3 + 8CO2
ii)

Conversion of Na2CrO4 to Na2Cr2O7

Sodium chromate solution so obtained is filtered and treated with con.H2SO4,


when sodium chromate is converted to sodium dichromate.
2Na2CrO4 + H2SO4 Na2Cr2O7 + Na2SO4 + H2O
121

iii) Conversion of sodium dichromate into potassium dichromate


Hot concentrated solution of sodium dichromate is treated with KCl, when
potassium dichromate, being much less soluble than sodium salt, crystallizes out
on cooling.
Na2Cr2O7 + 2KCl

K2Cr2O7 + 2NaCl

Properties
Physical properties
1.
2.

It forms orange red crystals which melt at 396C.


It is moderately soluble in cold water but freely soluble in hot water.

Chemical properties
1.

Action of Heat

On heating, K2Cr2O7 decomposes to give potassium chromate with evolution


of O2 gas.
4K2Cr2O7 4K2CrO4 + 2Cr2O3 + 3 O2
2.

With Alkalies

When an alkali is added to an orange-red solution of K2Cr2O7, a yellow


solution results due to formation of potassium chromate.
K2Cr2O7 + 2KOH 2K2CrO4 + H2O
Orange-red
Yellow
on acidifying the yellow colour of K2CrO4 again changes to orange red due to
reformation of K2Cr2O7.
2K2CrO4 + H2SO4 K2Cr2O7 + K2SO4 + H2O
Orange red
The inter conversion is explained on the basis of the fact that in K2Cr2O7 solution,
orange red Cr2O72- ions are in equilibrium with yellow CrO42- ions.
Cr2O72- + H2O
Orange red
3.

2CrO42- + 2H+
Yellow

Oxidising properties
K2Cr2O7 is a powerful oxidising agent. In presence of dil.H2SO4, one mole
122

of this compound gives three atoms of oxygen as shown below.


K2Cr2O7 + 4 dil.H2SO4 K2SO4 + Cr2 (SO4)3 + 4H2O + 3(O)
Some other examples of oxidising property of K2Cr2O7 are given below.
i)

It liberates I2 from KI
K2Cr2O7 + 7H2SO4 + 6KI 4 K2SO4 + Cr2 (SO4)3 + 3 I2 + 7H2O

ii)

It oxidises ferrous to ferric salt


K2Cr2O7 + 7H2SO4 + 6 FeSO4
K2SO4 + Cr2 (SO4)3 + 3 Fe2 (SO4)3+ 2H2O

iii) It oxidises H2S to sulphur


K2Cr2O7 + 4H2SO4 + 3H2S K2SO4 + Cr2 (SO4)3 + 7H2O + 3S
4.

Chromyl chloride test

When salt containing chloride is treated with K2Cr2O7 and con. H2SO4
reddish brown vapours of chromyl chloride are obtained.
K2Cr2O7 + 4KCl + 6H2SO4 2CrO2Cl2 + 6 KHSO4 + 3H2O
Chromylchloride
This reaction is used in the detection of chloride ions in qualitative analysis.
Uses
i)
ii)
iii)
iv)

It is used in volumetric analysis


In chrome tanning in leather industry
In calico printing and dyeing
In photography and in hardening gelatin film.

4.5.2 Copper Sulphate (CuSO4.5H2O); Blue vitriol


Preparation
In laboratory it is prepared by dissolving cupric oxide (or) cupric hydroxide
(or) cupric carbonate in dilute H2SO4
CuO + H2SO4
CuSO4 + H2O
Cu(OH)2 + H2SO4 CuSO4 + 2H2O
CuCO3 + H2SO4
CuSO4 + H2O + CO2
123

Properties
Physical properties
1.
2.

The anhydrous salt is colourless but the hydrated salt is blue in colour.
It readily dissolves in water but is insoluble in alcohol.

Chemical Properties
1.

Action of Heat

On heating CuSO4.5H2O loses its water of crystallization and decomposes


at 720C to give cupric oxide and sulphur trioxide.
C u S O 4 .5 H 2 O
(B lu e)

SO 3 + CuO
2.

1 0 0 C
-4 H 2 O
7 2 0 C

C u S O 4 .H 2 O
-H 2 O 2 3 0 C
CuSO 4
(W h ite)

Action of ammonia

Copper sulphate gives deep blue colour with NH4OH forming complex
compound.
CuSO4 + 4NH4OH [Cu (NH3)4]SO4 + 4H2O
3.

Action of KI

When KI is added to a solution of CuSO4, a white precipitate of cuprous


iodide is produced.
CuSO4 + 2KI Cu I2 + K2SO4
(unstable)
2CuI2 Cu2I2 + I2
(white ppt)
4.

Action with KCN

A yellow precipitate of cupric cyanide is first formed with KCN and it


decomposes to give cyanogen gas.
CuSO4 + 2KCN Cu(CN)2 + K2SO4
124

2Cu(CN)2 Cu2(CN)2 + (CN)2


cyanogen
5.

Action of alkalies
With alkalies, a pale blue precipitate of copper hydroxide is formed.
CuSO4 + 2NaOH Cu(OH)2 + Na2SO4
Pale blue precipitate

6.

Action with H2S


With H2S it gives a black precipitate of copper sulphide.
CuSO4 + H2S CuS + H2SO4
(Black ppt)

Uses
1.

It is used as a germicide and insecticide in agriculture.

2.

A mixture of copper sulphate and lime, commonly known as Bordeaux


mixture, is used as fungicide.

3.

It is used in electroplating, calicoprinting and in electrical batteries.

4.5.3 Silver nitrate or Lunar caustic (AgNO3)


Preparation
Silver nitrate is prepared by dissolving silver in dilute nitric acid.
3Ag + 4HNO3 3AgNO3 + 2H2O + NO
Properties
Physical
1.
2.

It is soluble in water.
Its aqueous solution may decompose on exposure to light.

Chemical Properties
1.

Action of Heat
On heating AgNO3 decomposes in two stages

125

2A gN O 3
A gN O 2
2.

723 K

980 K

2A gN O 2 + O 2
S ilv er n itrite
Ag

+ NO2

With NaCl
AgNO3 gives white precipitate of AgCl with soluble ionic chlorides.
AgNO3 + NaCl AgCl + NaNO3

3.

Silver nitrate is strongly caustic and oxidizing in nature.

4.

With KBr & KI

AgNO3 gives pale yellow precipitate of AgBr with bromides and yellow
AgI with iodides.
AgNO3 + KBr AgBr + KNO3
Yellow ppt
AgNO3 + KI AgI + KNO3
Yellow ppt
5.

Action with organic compounds

Ammoniacal silver nitrate (Tollens reagent) is reduced to silver mirror by


compounds like formic acid, formaldehyde or glucose
2AgNO3 + 2NH4OH Ag2O + 2NH4NO3 + H2O
Ag2O + HCOOH 2Ag + H2O + CO2
Uses
1.
2.
3.
4.
5.

It is used in the preparation of silver halides which are extensively used in


photography.
It is used in silvering mirrors.
It is used in preparation of marking inks and hair dyes.
It is used for silver plating.
It is used as laboratory reagent.

126

4.5.4 Zinc carbonate (ZnCO3)


Zinc carbonate occurs in nature as calamine.
Preparation
When NaHCO3 is added to Zinc sulphate solution, ZnCO3 is obtained.
ZnSO4 + 2NaHCO3 ZnCO3 + Na2SO4 + H2O + CO2
Properties
Physical properties
It is a white powder, insoluble in water.
Chemical properties
i)

Action of Heat

On heating at 300C , Zinc carbonate decomposes into Zinc oxide and


carbon dioxide
C
ZnCO3 300

ZnO + CO 2
Uses
i)
ii)
iii)

It is used in making ointment for curing skin diseases.


It is used in the preparation of cosmetics.
It is used a pigment for rubber.

4.5.5 Purple of cassius


Purple of cassius is only a form of colloidal gold. It is purple or red in colour
and after the name of Cassius who discovered it.
Preparation
It is prepared by mixing very dilute solution of gold chloride with stannous
chloride solution.
2AuCl3 + 3 SnCl2 2Au + 3SnCl4
The gold thus precipitated is adsorbed by stannic hydroxide formed by the
hydrolysis of SnCl4.
SnCl4 + 4H2O Sn(OH)4 + 4HCl
Uses
It is used in making ruby-red glass and high class pottery.
127

SELF EVALUATION
A. Choose the correct answer
1. The general electronic configuration of d-block elements is
a) (n-1)d1-10 ns0-2
b) (n-1) d1-5 ns2
c) (n-1)d0 ns1
d) None of these
2. Formation of coloured ions is possible when compounds contains
a) paired electrons
b) unpaired electrons
c) lone pairs of electrons
d) none of the above
3. Paramagnetism is common in
a) p-block elements
b) d-block elements
c) s-block elements
d) f-block elements
3+
4. The colour of Ti(H2O)6 ion is due
a) d-d transistion
b) Presence of water molecules
c) Inter atomic transfer of electrons
d) None of the above
5. The electronic configuration of chromium is
a) 3d6 4s0
b) 3d5 4s1
b) 3d4 4s2
d) 3d3 4s2 4p1
6. Paramagnetism is the property of
a) paired electrons
b) completely filled electronic subshells
c) unpaired electrons
d) completely vacant electronic subshells
7. d-block elements form coloured ions because
a) They absorb some energy for d-s transition
b) They absorb some energy for p-d transition
c) They absorb some energy for d-d transition
d) They do not absorb any energy
8. The correct electronic configuration of copper atom is
a) 3d10 4s1
b) 3d10 4s2
c) 3d9 4s2
d) 3d5 4s2 4p4
9. Copper is extracted from
a) cuprite
b) copper glance
c) malachite
d) copper pyrites
128

10. Silver salt used in photography is


a) AgCl
b) AgNO3
c) AgF
d) AgBr
11. Sodiumthiosulphate is used in photography because of its
a) Oxidizing behaviour
b) Reducing behaviour
c) Complexing behaviour
d) Photochemical behaviour
12. Excess of sodium hydroxide reacts with zinc to form
b) Na2 ZnO2
c) ZnO
d) Zn(OH)2
a) Zn H2
13. Which of the following compounds will not give positive chromyl chloride
test?
b) HgCl2
c) ZnCl2
d) C6H5Cl
a) CuCl2
14. Which of the ions will give colourless aqueous solution?
a) Ni2+
b) Fe2+
c) Cu2+
d) Cu+
15. Which of the following compounds is not coloured?
a) Na2CuCl4 b) Na2CdI4 c) K4 [Fe(CN)6]
d) K3[Fe(CN)6]
16. In the extraction of Cu, the reaction which does not take place in the
Bessemer converter is
a) 2CuFeS2 + O 2 Cu2S + FeS + SO2
b) 2Cu2S + 3O2 2Cu2O + 2SO2
c) 2Cu2O + Cu2S 6Cu + SO2
d) 2FeS + 3O2 2FeO + 2SO2
17. Select the wrong statement
a) All cuprous salts are blue in colour
b) Transition metals are highly reactive
c) All cuprous salts are white in colour
d) Mercury is a liquid metal
18. Choose the wrong statement regarding K2Cr2O7
a) It is a powerful oxidizing agent
b) It is used in tanning industry
c) It is soluble in water
d) It reduces ferric sulphate to ferrous sulphate
19. For a transistion metal ion, the effective magnetic moment in BM is given by
the formula

129

a)

n(n 1)

b)

n(n + 1)

c)

n(n + 2)

d)

n(n + 1)(n + 2)

20. The correct statement in respect of d-block elements is


a) They are all metals.
b) They show variable valency.
c) They form coloured ions and complex salts.
d) All above statement are correct.
21. Which compound is formed when excess of KCN is added to an aqueous
solution of copper sulphate
a) Cu2(CN)2
b) K2[Cu(CN)6]
c) K[Cu(CN)2]
d) Cu2(CN)2 + (CN)2
22. Which of the following has the maximum number of unpaired electrons?
a) Mn2+
b) Ti3+
c) V3+
d) Fe2+
23. Among the following statement, the incorrect one is
a) Calamine and siderite are carbonates.
b) Argentite and cuprite are oxides.
c) Zinc blende and pyrites are sulphides.
d) Malachite and azurite are ores of copper.
24. The chemical composition of slag formed during the smelting process in
the extraction of copper is
a) Cu2O + FeS
b) FeSiO3
c) CuFeS2
d) Cu2S + FeO
25. The transition element with the lowest atomic number is
a) Scandium
b) Titanium
c) Zinc
d) Lanthanum
26. Which transition element show highest oxidation state
a) Sc
b) Ti
c) Os
d) Zn
B. Answer in one or two sentences
27.
28.
29.
30.
31.

What are d-block elements?


How d-block elements are classified?
Explain why d-block elements exhibit variable oxidation states?
Why transistion elements form complexes?
Why does Mn(II) show maximum paramagnetic character among the bivalent
ions of the first transistion series?
32. Why Zn2+ salts are white while Ni2+ salts are coloured?
130

33. [Ti (H2O)6]3+ is coloured while [Sc (H2O)6]3+ is colourless. Explain.


34. A substance is found to have a magnetic moment of 3.9 BM. How many
unpaired electrons does it contain?
35. Explain why the melting and boiling points of Zn,Cd,Hg are low?
36. Explain why Mn2+ is more stable than Mn3+?
37. Write two alloys of copper and their uses.
38. Write short notes on alumino thermic process?
39. Name the first and last element in the second transition series.
40. Name the lightest and the heaviest elements (in terms of density) among the
transition elements.
41. Which of the following ions would form colourless complexes?
Cu2+, Zn2+, Ti3+, Ti4+, Cd2+
42. What happens when KI solution is added to an aqueous solution of copper
sulphate?
43. What is the action of heat on copper sulphate crystals?
C. Answer not exceeding 60 words
44. Explain briefly the extraction of copper from its chief ore.
45. Name the ores of gold. Explain how it is extracted from its alluvial gavel.
46. List the ores of silver. How silver is extracted from Argentite?
47. Briefly explain the extraction of zinc from zinc blende.
48. Explain how dichromate is extracted from its chromite are. Write the balanced
chemical equation for the reaction between an acidified solution of K2Cr2O7
and KI.
D. Exercise Problems
49. The chief ore of Zinc, on roasting gave a compound A, which on reduction
by carbon, gives B. Identity A and B, give the chemical reactions.
50. A sulphate compound of group 11. This compound is also called as Blue
vitriol.The compound undergoes decomposition at various temperature

B 373K

C 423K

D
A 305K

Identify the compounds A, B, C and D.


131

51. A compound of chromium, in which chromium exists in +6 oxidation state.


Its chief ore (A) on roasting with molten alkali gives compound (B).This
compound on acidification gave compound C. Compound C on treatment
with KCl gave compound D. Identify the compounds A,B,C and D. Explain
with proper chemical reactions.
Summary
The general characteristic properties of d- block elements are briefly
explained. General methods of extraction of metals, purification and properties
are thoroughly discussed .The methods of preparation of compounds, properties
and their uses are explained in detail.
References
1.

New concise Inorganic Chemistry by J.D.Lee, 3rd Edition, ELBS.

2.

Advanced Inorganic Chemistry, P.L.Soni.

132

5. f - BLOCK ELEMENTS
Learning Objectives
( To learn the general characteristics of f-block elements and extraction.
( To study the comparison of properties of Lanthanides and Actinides
( To know the general method of extraction of Lanthanides.
( To recognise the uses of Lanthanides and Actinides.

Sweedish chemist Carl mosander discovered the metallic element Lanthanum


in 1839.
In 1951 Nobel prize was shared between Edwin Mcmillan (USA) and Glenn
Seaborg (USA) for discovery and work in chemistry of transuranic elements.
Glean seaborg (University of California) discovered Californium.

133

d -B L O C K
T R A N S IT IO N E L E M E N T S

1 3 -1 7
p -B L O C K

1 8 in ert g ases

1 -2 s-B L O C K

3 -1 2

f- Block
INNER TRANSITION ELEMENTS

The position of f block elements in the periodic table, is explained above.


The elements in which the extra electron enters ( n- 2 )f orbitals are called
f- block elements. These elements are also called as inner transition elements
because they form a transition series within the transition elements. The f-block
elements are also known as rare earth elements. These are divided into two
series.
i) The Lanthanide series (4f-block elements)
ii) The Actinide series (5f- block elements )

5.1 General Characteristics of f-block elements and extraction


5.1.1 The Lanthanide Series
The Lanthanide series include fifteen elements i.e. lanthanum (57 La) to
lutetium (71 Lu). Lanthanum and Lutetium have no partly filled 4f- subshell but
have electrons in 5d-subshell. Thus these elements should not be included in this
series. However, all these elements closely resemble lanthanum and hence are
considered together.
134

General properties of Lanthanides


1. Electronic configuration
The electronic configuration of Lanthanides are listed in the table 5.1. The
fourteen electrons are filled in Ce to Lu with configuration [54 Xe ]4f1-14 5d1 6s2
2. Oxidation states
The common oxidation state exhibited by all the lanthanides is +3 (Ln3+) in
aqueous solutions and in their solid compounds. Some elements exhibit +2 and
+4 states as uncommon oxidation states.
La
+3
Ce
+3, +4, +2
Pr
+3, +4
Nd
+3, +4, +2
3. Radii of tripositive lanthanide ions
The size of M3+ ions decreases as we move through the lanthanides from
lanthanum to lutetium. This steady decrease in ionic radii of M3+ cations in the
lanthanide series is called Lanthanide contraction.
Cause of lanthanide contraction
The lanthanide contraction is due to the imperfect shielding of one 4f electron
by another in the same sub shell. As we move along the lanthanide series, the
nuclear charge and the number of 4f electrons increase by one unit at each step.
However, due to imperfect shielding, the effective nuclear charge increases causing
a contraction in electron cloud of 4f-subshell.
Consequences of lanthanide contraction
Important consequences of lanthanide contraction are given below.
i)

Basicity of ions
Due to lanthanide contraction, the size of Ln3+ ions decreases regularly with
increase in atomic number. According to Fajans rule, decrease in size of
Ln3+ ions increase the covalent character and decreases the basic character
between Ln3+ and OH- ion in Ln(OH)3. Since the order of size of Ln3+ ions
are
La3+ > Ce3+ ............... >Lu3+
135

ii)

There is regular decrease in their ionic radii.

iii)

Regular decrease in their tendency to act as reducing agent, with increase in


atomic number.
iv) Due to lanthanide contraction, second and third rows of d-block transistion
elements are quite close in properties.
v) Due to lanthanide contraction, these elements occur together in natural
minerals and are difficult to separate.
5.1.2 The Actinide Series (5f block elements)
In 1923 Neils Bohr postulated the existence of an actinide series analogous
to the lanthanide series.
The fifteen elements from actinium to lawrencium constitute the actinide
series of the periodic table.
General Properties of Actinide Series
The general electronic configuration of actinides is [Rn] 5f0,1-14 6d0,1-2 7s2
where Rn stands for radon core.
2.

Oxidation states

These elements shows the oxidation states of +2, +3, +4, +5 and +6. Out
of these, +4 oxidation state is most common state.
3.

Radii of M3+ and M4+ ions

The ionic radii of actinide elements decrease gradually as we move along


the actinide series. The steady decrease in the ionic radii with increase in nuclear
charge is called actinide contraction and is analogous to lanthanide contraction.
Cause of actinide contraction
Cause of actinide contraction is the imperfect shielding by 5f-electrons. As
we proceed from one element to the next one in actinide series, the nuclear
charge increases by +1 at each next element which is not compensated due to
poor shielding effect of 5f orbitals due to their more diffuse shape. Hence as the
atomic number increases, the inward pull experienced by 5f-electrons increase.
Consequently steady decrease in size occurs in the actinide series.

136

5.1.3 Extraction of Lanthanides from Monazite sand


The method used for extraction of lanthanides from monazite sand consists
of the steps which have been shown in flowsheet.
Flow sheet : Extraction of lanthanide from monazite sand

H 2 PO 4 )

Individual lanthanides are separated by a suitable physical method. The


anhydrous fluorides and chlorides are heated under argon atmosphere in presence
of calcium at 1270 K to get the individual metal. The pure metal is obtained by
heating the trifluorides of lanthanides in the presence of calcium and lithium.
5.2 Comparison of Lanthanides and Actinides
Points of Similarities and difference. Both show close resemblance
because these involve filling of f-subshells. Both have coloured ions, low

137

electronegativity, high reactivity and show magnetic properties. However, these


also differ from each other as shown in the following table.
Lanthanide s

Actinide s

i)

Binding energies of 4f
electrons are higher.

i)

Binding energies of 5f electrons are


lower.

ii)

Maximum oxidation satate


exhibited by lanthanides is +4
e.g. Ce 4+

ii)

Due to lower binding energies they


show higher oxidation states such
as +4, +5 and +6. Uranium
exhibits +6 oxidation state in UF 6
and UO 2Cl2

iii)

4f electrons have greater


shielding effect.

iii)

5f electrons have poor shielding


effect.

iv)

Most of their ions are


colourless.

iv)

Most of their ions are coloured U 3+


(red), U 4+ (green) and UO 22+
(yellow)

v)

They are paramagnetic but


magnetic properties can be
easily explained.

v)

They are also paramagnetic but


their magnetic properties are very
difficult to interpret.

vi)

They do not form complexes


easily.

vi)

They have much greater tendency


to form complexes.

vii)

Except promethium, they are


non-radioactive.

vii)

All of them are radioactive.

viii)

Their compounds are more basic.

viii) Their compounds are less


basic.
ix)

They do not form oxocations. ix)

They form oxocations such as


UO 22+ , UO + , N pO 2+ , PuO 2+ .

5.3 Uses of Lanthanides and actinides


Use of lanthanides
1.

A pyrophoric alloy which contains cerium, lanthanum and Neodymium; iron;


aluminium; calcium, carbon and silicon is used in cigarette lighters, toys,
flame throwing tanks and tracer bullets.

2.

Ceria (CeO2) and thoria (ThO2) are used in gas lamp materials.
138

3.

Cerium salts are used in dyeing cotton, lead storage batteries and as catalyst.

4.

Lanthanides are used in metallothermic reactions due to their extraordinary


reducing property. Lanthanido - thermic processes can yield sufficiently pure
Nb, Zr, Fe, Co, Ni, Mn, Y, W, U, B and Si.

5.

Alloys of Lanthanides are known as mish - metals .The major constituents


of mish-metals are Ce(45-50%), La(25%), Nd(5%) and small quantities
of other lanthanide metals and Fe and Ca impurities. Mish-metals are used
for the production of brands of steel like heat resistant, stainless and
instrumental steels. Mg- alloys containing 30% mishmetal and 1% Zr are
useful in making parts of jet engines.

Uses of Actinides
1.

U-235 is fissionable, it is used as fuel in nuclear power plants and as a


component in nuclear weapons.

2.

Plutonium - 238 is used as a power source in long mission space probes.


SELF EVALUATION

A. Choose the correct answer


1.

The electronic configuration of Lanthanides is


a)
c)

2.

[Xe] 4f1-7 5d1 6s1


[Xe]4f1-14 5d1-10 6s2

[Rn]5f0-14 6d0 7s0


[Rn]5f0-14 6d0-2 7s1

b)
d)

[Rn]5f0-14 6d0-2 7s0


[Rn]5f0-14 6d0-2 7s2

The lanthanide contraction is responsible for the fact that


a)
b)
c)
d)

4.

b)
c)

The electronic configuration of Actinides is


a)
c)

3.

[Xe]4f0 5d0 6s0


[Xe]4f1-14 5d1 6s2

Zn and Y have about the same radius


Zr and Nb have similar oxidation state
Zr and Hf have about the same radius
Zr and Zn have the same oxidation state

The most common oxidation state of lanthanides is


a) +2

b) +1

c)
139

+3

d)

+4

5.

Lanthanides are extracted from


a) Limonite b) Monazite

6.

The elements in which the extra electron enters (n-2)f orbitals are called
a)
c)

7.

c) Magnetite d) Cassiterite

s block elements
d block elements

b)
d)

p block elements
f block elements

The Lanthanides contraction is due to


a) Perfect shielding of 4f electron b) Imperfect shielding of 4f electron
c) Perfect shielding of 3d electron d) Imperfect shielding of 3d electron

8.

Ceria is used in
a) toys

9.

b) tracer bullets c) gas lamp materials d) none of the above

_______is used in gas lamp material


a) MnO2

b) CeO2

c) N 2O 5

d) Fe2O3

10. Alloys of Lanthanides are called as


a) Mish-metals b) Metalloids c) Plate metals

d) Actinides

11. Metallothermic processes involving Lanthanides are called as


a) Aluminothermic process
c) Reduction process

b) Lanthanido-thermic process
d) Oxidation process

12. _______form oxocations


a) Lanthanides
b) Actinides c) Noble gases
13. Maximum oxidation state exhibited by Lanthanides is
a) +1

b) +2

c) +3

d) Alkalimetals
d) +4

14. Lanthanides are separated by


a) Fractional distillation
c) Fractional Crystallisation

b) Steam distillation
d) Sublimation

B. Answer in one or two sentences


15. What are inner transition ( f-block) elements? Give two examples.
140

16. What is the difference in the electronic configuration of transition and innertransition elements?
17. What are lanthanides? Give the various oxidation states of lanthanides.
18. What are mish metals? Give their uses.
19. Write the uses of Lanthanides and Actinides.
C. Answer not exceeding 60 words
20. What is lanthanide contraction? Discuss its causes and consequences.
21. Account for the following.
i) +3 oxidation state of lanthanides is the most stable.
ii) A few 4f elements show +2 or +4 oxidation states in addition to the
characteristic oxidation state of +3.
iii) Lanthanides are grouped together.
22. Comparing La(OH)3 and Lu(OH)3, which is more basic and explain why?
23. Discuss the position of lanthanides in the periodic table.
24. Describe the extraction of Lanthanides from monozite sand.
Summary
The elements in which the extra electron enters (n-2) f orbitals are called
f-block elements. These elements are also called as inner transition elements.
The two series of f-block elements are lanthanide series and Actinide series. The
general properties of lanthanides and electronic configuration, oxidation states
radii of tripositive ions are discussed. Cause and consequences of lanthanide
contraction are discussed. General properties of actinide elements are given. A
flow chart is given for extraction of lanthanides from monazite sand. Similarities
and differences between lanthanides and actinides are tabulated.
References
1)

Advanced Inorganic Chemistry F.A.Cotton, G.Wilkinson, C.A.Murillo and


M.Bochmann, John Wiley & Sons, 2003.

2)

Advanced Inorganic Chemistry Vol.I Gurdeep Raj, Goel Publishing House,


2002.
141

6.1 INTRODUCTION
A salt is formed by the neutralisation of an acid by a base. There are different
types of salts. They are:-

a)

a) Simple salt
b) Molecular (or) addition compounds
Simple salt
A simple salt is formed by the neutralisation of an acid by a base.
KOH

+ HCl

KCl + H2O

Normally, a simple salt ionises in water and produces ions in solution. The
solution of the simple salt exhibits the properties of its component ions.
b)

Molecular (or) addition compounds

i)

Double salts

These are molecular compounds which are formed by the evaporation of


solution containing two (or) more salts in stoichiometric proportions. Hence the
molecular compounds which dissociate in solution into its constituent ions are
known as double salt. Double salts retain their properties only in solid state.
They are also called as lattice compounds.
Example
K2SO 4 . Al2(SO4)3 . 24H2O

- Potash alum

FeSO4 . (NH4)2 SO4. 6H2O

- Mohrs salt

K2SO 4 . Al2(SO4)3 . 24H2O 2K+ + 2Al3+ + 4SO42- + 24H2O


The double salts give the test of all their constituent ions in solution.
ii)

Coordination (or complex) compounds

Coordination compound is a compound formed from a Lewis acid and a


Lewis base. The molecular compounds, do not dissociate into its constituent
ions in solution are called coordination compounds.
Example
Fe(CN)2 + 4KCN

Fe(CN)2 . 4KCN (or) K4[Fe(CN)6]


143

Ferrous cyanide
Fe(CN)2 . 4KCN

4K+ + [Fe(CN)6]4Complex anion

In K4 [Fe (CN)6] the individual components lose their identity. The metal of
the complex ion is not free in solution unlike metal in double salt in solution.
Nature of coordination (or) complex compounds
i)

An anionic complex compound contains a complex anion and simple


cation.
K4 [Fe(CN)6]

ii)

[Fe (CN)6 ]4complex anion

A cationic complex contains complex cation and simple anion


[Co(NH3 )6] Cl3

iii)

4K+
+
simple cation

[Co(NH3)6]3+ + 3Clcomplex cation


simple anion

In the case of a complex compound, [Cr(NH3 )6] [Co(CN)6], it gives both


complex cation and complex anion
[Cr(NH3)6]3+ + [Co(CN)6]3complex cation complex anion

[Cr(NH3)6] [Co(CN)6]

6.2 TERMINOLOGY USED IN COORDINATION CHEMISTRY


(a) Lewis Acid
All electron acceptors are lewis acids.
(b) Lewis Base
All electron donors are lewis base.
(c) Central metal ion
In the complex ion an acceptor accepts a pair of electrons from the donor
atoms. The acceptor is usually a metal / metal ion to which one (or) more of
neutral molecules (or) anions are attached. The acceptor metal cation is referred
to as central metal cation. Hence, central metal cation in a complex serves as a
lewis acid.
144

(d) Oxidation state


This number denotes the charge, explaining the number of electrons it has
lost to form the cation. It is oxidation number that denotes the charge, if the
central metal atom would have if all the ligand in the complex were removed
along with their electron pairs that were shared with the central atom. It is usually
represented by Roman Numeral.
(e) Ligand (Latin word meaning to bind)
A ligand is an ion (or) a molecule capable of functioning as an electron
donor. Therefore the neutral molecules or ions which are directly attached to the
central metal ion are called as ligand (or) coordination groups. These coordination
groups or ligands can donate a pair of electrons to the central metal ion (or)
atom. Hence, in a complex compound ligands act as Lewisbases.
Types of ligands
When a ligand is bound to a metal ion through a single donor atom, as with
Cl , H2O or NH3, the ligand is said to be unidentate. Whenever a single
coordinating group (or) ligand occupies two (or) more coordination position on
the same central metal ions, a complex possessing a closed ring is formed. Such
ligands are called polydentate ligands. When a single ligand has two coordinating
positions, it is called bidentate ligand and when there are three coordinating positions
available, it is called a tridentate ligand and so on. For example, ethylenediamine
is a bidentate ligand because it has two amino groups each of which can donate
a pair of electrons.
-

..N H - C H - C H - ..N H
2

Name of the ligands


Positive ligands
The positive ligands are named with an ending -ium.
NH2 - NH3+ hydrazinium
This ligand, though positive can bind through the uncharged nitrogen.

145

Neutral ligands
The neutral ligands are named as such without any special name. But water
is written as aqua : Ammonia is written as ammine. Note that two ms to
distinguish from organic amine
CO-Carbonyl, NO-Nitrosyl, NH2 - CH2 - CH2 - NH2-ethylenediamine
(en), Pyridine C5H5N.
Negative Ligands
Negative ligands end in suffix O.
Example
F --Fluoro, Cl --Chloro, C 2O 42--Oxalato, CN --Cyano, NO 2--Nitro,
Br - -Bromo, SO 42- -Sulphato, CH 3COO - -acetato CNS -thiocyanato,
NCS--isothiocyanato, S2O32--thiosulphato.
Chelates
If a ligand is capable of forming more than one bond with the central metal
atom (or) ion then the ring structures are produced which are known as metal
chelates. Hence the ring forming group are described as chelating agents (or)
polydentate ligands.

2 N H 2C H 2C H 2N H 2 + C u

H 2C

..N H
..N H

2+

NH2

Cu
2

.. ..

H 2C

+2

NH2

CH2
CH2

Coordination sphere
In a complex compound, it usually, central metal ion and the ligands are
enclosed with in square bracket is called as coordination sphere. This represents
a single constituent unit. The ionisable species are placed outside the square
bracket.

146

[M(L)n](n-) (or) (n+)


[Fe(CN)6]4- ,

[Cu(NH3)4]2+

These ions do not ionise to give the test for constituent ions.
Coordination number
The coordination number of a metal ion in a complex can be defined as the
number of ligand donor atoms to which the metal is directly bonded. Numerically
coordination number represents the total number of the chemical bonds formed
between the central metal ion and the donor atoms of the ligands. For example in
K4[Fe(CN)6] the coordination number of Fe(II) is 6 and in [Cu(NH3)4]SO4 the
coordination number of Cu(II) is 4.
Charge on the complex ion
Charge on the complex ion is equal to the sum of the charges on the metal
ion and their ligands.
Example
1.

[Cu(NH3)4]2+ can be written as [Cu2+(NH3)4]2+ since NH3 ligand is neutral.


The sum of the charges on the metal ion and the ligands = +2.
This can be determined as shown below
Charge on the metal ion (Cu2+) = +2
Charge on the ligand (NH3) = 4 0 = 0
Net charge on the complex ion = +2 + 0 = +2

2.

Similarly for [Fe(CN)6]4- (or) [Fe2+(CN)6]4The sum of the charge on the metal ion and the ligand = 4.
Charge on the metal ion (Fe2+) = +2
Charge on the ligand (CN-)

= 6 (-1) = 6

Net charge on the complex = +2 6 = 4

147

6.3 IUPAC NOMENCLATURE OF MONONUCLEAR


COORDINATION COMPOUNDS
The rules are outlined below
1.

In naming the entire complex, the name of the cation is given first and the
anion second (just as for sodium chloride), no matter whether the cation or
the anion is the complex species.

2.

In the complex ion, the name of the ligand or ligands precedes that of the
central metal atom (This procedure is reversed for writing formulae).

3.

Ligand names generally end with O if the ligand is negative (chloro for
Cl-, cyano for CN-, hydrido for H-) and unmodified if the ligand is neutral
(methylamine for MeNH2).
Special ligand names are aqua for water, ammine for ammonia, carbonyl
for CO, nitrosyl for NO.

4.

A Greek prefix (mono, di, tri, tetra, penta, hexa, etc.) indicates the number
of each ligand (mono is usually omitted for a single ligand of a given type). If
the name of the ligand itself contains the terms mono, di, tri, like
triphenylphosphine, ligand name is enclosed in parentheses and its number
is given with the alternate prefixes bis, tris, tetrakis instead.
For example, [Ni(PPh3)2Cl2] is named dichlorobis(triphenylphosphine)
nickel(II).

5.

A Roman numeral or a zero in parentheses is used to indicate the oxidation


state of the central metal atom.

6.

If the complex ion is negative, the name of the metal ends in ate for example,
ferrate, cuprate, nickelate, cobaltate etc.

7.

If more than one ligand is present in the species, then the ligands are named
in alphabetical order regardless of the number of each. For example, NH3
(ammine) would be considered as a ligand and come before Cl- (chloro).

Some additional notes


i)

Some metals in anions have special names


B Borate
Au Aurate
Ag
Pb Plumbate Sn Stannate
Cu
148

Argentate
Cuprate

Fe
Ni

Ferrate
Nickelate

ii)

Use of brackets or enclosing marks.

Square brackets are used to enclose a complex ion or neutral coordination


species.
Examples
[Co(en)3]Cl3

tris(ethylenediamine)cobalt(III) chloride

[Co(NH3)3(NO2)3]

triamminetrinitrocobalt (III)

K2[CoCl4]

potassiumtetrachlorocobaltate(II)

note that it is not necessary to enclose the halogens in brackets.


A systematic approach to drawing and naming coordination complexes
For the complex K3[Cr(C2O4)3].3H2O
Q1) What is the central metal ion?

A1) Central metal is Chromium

Q2) What is its oxidation state?

A2) O.S. is III

Q3) What is its electronic configuration? A3) electronic configuration is d3


Q4) What is its coordination number?

A4) C.N. is 6(3 bidentate ligands


present)

Q5) What is the shape of the ion?

A5) structure is octahedral

Q6) Can the structure have isomers?

A6) Yes, optical isomers are possible

Q7) What is the IUPAC name of the


complex?

A7) Potassiumtris(oxalato)
chromate(III) trihydrate

IUPAC Nomenclature of mono nuclear coordination compounds


[CoIII (NH3)5Cl]2+

- pentaamminechlorocobalt(III) ion

[CoIII (NH3)6]Cl3

- Hexaamminecobalt(III) chloride

[CrIII (en)3]Cl3

- Tris (ethylenediamine)chromium(III) chloride

K4[FeII(CN)6]

- Potassium hexacyanoferrate(II)

[NiII(CN)4]2-

- Tetracyanonickelate(II) ion

[CuII(NH3)4]2+

- Tetraamminecopper(II) ion

[PtII Cl2(NH3)2]

- Diamminedichloroplatinum(II)
149

6.4 ISOMERISM
Compounds having the same chemical formula but different physical and
chemical properties due to the different structural arrangements are called isomers.
This phenomenon is known as isomerism.
Coordination compounds exhibit two major types of isomerism, namely
(A) structural isomerism and (B) stereoisomerism (space isomerism). Each of
these is further classified as shown below.
A) Structural isomerism
a) Coordination isomerism
c) Hydrate or Solvate isomerism
e) Ligand Isomerism

b) Ionisation isomerism
d) Linkage isomerism

B) Stereoisomerism
a) Geometrical isomerism

b) Optical isomerism

6.4.1 A) Structural isomerism


a) Coordination isomerism
In a bimetallic complex, both complex cation and complex anion may be
present. In such a case the distribution of ligands between the two coordination
spheres can vary, giving rise to isomers called the coordination isomers. This
phenomenon is called coordination isomerism. This isomerism is illustrated by
the following pairs of complexes where the complex cation and anion contain
different metal centres.
1.

[CoIII(NH3)6] [Cr(CN)6] and [CrIII(NH3)6] [CoIII(CN)6]


Hexammine hexacyano
Hexamine
hexacyano
cobalt(III) chromate(III)
chromium (III) cobaltate (III)

2.

[PtII(NH3)4] [CuCl4] and [Cu(NH3)4] [PtCl4]


Tetraammine Tetrachloro Tetraammine Tetrachloro
platinum (II) cuparate (II) copper (II) platinate (II)

b)

Ionisation isomerism

Coordination compounds having the same molecular formula but forming


different ions in solution are called ionisation isomers. This property is known as
ionisation isomerism.
150

An example of this type of isomerism is furnished by the red-violet,


[Co(NH3)5Br]SO4

[Co(NH3)5 SO4]Br

pentaamminebromocobalt(III) sulphate

pentaamminesulphatocobalt (III) bromide

The red-violet isomer yields sulphate ion and the red isomer furnishes bromide
ion in solution.
[Co(NH3)4Cl2]NO2

and

[Co(NH3)4 NO2Cl]Cl

Tetraamminedichlorocobalt(III) nitrite

[Co(NH3)5NO3]SO4

Tetraamminechloronitrocobalt(III) chloride

and

[Co(NH3)5 SO4]NO3

pentaamminenitratocobalt(III) sulphate
c)

pentaamminesulphatocobalt(III) nitrate

Hydrate isomerism or Solvate isomerism

The best known examples of this type of isomerism occurs for chromium
chloride CrCl3.6H2O which may contain 4, 5, (or) 6 coordinated water
molecules.
1.

[Cr(H2O)4Cl2]Cl.2H2O - Bright green


Tetraaquadichlorochromium(III) chloride dihydrate

2.

[Cr(H2O)5Cl]Cl2.H2O - grey-green
Pentaaquachlorochromium(III) chloride monohydrate

3.

[Cr(H2O)6]Cl3 - Violet
Hexaaquachromium(III) chloride

These isomers have very different chemical properties and on reaction with
AgNO3 to test for Cl- ions, would find 1,2, and 3 Cl- ions in solution respectively.
d)

Linkage isomerism

Linkage isomerism occurs with ambidentate ligands. These ligands are


capable of coordinating in more than one way. The best known cases involve the
monodentate ligands SCN-/NCS- and NO2-/ONOFor example
[Co(NH3)5ONO]Cl2 the nitrito isomer - red colour
pentaamminenitritocobalt(III) chloride - O attached
[Co(NH3)5 NO2]Cl2 the nitro isomer - yellow colour
pentaamminenitrocobalt(III) chloride - N attached
151

e)

Ligand isomerism

Ligand isomerism arises from the presence of ligands which can adopt
different isomeric forms. An example is provided by diaminopropane, which
may have the amine groups in the terminal (1,3-) positions or in the 1,2-positions.
H2N - CH2 - CH2 - CH2 - NH2 or

H2N - CH2 - CH - CH3


|
NH2
6.4.2 Stereoisomerism (space isomerism)
Consider two compounds containing the same ligands attached to the same
central metal ion, but the arrangement of ligands in space about the central metal
ion are different, then these two compounds are said to be stereoisomers and
this phenomenon is known as stereoisomerism. There are two different types of
stereoisomerism. a) Geometrical isomerism or b) Optical isomerism.
a)

Geometrical (or) cis-trans isomerism

Geometric isomers are possible for both square planar and octahedral
complexes, but not tetrahedral. In a cis-isomer two identical (or) similar groups
are adjacent to each other whereas in a trans-isomer they are diametrically
opposite to each other.
Square planar complexes of the type [Ma2b2]n+ where a and b are
monodentate ligands, exist as cis and trans-isomers as shown below. Example
of this type of complexes are [Pt (NH3)2 Cl2] and [Pd(NH3)2 (NO2)2]. The cistrans isomers of these compounds are represented as
a

M
b

b
a
tra n s-iso m e r

b
c is-iso m e r

H 3N

NH3

H 3N

Pt

Pt

NH3
Cl
tra n s-iso m e r

Cl
Cl
c is-iso m e r
c is-d ia m m in ed ich lo ro p la tin u m (II)

Cl

tra n s - d ia m m in ed ic h lo ro p la tin u m (II)

152

H 3N

H 3N

NH3

NO2
Pd

Pd
O 2N

NH3
O 2N
tran s-iso m er

NO2

cis-iso m er
cis-d iam m in ed in itro p allad iu m (II)

tran s-d iam m in ed in itro p a lla d iu m (II)

In the octahedral complex, the different coordination positions are numbered


as shown below

1
2

5
M

4
6

Along the twelve edges of the octahedron, there are twelve cis positions.
They are (1,2) (1,3) (1,4) (1,5) (2,6) (3,6) (4,6) (5,6) (3,4) (4,5) (2,5) and
(2,3). In order to avoid confusion, generally it is assumed that the 1,2 positions
are cis-positions. There are three trans positions; they are (1,6) (2,4) and (3,5).
Normally it is taken that 1,6 positions are trans-positions in order to avoid
confusion.
An octahedral complex of the type [Ma4b2] where a and b are monodentate
ligands, exists as two geometrical Isomers:
n+

b
a

M
a

n+

b
a
M

a
cis-iso m e r

a
b
tran s-isom er

153

A specific example for such Isomerism is [Co(NH3)4 Cl2]+ which exists as


two geometrical isomers.
The octahedral complex are of the type [M(AA)2a2]n where (AA) is a
symmetrical bidentate ligand such as ethylenediamine H2N-CH2-CH2-NH2 and
a is a monodentate ligand. A specific example for this is [Co(H2N-CH2-CH2NH2)2 Cl2]+

H 2C

H2
N

Cl
Cl

Cl
CH2

NH2

NH2

Co
H 2C

N
H2

CH2

Co
NH2

H 2N

H 2C

CH2

H 2N

NH2

CH2

CH2

Cl

cis-iso m e r

tran s-iso m e r

The octahedral complex of the type, [Ma3b3]n, where a and b are


monodentate ligands also exist as geometrical isomers, For example, [Rh(py)3
Cl3] exist as cis-(1,2,3 trichlorocomplex) and trans-(1,2,6-trichloro complex)
isomers as represented below
Cl

Cl
py

py

Cl

Rh

Rh

Cl
tran s-iso m er

py
cis-iso m ers
b)

py

py

Cl

py

Cl

Optical Isomerism

This is a phenomenon in which certain organic or inorganic compounds


have the property of rotating plane polarised light. The compounds which exhibit
this property are called optical isomers. The optical isomers of a compound have
identical physical and chemical properties. The only distinguishing property is
154

that the isomers rotate the plane of polarised light either to the left or right. In a
coordination compound of type [PtCl2(en)2]12+, two geometrical isomers are
possible. They are cis and trans. Among these two isomers, cis isomer shows
optical activity because the whole molecule is asymmetric.
en

en
Cl

lC

Pt

Pt
Cl

lC

en

en

Optical isomers of cis (PtCl2(en)2]2+


6.5 THEORIES OF COORDINATION COMPOUNDS
6.5.1 Werners Theory
Alfred Werner (1866-1919) French born Swiss chemist founded the modern
theory on coordination compounds. His theory and pioneering experimental work
on metal complexes won for him the Nobel Prize for chemistry in 1913. Werner
was the first inorganic chemist to be awarded the nobel prize in chemistry. He is
considered at Father of coordination chemistry.
Brief concepts of Werners theory of coordination compounds
Alfred Werner studied the structure of coordination complexes and put
forward his ideas in the year 1893 which were known as Werners coordination
theory.
Postulates of Werners theory
1)

2)

Every metal atom has two types of valencies


i) Primary valency or ionisable valency
ii) Secondary valency or non ionisable valency
The primary valency corresponds to the oxidation state of the metal ion.
The primary valency of the metal ion is always satisfied by negative ions.
155

3)

4)

Secondary valency corresponds to the coordination number of the metal


ion or atom. The secondary valencies may be satisfied by either negative
ions or neutral molecules.
The molecules or ion that satisfy secondary valencies are called ligands.

5)

The ligands which satisfy secondary valencies must project in definite


directions in space. So the secondary valencies are directional in nature
whereas the primary valencies are non-directional in nature.

6)

The ligands have unshared pair of electrons. These unshared pair of electrons
are donated to central metal ion or atom in a compound. Such compounds
are called coordination compounds.

Werners representation
Werner represented the first member of the series [Co(NH3)6]Cl3 as follows.
In this representation, the primary valency (dotted lines) are satisfied by the three
chloride ions. The six secondary valencies (solid lines) are satisfied by the six
ammonia molecules.
NH3 Cl
H 3N
Cl

NH3
Co

H 3N

Cl
NH3

NH3
Defects of Werners theory
Werners theory describes the structures of many coordination compounds
successfully. However, it does not explain the magnetic and spectral properties.
6.5.2 Valence bond theory (VB Theory)
Valence bond theory, primarily the work of Linus Pauling regarded bonding
as characterized by the overlap of atomic or hybrid orbitals of individual atoms.
The postulates of valence bond theory
1)

The central metal atom/ion makes available a number of vacant orbitals


equal to its coordination number.

156

2)

These vacant orbitals form covalent bonds with the ligand orbitals.

3)

A covalent bond is formed by the overlap of a vacant metal orbital and filled
ligand orbitals. This complete overlap leads to the formation of a metal
ligand, (sigma) bond.

4)

A strong covalent bond is formed only when the orbitals overlap to the
maximum extent. This maximum overlapping is possible only when the metal
vacant orbitals undergo a process called hybridisation. A hybridised orbital
has a better directional characteristics than an unhybridised one.

The following table gives the coordination number, orbital hybridisation and
spatial geometry of the more important geometrics.
Coordination number

Types of hybridisation

2
4
4
6
6

sp
sp3
dsp2
d2sp3
sp3d2

Geometry
linear
tetrahedral
square planar
octahedral
octahedral

Magnetic moment
A species having atleast one unpaired electron, is said to be paramagnetic.
It is attracted by an external field. The paramagnetic moment is given by the
following spin-only formula.

s = n(n+ 2) BM
s = spin-only magnetic moment
n = number of unpaired electrons
BM = Bohr magneton, the unit which expresses the magnetic moment. When
the species does not contain any unpaired electron, it is diamagnetic.
Number of unpaired electrons

Spin-only moment (BM)

1(1 + 2) = 3 = 1.73

2(2 + 2) = 8 = 2.83
157

3(3 + 2) = 15 = 3.87

4(4 + 2) = 24 = 4.90

5(5 + 2) = 35 = 5.92

Applications of valence bond theory


1)

Nickel atom
Outer electronic configuration 3d8
3d

4s2
4s

4p

Ni atom
Ni +2 ion
[Ni(NH3)4]2+

N
N

N
N

N
N

N
N

NH3 NH3 NH3 NH3


3

sp h y brid isa tio n


Number of unpaired electrons = 2

s = 2(2 + 2) = 2.83 BM
Since the hybridisation is sp3, the geometry of the molecule is tetrahedral.
2)

[Ni(CN)4]2-

Another possible geometry for the 4 coordinated complex is the square


planar configuration involving dsp2 hybridisation.
4s
4p
3d
2+
N i io n
The ligand CN- is a powerful ligand. Hence it forces the unpaired electrons to
pair up in d orbitals. Hence this complex ion does not contain unpaired electrons.
It is diamagnetic.

158

4s

3d
[N i(C N ) 4 ]

2-

N
N

4p

N
N

NN

NN

CN CN CN CN

d sp h y brid isatio n
The geometry of the molecule is square planar.
Octahedral complexes
1)

Fe atom
3d6 4s2

Outer electronic configuration


3d

4s

4p

3d

4s

4p

3d

4s

F e ato m
F e + 2 io n
II

[F e (F ) 6 ]

4d

4p
N
N

N
N

F-

N
N

F- F-

N
N

N
N

F-

N
N

F- F-

sp 3 d 2 h y b rid is atio n

Number of unpaired electron = 4

s 4(4 + 2) = 24 = 4.90 BM
The molecule is paramagnetic. The geometry of the molecule is octahedral.
2)

Fe+2 ion
4s

3d

4p

In [Fe(CN)6]4- complex the CN- ligand is a powerful ligand, it forces the unpaired
electrons in 3d level to pair up inside. Hence the species has no unpaired electron.
The molecule is diamagnetic.

159

4s

3d
[F e (C N ) 6 ] 4 -

N
N

N
N

N
N

4p
NN

NN

NN

CN- CN- CN - CN - CN- CNd 2 sp 3 h y b rid isa tio n


The molecular geometry is octahedral.
Defects of Valence bond theory
Although VB theory was the principal way in which chemist visualized
coordination compounds until the 1950s, it has fallen into disfavour due to its
inability to account for various magnetic, electronic and spectroscopic properties
of these compounds.
6.6 Uses of coordination compounds
1.

Dyes and Pigments

Coordination compounds have been used from the earliest times as dyes
and pigments, for example madder dye which is red, was used by the ancient
Greeks and others. It is a complex of hydroxyanthraquinone. A more modern
example is the pigment copper phthalocyanine, which is blue.
2.

Analytical Chemistry

The coordination compounds used for various purpose, in the laboratary are as
follows.
a) Colour Tests : Since many complexes are highly coloured they can be used as
colourimetric reagents e.g. formation of red 2,2-bipyridyl and 1,10-phenanthroline
complexes as a test for Fe2+
b) Gravimetric Analysis : Here chelating ligands are often used to form
insoluble complexes e.g. Ni(DMG)2 and Al(oxine)3.
c) Complexometric Titrations and Masking Agents : An example of this
is the use of EDTA in the volumetric determination of a wide variety of metal ions
in solution, e.g. Zn2+, Pb2+,Ca2+,Co2+,Ni2+,Cu2+, etc. By careful adjustment of
160

the pH and using suitable indicators, mixtures of metals can be analysed, e.g. Bi3+
in the presence of Pb2+. Alternatively, EDTA may be used as a masking agent to
remove a metal ion which would interfere with the analysis of a second metal ion
present.
3.

Extraction of Metals

Sometimes certain metals can be leached from their ores by formation of


stable complexes e.g. Ag and Au as complexes of cyanide ion.
4.

Bio-Inorganic Chemistry
Naturally occurring complexes include haemoglobin, chlorophyll, vitamin
B12 etc.
Therapeutic chelating agents are used as antidotes for heavy metal poisoning.
EDTA and other complexing agents have been used to speed the elimination
of harmful radioactive and other toxic elements from the body. (e.g. Pb2+). In
these cases a soluble metal chelate is formed.
5.

Chemotherapy
An example here is the use of cis-Pt(NH3)2Cl2 as an anti-tumour drug.

6.

Synthetic detergents

Synthetic detergents containing chelating agents such as tripolyphosphate.


The chelating agent sequesters hard-water cations, rendering them incapable of
interfering with the surfactant.
6.7 BIO COORDINATION COMPOUNDS
Coordination compounds play an important role in many biological processes
in plants and animals.
The following table gives some of the important bio coordination compounds.
Name
1.
2.
3.

Haemoglobin
Chlorophyll
Ferredoxins Rubredoxins

Function
Transport and storage of oxygen
Photosynthesis
Electron Transfer

Among the Bio-coordination compounds function and nature of haemoglobin


and chlorophyll play dominant role in natural process.
161

6.7.1 Haemoglobin
Haemoglobin in the red blood cells carries oxygen from the lungs to the
tissues. It delivers the oxygen molecule to myoglobin in the tissues. When the
oxygen has been released for cell respiration, haemoglobin loses its bright red
colour and becomes purple. It then combines with the waste carbon dioxide
produced by the cells and deposits in the lungs so that the gas can be exhaled.
Nature of haemoglobin and myoglobin
Both are having the same structure excepting the fact that myoglobin is a
monomer and haemoglobin is a tetramer. Both are iron-porphyrin complex.
These are biocoordination complexes formed between porphyrin and iron
in its +2 oxidation state (Fe2+). The iron-porphyrin complex is called the heme
group, which is a part of haemoglobin. Each haemoglobin molecule consists of
four subunits, each unit is being a folded chain.
The working part of haemoglobin is a hemegroup containing an Fe2+ cation
coordinated to four nitrogen atoms of porphyrin group and one nitrogen atom of
histidine group. The sixth octahedral site is available to bind oxygen molecule.
6.7.2 Chlorophyll
Chlorophyll is a magnesium - porphyrin complex. The magnesium is at the
centre of the modified porphyrin ring septeon (corrin). The oxidation state of
magnesium is +2 (Mg2+). The modified porphyrin acts as the ligand.
There are several kinds of chlorophyll that vary slightly in their molecular
structure.
In plants, chlorophyll a is the pigment directly responsible for the
transformation of light energy to chemical energy. Hence in plants, the green
pigment chlorophyll helps photosynthesis. The conversion of atmospheric
carbondioxide and atmospheric moisture into carbohydrate and molecular oxygen
in the presence of sunlight, by the plant is called as photosynthesis. Chlorophyll
acts as a light sensitiser in this important process.
xCO 2 + yH 2O chlorophyl
l Cx(H 2O)y + O 2
sunlight

162

Photosynthesis requires, in addition to chlorophyll, the help of four other metal


complexes, a manganese complexes, two iron complexes and a copper complex.
All oxygenated animals take molecular oxygen through haemoglobin and
release CO2. But chlorophyll helps in the conversion of atmosphere CO2 into
molecular oxygen which act as a fuel for human cell.
SELF EVALUATION
A. Choose the correct answer
1.
2.

3.
4.

Which a double salt


a) K2SO4.Al2(SO4)3.24H2O b) NaCl c) K4[Fe(CN)6] d) KCl
An example of a complex compound having coordination number 4.
a) K4[Fe(CN)6]
b) [Co(en)3]Cl3
c) [Fe(H2O)6]Cl3
d) [Cu(NH3)4]Cl2
The geometry of [Cu(NH3)4]2+ complex ion
a) Linear
b) Tetrahedral
c) Square planar
d) Angular
An example of a chelating ligand is
a) NO-2

5.

b) Chloro

d) triangular

b) -1

c) +2

d) -2

[Cu(NH3)4]Cl2
K3[Fe(CN)6]

b)
d)

K4[Fe(CN)6]
[NiCl4]2-

b)
d)

Square planar
Octahedral

The geometry of [Ni(CN)4]2- is


a)
c)

9.

c) Octahedral

Which is not an anionic complex?


a)
c)

8.

b) square planar

The oxidation number of Nickel in the complex ion, [NiCl4]2- is


a) +1

7.

d) en

The geometry of complex ion [Fe(CN)6]4- is


a) tetrahedral

6.

c) Bromo

Tetrahedral
Triangular

An example of an ambidentate ligand is


a) CN-

c) NO2-

b) Cl163

d) I-

10. [FeF6]4- is paramagnetic because


a) F- is a weaker ligand
b) F- is a flexidentate ligand

b) F- is a strong ligand
d) F- is a chelating ligand

11. In [FeII(CN)6]4-, the central metal ion is


a) Fe

b) Fe+2

c) Fe+3

d) CN-

12. The coordination number of Ni(II) in [Ni(CN)4]2- is


a) 2

b) 4

c) 5

d) 6

13. The name of [PtIV(NH3)2Cl2]2+ is


a) Diamminedichloroplatinum(IV) ion
b) Diamminedichloroplanitate(IV)
c) Diamminedichloroplatinum
d) Dichlorodiammineplatinum(IV) ion
14. For a compound K4[Fe(CN)6] 4K+ + [Fe(CN)6]4-, the complex ion is
a) K+

b) CN-

c) FeII

d) [Fe(CN)6]4-

15. A metal ion from the first transition series forms an octahedral complex with
magnetic moment of 4.9 BM and another octahedral complex which is
diamagnetic. The metal ion is
a) Fe2+

b) Co2+

c) Mn2+

d) Ni2+

c) BM

d) ergs

16. Paramagnetic moment is expressed in


a) Debye unit

b) K Joules

17. The type of isomerism found in the complexes [Co(NO2)(NH3)5]SO4 and


[Co(SO4)(NH3)5] NO2
a) Hydrate isomerism
c) Linkage isomerism

b) Coordination isomerism
d) Ionisation

18. Valence bond theory does not explain the property of complex compound
a) geometry

b) magnetic

c) nature of ligand

B. Answer in one or two sentences


19. What are simple salts? Give one example.
164

d) colour

20. What are double salts? Give one example.


21. In what way complex salt differs from double salt?
22. What are ligands and coordination number?
23. Give one example for a monodentate ligand, a bidentate ligand and a chelating
ligand.
24. Calculate the charge on the central metal ion present in the following
complexes.
a) [Fe(NH3)4Cl2] NO3

b) Na[B(NO3)4]

25. Name the following complexes


a) [Co(NH3)5(H2O)]Cl3

b) Na[B(NO3)4]

26. Write the formula structure of the following


a) tris(ethylenediamine)cobalt(III) ion
b) pentaamminesulphatocobalt(III) chloride
27. Draw the structure of cis and trans-[Pt(NH3)2Cl2]
28. What are chelates? Give one example.
C. Answer not exceeding 60 words
29. Explain coordination and ionisation isomerism with suitable examples.
30. Mention the type of hybridisation and magnetic property of the following
complexes using VB theory
a) [FeF6]4-

b) [Fe(CN)6]4-

31. For the complexes K4[Fe(CN)6], [Cu(NH3)4] SO4 mention


a) Name b) Central metal ion c) Ligands d) Coordination number
32. How is the paramagnetic moment related to the number of unpaired electrons
in?
a) K4[Fe(CN)6]

b) K3[Fe(CN)6]

33. In what way [FeF6]4- differs from [Fe(CN)6]4-.


34. [Ni(CN)4]2- diamagnetic, whereas [NiCl4]2- is paramagnetic. Explain.
165

35. [Cu(NH3)4]2+ is square planar, where as [NiCl4]2- is tetrahedral. Explain.


36. Explain the limitations of VB theory.
37. Taking [FeF6]4- as an example, discuss geometry, nature of d-orbital splitting
and magnetic property using VB theory.
38. Mention the function of haemoglobin in natural process.
39. How chlorophyll is important in environmental chemistry? Mention its function.
Summary
The nature of coordination compounds are discussed in detail. The
terminology used in coordination chemistry and types of isomerism found in
coordination compounds are explained with specific examples. The development
of the nature of bonding is discussed using Werners theory and valence bond
theory. The scope and limitations of these theories are also compared. A brief
discussion on applications of coordination compounds is presented. The function
and role of haemoglobin and chlorophyll are explained.
Reference
1.

Coordination Chemistry, S.F.A.Kettle, The English language book society


and Nelson, 1969.

2.

Concise Inorganic Chemistry, J.D.Lee, Chapman and Hall, London, 1992.

166

7. NUCLEAR CHEMISTRY
Learning Objectives
( Review of basic nuclear chemistry.
( Know about the nuclear reactions and chemical reactions.
( Learn about nuclear energy and nature of nuclear fission and nuclear
fusion reactions.
( Learn about principle of nuclear reactors.
( Know about the nuclear reactions in sun.
( Learn about the application of radioactive isotopes including tracer technique
adopted in understanding reaction mechanisms.
Henry Becquerel (France) was awarded nobel prize for his discovery of
spontaneous radioactivity in 1903.
In the same year Pierre Curie (France) and Mary Curie (France) were
awarded for their research on radiation phenomenon. In 1911, Marie Curie
(France) was awarded nobel prize for the discovery of radium and polonium,
and the isolation of radium. In 1938, Enrico Fermi (Italy) was awarded
Nobel Prize for the discovery of nuclear reactions induced by slow neutrons.

167

Nuclear Chemistry
*

Radioactivity : The phenomenon of spontaneous disintegration of certain


atomic nuclei resulting in the emission of radioactive rays is called radioactivity.
Radioactivity is a nuclear phenomenon and it is not affected by external
factors such as temperature, pressure etc. This phenomenon was discovered
by Henry Becqurel.

To explain the spontaneous decay of radioactive elements, Rutherford and


Soddy put forward the theory of radioactive disintegration. According to
this theory the quantity of a radioactive element which disappears in unit
time is directly proportional to the amount (atoms) of radioactive substance
present at that time.
Based on the above theory, the following equation is derived which confirms
that all radioactive reactions follow I order
t=

= decay constant

2.303

N0
N

log

N0
N

= Number of radioactive atoms


present initially
= Number of radioactive atoms
at time t

Half life period : The time required to disintegrate one half of any radioactive
substance is called half life period (t). The half life period (t) of a
radioactive substance is independent of initial concentration. It depends only
on the disintegration constant () of the radioactive element. t is used to
indicate the relative stability of radioactive substance. If t is the shorter,
faster is the rate of decay and hence the substance is more unstable and
viceversa.
0.693

t =

Average life, (Tau) =

1
t
=
= 1.44 t
0.693
168

Since radioactivity is a nuclear phenomenon, it must be connected with the


instability of the nucleus.

An - particle is equal to the bundle of two protons and two neutrons and
hence it is equal to the Helium nucleus (2He4).

-particle is a fast moving electron.

-radiation is a waver of very short wavelength with very high energy.

Radioactive decay series : Radioactive heavy nuclei decay by a series of


- emission or emissions, finally resulting in the formation of a stable
isotope of lead. There are about 4 decay series.
4n - Thorium series
4n+1 - Neptunium series
4n+2 - Uranium series
4n+3 - Actinium series

Binding energy of Nucleus


Whenever a nucleus is formed, certain mass is converted into energy. Hence
for atom, the atomic mass is lower than the sum of masses of protons,
neutrons and electrons present. The difference in mass is termed as mass
defect. This is the measure of the binding energy of proton and neutron in
the nucleus. The relationship between mass - energy is explained by Einstein
equation E = m C2.

7.1 Difference between chemical reactions and nuclear reactions


In ordinary chemical reactions, the nuclei of the atoms taking part in a
chemical reaction remain unaffected. Only the electrons in the extranuclear part
of atoms take part in the chemical process.
However, during disintegration of atoms (naturally or artificially), the nuclei
of atoms are affected resulting in the formation of new nuclei. Such reactions in
which the nuclei of the atoms interact with other nuclei or lighter particles or
photons resulting in the formation of new nuclei and one or more lighter particles
are called nuclear reactions.

169

Chemical reactions

Nuclear reactions

1. These reaction involve some loss,


gain or overlap of outer orbital
electrons of the reactant atoms.

1.

Nuclear reactions involve emission of


alpha, beta and gamma particles from
the nucleus.

2. A chemical reaction is balanced in


terms of mass only

2.

Nuclear reaction is balanced in terms


of both mass and energy.

3. The energy changes in any chemical 3.


reaction is very much less when
compared with nuclear reaction.

The energy changes are far exceed


than the energy changes in chemical
reactions.

4. In chemical reactions, the energy is


expressed in terms of kilojoules per
mole.

4.

In nuclear reactions, the energy


involved is expressed in MeV (Million
electron volts) per individual nucleus.

5. No new element is produced since


nucleus is unaffected.

5.

New element / isotope may be


produced during the nuclear reaction.

The following facts are taken into account while expressing a nuclear reaction:
i)

Reactions are written like a chemical equation. Reactants are written on the
left hand side and products on the right hand side with an arrow in between.

ii)

Mass number is written as super script on the symbol of the element. For
example 7N14 stands for an atom of nitrogen with mass number 14 and
atomic number 7.

iii)

In a chemical reaction the total number of atoms of various elements are


balanced on the two sides. Similarly in nuclear reaction , the total mass
number and atomic number are balanced on the two sides.

iv) Symbols used for projectiles:


The bombarding particles are called projectiles. These projectiles are
represented by the following symbols.
n1
H1 or p
1
He4 or
2
H2 or 1D2
1
e0 or e
-1
e0
+1
0

neutron
proton
particle
deuteron
electron or -particle
positron
170

The nucleus to be attacked is called as target nucleus or parent. The new


nuclide is called as recoil nucleus or daughter. The particle ejected during a
nuclear reaction is called as ejected particle.
Representation of nuclear reaction:
7

N14

He4

O17

projectile

H1

ejected particle

This reaction can be represented as (, p) type reaction .Hence the above


reaction is represented as 7N14 (,p) 8O17.
Balancing of nuclear reaction
Example

17

Cl37 + 1H2

17

Cl37 + 1H2

18

Ar38 + ?

Solution

18

Ar38

x1

x is neutron
Hence
17

Cl37 + 1H2

18

Ar38 + 0n1

This reaction is represented as


17

Cl37 (D, n)

18

Ar38

Q value of a nuclear reaction


The amount of energy absorbed or released during nuclear reaction is called
Q-value of nuclear reaction.
Qvalue
where

mr
mp

(mp-mr) 931 MeV

- Sum of the masses of reactants


- Sum of the masses of products

In the case of energy absorbed then mp>mr, then Q value will be positive.
Q value of a nuclear reaction in the case of energy released = (mpmr)
931 MeV. In the case of energy released, mr>mp, and hence Q value will be
negative.
171

7.2 TYPE OF NUCLEAR REACTION


1.

Spallation reaction

These are the reactions in which high speed projectiles may chip a heavy
nucleus into several fragments.
29

2.

Cu63 + 2He4 + 400 MeV 17Cl37 + 14 1H1 + 16 0n1

Nuclear fission reaction

Nuclear fission is the process in which a heavy nucleus breaks up into two
lighter nuclei of almost equal size with the release of an enormous amount of
energy. This type of nuclear fission reaction was first observed by German
Chemists Otto Hahn, F.Strassman and Meitner by bombarding 92U235 with slow
moving neutrons. The process is usually accompanied by emission of neutrons.
The nuclear fission has been produced in heavy nuclei such as 235U,238U, 232Th
by neutrons, protons, deuterons.
Mechanism of fission
In the fission process, the heavy nucleus absorbs a neutron and forms an
unstable compound nucleus. The compound nucleus then breaks up more or less
in the middle to give fission product.
Example
A typical example of the fission process in the fission of uranium by neutrons
is explained by the following equation.
92

U235 + 0n1

56

Ba141 + 3 0n1 + 200 MeV

Further, the neutrons released (say three) from the fission of first uranium atoms
can hit three other uranium atoms. In this way a chain reaction is set up resulting
into the liberation of an enormous amount of energy. In the case of nuclear fission,
U236 formed breaks up in several ways.
92
140

92

235

+ 0n

1
92

93

B a + 36K r + 3 0n
144
+ 38 S r 90 + 2 0 n 1
5 4X e
144
90
1
+ 3 7R b + 2 0n
55C s

56
236

172

This fission process is self multiplying process and hence a tremendous amount
of energy is released in a very short interval of time. Therefore, explosion takes
place. Atom bomb is based on nuclear fission process.
Energy released in nuclear fission reaction
92

U235 + 0n1

42

Mo95

57

La139 + 20n1 + 7-1e0

The isotopic mass of U235


= 235.118 amu
The isotopic mass of 42Mo95 = 94.936 amu
The isotopic mass of 57La139 = 138.95 amu
The isotopic mass of 0n1
= 1.009 amu
235.118 + 1.009 94.936 + 138.95 + 2 1.009
236.127 amu 235.906 amu
The mass converted into energy is
= (236.127 235.906) amu
= 0.213 amu
Since 1amu (atomic mass unit) = 931 MeV, for one 235U fission energy
released = 0.213 931.48 = 200 MeV
The first atom bomb used in Hiroshima (Japan) utilised 92U235 isotope as
the main reacting substance and second bomb in Nagasaki made use of
Plutonium (239) (August 1945). The fission in both the cases is similar and
uncontrolled. Enormous amount of energy equal to that produced by 20000
tons of TNT is produced accompanied by heat, light and radioactive
radiations.
Nuclear Power Generator
A nuclear reactor or nuclear power generator is a kind of furnace for carrying
out the controlled fission of a radioactive material like U235 for producing power.
The core of the nuclear reactor produces heat through nuclear fission. Heavy
water at high pressure takes heat away from the core. In the heat exchanger, the
heavy water inside the reactor gives up its heat to water outside the reactor,
which boils to form steam. The steam is taken away to drive turbines that make
electricity. In Tamilnadu atomic power stations generating electricity are situated
at Kalpakkam and another one is being constructed at Koodamkulam.
173

3)

Nuclear Fusion

When lighter nuclei moving at a high speed are fused together to form a
heavy nucleus, the process is called nuclear fusion.
In fusion reaction, the mass of heavier nucleus formed is less than the total
mass of two lighter nuclei. Thus, just like a fission reaction, the source of energy
in a fusion reaction is also the disappearance of mass, which gets converted into
energy.
Nuclear fusion reaction takes place at very high temperature of about 108K.
Therefore, this reaction is called thermonuclear reaction.
H2 + 1H3
Deuterium Tritium
1

He4 + 0n1 +
Helium

Energy

The Mass loss is equal to 0.018 amu and the corresponding energy released
is 1.79 109 KJmol-1.
Hydrogen Bomb
The highly destructive hydrogen bomb is also based on the fusion reactions
of hydrogen to form helium producing large amount of energy. Hydrogen bomb
consists of an arrangement for nuclear fission in the centre surrounded by a mixture
of deuterium (1H2) and lithium isotope (3Li6). Fission reaction provides the high
temperature necessary to start the fusion.
Fusion reactions take place in hydrogen bomb.
i)
ii)

Fission
Li6 + 0n1
3
H2 + 1H3
1

heat + neutrons
H3 + 2He4 + 4.78 MeV
1
He4 + 0n1 + 17.6 MeV
2

7.3 RADIOCARBON DATING


This method was developed by Willard and Libby to determine the age of
wood or animal fossils. This method is based onthe fact that 6C14, radioactive
isotope of carbon is formed in the upper atmosphere by reaction with neutrons
(from cosmic rays).
7

N 14 +

n1

C 14 + 1H1

The C14 atoms thus produced are rapidly oxidised to 14CO2 which in turn is
incorporated in plants as result of photosynthesis. Animals too consume C14 by
174

eating plants. On death, organisms cease to take in fresh carbonations. Carbon14 begins to decay.
6

C 14

N 14 +

-1

e0

5700 years a fossil (plant or animal) will lose half the amount of carbon-14
present in its living state. Therefore by knowing either the amount of C14 or the
number of -particles emitted per minute per gram of carbon at the initial and
final stages, the age of carbon material can be determined by the following equation.
t=

2.303 t
0.693

log

Amount of C14 in fresh wood


Amount of C14 in dead wood

Uses
1)

Carbon dating has proved to be a great tool for correlating facts of historical
importance.

2)

It is very useful in understanding the evolution of life, and rise and fall of
civilizations.

7.4 NUCLEAR REACTIONS TAKING PLACE IN SUN (STARS)


It has been estimated that the sun is giving out energy equally in all possible
directions at the rate of 3.7 1033 ergs/sec. The energy of the sun is supposed to
arise from the fusion of hydrogen nuclei into helium nuclei which in going on
inside it all the time.
The various fusion reactions taking place in the sun are as follows:
a)

Proton - proton chain reaction:


2
0
H1 + 1H1 fusion
+ energy
1H + +1e
1
positron
2
1
3
fusion
H + 1H
2He + energy
1
He3 +1H1

4
0
fusion
2He + +1e + energy

The overall reaction, therefore, may be written as:


4
0
4 1H1 fusion
2He + 2 +1e + energy

175

7.5 USES OF RADIOACTIVE ISOTOPES


a) Study of reaction mechanism
i) Mechanism of photosynthesis in plants
*
A small quantity of Radioactive C O 2 containing radioactive oxygen O18 is
mixed with ordinary carbondioxide and the process is carried out. It has been
found that oxygen gas evolved along with sugar formation is non-radioactive.
Therefore O2 produced comes from water and not from carbondioxide. So the
correct mechanism is as follows.
*
*
6C O 2 + 6H2O C6H12 O 6 + 6O2
ii)

Study of hydrolysis of ester

By labelling oxygen, the mechanism of ester hydrolysis can be studied by


using water labelled with O18. The hydrolysis of an ester by water enriched with
radioactive oxygen is indicated as :
O

O
*
+ HOH

R -C

R -C

+ R - OH
*
OH
Therefore it is the acid and not alcohol produced which is radioactive confirming
the above mechanism.
OR

Radioactive isotopes which are useful in medicine


Isotope

Use

H3

Tritium

Measure water content of the body

C 11

Carbon - 11

Brain scan

C 14

Carbon - 14

Radio immunology

I131

Iodine - 131

Diagnosis of damaged heart muscles and hyper


thyroidism

Hg197

Mercury - 197

Kidney scan

15

P 32

Phosphorous-32

Detection of eye tumours

26

Fe59

Iron - 59

Diagnosis of anemia

27

Co60

Cobalt - 60

Treatment of cancer

53

80

176

Na24

Sodium - 24

Location of blood clots and circularity


disorders

Au198

Gold - 198

Curing of cancers

11

79

Radio isotopes which are useful in industry and in agriculture


38

Sr90

Strontium - 90 Thickness of coatings or levels of liquids in tanks

Practice Problems
1)

On neutron bombardment fragmentation of U-235 occurs according to the


equation
92

U235 + 0n1

42

Mo95 + 57La139 + x -1e0 + y 0n1

Calculate the values of x and y.


[Ans : x = 7, y = 2]
2)

On neutron bombardment fragmentation of U-235 occurs according to the


equation.
92

U235 + 0n1

42

Mo98 + 54Xe136 + x -1e0 + y 0n1

Calculate the values of x and y.


[Ans : x = 4, y = 2]
Solved Problems
1.

After 24 hours, only 0.125 g out of the initial quantity of 1g of a radioisotope


remains behind. what is half-life period?

Solution
N0 = 1g
=

N = 0.125 g, t = 24 hours
2.303
N
log 0
t
N

2.303
1
log
24
0.125
= 0.0866 hour-1
=

t =

0.693 0.693
=
= 7.99 hours

0.0866
177

2.

Half-life period of a radioactive element is 100 seconds. Calculate the


disintegration constant and average life period. How much time will it take
for 90% decay?

Solution
t
=

= 100 sec
0.693
t

0.693
= 0.00693 sec 1
100

1
1
=
= 144.3 sec
0.00693
For 90% decay, N0 = 100; N = (100 - 90) = 10

Average life period, =

3.

t =

2.303

2.303
0.00693

log

2.303
0.00693

log 10 = 332.3 sec

log

N
N

100
10

The half-life of cobalt - 60 is 5.26 years. Calculate the % activity remaining


after 4 years.

Solution
t = 5.26 years

0.693
year1
5.26
= 4 years

N
Here to find the % of activity (i.e) to find N
0
2.303
N

log 0
=
t
N

178

log

t
2.303

N0
=
N

0.693
4

5.26 2.303
0.2288

Antilog (0.2288)

N0
N

=
N
N0

1.693
1
1.693

0.59 100
59%

% of activity =
=
4.

= 0 .59

Wooden artifact and freshly cut tree are having 7.6 and 15.2 counts
min-1g-1 of carbon (t = 5700 years) respectively. Calculate the age of the
artifact.
Age of the artifact
But

Amount of fresh wood


2.303
log

Amount of old wood

t =

0.693

0.693
t

Age of the artifact =

Amount of fresh wood


2.303 t
log

0.693
Amount of old wood

2.303 5700
15.2
log
0.693
7.6
= 5700 years

5.

Half life period of a radio active element is 1500 years. Find the value of
disintegration constant interms of second.
179

=
=

0.693
0.693
=
t
1500 yrs
0.693
1500 365 24 60 60 sec

0.693
sec 1
4
4730 4 10
= 0.1465 10-10 sec-1
=

6.

Calculate the number of and particles emitted in the conversion of


Th 232 to 82pb208.
90
Let a and b be the number of particles emitted during the change

Th232 82pb208 + a 2He4 + b -1e0


Comparing the mass numbers,
232 = 208 + 4a + b 0
4a = 232 - 208
= 24
a = 6
90

Comparing the atomic numbers


90 = 82 + 2 a + (-1)b
= 82 + 2a - b
2a-b= 90 - 82 = 8
2(6) - b = 8
b = 12-8 = 4
Number of - particle emitted = 6
Number of - particles emitted = 4
7.

The atomic masses of Li, He and proton are 7.01823 amu, 4.00387 amu
and 1.00715 amu respectively. Calculate the energy evolved in the reaction,
Li7 + 1H1 2 2He4 + E Given 1 amu = 931 MeV.
3

Solution
Mass of reactants = mass of Li + mass of H
= 7.01823 + 1.00715
= 8.02538 amu
180

Mass of products = 2 mass of He


= 2 4.00 387
= 8.00 774 amu
Mass loss during change = (8.02538-8.00774) amu
= 0.01764 amu
Energy evolved during reaction
= 0.0176 931 MeV
= 16.423 MeV
8.

Calculate the number of neutrons in the remaining atom after emission of an


particle from 92X238 atom. also report the mass number and atomic number
of the product atom.

Solution

92

X238 AXm + 2He4

Comparing mass number of both sides,


238 = m + 4
m = 238 - 4 = 234
Comparing atomic number on both sides,
92 = A + 2
A = 92-2 = 90
X has atomic number = 90
and mass number = 234
Number of neutrons = 234-90 = 144.
9.

Determine the average life of U238 having t = 140 days.

Solution
0.693

= 0.693

t =

( Average life, =

t
0.693

140
days
0.693
= 202.02 days
=

181

1
)

10. The activity of a radioactive isotope falls to 12.5% in 90 days. Calculate


the half life and decay constant.
Solution
N0 = 100 N = 12.5 t = 90 days
decay constant =

2.303
N
log 0
t
N

2.303
100
log
90
12.5
= 0.02558 log 8
= 2.311 10-2 days-1
=

t =

0.693
0.693
=
= 29.99 days

2.311 10 2

11. Calculate Q value of the following nuclear reaction 13Al27 + 2He4 14Si30 +
H1+ Q. The exact mass of 13Al27 is 26.9815 amu, 14Si30 is 29.9738, 2He4
1
is 4.0026 amu and 1H1 is 1.0078 amu.
m =
=
Q =
=

(29.9738 + 1.0078) - (26.9815 + 4.0026)


-0.0025 amu
0.0025 931 MeV
2.329 MeV
SELF EVALUATION

A. Choose the correct answer


1.

The phenomenon of radioactivity was discovered by


a) Madam curie
b) Pierre curie c) Henry Becquerrel d) Rutherford

2.

The most penetrating radiations are


a) rays
b) rays
c) rays

3.

d) all are equally penetrating

In the nuclear reaction, 92U238 82Pb206, the number of and particles


emitted are
a) 7, 5

b) 6, 4

c) 4, 3
182

d) 8, 6

4.

Which one of the following particles is used to bombard 13Al27 to give


p30 and a neutron
15
a) particle
b) deuteron
c) proton
d) neutron

5.

The reaction 5B8 4Be8 takes place due to


a) decay
b) decay
c) electron capture

6.

7.

8.

9.

Radioactivity is due to
a) Stable electronic configuration
c) Unstable nucleus

d) positron decay

b) Stable nucleus
d) Unstable electronic configuration

In the following radioactive decay, 92x232 89y220, how many and


particles are ejected.
a) 3 and 3
b) 5 and 3
c) 3 and 5
d) 5 and 5
U235 nucleus absorbs a neutron and disintegrates into 54Xe139, 38Sr94 and
x. What will be the product x?
a) 3 neutrons
b) 2 neutrons c) particle d) particle
92

Loss of a -particle is equivalent to


a) Increase of one proton only
b) Decrease of one neutron only
c) Both (a) and (b)
d) None of these

10. Which of the following is used as neutron absorber in the nuclear reactor?
a) Water b) Deuterium c) Some compound of uranium d) Cadmium
B. Answer in one or two sentences
11.
12.
13.
14.
15.
16.
17.
18.
19.

Define radio activity.


What is half life period.
Write two difference between chemical reaction and nuclear reaction.
What is Q value of a nuclear reaction?
What are the types of nuclear reaction. Give example for each type.
Explain the principle behind the Hydrogen bomb.
What is Radio carbon dating?
State two uses of radio carbon dating.
What is binding energy of Nucleus?

183

20. Complete the following nuclear reactions


i) 42Mo96 (....., n) 43Tc97
ii)

.......(, 2n) 85At211

iii)

96

Cm246 + 6C12 .....+4(0n1)

iv) 7N15 (p, ) .........


v) 11Na23 (n, ) ........
vi) 19K39 (p, d) ..........
vii) 27Co59 (d, p) .......
viii) 13Al27 (, n) ..........
ix) 11Na23 + ......... 12Mg23 + 0n1
C. Answer not exceeding 60 words
21. What is radioactivity? How was the phenomenon discovered?
22. What is nuclear fission? What are controlled and uncontrolled fission
reactions? How can the energy released in such reactions be used for practical
purposes?
23. What is nuclear fusion? How do nuclear fusion reactions differ from fission
reactions?
24. Differentiate chemical reactions from nuclear reactions.
25. Explain the use of radioactive isotopes with specified examples.
D. Problems
26. How many and particles will be emitted by an element 84A218 is changing
to a stable isotope of 82B206?
27. Calculate the decay constant for Ag108 if its half life is 2.31 minutes.
28. The half life of Th233 is 1.4 1010 years. Calculate its disintegration constant.
29. Complete the following nuclear reactions
i)

18

Ar40 +

ii)

iii)

88

Ra236

iv)

92

U238

19

K40 + 0n1

+ 1H1 2He4 + 2He4


?
56

+ 2He4

Ba143 + _______+0n1
184

30.

U238 undergoes a series of changes by emitting and particles and


finally 82pb206 is formed. Calculate the number of and particles emitted during
the change.

92

31. The atomic mass of Th is 232 and its atomic number is 90. In terms of its
radioactivity six and four particles are emitted. What is the mass number
and atomic number of the product.
32. Calculate the average life of 79Au198 leaving t = 150 days.
33. Complete the following
N14 +2He4 8O17 +

i)

ii)

92

U235 +0n1

iii)

29

Cu53

28

56

Ba137 + 36Kr93 +

Ni58 +

iv) 21H3 2He4 +

34. Predict the bombarding projectile in the following nuclear reactions


i)

13

Al27 + ?

11

ii)

34

Se83 + ?

34

iii)

Na24 + 2He4

Se84 + rays

N14 + ? 8O17 + 1H1

35. The decay constant for 6C14 is 2.31 10-4 year-1 calculate the half life period.
Summary
*

This chapter explains the basic concept of nuclear chemistry.

Difference about nuclear reaction and chemical reactions.

Nature of nuclear fission and nuclear fusion reactions are briefly explained.

Principle of nuclear reactors, nuclear reactions in sun and applications of


radioactive isotopes are thoroughly discussed.

Reference
1.

Inorganic Chemistry by Puri and Sharma.

2.

Inorganic Chemistry by P.L.Soni.

185

PHYSICAL CHEMISTRY
8. SOLID STATE - II
Learning Objectives
( To study the analysis of crystal structure using X-rays.
( To recognise the properties and types of ionic crystals.
( To know the elementary idea about the conducting and
superconducting properties of crystals.
( To learn the nature of Amorphous solids.

188

REVIEW
Solids are characterised by incompressibility, rigidity and mechanical strength.
Solids are usually classified as either crystalline or amorphous. Crystalline solids
have definite and ordered arrangement of the constituents extended over a long
distance and is called a long-range order. They possess a sharp melting point.
Amorphous solids like glass, rubber etc., although possessing many characteristics
of crystalline solids such as definite shape, rigidity and hardness, but are devoid
of a regular internal structure and melt gradually over a range of temperature. For
this reason they are not considered as true solids but rather highly supercooled
liquids.
Crystallography : A study of internal structure of crystals. 1913 - English
physicists, Father and Son, William and Lawrence Bragg developed X-ray
crystallography further by establishing laws that govern the orderly arrangement
of atoms in crystal interference and diffraction patterns. They also demonstrated
the wave nature of X-rays. In 1915 William Bragg and Lawrence Bragg were
awarded Nobel prize for physics for X-ray analysis of crystal structure.
UNIT CELL
Unit cell is the smallest fundamental repeating portion of a crystal lattice
from which the crystal is built by repetition in three dimension.
Characteristic parameters of a unit cell
z

Crystallographic axes : ox, oy, oz

Interfacial angles : , ,
Primitives (Intercepts) : a, b, c

a
x

189

Types of Cubic System


Simple cubic

Body - centred cubic

Face - centred cubic

Assignment of Atoms per unit cell in a cubic lattice


Simple Cubic
In a simple cubic where atoms are present at the corners only, each atom at
the corner is shared equally by eight other unit cells. Hence the contribution of
1
each atom to the unit cell is .
8
Nc

The total number of atoms per unit cell


Nc
1
= 8 = 1
=
8
8
Nc is the number of atoms at the corners.

fcc
A face atom is shared equally between two unit cells and therefore a face
N

f
atom contributes only 2 to the unit cell.

The number of atoms per unit cell in fcc =


Nf = Number of atoms at the faces.
190

Nc Nf 8 6
+
= + = 1+ 3 = 4
8
2
8 2

Nf = Number of
atoms at the
faces

Nf

BCC
In a bcc lattice, the body centred atom belongs exclusively to the unit cell.
The total number of atoms per unit cell in bcc
=
Nb

Nc Nb 8 1
+
= + = 1+1 = 2
8
1
8 1

Nb = Number of atoms inside the body

An Edge atom (or) Edge centred


An edge atom and edge centred is common to four unit cells and there are
twelve edges of the unit cell. The contribution from each edge atom is therefore
1/4. The number of atoms per unit cell in edge centre.
=

Nc Ne
+
8
4

8 12
+
= 1+3=4
8 4

Ne = Number of atoms at the edge centre

Ne

Ne

191

8.1 X-RAYS AND CRYSTAL STRUCTURE


X-rays are electromagnetic waves of very short wavelength. The wave nature
of X-rays is not confirmed by diffraction experiment, because a grating of about
40 million ruling per cm is required for diffraction experiment. The preparation of
such a grating is highly impossible. At the same time, crystallographers believed
that atoms in crystals are regularly arranged with an interatomic distance of about
10-8 cm. The wavelength of X-rays is, also, in the order of 10-8 cm. Based on
this, Laue suggested that crystal can be used as a three dimensional diffraction
grating for X-rays. This suggestion is carried out successfully by Laue in his
experiment using zinc sulphide crystal. The photograph obtained is known as
Laue diffraction pattern.
The Laue experiment confirmed the wave nature of X-rays and also
established the fact that atoms or ions in crystals are arranged in regular three
dimensional lattice. Though Laue diffraction pattern gives more information about
the symmetry of crystals, the interpretation of the pattern seems to be difficult.
8.1.1 Braggs Equation
W.L.Bragg and W.H.Bragg derived a mathematical relation to determine
interatomic distances from X-ray diffraction patterns. The scattering of X-rays
by crystals could be considered as reflection from successive planes of atoms in
the crystals. However, unlike reflection of ordinary light, the reflection of X-rays
can take place only at certain angles which are determined by the wavelength of
the X-rays and the distance between the planes in the crystal. The fundamental
equation which gives a simple relation between the wavelength of the X-rays,
the interplanar distance in the crystal and the angle of reflection, is known as
Braggs equation.
Braggs equation is
where n

n = 2d sin

is the order of reflection


is the wavelength of X-rays
is the interplanar distance in the crystal
is the angle of reflection

8.1.2 Significance of Braggs equation


1)

If we use X-rays of known wavelength (), then the interatomic distance


(d) in an unknown crystal can be calculated. On the other hand, if we use a
192

crystal whose interatomic distance d is known, then the wavelength of


X-rays can be calculated.
2)

The Braggs equation gives the essential condition for diffraction to occur.

3)

When the experiment is done, there will be a maximum reflection at a


particular angle . That angle is noted. It corresponds to first order reflection
(n=1). If the angle is increased, maximum reflection occurs at some
other higher angle. It corresponds to second order reflection (n=2). Similarly,
third, fourth and higher order of reflection occur at certain specific angles.
The values of angles obtained are in accordance with the Braggs equation.
Hence Braggs equation is experimentally verified.

8.1.3 Braggs spectrometer method


This method is one of the important method for studying crystals using
X-rays. The apparatus consists of a X-ray tube from which a narrow beam of
X-rays is allowed to fall on the crystal mounted on a rotating table.The rotating
table is provided with scale and vernier, from which the angle of incidence, can
be measured.
X -ra y tu b e

S lit

P ath o f
R e co rd e r

D iffra cte d
X -ra y s

Io n isatio n
ch am b e r
In c id e n t
X -ra y s

Tu rn ta b le

C ry sta l
S ca le to m e asu re
ro tatio n o f cry sta l

Fig. 8.1 X-ray spectrometer


An arm which is rotating about the same axis as the crystal table, carries an
ionisation chamber. The rays reflected from the crystal enter into the ionisation
chamber and ionise the gas present inside. Due to the ionisation, current is
produced which is measured by electrometer. The current of ionisation is a
direct measure of intensity of reflected beam from the crystal. For different angles
of incidence, the corresponding ionisation current is measured from the
electrometer. These values are plotted in the form of graph.
193

For sodium chloride, the maximum reflection or peaks for 100 plane occurred
at = 5.9, 11.85 and 18.15. The sines of these angles are 0.103, 0.205 and
0.312 which are in the ratio 1:2:3. These peaks represent the first,second and
third order reflections. The ratio confirms the correctness of Braggs equation.
8.2 TYPES OF CRYSTALS
Crystals are classified into the following four types depending upon the
nature of the units which occupy the lattice points.
1. Molecular Crystals
3. Metallic Crystals

2. Covalent Crystals
4. Ionic Crystals

8.2.1 Molecular Crystals


The lattice points in molecular crystals consist of molecules which do not
carry any charge. The forces binding the molecules together are of two types
(i) Dipole-dipole interaction and (ii) Vanderwaals forces. Dipole-dipole forces
occur in solids which consists of polar molecules e.g., ice. The Vanderwaals
forces are more general and occur in all kinds of molecular solids.
8.2.2 Covalent Crystals
The lattice in covalent crystals consists of atoms linked together by a
continuous system of covalent bonds. Diamond is a good example for this type.
8.2.3 Metallic Crystals
Metallic crystal consists of an assemblage of positive ions immersed in a sea
of mobile electrons. Thus, each electron belongs to a number of positive ions and
each positive ion belong to a number of electrons. The force that binds a metal
ion to a number of electrons within its sphere of influence is known as metallic
bond. This force of attraction is strong and is thus responsible for a compact
solid structure of metals.
8.2.4 Ionic Crystals
In ionic crystals, the units occupying lattice points are positive and negative
ions. Each ion of a given sign is held by coulombic forces of attraction to all ions
of opposite sign. The forces are very strong. The ionic crystals have the following
characteristics.
194

1.
2.
3.
4.
5.
6.
7.

The heats of vapourisation of ionic crystals are high.


The vapour pressure of ionic crystals at ordinary temperature are very low.
The melting and boiling points of ionic crystals are very high.
Ionic crystals are hard and brittle.
Ionic crystals are insulators in the solid state.
Ionic crystals are soluble in water and also in other polar solvents.
Ionic solids are good conductors when dissolved in water.

8.2.5 Types of Ionic Crystals


The structure of ionic crystals is determined by the ratio of the numbers, the
ratio of the sizes and the structural units. In general, ionic crystals are classified
into AB and AB2 type.
Substance of the general formula AB mostly crystallise in one of the following
six forms.
Lattice type
Coordination number

AB
: CsCl
: 8

AB
NaCl
6

AB
FeS
6

AB
ZnO
4

AB AB
ZnS BN
4
3

Let us discuss the structure of CsCl for AB type. It is body centered cubic
system. The chloride ions are at the corners of a cube where as Cs+ ion is at the
centre of the cube or vice versa. Each Cs+ ion is connected with eight Cl- ion and
Cl- is connected with eight Cs+ ions.
+

Cs
Cl

Number of chloride ions per unit =

Nc 8
= =1
8 8

Nb 1
= =1
1 1
Thus number of CsCl units per unit cell is one.

Number of cesium ion per unit

Compounds having the general formula AB2 generally crystallise in forms


based on the following eight typical lattices like CO2, SiO2, TiO2, CaF2, Cu2O,
FeS2, CdI2 and MoS2. For example Rutile (TiO2) has the following structure.
195

- Ti
- O x y g en

8.3 IMPERFECTIONS IN SOLIDS


Almost all the crystals encountered in practice suffer from imperfections or
defects of various kinds. An ideally perfect crystal is one which has the same unit
cell and contains the same lattice points throughout the crystal. The term
imperfection or defect is generally used to describe any deviation of the ideally
perfect crystal from the periodic arrangement of its constituents.
8.3.1 Point Defects
If the deviation occurs due to missing atoms, displaced atoms or extra atoms,
the imperfection is named as a point defect. Such defects arise due to imperfect
packing during the original crystallisation or they may arise from thermal vibrations
of atoms at elevated temperatures. The most common point defects are the
Schottky defect and Frenkel defect. Comparatively less common point defects
are the metal excess defect and the metal deficiency defect.
Schottky defects
This defect is caused if some of the lattice points are unoccupied. The points
which are unoccupied are called lattice vacancies. The number of missing positive
and negative ions is the same in this case and thus, the crystal remains neutral.
The existence of two vacancies, one due to a missing Na+ ion and the other due
to a missing Cl- ion in a crystal of NaCl is shown in Fig. 8.2.

N a m issin g

C l m issin g

Fig. 8.2 Schottky Defects in a Crystal


196

Schottky defects appears generally in ionic crystals in which the positive and
negative ions do not differ much in size.
Frenkel defects
This defect arise when an ion occupies an interstitial position between the
lattice points. This defect occurs generally in ionic crystals in which the anion is
much larger in size than the cation. AgBr is an example for this type of defect.
One of the Ag+ ion occupies a position in the interstitial space rather than its own
appropriate site in the lattice is shown in Fig. 8.4.
+

Ag
Br
+
Ag
Br

Br Ag
+
Ag Br
Ag
Br
+
Ag Br

Br
+
Ag
Br
+
Ag

Ag
Br
+
Ag
Br

Br
+
Ag
Br
+
Ag

Ag
Br
+
Ag
Br

Br
+
Ag
Br
+
Ag

Ag
Br
+
Ag
Br

Fig. 8.3 Frenkel Defects in a Crystal


The crystal remains neutral since the number of positive ions is the same as
the number of negative ions.
Metal excess defects
If a crystal of NaCl is heated in sodium vapour, it acquires a yellow colour.
This yellow colour is due to the formation of a non-stoichiometric compound of
NaCl in which there is a slight excess of sodium ions. This defect is called the
metal excess defect.
Metal deficiency defects
In certain cases, one of the positive ions is missing from its lattice site and
the extra negative charge is balanced by some nearby metal ion acquiring additional
charges instead of original charge. This type of defect is generally found in
compounds of transition metals which can exhibit variable valency. FeO and FeS
show this type of defects.
8.4 PROPERTIES OF CRYSTALLINE SOLIDS
Crystalline solids exhibit an important property called conductivity.
Conductivity is the property of a material by which it allows the flow of electric
current. Conducting materials are generally classified into three types namely
conductors, semi conductors and super conductors.
197

Typical metals are good conductors of electricity while elements like silicon
and germanium are non conductors at ordinary temperature. However, they exhibit
appreciable conductivity upon addition of impurities as Arsenic and Boron. The
resulting materials are called semiconductors. Semi conductors which exhibit
conductivity due to the flow of excess negative electrons are called n-type
semiconductors. The conductivity due to the positive holes are called p-type
semiconductors. Semiconductors find application in modern devices as recitifiers,
transitors and solar cells.
8.4.1 Super conductors

R esistiv ity

The ability of certain ultra cold substances to conduct electricity without


resistance is called super conductivity. This superconductivity state is a state in
which a material has virtually zero electrical resistance. Substances having this
property are called super conductors.

N o rm al
m etal

S u p er co n d u cto r

Tc

The super conducting transition temperature Tc of a material is defined as


a critical temperature at which the resistivity of the material is suddenly changed
to zero. Thus at that temperature a material is changed from normal material to
superconductor.
At the extremely low temperatures, vibration of the nuclei of certain atoms
slow down so much and they synchronise with the passing waves of electrons in
a flow of electric current. When this happens, resistance to electric current
disappears.
8.4.2 Application of superconductors
1)

It is a basis of new generation of energy saving power systems. Super


conducting generators are smaller in size and weight when we compare
with conventional generators. These generators consume very low energy
and so we can save more energy.
198

2)

High efficiency ore separating machines may be built using superconducting


magnets.

3)

Superconducting solenoids are used in Nuclear Magnetic Resonance Imaging


equipment which is a whole body scan equipment.

8.5 AMORPHOUS SOLIDS


Amorphous solids possess properties of incompressibility and rigidity to a
certain extent but they do not have definite geometrical forms.
8.5.1 Glasses
When certain liquids are cooled rapidly there is no formation of crystals at a
definite temperature, such as occurring on slow cooling. The viscosity of the
liquid increases steadily and finally a glassy substance is formed.
The chief characteristics of a glass are hardness, rigidity and ability to withstand
shearing stresses which are all properties of the solid state. On the other hand
glasses are optically isotropic and on heating without any sharp transition passes
into a mobile liquid. At a high temperature glasses undergo phase transition when
crystals separate first as they do form supercooled liquid. Therefore, glasses are
regarded as amorphous solids or super cooled liquids as well. Thus, glassy or
vitreous state is a condition in which certain substance can exist, lying between
the solid and liquid states.
Solved Problems
1)

Determine the number of formula units of NaCl in one unit cell. NaCl is face
centred cubic.

Solution
1

In the fcc arrangement, there are Eight corners 8 = Cl ion


8
1
6 = 3Cl ions
At the six faces
2
1
+
Along the 12 edges 12 = 3Na ions
4

199

1 1 = 1Na + ion
At the cube centre ___________________
Total 4 Cl and 4Na+ ions
Hence, the unit cell contains four NaCl units.
2)

The diffraction of crystal of Barium with X-ray of wavelength 2.29A gives


a first order reflection at 278. What is the distance between the diffracted
planes?
Braggs equation is n = 2d sin
= 2.29 A

n = 1,

d=?

= 278

on substitution, 1 2.29A = 2d sin 278


2.29A = 2d (0.456)
2.29A
= 2.51 A
2 0.456
In a fcc arrangement, the corner atoms are A type and those at face centres
are B type. What is the simplest formula of the compound ?
d=

3)

Solution
1
Number of A type atoms in the unit cell, 8 = 1
8

Number of B type atoms in the unit cell, 6

1
=3
2

Hence the formula is AB3


4)

In a fcc lattice of A and B type atoms are present. A atoms are present at
the corners while B type are at face centres. If in each unit cell, one of the A
type atom is missing from the corner, what is the simplest formula of the
compound?
1 7
Number of atoms of A type in the unit cell = 7 =
8 8

Number of atoms of B type in the unit cell = 6


Hence the formula is A7/8 B3 or A7 B24
200

1
=3
2

Problems for practice


1.

The diffraction of a crystal with X-ray of wavelength 2.31A gives a first


order reflection at 28.9. What is the distance between the diffracted planes.
[Ans : 2.447 A]

2.

Diffraction angle 2 equal to 14.8 for a crystal having interplanar distance


in the crystal is 0.400 nm when second order diffraction was observed.
Calculate the wavelength of X-ray used.
[Ans : 0.0515 nm]

3.

Find the interplanar distance in a crystal in which a series of planes produce


a first order reflection from a copper X-ray tube ( = 1.542 A) at an angle
of 23.2.
[Ans : 1.9573 A]

4.

The X-ray of wavelength 1.5A are incident on a crystal having an interatomic


distance of 1.6A. Find out the angles at which the first and second order
reflection take place.
[Ans : 2757; 6938]

5.

Calculate the angle at which (a) first order reflection and (b) second order
reflection will occur in an X-ray spectrometer when X-ray of wavelength
1.54A are diffracted by the atoms of a crystal, given that the interplanar
distance is 4.04A.
[Ans : 1059 ; 2224]
SELF EVALUATION

A. Choose the correct answer


1.

The number of chloride ions that surrounds the central Na+ ion in NaCl
crystal is_______.
(a) 12

2.

(b) 8

(c) 6

The Braggs equation is


(a) = 2d sin (b) nd = 2 sin

3.

(c)2 = nd sin

(d) n = 2d sin

A regular three dimensional arrangement of identical points in space is called


(a) Unit cell

4.

(d) 4

(b) Space lattice

(c) Primitive

(d) Crystallography

The smallest repeating unit in space lattice which when repeated over and
again results in the crystal of the given substance is called
(a) Space lattice

(b) Crystal lattice (c)Unit cell

201

(d) Isomorphism

5.

The crystal structure of CsCl is


(a) Simple cubic
(c) Tetragonal

6.
7.

An example for Frenkel defect is


(a) NaCl
(b) AgBr

10.

11.
12.

13.
14.
15.

(d) FeS

(b)
(d)

n-type semiconductors
Insulators

In the Braggs equation for diffraction of X-rays,n represents


(a) The number of moles
(c) A quantum number

9.

(c) CsCl

Semiconductors which exhibit conductivity due to the flow of excess negative


electrons are called
(a) Super conductors
(c) p-type semiconductors

8.

(b) face-centred cubic


(d) Body centred cubic

(b)
(d)

Avogadro number
Order of reflection

The number of close neighbours in a body centred cubic lattice of identical


spheres is
(a) 6
(b) 4
(c) 12
(d) 8
The crystals which are good conductors of electricity and heat are
(a) Ionic crystals
(b) Molecular crystals
(c) Metallic crystals
(d) Covalent crystals
In a simple cubic cell, each point on a corner is shared by
(a) One unit cell
(b) Two unit cell (c) 8 unit cell (d) 4 unit cell
The ability of certain ultra cold substances to conduct electricity without
resistance is called
(a) Semiconductor (b) Conductor (c) Superconductor (d) Insulator
The total number of atoms per unit cell is bcc is
(a) 1
(b) 2
(c) 3
(d) 4
Rutile is
(a) TiO2
(b) Cu2O
(c) MoS2
(d) Ru
Semiconductors are used as
(a) rectifiers (b) transistors
(c) solar cells (d) all the above

202

16. An example of metal deficiency defect


(a) NaCl

(b)

AgCl

(c)

CsCl

(d)

FeS

B. Answer in one or two sentences


17. Define the terms; space lattice and unit cell.
18. State Braggs law.
19. What are superconductors?
20. Sketch the (a) simple cubic (b) face-centred cubic and (c) body centred
cubic lattices.
21. How crystals are classified?
22. Give example for molecular and ionic crystals.
23. What is a vitreous state?
24. Give two example for AB and AB2 type ionic crystals.
25. What is imperfection in solids?
26. What is coordination number?
27. Write a note on the assignment of atoms per unit cell in fcc.
28. Write a short note on metallic crystals.
29. How are glasses formed?
C. Answer not exceeding 60 words
30.
31.
32.
33.
34.
35.
36.
37.

What is Braggs equation? Give its significance.


Write the properties of ionic crystals.
Explain Schottky and Frenkel defects.
What is super conductivity? Give its uses.
Explain AB and AB2 type ionic crystals with one example for each.
How Braggs equation is used for determining crystal structure.
Explain Braggs spectrometer method.
Explain the nature of glass.

203

Summary
The study of crystals by X-rays are discussed.Types of ionic crystals AB
and AB2 type are explained with examples. An elementary idea about imperfections
in solids. The properties of ionic crystals and nature and properties of glasses
are discussed. Braggs equation and its significance are discussed.
References
1)

C-Kittel, Introduction to solid state physics,Third edition, John Wiley,1966.

2)

A Text book of Physical chemistry, A.S.Negi, S.C.Anand, Fifth


Edition,1997.

3)

Problems in Physical chemistry, K.K.Sharma, Second Edition, 1997.

4)

Physical Chemistry, Peter Atkins Julio de Paula, 7th Edition 2003, Oxford
Press.

204

9. THERMODYNAMICS II
Learning Objectives
( To review first law of thermodynamics and to know its limitations.
( To learn the definition of second law of thermodynamics and the
mathematical statements.
( To study the differences of spontaneous and non spontaneous reactions
with examples. Also to learn the mathematical representation of entropy
S.
( To learn about Gibbs free energy change and to know the relation
G =H-TS.
( To study the significance of G

205

9.1 LIMITATIONS OF FIRST LAW OF THERMODYNAMICS


The first law of thermodynamics tells us that energy can be changed from
one form to another but can be neither created nor destroyed in any process.
The mathematical expression which is used to represent the first law of
thermodynamics is E = q-w, where E refers to the internal energy change of
the system when w amount of work is done by the system when it absorbs q
amount of heat and carries out w amount of work. However, this law possesses
many limitations such as given below.
1. The first law of thermodynamics merely indicates that in any process
there is a transformation between the various forms of energy involved in the
process but provides no information regarding the feasibility of such transformation.
2. First law does not provide any information regarding the direction a
processes will take whether it is a spontaneous or a non spontaneous process.
9.2 SECOND LAW OF THERMODYNAMICS
Second law of thermodynamics can be stated in many ways:
i)

It is impossible to construct an engine which operated in a complete cycle


will absorb heat from a single body and convert it completely to work
without leaving some changes in the working system.
This is called as the Kelvin Planck statement of II law of thermodynamics.
ii) It is impossible to transfer heat from a cold body to a hot body by a machine
without doing some work.
This is called as the clausius statement of II law of thermodynamics.
iii) A process accompanied by increase in entropy tends to be spontaneous.
This statement is called as the entropy statement of II law of thermodynamics.
Entropy is a measure of randomness or disorder of the molecules of a system
and it is a thermodynamic state function. A system always spontaneously
changes from ordered to a disordered state. Therefore entropy of a
spontaneous process is constantly increasing.
iv) Efficiency of a machine can never be cent percent.
v) The heat Efficiency of any machine is given by the value of ratio of output to
input energies. Output can be in the form of any measurable energy or
temperature change while input can be in the form of heat energy or fuel
amount which can be converted to heat energy.
206

thus % efficiency =

output
x 100
input

The machine can be a heat engine also. Consider a heat engine which has
an initial temperature T1 and final temperature as T2, then if T1>T2 then when
some amount of heat is being converted into work, T2 is the lowered temperature.
The efficiency is given by,
T T

1
2
% efficiency = T x 100
1

According to II law of thermodynamics it is impossible to have a machine


or heat engine which converts the input energy completely into output energy or
output work without any amount of heat or energy being absorbed by the machine.
Hence, % efficiency can never be achieved as cent percent.

T2
% efficiency = 1 T x 100

1
By II law, T2<T1 % efficiency less than 100.
9.3 ENTROPY AND ENTROPY CHANGE
The entropy function S introduced in the second law of thermodynamics
is explained as below.
Entropy function S represents the ratio of the heat involved (q) to the
q
temperature (T) of the process. That is S = . This relation is valid only for
T
reversible processes. If a system is changed from state 1 to state 2 at constant
temperature and if q rev is the heat involved in the process, then entropy change
of the process (S) is given by,
2

S2 S1 = S

= =

q rev
T

where the process is a reversible one. Entropy (S) and the change in entropy of
207

the process (S) are each state functions even though q and q path functions.
In a reversible process, entropy of universe remains a constant.
S universe = S system + S surroundings

= Constant

Entropy change (S) can be derived for various thermodynamic processes


as below:
Isothermal process (T = constant)
1
q q
q rev = 2 1

T
T
2

Isothermal and isobaric process (T and P = Constant)


2

1
= T q p, rev
1

Isothermal, and isochoric process (T and V- Constant)


2

1
S = T q v, rev
1

The term natural process means that the process is spontaneous and does
not need to be induced. In order to find out whether a process is spontaneous
or not, the entropy changes of the system and the surroundings for the stipulated
process is considered. If this change is positive i.e. if the entropy of the universe
increases, the process will take place spontaneously and irreversibly.
If the entropy change of the universe is zero or negative (S<0) the system
will behave as non spontaneous.
When the external pressure is less than the internal pressure of a gaseous
system, the gas expands spontaneously. When volume increases in expansion,
the disorder in the movement of gaseous molecules increases. Thus, spontaneous
processes are associated with increase in disorder. When disorder in a process
is favoured it occurs spontaneously and we say, the entropy change is positive.
Entropy is a measure of microscopic disorder in the system and also represents
spontaneity.
208

For a reversible process,


S system = S surroundings
S

universe

= S system + S surroundings = 0.

For an irreversible (spontaneous) process.


Suniv > 0 (positive value)
Entopy change in a physical (phase) transformation can be determined
particularly for evaporation of liquids at the boiling points, using Troutons rule.
According to this rule, the heat of vaporisation (Hvap)in calories per mole divided
by the boiling point of the liquid in Kelvin is a constant equal to 21 cal deg-1
mole-1 and is known as the entropy of vapourisaiton.
S

H vap
Tb

vap

= 21cal.deg

.mole 1

Hvap = Enthalpy change of vapourisation = Latent heat of vapourisation.


This equation is useful for estimating the molar heat of vaporization of a liquid of
known boiling point. Substances that deviate from this rule are as follows:
i)

Low boiling liquids such as hydrogen and Helium which boil only a little
above 0K.

ii)

Polar substances like water, alcohol which form hydrogen bonded liquids
and exhibit very high boiling points as well as high Hvap.

iii)

Liquids such as acetic acid whose molecules are partially associated in the
vapor phase and possess very low entropy vaporization which is very much
less than 21 cals/ mol/deg.
Those liquids that obey Troutons rule are said to behave ideally.

Example 1
The normal boiling point CCl4, CHCl3 and H2S are 76.7oC, 61.5oC and
59.6oC respectively. Calculate the molar heat of vapourisation of each liquid,
assuming ideal behaviour.
Since the liquids behave ideally, Troutons rule is obeyed.
Svap =

H vap
Tb

= 21cal.deg

.mole

209

-1

-1

Hvap of CCl4

= (21 cal. mole . deg 4.184J) (273 + 76.7)K


= 30.71 kJ mol.-1

Hvap of CHCl3

= (21 cal. mole-1.deg-1 4.184 J) (273 + 61.5)K


= 29. 376 kJ mol-1

Hvap of H S

= (21 cal mol-1.deg-1 4.184 J) (27359.6)K


= 18.74 kJ.mol-1

Characteristics of entropy S
i)

The term S entropy is evolved from the formulation of II law of


thermodynamics as a thermodynamic state function.

ii)

Entropy change S of a system under a process is defined as the constant


equal to the ratio of the heat change accompanying a process at constant
temperature to the temperature of the system under process. The process
should be reversible at that temperature.
Srev =

q rev
T(K)

Heat, q is not a state function , But for a reversible process q = (q2-q1)


divided by temperature (T) of the process is a state function.
iii) A spontaneous process is accompanied by increase in the disorder (or)
randomness of the molecules constituting the system. Entropy increases in all
spontaneous processes. Hence entropy may be regarded as a measure of disorder
(or) randomness of the molecules of the system.
iv) When a system undergoes a physical (or) a chemical process, there occurs
a change in the entropy of the system and also in its surroundings. This total
change in the entropy of the system and its surroundings is termed as the entropy
change of the universe brought about by the process. For an isothermal process
(T=constant), the entropy change of the universe during a reversible process is
Zero.
The entropy of the universe increases in an irreversible process.
v) The energy of the universe remains constant although the entropy of the
universe tends to a maximum.
210

vi) For a spontaneous process, at constant T, S is positive (S > 0).


S is positive (S > 0). For an equilibrium process, S is zero.
For a non spontaneous process,
S is negative or (S < 0).
vii) Units of entropy: The dimension of entropy are energy in terms of
heat X temperature-1. The entropy is expressed as calories per degree which is
referred to as the entropy units (eu). Since entropy also depends on the quantity
of the substance, unit of entropy is calories per degree per mole (or) eu. per
mole.
cgs units of entropy is cal.K-1 denoted as eu. The SI unit is JK-1 and denoted
EU. 1 eu = 4.184 EU.
viii)

Entropy change is related to enthalpy change as follows:


For a reversible and isothermal process,

q rev
. Since H is the heat absorbed (or) evolved in the process at
T
H
constant T and pressure P.S is also calculated from H as S =
where T
T
is the temperature of the process involving H, amount of enthalpy change, at
constant pressure.
S =

Example 2
Calculate the entropy change involved in the conversion of 1 mole of ice at
0oC and 1 atm to liquid at 0oC and 1 atm. The enthalpy of fusion per mole of ice
is 6008 J mol-1.
H2O (s)
Ice
S

fusion

C
0

273 K

H2O (l)
Water liquid

H fusion
6008 J.mol 1
=
=
Tm(K)
(0 + 273) K

Sfusion = 22.007 J mol-1 K-1.


211

Example 3
Calculate the change of entropy for the process, water (liq) to water (vapor,
373K) involving Hvap = 40850 J mol-1 at 373K.
Hvab
40850 J/mol
= 109.517 J.K.1 mol1
S vap = Tb (K) =
373 K

S vap = 109.52 J mole1 K-1


Example 4
Evaluate the entropy change for the following process possessing H
transition = 2090 J.mol-1
1 mole Sn (, 13oC)
T

1 mole Sn (, 13oC).

= 13+273 = 286 K.

transition

Strans

H trans
2090 J.mol 1
=
Ttrans (K)
286 K

Strans = 7.307 J.K 1 mol.-1


Example 5
When does entropy increase in a process?.
a)

In a chemical reaction, when number of molecules of products are more


than the number of molecules of reactant entropy increases.

b)

In physical process, when a solid changes to liquid, when a liquid changes


to vapour and when a solid changes to vapour, entropy increase in all these
processes.

Example 6
Calculate the entropy changes in the system, and in the surroundings and
the total entropy change in the universe when during a process 75 J of heat flow
out of the system at 55oC to the surroundings at 20oC.
Tsystem

= 273+55 = 328 K.

Tsurroundings = 20+273 = 293 K.


212

S univ

= Stotal = Ssystem + Ssurroundings

q system
75J
=
= 0.2287Jk 1
Ssystem = T
328K
system
SSurroundings

q surroundin gs
Tsurroundin gs

+ 75J
= + 0.260 JK 1
293K

Suniv = Stotal = (0.2287 + 0.26)


= + 0.0313 JK-1
Example 7
1 mole of an ideal gas maintained at 4.1 atm and at a certain temperature
absorbs 3710J heat and expands to 2 litres. Calculate the entropy change in
expansion process.
For 1 mole of an ideal gas,
PV = RT,

P = 4.1 atm

Temperatur e =

S =

V = 2 lit

4.1 atm 2lit 1 mole


0.082 lit atm K 1 mol 1

= 100 K.

q 3710 J
=
= = 37.1 J K-1mol-1.
T 100 K

S of expansion = 37.1 J K-1mol-1.


Standard Entropy
The absolute entropy of a pure substance at 25C (298 K) and 1 atm
pressure is called the standard entropy, S. The standard entropies of all substances
either elements or compounds at any temperature above 0K always have positive
values.
When the standard entropies, S of various substances are known, the
standard entropy change of a chemical process or reaction is written as
S = S

products

reactants

213

This S is the standard entropy change of the reaction.


Standard entropy change of formation, Sf is defined as the entropy of
formation of 1 mole of compound from the elements present in the standard
conditions. Sf can be calculated for chemical compounds using the S values
of elements from which the compound is formed.
S

compound

= S

compound

elements

Example 8
Calculate the standard entropy of formation Sf of CO2(g). Given the
standard entropies of CO2(g), C(s), O2(g) as 213.6, 5.740 and 205.0 JK-1
respectively.
Sf

compound

= Scompound Selements
= SCO2(g) [SC + SO2(g)] JK-1
(s)

= 213.6 5.74 205.0


Sf, CO (g) = 2.86 JK-1
2

When standard entropy of formation of compounds are known, the standard


entropy change for a stoichiometrically balanced chemical reaction can be written
as,
Sreaction = Sf products Sf reactants
Example 9
Urea hydrolysis in presence of water to produce ammonia and
carbondioxide. The standard entropies of reactants and products are given, for
urea, H2O(l), CO2(g), NH3(g) are 41.55, 16.72, 51.06 and 46.01 cals. mol-1.
K-1 respectively. What is the standard entropy change for this reaction. Predict
the spontaneity of the reaction.
Sreaction = S( product) S( reactants)
The reaction is,
CO(NH2)2(aq) + H2O(l) CO2(g) + 2NH3(g)
Sreaction = (SCO (g) + 2SNH3(g)) - (Surea(aq) + SH2O(l))
2

= (51.06 + 2 46.01 - 41.55 - 16.72) cal.K-1


= 84.81 cal. K-1.
214

Sreaction is a positive value. that is Sreaction increases. Hence urea hydrolysis


in water is a spontaneous reaction.
9.4 Gibbs free energy G
According to II law of thermodynamics, inorder to predict the spontaneity
of a process entropy of universe is considered. Suniverse is the sum of Ssystem and
Ssurroundings. It is difficult to determine Ssurroundings in most of the physical and
chemical processes. Therefore a thermodynamic function which reformulates the
spontaneity criterion considering only the system under study is required.
For this purpose, a free energy function has been introduced by II law of
thermodynamics. The free energy function, called the Gibbs free energy function,
denoted by the symbol G is mathematically defined as,
G = H - TS
where H = enthalpy or heat content of the system, T = Temperature in Kelvin
and S = entropy
This expression is valid for constant temperature and pressure processes.
In an isothermal process, if H and S are the changes in enthalpy and entropy
of the system, then free energy change G is given by,
G = H - TS
If 1 and 2 refer to the initial and final states of the system during the isothermal
process, then
G = (G2-G1) = (H2-H1) - T(S2-S1)
from I law of thermodynamics
H = E + PV
Therefore

G = E + PV - TS.

For a spontaneous process, the enthalpy change at constant pressure will


be negative. This is because in an exothermic process, the enthalpy of the final
state (H2) is lower than the enthalpy of the initial state (H1) so that (H2-H1) is
negative and the process take place spontaneously to attain the lower enthalpy
state. Similarly, the entropy change (S) increases in a spontaneous process
since entropy of the final state S2 will be greater than the initial state S1 so that
(S2-S1) = S, is positive. Combining negative H and positive S, in the
215

expression for free energy change G, at constant temperature, the overall


magnitude of G becomes negative for a spontaneous process. Here, H and
S terms refer only to the system.
G = H TS
Hence, criterion for the prediction of feasibility of a reaction (or) the prediction
of thermodynamic spontaneity of a process based on the free energy change
(G) of the process is given as : when at constant temperature and pressure of
the system, if,
G < 0,

G is ve, the process is spontaneous and feasible

i.e.

G = 0,

the process is in equilibrium

i.e.

G < 0,

G is +ve, the process is non spontaneous and non feasible.

In chemical thermodynamics, spontaneous processes are also known as


irreversible (or) feasible processes while non spontaneous processes are known
as non feasible processes since time factor of the process is not considered here.
All reversible processes are considered as equilibrium processes.
Thermodynamic conditions for spontaneity and equilibrium
Spontaneous
(irreversible)

Equilibrium
(reversible)

Non spontaneous
(nonfeasible)

G = 0
H = 0
S = 0

G > 0
H > 0
S < 0

at constant P and T
G < 0
H < 0
S > 0

Characteristics of Free energy G


i)

G is defined as (H-TS) where H and S are the enthalpy and entropy of the
system respectively. T = temperature. Since H and S are state functions, G
is a state function.

ii)

G is an extensive property while G = (G2-G1) which is the free energy


change between the initial (1) and final (2) states of the system becomes the
intensive property when mass remains constant between initial and final states
(or) when the system is a closed system.
216

iii)

G has a single value for the thermodynamic state of the system.

iv) G and G values correspond to the system only. There are three cases of
G in predicting the nature of the process. When, G<0 (negative), the
process is spontaneous and feasible; G = 0. The process is in equilibrium
and G > 0 (positive), the process is nonspontaneous and not feasible.
v)

G = H TS. But according to I law of thermodynamics,


H = E + PV and E = q w.
G = q w + PV TS
But S =

q
and TS = q = heat involved in the process.
T

G = q w + PV q = w + PV
(or) G = w PV = network.
The decrease in free energy G, accompanying a process taking place at
constant temperature and pressure is equal to the maximum obtainable work
from the system other than work of expansion.
This quantity is called as the net work of the system and it is equal to
(w PV).
Net work = G = w PV.
G represents all others forms of work obtainable from the system such
as electrical, chemical or surface work etc other than P-V work.
Standard free energy (G)
Like standard enthalpy of formation of substances, standard enthalpy change
of a reaction, standard free energy of formation of substances and standard free
energy change of reactions are considered. The standard free energy value (G)
of all substances either elements or compounds may be calculated from H and
S values at standard conditions of temperature (298 K) and pressure (1 atm)
and the substance being present in the standard state.
i.e

G = H TS

Standard free energies of formation of elements are taken as zero. Hence,


standard free energy change of a reaction which is stoichiometrically balanced, is
217

equal to the difference between the total sum of the standard free energies of
products and the total sum of the standard free energies of reactants, at standard
conditions.
Greaction = G product G reactants
Greaction can also be calculated from Hreaction and Sreaction values. Hreaction
and Sreaction can be calculated from Hf and S values of respective product
and reactant molecules at the constant temperature and pressure.
Example 10
For a chemical reaction the values of H and S at 300 K are 10 k cal
mol-1 and 20 cal. deg-1 mol-1 respectively. What is the value of G of the reaction?
Calculate the G of reaction at 400 K assuming H and S values are constant.
Predict the nature of the reaction.
G = H TS
at 300 K; G = 10,000 20 300
= 16,000 cals. mole-1
at 400 K; G = 10,000 20 400
= 18,000 cals. mole-1
At 300 K and 400 K, the values of G reaction are negative (<0). Therefore
the reaction is spontaneous (feasible) at both temperatures.
Example 11
C6H6(l) is -631 kJ. mol-1 at 25C.
H for the reaction 3C2H2(g)
Calculate G reaction and predict the direction in which the reaction is
spontaneous at 1 atm pressure. Given SC2H2 = 200.8 JK-1mol-1 and
SC6H6=172.8 JK-1 mol-1.
3C2H2(g)

C6H6(l)

S = S products S reactants
= SC

6H6(l)

3 SC H

= 172.8 3 200.8

2 2

= 429.8 JK-1

G = H TS; T = 298K
H

= 631 KJ. mol-1


218

G = 631000 + (298 429.8)


= 502.979 kJ.
Since G is a ve value, the reaction is spontaneous.
Example 12
Show that the reaction CO(g) + O2(g) CO2(g) at 300 K is spontaneous
and exothermic, where the standard entropy change is 0.094 kJ mol-1K-1. The
standard Gibbs free energies of formation for CO2 and CO are 394.4 and
137.2 kJ.mol-1 respectively.
CO(g) + O2(g)

CO2(g)

Greaction = Gf products Gf reactants


= Gf CO Gf CO GfO2
2

= 394.4 + 137.2 0
= 257.2 kJ mol-1
Greaction = 257.2 = Hreaction 300 Sreaction
Hreaction = 257.2 300 (0.094)
Hreaction = 285.4 kJ. mol-1
Greaction has ve value. Therefore the reaction is spontaneous.
Also Hreaction has ve value. Therefore the reaction is exothermic.
SELF EVALUATION
A. Choose the correct answer
1.

The amount of heat exchanged with the surrounding at constant temperature


and pressure is called
a) E

2.

b) H

c) S

d) G

All the naturally occuring processes proceed spontaneously in a direction


which leads to
a) decrease of entropy
c) increase in free energy

b) increase in enthalpy
d) decrease of free energy
219

3.

In an adiabatic process which of the following is true?


a) q = w

4.

b) q = 0

c) E = q

d) PV =0

When a liquid boils, there is


a) an increase in entropy
b) a decrease in entropy
c) an increase in heat of vapourisation d) an increase in free energy

5.

If G for a reaction is negative, the change is


a)
c)

6.

Spontaneous
Reversible

b)
d)

Non-spontaneous
Equilibrium

Which of the following does not result in an increase in the entropy?


a) crystallisation of sucrose from solution
c) conversion of ice to water

7.

In which of the following process, the process is always non-feasible?


a)
c)

8.

H > 0, S > 0
H > 0, S < 0

b)
d)

H < 0, S > 0
H < 0, S < 0

Change in Gibbs free energy is given by


a)
c)

9.

b) rusting of iron
d) vaporisation of camphor

G = H + TS
G = H TS

G = H TS
None of the above

a)
d)

For the reaction 2Cl(g) Cl2(g), the signs of H and S respectively are
a) +,

b) +, +

c) ,

B. Answer in one or two sentences


10. What is entropy? What are the units of entropy?
11. Predict the feasibility of a reaction when
i) both H and S increase
ii) both H and S decrease
iii) H decreases but S increases
12. What is Gibbs free energy?
13. Give Kelvin statement of second law of thermodynamics.

220

d) , +

14. How G is related to H and S? What is the meaning of G = 0?


15. Mention the essential condition for spontaneity in a chemical reaction.
C. Answer not exceeding 60 words
16. State the various statements of second law of thermodynamics.
17. What are spontaneous reactions? What are the conditions for the spontaneity
of a process?
Exercises
18. Calculate the maximum efficiency % possible from a thermal engine operating
between 110C and 25C.
[Ans : 22.2%]
19. What is the entropy change of an engine that operates at 100C when 453.6
k.cal of heat is supplied to it?
[Ans : S= 1216.1 cals K-1]
20. Calculate the entropy increase in the evaporation of 1 mole of a liquid when
it boils at 100C having heat of vaporisation at 100C as 540 cals\gm.
[Ans : S = 26.06 cal K-1 mol-1]
21. In the reaction N2 (g) + O2 (g) 2NO (g), H reaction is + 179.9 kJmol-1
and Sreaction = 66.09 JK-1 mol-1. calculate G reaction at 300K.
[Ans : Gr = 160.07 kJ. mol-1]
22. Calculate the standard free energy change ( G) of the following reaction
and say whether it is feasible at 373 K or not H2(g) + I2(g) HI(g); Hr
is +25.95 kJ mole-1. Standard entropies of HI(g), H2(g) and I2(g) are 206.3,
130.6 and 116.7 JK-1 mole-1.
[Ans : Spontaneous]
23. Calculate standard free energy of formation of H2O(l). The standard enthalpy
of formation of H2O(l) is 285.85 kJ and standard entropies of H2(g), O2(g)
and H2O(l) are130.5, 205.0 and 70.3 J.K-1 mole-1 respectively.
[Ans : -237.36 kJ mole-1]
3
24. In the reaction N2(g) + H2(g) NH3(g). The standard entropies of N2(g),
2
H2(g) and NH3(g) are 191.6, 130.5 and 192.5 JK-1 mol-1 respectively. If free
energy change of the reaction is 16.67 kJ. Calculate the Hreaction for the
formation of NH3 at 298K.
[Ans : 46.19 kJ]
221

25. Predict whether the reaction CO(g) + H2O(g) CO2(g) + H2(g) is spontaneous
or not. The standard free energies of formation of CO(g), H2O(g) and CO2(g)
are 137.27, 228.6 and 394.38 kJ mole-1 respectively.
[Ans : Gr = 28.51 kJ]
26. Calculate the standard free energy change of the reaction : 4NH3(g) + 5O2
4NO(g) + 6H2O(l) and predict on the feasibility of the reaction. Standard
free energies of formation of NH3(g), NO(g) and H2O(l) are 16.65, 86.61,
237.20 kJ. mole-1 respectively.
[Ans : 1010.02 kJ mole-1]
27. The standard heat of formation of H2O(l) from its elements is 285.83 kJ.
mole-1 and the standard entropy change for the same reaction is 327 JK-1
at 25C. Will the reaction be spontaneous at 25C?
[Ans : Gr = ve; spontaneous]
28. The boiling point of benzene at 1 atm is 80.2C. Calculate the enthalpy of
vaporisation of benzene at its b. pt.
[Ans : 30.022 kJ.mol-1]
29. The standard entropy change Sr for
CH4(g) + 2O2(g)

CO2(g) + 2H2O(l)

is -242.98 JK-1 at 25C. Calculate the standard reaction enthalpy for the
above reaction if standard Gibbs energy of formation of CH4(g), CO2(g) and
H2O(l) are -50.72, -394.36 and - 237.13 kJ mol-1 respectively.
[Ans : Hr = 890.31 kJ.mol-1]
30. Standard enthalpy change for combustion of methane is 890 kJ mol-1 and
standard entropy change for the same combustive reaction is -242.98
J.K-1 at 25C. Calculate G of the reaction. [Ans : 817.6 kJ mole-1]
31. The standard entropy change for the reaction
9
O 3CO2(g) + 3H2O(l)
2 2(g)
is 339.23 JK-1 at 25C. Calculate the standard reaction enthalpy change
if the standard Gibbs energy of formation of C3H6(g), CO2(g) and H2O(l) are
62.78, 394.36 and 237.13 kJ.mol1 respectively.
[Ans : -2058.2 kJ mole-1]

C3H6(g) +

222

Summary
*

I law of thermodynamics possesses limitations on the directional, spontaneity


and probability of occurrence characteristics of a process.

II law of thermodynamics can be stated in many ways. Entropy function S


is a state function defined as qrev/T. For a process with S equals to positive
(or) zero (or) negative value becomes spontaneous (or) equilibrium (or)
non spontaneous respectively. Trouton rule is Svap =

H vap
Tb

Sreaction = S products S reactants


*

Entropy S, is a measure of randomness or disorder of the process. S


refers to spontaneity of a process.

Gibbs free energy function G = H TS is a state function and for a system


at constant T, the free energy change G = H TS. G value is
characteristic of a system and feasibility of process can be predicted as
follows : At constant temperature, if G is > 0 (or = 0 or < 0 then the
process becomes nonspontaneous (or a equilibrium (or) spontaneous
process.

References
1)

Thermodynamics for Chemists by S.Glasstone, TMH Publishing.

2)

Physical Chemistry by P.W.Alkins Oxford University Press.

223

10. CHEMICAL EQUILIBRIUM - II


Learning Objectives
( To study the applications of law of mass action for equilibrium reactions
with gaseous phase reactants and products.
( To relate Kp and Kc as Kp = Kc (RT)ng and to study the equilibria with
ng = 0, +ve and -ve.
( To learn the statement of Le Chatliers principle.
( To learn to apply Le Chatliers principle to Habers process and Contact
process.

224

10.1 ATTAINMENT OF EQUILIBRIUM IN CHEMICAL REACTIONS


A chemical reaction in equilibrium involves the opposing reactions. One of
the reactions produces the products and is known as the forward reaction while
the other produces the reactants from products and is known as the reverse
reaction. Chemical equilibrium is dynamic in nature. At equilibrium, reactant and
product molecules are both present in the reaction mixture in definite amounts.
The equilibrium concentrations of the reactants and products do not change under
constant temperature, pressure and catalysts etc.
Consider a general equilibrium reaction at constant temperature represented
by
kf

aA + bB

kr

cC + dD

According to law of mass action, the rate of forward reaction is


Rf = kf [A]a [B]b
and the rate of reverse reaction is
Rr = kr [C]c [D]d
where kf and kr are the rate constants of the forward and reverse reactions
respectively.
At equilibrium Rf= Rr
kf [A]a [B]b = kr [C]c [D]d
k f [C]c [D] d
=
k r [A]a [B] b
kf
= K c = equilibrium constant
kr

Kc =

[C]c [D]d
[A]a [B]b

This equation of Kc is also known as equilibrium law equation. Kc is the


equilibrium constant expressed in terms of molar concentrations of reactants and
225

products. For reactions involving gaseous reactants or products or both, it is


more convenient to use partial pressures instead of molar concentrations. Thus
Kc in equilibrium law equation becomes Kp which is the equilibrium constant
expressed in terms of partial pressure.
10.1.1 Relationship between Kp and Kc
Consider a general chemical equilibrium reaction in which the reactants and
products are in gaseous phases,
lL + mM + nN + .....

aA + bB + cC + ........
Kp =

then

p lL p mM p nN .....
paA p bB peC ......

where p is the partial pressure of the respective gases. In terms of molar


concentrations of reactants and products
Kc =

[L]l [M]M [N]n ....


[A]a [B]b [C]c ......

For any gaseous component i in a mixture, its partial pressure pi is related


to its molar concentration Ci as
Ci =

where

pi
RT

since pi =

ni
RT
V

ni
= Ci = number of moles of i per litre. V = volume in litres.
V

Substituting, concentration terms by partial pressures,


Kc =

(p L /RT)l (pM /RT) m (p N /RT)n ...


(pA /RT)a (pB /RT)b (pC /RT)c ...

p lL p mM p nN ..... 1
= a b e

p A p B p C ...... RT

(l+ m + n +....)(a + b + c +...)

226

Kp
(RT) ng

and Kp = Kc(RT)ng

where ng = total number of stoichiometric moles of gaseous products - total


number of stoichiometric moles of gaseous reactants.
Usually, depending on the sign of ng, Kp and Kc are related in three ways.
Case (i)
When ng = 0, the total number of moles of gaseous products are equal to
the total number of moles of gaseous reactants.
For example, in the formation equilibrium of HI,
H2(g) + I2(g)

2HI(g)

ng = 2-(1+1) = 2-2
Kp
Kp

= 0

= Kc (RT)O
= Kc

Case (ii)
When ng = +ve, the total number of moles of gaseous products are greater
than the total number of moles of gaseous reactants.
For example, 2H2O(g) + 2Cl2(g)

4HCl(g) + O2(g)

ng = (4+1) (2+2)
= 54=1
Kp
Kp

= Kc (RT)1
= Kc RT

and Kp > Kc
Case (iii)
When ng = ve, the total number of moles of gaseous products are lesser
than the total number of moles of gaseous reactants.
For example, consider the formation equilibrium of ammonia,

227

3H2(g) + N2(g)
ng = 2 (3+1)
= 2 4 = 2
K p = Kc (RT)-2

2NH3(g)

Kc
(RT) 2
< Kc

Kp =
and Kp

10.1.2 Dependance of dissociation constant with formation equilibrium


constant
In a formation equilibrium reaction, the reactants and products are written
at the LHS and RHS of the equilibrium sign respectively. For the same reaction,
the dissociation equilibrium consists of the products in the place of reactants and
reactants in the place of products being written at the LHS and RHS of the
equilibrium sign respectively.
In such cases, the equilibrium constant of the dissociation equilibrium reaction
which is also known as the dissociation constant, is found to be the reciprocal
value of the equilibrium constant for the formation equilibrium reaction. For
example, consider the formation equilibrium reaction of SO3, from SO2 and O2
gases,
2SO2(g) + O2(g)
2SO3(g)
The equilibrium constant, Kc, is given by
Kc =

[SO3 ]2
dm 3 /mole
2
[SO 2 ] [O 2 ]

In the dissociation equilibrium reaction of SO3, the reactants become


products and vice versa.
2SO3(g)

2SO2(g)+ O2(g)

The equilibrium constant of the dissociation equilibrium is Kc, given by


K 'c =

[SO 2 ]2 [O 2 ] 1
=
mole/dm3
2
[SO3 ]
Kc
228

Kc is considered as the dissociation constant of SO3 gas. Usually, the equilibrium


constant of the dissociation equilibrium is the reciprocal of the equilibrium constant
of the formation equilibrium reaction.
10.1.3 Applications of law of chemical equilibrium to homogeneous
equilibria
Formation equilibrium of HI
H2(g) + I2(g)

2HI(g)

In this equilibrium reaction, the number of moles of the products is equal to


the number of moles of the reactants (ng = 0). Let us assume a and b moles
of H2 and I2 gases being present in V litres of the reaction vessel. At equilibrium,
let x moles each of H2 and I2 react to form 2x moles of HI. Then, the equilibrium
concentrations in moles litre of H2, I2 and HI in the reaction mixture will be
(a-x)/V, (b-x)/V and 2x/V respectively. Since ng = 0, Kc = Kp.
Kc =

[HI] 2
[H 2 ] [I 2 ]

(2x/V) 2
(a x) (b x)

V
V

4x 2
V2
= 2
V
(a x)(b x)

4x 2
=
= Kp
(a x)(b x)
x is also known as the extent of reaction.
Problem
Calculate the Kc, when a mixture containing 8.07 moles of H2 and 9.08 moles of
I2 are reacted at 448C until 13.38 moles of HI was formed at the equilibrium.
The reaction equilibrium is
H2(g) + I2(g)
Kc =

2HI(g)

(2x) 2
(a x)(b x)
229

a = 8.07 moles

b = 9.08 moles
x = 6.69 moles

Kc =

2x = 13.38 moles

(13.38)2
(8.07 6.69)(9.08 6.69)

= 54.29.
The equilibrium constant, Kc, value determines the direction and the extent
of the reaction that may proceed for maximum yield of the product for constant
conditions of temperature, pressure, initial concentrations of reactants or products
as applied on the reaction equilibrium.
In order to find the direction in which a reaction equilibrium may proceed
under different sets of initial concentrations of reactants and products which are
not equal to the respective equilibrium concentrations, a term known as reaction
quotient Q is used. Q is defined as the ratio of product of initial concentrations
of products to the product of initial concentrations of reactants under nonequilibrium conditions. For example, in the equilibrium.
lL + mM

aA + bB

Let [A], [B], [L] and [M] be the actual concentrations present before the
occurrence of equilibrium. These concentrations are considered as the nonequilibrium concentration conditions and the reaction quotient Q is given as

[L]l [M]m
Q=
[A]a [B]b
Let Kc be the equilibrium constant value of the equilibrium reaction in terms of
molar concentrations of reactants and products and the values of Kc and Q can
be compared.
When Q is greater than Kc (Q>Kc) the reaction will proceed so as to reduce
Q. That is, more of reactants will be formed from the products which means the
reverse reaction is favoured. When Q is lesser than Kc (Q<Kc) the reaction will
proceed so as to increase the concentration of products which is the forward
reaction. These aspects will hold good only when Q and Kc are under the same
conditions of temperature and pressure.

230

Problem
Initially, 0.1 moles each of H2 and I2 gases and 0.02 moles of HI gas
are mixed in a reaction vessel of constant volume at 300K. Predict the direction towards which the reaction proceeds [Kc = 3.5 10-2].
The formation equilibrium is
H2(g) + I2(g)
2HI(g)
Kc =

[HI] e2
= 3.5 10 2 at 300 K
[H 2 ]e [I 2 ]e

Under non equilibrium conditions


Q=

[HI]2
[H 2 ][I 2 ]

(2 10 2 ) 2
= 4 10 2
0.1 0.1

Thus Q > Kc.


Therefore, the reaction will proceed initially before attaining the equilibrium
in a direction such that Q value is reduced. That is, concentrations of H2 and I2
should be increases, which is a reverse reaction.
The reaction proceeds in the left side of formation equilibrium of HI and HI
decomposes initially to H2 and I2 until Q = Kc.
Dissociation equilibrium of PCl5
The dissociation equilibrium of PCl5 in gaseous state is written as
PCl5(g)

PCl3(g) + Cl2(g)

Let a moles of PCl5 vapour be present in V litres initially. If x moles of


PCl5 dissociate to PCl3 and Cl2 gases at equilibrium at constant V litres, then
molar concentrations of PCl5, PCl3 and Cl2 gases at equilibrium will be a x ,
V
x
x
and
respectively.
V
V
[PCl3 ][Cl2 ]e
Kc =
[PCl5 ]e

x/V x/V x 2
V
= 2
(a x)/V V (a x)
231

Kc =

x2
(a x)V

x is also known as the degree of dissociation which represents the fraction of


total moles of reactant dissociated.
Number of moles dissociated
____________________________
Total number of moles present initially

x =

If initially 1 mole of PCl5 is present then


x2
_____
=
(1x)V

Kc

x2P
______
(1x)RT

In terms of partial pressures of PCl5, PCl3 and PCl2 then


K

and K p =

p PCl 3 .p Cl 2
p PCl 5

atm

x 2P
atm
(1 x 2 )

If the degree of dissociation is small compared to unity, then (1x) is


approximately equal to 1.0.
Kc =

x2
V

(or)

x V But V

x 2 = Kc V

1
P

1
P

where x is small, degree of dissociation varies inversely as the square root of


pressure (or) varies directly as the square root of volume of the system.

232

Problem
Degree of dissociation of PCl5 at 1 atm and 25C is 0.2. Calculate the
pressure at which PCl5 is half dissociated at 25C.
For PCl5 dissociation equilibrium,
x 2P
Kp =
1 x2

P = total pressure = 1 atm


x = 0.2

Kp =

(0.2)2 (1.0)
0.04
0.04
=
=
= 0.042 atm
2
1 (0.2)
1 - 0.04 0.96

when x = 0.5, P = ?
P=

10.2

K p (1 x 2 )
x2

0.042(1 (0.5)2 )
0.042(1 0.25)
=
=
2
(0.5)
0.25

0.042(0.75 )
= 0.126 atm
0.25

Le Chateliers Principle

There are three major factors that alter the state of equilibrium. They are
concentration, temperature and pressure. The addition of a catalyst has no effect
on the state of equilibrium. Its presence merely hastens the approach of the
equilibrium.
Le Chateliers Principle
According to this principle, if a system at equilibrium is subjected to a
disturbance or stress, then the equilibrium shifts in the direction that tends to
nullify the effect of the disturbance or stress. Let us consider the effects of changes
in temperature, concentration and pressure, on the equilibrium reactions and the
predictions of Le Chateliers principle.
Effect of change of concentration
Consider the following equilibrium reaction
N2(g) + O2(g)

2NO(g)
233

At the equilibrium conditions the reaction mixture contains both the reactant and
product molecules, that is, N2, O2 and NO molecules. The concentrations of
reactant and product molecules are constant and remain the same as long as the
equilibrium conditions are maintained the same. If a change is imposed on the
system by purposely adding NO into the reaction mixture then the product
concentration is raised. Since the system possesses equilibrium concentrations
of reactants and products, the excess amount of NO react in the reverse direction
to produce back the reactants and this results in the increase in concentrations of
N2 and O2. Similarly if the concentration of reactants such as N2 and O2 are
purposely raised when the system is already in the state of equilibrium, the excess
concentrations of N2 and O2 favour forward reaction. Concentration of NO is
raised in the reaction mixture.
In general, in a chemical equilibrium increasing the concentrations of the
reactants results in shifting the equilibrium in favour of the products while increasing
the concentrations of the products results in shifting the equilibrium in favour of
the reactants.
Effect of change of temperature
A chemical equilibrium actually involves two opposing reactions. One
favouring the formation of products and the other favouring the formation of
reactants. If the forward reaction in a chemical equilibrium is endothermic
(accompanied by absorption of heat) then the reverse reaction is exothermic
(accompanied by evolution of heat).
Let us consider the example
N2O4(g)
2NO2(g) ; H = +59.0 kJ/mole
In this equilibrium, the reaction of the product formation (NO2) is endothermic
in nature and therefore, the reverse reaction of reactant formation (N2O4) should
be exothermic. If the above equilibrium reaction mixture is heated then its
temperature will be raised. According to Le Chateliers principle, the equilibrium
will shift in the direction which tends to undo the effect of heat. Therefore,the
equilibrium will shift towards the formation of NO2 and subsequently dissociation
of N2O4 increases. Therefore, generally, when the temperature is raised in a
chemical equilibrium, among the forward and reverse reactions, the more
endothermic reaction will be favoured. Similarly, if the temperature of the
234

equilibrium is decreased i.e., cooled, then the exothermic reaction among the
forward and reverse reaction of the equilibrium will be favoured.
Effect of change of pressure
If a system in equilibrium consists of reactants and products in gaseous
state, then the concentrations of all components can be altered by changing the
total pressure of the system. Consider the equilibrium in the gaseous state such as
N2O4(g)

2NO2(g)

Increase in the total pressure of the system in equilibrium will decrease the volume
proportionately. According to Le Chatliers principle, the change can be
counteracted by shifting the equilibrium towards decreasing the moles of products.
Hence, the reaction of combination of NO2 molecules to N2O4 formation will be
favoured.
In case of a gas phase equilibrium which is accompanied by decrease in
number of moles of products formed, the effect of pressure can be considered as
follows,
2NH3(g)
N2(g) + 3H2(g)
If the pressure is increased then the volume will decrease proportionately.
Consequently, the equilibrium will shift in the direction in which there is a decrease
in the total number of moles, ie., favours the formation reaction of NH3. Here
from four moles of reactants two moles of NH3 are formed. Thus at higher
pressures, the yield of ammonia will be more.
Habers Process
Ammonia is mainly used as a source of nitrogen fertiliser, in nitric acid
production and in nitrogen containing pharmaceuticals. Ammonia is commercially
produced in industries from the gaseous elements nitrogen and hydrogen in air by
means of Habers process. Ammonia formation reaction is an equilibrium reaction.
Fe
N2(g) + 3H2(g)

2NH3(g)

H0f = 22.0 kcal/mole

The forward reaction is accompanied by decrease in the number of moles of


reactants and according to Le Chatliers principle, an increase in pressure favours
235

such a reaction and shifts the equilibrium towards the product formation direction.
Therefore, nearly 300-500 atm pressure is applied on 3:1 mole ratio of H2:N2
gas mixture in the reaction chamber for maximum yield of ammonia. The ammonia
formation reaction is exothermic. By Le Chatliers principle, increase in temperature
favours decomposition reaction of ammonia. However, at low temperature the
time to reach the equilibrium becomes very long. Hence an optimum temperature
close to 500C-550C is maintained. Iron catalyst is chosen to speed up the
attainment of the equilibrium concentration of ammonia. In order to maintain the
equilibrium conditions, steam is passed to remove away the ammonia as and
when it is formed so that the equilibrium remains shifted towards the product
side. The maximum yield of ammonia is nearly 37%.
Contact Process
This process involves the equilibrium reaction of oxidation of SO2 gas by
gaseous oxygen in air to manufacture large quantities of SO3 gas.
v2o5
2SO2(g) + O2(g)

2SO3(g)

H0f = -47 kcal/mole

The formation reaction of SO3 involves a decrease in the overall moles of the
reactants. By Le Chatliers principle, when large pressure is applied, forward
reaction is favoured. 700 atm - 1200 atm pressure is maintained on the 2:1 mole
ratio mixture of pure SO2 and O2 gases in the reaction chamber. SO3 production
is an exothermic reaction. Hence, increase in temperature favours SO 3
dissociation. However, lowering of temperature prolongs the time of attainment
of equilibrium. Therefore, an optimum temperature at nearly 400C to 450C is
maintained to favour the equilibrium.
The most widely used catalyst for SO3 production is porous vanadium
pentoxide (V2O5). Presence of moisture deactivates the catalyst. Only dry and
pure SO2 and O2 gases are used over the catalyst. Since oxidation of SO2 is a
slow process, presence of V2O5 speeds up the equilibrium process and high
yield of SO3 is achieved in a short period. SO3 is the anhydride of H2SO4.
Therefore, SO3 from contact process along with steam is used in oleum and
H2SO4 manufacturing processes in contact process, the yield of SO3 is nearly
97%.

236

SELF EVALUATION
A. Choose the correct answer
1.
2.

State of chemical equilibrium is:


a) dynamic
b) stationery

d) both

If the equilibrium constants of the following reactions are 2A


and B 2A is K2, then
a) K1 = 2K2

3.

c) none

d) K1 = 1/K22

c) K2 = (K1)2

b) K1 = 1/K2

B is K1

In the reversible reaction 2HI


H2 + I2, Kp is
a) greater than Kc
b) less than Kc
c) Equal to Kc

d) Zero

4.

In the equilibrium N2 + 3H2


2NH3, the maximum yield of ammonia will
be obtained with the process having
a) low pressure and high temperature
b) low pressure and low temperature
c) high temperature and high pressure
d) high pressure and low temperature

5.

For the homogeneous gas reaction at 600 K


4NH3 + 5O2
4NO(g) + 6H2O(g)
(g)
(g)
the equilibrium constant Kc has the unit
a) (mol dm-3)-1

b) (mol dm-3) c) (mol dm-3)10

d) (mol dm-3)-9

6.

Two moles of ammonia gas are introduced into a previously evacuated 1.0
dm3 vessel in which it partially dissociates at high temperature. At equilibrium
1.0 mole of ammonia remains. The equilibrium constant Kc for the dissociation
is
a) 27/16 (mole dm-3)2
b) 27/8 (mole dm-3)2
c) 27/4 (mole dm-3)2
c) None of these

7.

An equilibrium reaction is endothermic if K1 and K2 are the equilibrium


constants at T1 and T2 temperatures respectively and if T2 is greater than T1
then
a) K1 is less than K2
b) K1 is greater than K2
c) K1 is equal to K2
d) None
[Ans: 1-a; 2-b; 3-c; 4-d, 5-b, 6-a and 7-a]
237

B. Answer in one or two sentences


8. Dissociation of PCl5 decreases in presence of increase in Cl2 why?
9. Write the equilibrium constant for the following
H2O(g) + O2(g)
i) H2O2(g)

10.
11.
12.
13.
14.

ii)

CO(g) + H2O(g)

iii)

N2O4(g)

CO2(g) + H2(g)

2 NO2(g)

State Le Chateliers principle.


What is equilibrium constant?
Why do equilibrium reactions referred to as dynamic equilibrium?
What happens when ng = 0, ng = ve, ng = +ve in a gaseous reaction.
Calculate ng, for the following reactions
i) H2(g) + I2(g)
2HI(g)
ii) 2H2O(g) + 2Cl2(g)
4HCl(g) + O(g)

C. Answer not exceeding 60 words


15. Derive the relation Kp = Kc (RT)ng for a general chemical equilibrium
reaction.
16. State Le Chateliers principle. Discuss the effect of pressure, concentration
and temperature on the following reaction.
N2g) + O2(g)
2NO(g)
17. Derive the expressions for Kc and Kp for decomposition of PCl5.
D. Practice Problems
18. The equilibrium constant Kc for A(g)
B(g) is 2.5 10-2. The rate constant
of the forward reaction is 0.05 sec-1. Calculate the rate constant of the
reverse reaction.
[Ans : 2.0 sec-1]
19. In the equilibrium H2 + I2
2 HI the number of moles of H2, I2 and HI are
1,2,3 moles respectively. Total pressure of the reaction mixture is 60 atm.
Calculate the partial pressures of H2, I2 and HI in the mixture.
[Ans: 10 atm, 20 atm, 30 atm]
20. In 1 litre volume reaction vessel, the equilibrium constant Kc of the reaction
PCl5
PCl3 + Cl2 is 2 10-4 lit-1. What will be the degree of dissociation
assuming only a small extent of 1 mole of PCl5 has dissociated?
[Ans: x = 1.414 10-2]
238

21. At temperature T1, the equilibrium constant of reaction is K1. At a higher


temperature T2, K2 is 10% of K1. Predict whether the equilibrium is
endothermic or exothermic.
[Ans: Exothermic]
22. At 35C, the value of Kp for the equilibrium reaction N2O4
2NO2 is
0.3174, Calculate the degree of dissociation when P is 0.2382 atm.
[Ans: x = 0.5768]
23. For the equilibrium 2NOCl(g) 2NO(g) + Cl2(g) the value of the equilibrium
constant Kc is 3.75 10-6 at 790C. Calculate Kp for this equilibrium at the
same temperature. Hint: Kp = Kc(RT)ng
[Ans: Kp = 3.29 x 10-4]
24. For the equilibrium 2SO3(g)
SO2(g) + O2(g), the value of equilibrium
constant is 4.8 10-3 at 700C. At equilibrium, if the concentrations of SO3
and SO2 are 0.60M and 0.15M respectively. Calculate the concentration
of O2 in the equilibrium mixture.
[Ans: 0.0768M]
25. Hydrogen iodide is injected into a container at 458C. Certain amount of
HI dissociates to H2 and I2. At equilibrium, concentration of HI is found to
be 0.421M while [H2] and [I2] each equal to 6.04 10-2M, at 458C.
Calculate the value of the equilibrium constant of the dissociation of HI at
the same temperature.
[Ans: Kc = 2.06 10-2]
26. Dissociation equilibrium constant of HI is 2.06 10-2 at 458C. At
equilibrium, concentrations of HI and I2 are 0.36M and 0.15M respectively.
What is the equilibrium concentration of H2 at 458C.
[Ans: [H2] = 1.78 10-2M]
27. The equilibrium constant for the reaction 2SO3(g)
2SO2(g) + O2(g) is
0.15 at 900 K. Calculate the equilibrium constant for the reaction
2SO3(g) at the same temperature.
2SO2(g) + O2(g)
[Ans: 6.67 mol-1 dm3]
28. For the reaction A + B
3C at 25C, a 3 litre volume reaction vessel
contains 1,2 and 4 moles of A, B and C respectively at equilibrium, calculate
the equilibrium constant Kc of the reaction at 25C.[Ans: 10.66 mol dm-3]
29. How much PCl5 must be added to one litre volume reaction vessel at
250C in order to obtain a concentration of 0.1 mole of Cl2, Kc for
PCl5
PCl5 + Cl2 is 0.0414 mol dm-3 at 250C.
[Ans: 0.341 moles PCl5]
30. At 540K, the equilibrium constant Kp for PCl5 dissociation equilibrium at
239

1.0 atm is 1.77 atm. Calculate equilibrium constant in molar concentration


(Kc) at same temperature and pressure.
[Ans: Kc = 4 10-2 moles/litres]
Summary

Law of mass action was applied to equilibrium reactions to determine the


equilibrium constant.
aA + bB
K=

lL + mM

[L]l [M]m k f
=
[A]a [B]b k r

Equilibrium constants in terms of molar concentration (Kc) and partial


pressures (Kp) are related as Kp = Kc(RT)ng for gaseous reactants and
products in equilibrium.
When ng = 0, Kp = Kc; ng = -ve, Kp< Kc and ng = +ve, Kp> Kc.

The reaction quotient (Q) of non equilibrium concentrations to equilibrium


concentrations of reactants and products is related to equilibrium constant
(K) of an equilibrium reaction as: when Q<K, more of product is formed;
Q=K, equilibrium is attained; Q>K, more of reactant is formed.
no.of moles dissociated
Degree of dissociation x= ________________________
total no of moles present initially
Application of Le Chateliers principle to explain effect of pressure,
temperature and concentration on the equilibrium reactions. i) When the
total number of moles are decreased in the equilibrium increase in pressure
favour product formation. ii) For endothermic equilibrium, increase in
temperature favours product formation. iii) Increase in reactant concentration
(or) decrease in product concentration favours the product formation in
equilibrium.

References
1.

Text book of physical chemistry by S. Glasstone, Mac Millan, India Limited.

2.

Physical chemistry by G.Castellan Narosa Publishing Company.

240

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
expression can be written as,
1

products, the overall rate

rate =

k[A]p [B]q

p =

a or less than a

q =

b or less than b

... (11.1)

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


(ii)

H2O2 + 2I + 2H+

Order = 1 + 2 + 2 = 5

I2 + 2H2O
Order = 1 + 1 = 2

r = k [H2O2] [I]

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
A

k1

Rate of reaction =

products
-d[A] = k
1.0
_____
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.lit1. After the reaction has proceeded for some time t, let the
concentration of A that has reacted be x mole.lit1. The concentration of
unreacted A remaining at time t will be (a x) mole.lit1. 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

dx
_____
(a x)

= k1

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
Rearranging,

(or)

k1 =

a
1
ln a x
t

k1 =

2. 303
a
log
t
ax

... (11.4)

Unit of k1 is sec1.
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
2
1
2
t1 and t2 periods of time.

where x1 and x2 are the amounts reacted in

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 sec1 or time1.
rate
mol.lit 1 sec 1
=
k1 =
= sec1
(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 uth fraction of reaction to take place then from equation
11.4,
a
x=
u

t1/u =

and

t1/u

2. 303
a
log
a
= k1
a
u

2. 303
u
log
k1
( 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
92U

90Th

234

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.
C12H22O11 + H2O

H+

C6H12O6 +
Glucose

C6H12O6
Fructose

4. Decomposition of nitrogen pentoxide in CCl4 medium also exhibits


first order kinetics.
N2O5

2NO2 + 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

+ O2

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.
k1 =

2. 303
V
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,


k1

V = 34.75 cc

2. 303
V
log
sec 1
t
(V Vt )

1 min = 60 secs
6

t(min)

2. 303
V
k1 = t 60 log V V sec1
o
t

(V - Vt)

10

28.45

2. 303
34. 75
log
= 2.079 104 sec1
10 60
28. 45

15

25.8

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

20

23.35

2. 303
34. 75
log
= 1.267 104 sec1
20 60
23. 35
Mean value = 1.6253 10-4 sec1

k1 = 1.625 104 sec1 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
H2O2

Pt

H2O + O2

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,
k1 =

Vo
2. 303
log V sec1.
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)

10

20

30

40

vol of KMnO4
(CC)

25

20

15.6

12.7

9.4

time(min)

2. 303
Vo
k1 = t 60 log V sec1
t

Vt

10

20

2. 303
25
log
= 2.68 104 sec1
10 60
15. 6

20

15.6

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

30

12.7

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

40

9.4

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

Mean value = 1.81 104 sec1


Since all the k1 are nearly constant. This is a first order reaction
k1 = 1.81 104 sec1.
Half life period t
Half life period, t, of a reaction is defined as the time required to
reduce the concentration of a reactant to one half of its initial value. t
values are calculated by using the integrated rate equation of any order of a
reaction.
For first order reaction,

k1 =

2. 303
a
log
t
ax
a

if amount reacted x = 2 then t = t

t =

2. 303
a
log
k1
aa / 2

t =

2. 303log 2. 0
k1

t =

0. 693
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 25C, the rate
constant of the reaction is 0.45 sec1. What is the half life of A at 25C.
What is the time required to have 12.5% unreacted A for first order reaction,
t =

0. 693 0. 693
k1 = 0. 45

= 1.54 secs
No. of t

Amount unreacted from 100%

50%

25%

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.
t99% =

2. 303
100
2. 303
log
=
log 100
k1
100 99
k1

t90% =

2. 303
100
2. 303
log
=
log 10
k1
100 90
k1

t99%
log 100
2. 0
=
=
= 2.0
t90%
log 10
1. 0

t99% = 2.0 t90%


Example : In the thermal decomposition of N2O at 764C, 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 ?
Solution :

FG IJ
H K

t1
a2
=
t2
a1

n 1

a1

= 290 mm of Hg t1 = 263 seconds

a2

= 360 mm of Hg t2 = 212 seconds

263
=
212

FG 360 IJ
H 290 K

n 1

1.24 = (1.24)n1
n1= 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.
k =

2. 303
a
2. 303
a
log
log
=
t
ax
40.5 min
0. 75a

= 0.05686 log 1.33 min1


= 0.05686 0.1249 min1
= 7.1 103 min1
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.
t =

t99.9% =

2. 303
a
log
k
ax
2. 303
100
log
100 99. 9
k

2. 303
100
log10
k
0.1

2. 303
log10 1000
k

t(50%) =

... (1)

2. 303
100
log10
100 50
k

2. 303
100
log10
k
50

2. 303
log10 2
k

... (2)

11

(1)
(2)

t(99.9%)
t(50%)

2. 303
log10 1000
k
= 2. 303
log10 2
k

3. 000
= 10
0. 3010

Example : The rate constant for a first order reaction is 1.5410-3sec-1.


Calculate its half-life period.
t

0. 693
k

0. 693
= 450 seconds.
1.54 103 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,
A+B=

k2

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 :
CH3COOCH3 + H2O

H+

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)
No. of moles of water in 1 lit =
Concentration of pure water
13

1000
18

= 55.55 moles

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 x )

(V Vo )

= (V V )
t

The first order rate expression for the hydrolysis of ester can be
written as
(V Vo )
2. 303
log10 (V V )
t
t

k =

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 25C. 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)

20

40

60

v (mL)

20.2

25.6

29.5

32.8

50.4

Show that the reaction is the first order reaction.


Solution :

(V Vo )
2. 303
log (V V )
t
t

V Vo = 50.4 20.2 = 30.2


when t = 20 mts. k =

50. 4 20. 2
2. 303
log 50. 4 25. 6
20

= 0.1151 log

30. 2
24.8

= 0.1151 log 1.2479


= 0.1151 0.0959 = 11.03 103 min1
when t = 40 mts
15

k =

50. 4 20. 2
2. 303
log 50. 4 29.5
40

= 0.0576 log

30. 2
= 0.0576 0.1596
20. 9

= 9.19 103 min1


when t = 60 mts
k =

50. 4 20. 2
2. 303
30. 2
log 50. 4 32.8 = 0.03838 log
60
17. 6

= 0.03838 0.2343 = 8.99 103 min1


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 eEa/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 T 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
Ea

log k2 = log A 2. 303 R T


2
16

... (1)
... (2)

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

= 2. 303 R
k2

log k
1

Ea

= 2. 303 R

FG T T IJ
H TT K
FG T T IJ
H TT K
1

1 2

1 2

If R = 1.987 cals.mol1, then unit of Ea is 103 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 (K1)
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.

P.E. of products

Ea

P.E.
o

f re

acta

nts

Energy

Threshold energy

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 105 sec1

25

3.46

35

13.50

Calculate the Arrhenius frequency factor and activation energy Ea.


k2

Ea

Solution : log k = 2. 303 R


1

FG T T IJ
H TT K
2

1 2

18

k1 = 3.46 105 sec1 T1 = 298K


k2 = 1.35 104 sec1 T2 = 308 K
1. 35 104
log
3. 46 105

Ea

= 2. 303 1. 987

Ea =

FG 308 298 IJ
H 308 298 K

2. 303 1. 987 308 298


1. 35 104
log
10
3. 46 105

= 2.4830 cals.
Ea

log k1 = 2. 303 RT + log A


24830

log 3.46 105 = 2. 303 1.987 298 + log A


log A = 13.7491
A = 5.611 1013 sec1
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 25C to 35C ? Let the rate constants at 25C be k1 and at
35C be k2 respectively.
k1

log k
2
k1

k
2

Ea
2. 303 R

LM 1 1 OP
NT T Q
2

100000 J / mol
2. 303 8. 314 JK 1mol 1

= 0.5745
k1

k
2

= antilog (0.5745)
= 0.2664
19

LM 1 1 OP
N 308 298 Q

k2 =

1
k = 3.75 times k1.
0. 2664 1

k2, the rate constant at 35C will be 3.75 times the rate constant at
25C.
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 390C is same as that for propylbromide
at 320C. 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

2. 303 8. 314 663

Ea

= 2. 303 8. 314 593

Ea =

230000 593
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


small. Total and pseudo
order values lie between
0,1,2 and 3.

Overall order values are large and


greater than 3.0. Sometimes
fractional orders such as 1/2, 1/3,
3/2 etc. are seen.

3.

No side reactions

Many side reactions are present.

4.

Products are formed directly


from the reactants

In some complex reactions


products are not formed in steps
directly involving the reactants.

5.

Experimental rate constant


values agree with the
calculated values. Theories
of reaction rates apply well
on simple reactions.

Experimental overall rate constant


values differ from the calculated
values. Theories of reaction rates
do not agree well on complex
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 :
A

k1

k2

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 :
R'OOC (CH2)nCOOR

k1

R'OOC(CH2)nCOOH

k2

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
k2
A
C
k3

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
|
H3CCCH2CH3
|
OH

CH3
|
CH3C=CHCH3
2-methyl 2-butene

2-methyl-2-butanol

CH3
|
CH2 = CCH2CH3
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.
A+B

kf

C + D,

kr
Examples of opposing reactions
(i)

Reaction between CO and NO2 gases


CO(g) + NO2(g)

(ii)

kf
kr

CO2(g) + NO(g)

Isomerisation of cyclopropane to propene


CH2

H2C CH2
(iii)

kf
kr

CH3 CH = CH2

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
(b) mol litre1 sec1
(a) litre mol1 sec1
1
(c) sec
(d) litre2 sec1
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 = Ae1/RT (b) k = AeRT/Ea

(c) k = AeEa/RT (d) k = AeEa/RT

5. The term A in Arrhenius equation is called as


(a) Probability factor
(c) Collision factor

(b) Activation of energy


(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 min1
(b) 0.693 102 min1
2
1
(c) 6.932 10 min
(d) 69.3 101 min1
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
10. 2N2O5

(b) k [A]
4NO2 + O2,

(c) k [A]1/a (d) k [A]


d [N 2 O5 ]
= 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
(c) 2k1 = k2 = 4k3

(b) k1 = k2 = k3
(d) 2k1 = k2 = k3

11. For a reaction, Ea = 0 and k = 4.2 105 sec1 at 300K, the value of k at
310K will be
(a) 4.2 105 sec1
(b) 8.4 105 sec1
(c) 8.4 105 sec1
(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 2.45 105 sec1 at
273 K and 16.2 104 sec1 at 303 K. Calculate the activation energy.
(Ans. 96.101 kJ/mole)
2. Rate constant of a first order reaction is 0.45 sec1, 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 103 min1, t = 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 5.2 106 mol.lit1.s1 at
298 K. When the initial concentration of reactant is 2.6 103 mol.lit1,
calculate the first order rate constant of the reaction at the same
temperature.
(Ans. 2 103 s1)
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 t depend on the order n.


Unit of k

= lit(n1) mole(1n) sec1

t (a)(1n).

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 waals 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 waals 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
Vander waals force.

1. It is due to chemical bond


formation.

2. Depends on the nature of gas.


Easily liquefiable gases are
adsorbed readily.

2. More specific than the physical


adsorption.

3. Heat of adsorption is small.

3. Heat of adsorption is large.

4. Reversible.

4. Irreversible.

5. If occurs rapidly at low


temperature and decreases with
increase of temperature.

5. Increases with increase


of temperature.

6. Increase of pressure increases


adsorption.

6. Change of pressure has no


effect.

7. Forms multimolecular layers


on adsorbent surface.

7. Forms unimolecular layer

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 chateliers 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 waals 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,
2KClO3

MnO2

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 Habers 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.


2KClO3

MnO2

2KCl
32

3O2

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.
5

COOH
|
+ 2 KMnO4 + 3 H2SO4
COOH

2 MnSO4 + K2SO4 + 10 CO2 + 8H2O

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 Habers 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
A + B

AB

which occurs in presence of a catalyst C, may take place as


AC

A + C
Catalyst

AC

Intermediate
compound

+ 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

NO2

Intermediate
compound

+ SO2

SO3
Product

+ NO
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 vanderwaals 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. Habers process for the manufacture


of ammonia.

Finely divided iron. Molybdenum


as promoter.

2. Ostwalds process for the manufacture Platinished asbestos


of nitric acid.
3. Lead chamber process for the
manufacture of sulphuric acid.

Nitric oxide.

4. Contact process for the manufacture


of sulphuric acid.

Platinised asbestos or vanadium


pentoxide (V2O5).

5. Deacons process for the


manufacture of chlorine.

Cupric chloride (CuCl 2)

6. Boschs process for the manufacture


of hydrogen.

Ferric oxide (Fe 2O3). Chromic oxide


as a promoter.

7. Hydrogenation of vegetable oils


Oil + H2 Vanaspati ghee

Nickel (finely divided).

8. Bergius process for the synthesis of


petrol from coal.

Ferric oxide (Fe2O3)

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
phase

Dispersion
medium

Name

Examples

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.
4.

Ultrasonic dispersion
Peptization

3. Chemical methods
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: (Bredigs 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
not the large colloidal particles.

Fig. 12.4 Dialysis of a sol containing


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 nonelectrolyte 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
do not settle on account of mutual repulsions

45

Fig. 12.10 Helmholtz Double layer

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 electroosmosis 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
(c) gas in solid

(b) liquid in gas


(d) solid in gas.

4. The phenomenon of Tyndalls effect is not observed in


(a) emulsion
(b) colloidal solution
(c) true solution
(d) None
5. The Tyndalls 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 250C
(b) Pt at 25C
(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
(c) dialysis

(b) coagulation
(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
C = (A + B) C ,
the relation between equivalent conductance and concentration of
strong electrolytes will be studied.
@ Statements of Faradays laws of electrolysis and their significances
will be studied. Quantitative calculations on Faradays 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 Kohlraushs 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


solid solutions such as alloys
are called as metallic conductors.

Electrovalent (or) ionic


compounds conduct electricity
through their ions present in
fused state or in dissolved state.

2.

Free and mobile electrons of


the metallic atoms or alloys
are responsible for electrical
conductance.

Ions with positive and negative


charges conduct electricity and
move towards cathode and
anode respectively.

3.

Positive holes in the metals


move in the opposite
direction to electrons.

Electrolysis occurs when


electrical current is passed
through electrolytic solutions.

4.

There is no chemical change in


the material when electricity
is passed.

Chemical change occurs.

5.

There is only flow of electrical


energy but there is no transfer
of matter.

There is actual transfer of


matter since ions move towards
respective electrodes.

6.

Conductivity of metal decreases


with increase in temperature due
to the enhanced thermal vibration
of metal atoms disrupting the
movement of electrons passing
through them.

The conductivity of electrolytes


increases with increase in
temperature. This is due to
increase with ionic mobility.

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.,)

2Al3+ + 3SO42

Al2 (SO4)3

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.
Ostwalds 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. Ostwalds 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.
CH3COO + H+

CH3COOH

Ka =

[H + ][CH 3COO ]
[CH 3COOH]

is the degree of dissociation which represents the fraction of total


concentration of CH3COOH that exists in the completely ionised state. Hence
(1 ) 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 C, C and C (1 ) represent the concentration of H+,
CH3COO and CH3COOH respectively.
Then

Ka =

C .C 2 C
=
C(1 ) 1

if is too small, then Ka = 2C and


=
[H+]

a
. Also [H+] = [CH3COO] = C.
C

FK I
=CG J
HCK
a

1/ 2

= (Ka.C)1/2 = K a .C
62

Ka =
Kb =

2 C
is known as the Ostwalds dilution law. For weak bases,
1
b
2 C
and =
at = small values. Kb = dissociation constant
C
1

for weak base.


This law fails for strong electrolytes. For strong electrolytes, tends to
1.0 and therefore Ka increases tremendously.
13.4 FARADAYS 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.
Faradays 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.
Faradays 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
mQ

... First law


63

We know that

Q = It

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.
1 coulomb current liberates =

equivalent mass
g.coulomb-1
96495

Z = electrochemcial equivalent mass


=

equivalent mass
10-3 kg.coulomb-1
96495

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

96495
=

6.023 10

1.602 10-19 Coulomb.

23

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
1 gm atom of copper requires 2F current
65

Cu(s)

63.5 g.mol 1 180 C


=
2 96500 C

amount of copper deposted

= 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
Amount of copper deposited by 1 coulomb =

0.1978
g = 0.0003296 g
600

Electrochemical equivalent of copper = 0.0003296 = 3.296 104gc1


= 3.206 107 kg c1
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
10 g of iodine is liberated by

Let the current strength be =


Time in seconds =

96,500
10 coulomb
127
I
1 60 60

We know that the quantity of electricity, Q, used is given by the expression


Q = I time in seconds
Curernt strength, I =

96,500 10
Q
= 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

Solution : Wt.of Iodine

1. 25
x

or

Hence, Wt. of Iodine

Also,

Eqvt.wt.copper
Eqvt. wt.of Iodine

31.7
,
127

x =

x=

1. 25 127
31. 7

5.0 g of iodine

Wt.of Copper
1.25
=
Wt.of Silver
y
Eqvt.wt.of Cu ( = 31.7)
= Eqvt.wt.of Silver ( =108)
Wt. of silver (y)

108 1.25
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
Ohms 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

Thus, I =

V
, 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
a

and R =

l
a

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 () [ is called kappa].
is defined as the conductance of one metre cube of an electrolyte
solution
=

1 1 l
= .
R a

Unit of specific conductance is ohm-1 m-1 (or) mho.m-1


Since ohm-1 = mho
=

1
m

= ohm-1.m-1
ohm m2

Also, 1 siemen = 1 mho. is also expressed as S.m-1.


Conductance is the reciprocal of resistance R.
Conductance =

1
R

l
is called as the cell constant (m-1) and is constant for a given
a
conductance cell.
68

Thus specific conductance = cell constant conductance


=

Cell constant
Resistance

Equivalent conductance : Equivalent conductance (C) 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 () of
the solution and the volume (V) of the solution that contains one gram
equivalent of the electrolyte.
(C) = 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
equivalent will be

1000
N

10-6 m3 (1 cc = 10-6 m3)

C =

103
N

mho.m2 gm.equiv.-1

for 1 : 1 electrolyte normality N equals to molarity C. Then


C =

103
mho.m2.(gm.equiv)-1
C

C values depend on the type of the electrolyte, concentration of the


solution and temperature.
Molar conductance : Molar conductance C is defined as the
conductance of a solution containing one mole of the electrolyte dissolved
in it.
C =

103
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

Resistance
Resistivity (or)
specific resistance

Conductance
Specific conductivity
(or) specific conductance
Volume (or) dilution
Equivalent conductance
Molar conductance

1
R

V
C
C

Unit
ohm (or)
ohm.m.
ohm-1 (or) Siemen
ohm-1 m-1
m3
ohm-1 m2 (gm.equiv)-1
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 C 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 C
decreases linearly with increase in C while for weak electrolytes, there is a
curve type of non linear decrease of C with C .

C
Fig. 13.2 Variation of equivalent conductivity C with C for
(a) strong electrolytes and (b) weak electrolytes.

70

For strong electrolytes Debye, Huckel and Onsager equation can be


applied.
C = (A + B ) C to the linear plot of C versus C for strong
electrolytes, the intercept value equals to value which is obtained by
extrapolating the line to y axis ( C = 0). The slope value equals to
(A + B ). A and B are called as Debye constants for strong electrolytes.
In case of weak electrolytes, degree of dissociation () increases when
concentration decreases. Hence, (1 ) value tends to zero at infinite dilution,
such that C increases and tends to value.
of weak electrolytes are experimentally obtained by extrapolating
the upper arm of the curve to the Y axis and the intercept value corresponds
to . In the intermediate concentration range, C is lower than since the
weak electrolyte exists in partially ionised state. The degree of dissociation
equals to the ratio of C to value. (i.e., = C / ).
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.
Solution : R = 210 ohm ;

l
= 0.88 cm-1
a

Specific conductance =

l
1

a
R
0.88 cm1

= 210 ohm = 4.19 10-3 mho.cm-1


= 4.19 103 mho.m1
Equivalent conductance, = V
71

V has 1 gram equivalent dissolved given is 0.01 N in 1000 ml.


1000
= 1,00,000 ml
0. 01

V =

= 4.19 10-3 1,00,000


= 419.05 mho.cm2.gm.equiv.-1
= 4.1905 102 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 = 4.23 10-4 mho.cm-1
C

1000
= C

4. 23 104 1000
=
0. 04

= 10.575 mho.cm2.eq-1.
C

10.575

= 0.0612 = =

= 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.
C

5. 2

Solution : = = 390.7 = 0.01333 = 1.33%

CH3COOH
C (1 )

H+
C

+ CH3COO
C

[H+] = C = 0.1 0.0133 = 0.00133 M


2 C 0. 01332 0.1
=
K=
= 2.38 10-5 M
1 (1 0. 0133)
72

13.7 KOHLRAUSHS 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+ + nBmThen at infinite dilution, according to Kohlrauschs law, the total
equivalent conductance of the electrolyte, =

1
1
+
where +
+ A +
n
m B

and 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.
, NaCl

= Na+ +

, BaCl2

, AlCl3

= 1 Al3+ + Cl

1 Ba2+

Cl
Cl

1
, Al2(SO4)3 = 1 Al3+ + SO42
2

For weak electrolytes,


, CH3COOH = + H+ + CH3COO
, NH4OH

= + NH4+ + OH

Application of Kohlraushs law : The important use of Kohlraushs


law is to deduce the value of the weak electrolytes correctly by
arithmetically combining the values of strong electrolyte in appropriate
manner.
For example of CH3COOH which is a weak electrolyte is deduced
from values of NaCl, HCl, and CH3COONa in such a manner that 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 Kohlraushs law,
73

CH3COONa + HCl NaCl =


CH3COO + Na+ + H+ + Cl Na+ Cl
CH3COO + H+ = CH3COOH
This method produces agreeable values of for weak electrolytes.
Similarly NH4OH can be deduced as,
NH4OH

= NH4+ + OH
= NH4+ + Cl + Na+ + OH Na+ Cl
= NH4Cl + NaOH NaCl

Molar conductances at infinite dilution : () when an electrolyte


dissociates into + number of cations and number of anions then total
molar conductance at infinite dilution of the electrolyte is given by
A+ B

+ A+ + B

then = + + +
where and + are the ionic conductances at infinite dilution.
BaCl2 = Ba2+ + 2 Cl
Na2SO4 = 2 Na+ + SO42
Example 4 : Ionic conductances at infinite dilution of Al3+ and SO42
are 189 ohm1 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
Al2(SO4)3 = Al3+ + SO42
3
2
Al2(SO4)3 =

189 160
+
= 63 + 80 = 143 mho cm2 gm.equi1
3
2

Al2(SO4)3 = 2 189 + 3 160 = 858 mho cm2 mol1

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.
A+ + B

AB

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


Therefore, according to Le Chateliers 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
Ag+(aq) + Cl(aq)

AgCl(s)

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
H+ + F

HF

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
K = 7.2 10-4 =

( x) ( x )
[H + ][F ]
= (1 x )
[HF]

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


7.2 10-4 =

x2
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,
H3O+ + OH

2H2O
According to law of mass action,
Keq =

[H 3O+ ][OH ]
[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+] = 10pH
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+] = 10pH

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 1014 = 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

7
pH < 7

14
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 :
[H+]

Kw
[OH ]

[OH]

Kw
[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
or
Thus
Since

log Kw = log [H+] + log [OH]


log Kw = log [H+] log [OH]
pKw = pH + pOH
Kw = 1.0 1014
pKw
=
log (1.0 1014) = 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+] = 3.9 108 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
antilog [pOH]

pOH = 8.5

[OH] = antilog [8.5] = 3.2 109 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
1 107 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
1.8 105 0.1 = 1. 8 106

= 1.34 103 M

pH = log [H+] = log (1.34 103 )

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.
Ba2+ + 2OH

Ba(OH2)

[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).
H+ + CH3COO

CH3COOH

Na+

CH3COONa

+ 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
H+ + A

HA
and

or

Ka

[ H + ][ A ]
=
[ HA ]

[H+] =

[HA]Ka
[A ]

... (1)

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
[H+] = Ka

[acid ]
[ salt ]

... (2)

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
log [H+] = log Ka log
But

log [H+] = pH

Thus from (3) we have

85

and

[acid ]
[ salt ]

log Ka = pKa

... (3)

Hence,

pH = pKa log

[acid ]
[ salt ]
= pKa + log
[ salt ]
[acid ]

pH = pKa + log

[ salt ]
[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 :
pOH = pKb + log

[salt]
[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.
pH = pKa + log
Since,

[salt] = [acid],

log

[ salt ]
[acid ]

[ salt ]
= 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 = 1.8 105
pKa = log (1.8 105) = 4.7447
[ salt ]
[acid ]
... Henderson - Hasselbalch equation

pH = pKa + log

0. 20
0.15
4
pH = 4.7447 + log
3
= 4.7447 + log

= 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 = 1.34 105

pKa = log Ka = log (1.34 105)


= 4.87
By Herderson - Hasselbalch equation
pH = pKa + log
= 4.87 + log
pH = 4.87
87

[ salt ]
[acid ]
0. 5
0. 5

Alternative solution : The dissociation equilibrium of propionic acid


will be
C2H5COOH
C2H5COO + H+
Ka

[C 2 H 5COO ][ H + ] 0. 5 [ H + ]
=
=
[ C 2 H 5COOH ]
0. 5

=
pH =
=
pH =

[H+]
log [H+]
log Ka = log (1.34 105)
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

8.3 - 10

Colourless

Pink

Phenolphthalein

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 acidbase 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


strong base

(b) weak acid vs


strong base

(c) strong acid vs


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. Ostwalds theory
This theory was proposed by Ostwalds 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+

Unionised form
(colourless)

Ph
ionised form
(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+

Unionised form
(yellow)

OH
ionised form
(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
||
C

O
||
C
O

O
OH

C
H+
O

OH

OH

OH

Benzenoid form, colourless,


exists predominantly in acidic
medium

O
||
C
O
C

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
(c) electrolysis

(b) hydrolysis
(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. Faradays 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 ohm1 cm2 eq1
(c) 1.4 ohm1 cm2 eq1

(b) 140 ohm1 cm2 eq1


(d) 0.14 ohm1 cm2 eq1

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
(c) does not change

(b) decreases
(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 Ostwalds dilution law


for a binary electrolyte whose degree of dissociation is and
concentration C.
2C
2C
(1 ) C
(1 ) C
(b) K =
(a) K =
(c) K =
(d) K =
1
(1 ) C

2
10. Ostwalds dilution law is applicable in the case of the solution of ...............
(c) NaOH (d) H2SO4
(a) CH3COOH (b) NaCl
11. Which one of the following relationship is correct ?
(a) pH =

1
[H+ ]

(c) log10 pH = [H+]

(b) pH = log10 [H+]


(d) pH = log10

1
[ H+ ]

12. When 106 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 1012 (b) 1 102 (c) 1 107 (d) 1 104
14. The pH of a solution containing 0.1 N NaOH solution is ..........
(c) 13
(d) 1013
(a) 1
(b) 101
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 .............
(a) [H+] = Ka

[Acid ]
[Salt ]

(c) [H+] = Ka [Acid]

(b) [H+] = Ka [Salt]


(d) [H+] = Ka
94

[Salt ]
[ Acid ]

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 Ostwalds 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 Faradays laws of electrolysis.
3. Explain Ostwalds dilution law.
4. Explain buffer action with example.
5. Derive Henderson equation.
6. Write notes on (i) Ostwalds 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 Kohlrauschs 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. 2.25 103 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 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.


+ Onsagers equation for equivalent conductors of strong electrolytes is
learnt and its dependence with C is studied.

+ Statements of Faradays 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.

+ Kohlrauschs law is defined and studied. Its 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.
Zn2+(aq) + 2e

Zn(s)

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

Zn

Zn2+

Cu2+

ANODE HALF-CELL

Cu

Phase
Boundary

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+

ANODE HALF-CELL

Cu

CATHODE HALF-CELL

(5) The symbol for an inert electrode, like the platinum electrode is
often enclosed in a bracket. For example,

Mg

||

Mg2+

H+

ANODE HALF-CELL

Inert
Electrode

H2(Pt)

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)
103

Cu

Eo = 1.10 V

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
2H+

H2

+ 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

2F

2.87

F2 + 2e
H2O2 + 2H+ + 2e

2H2O

PbO2 + SO42 + 4H+ + 2e

1.78
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)

106

Ag

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
Eocell = + ve, the reaction is feasible

In general, if

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

Cathode :

2Ag(s)

2Ag+(aq) + 2e

Eo = 0.80 V

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

Cathode :

2Al3+ + 6e

2Al(g)
3Sn4+ + 6e

3Sn2+

Eocell = 0.15 ( 1.66)

Eo = 1.66 V
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.
Zn2+ + 2e

Zn
Cu2+

Cu

+ 2e

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
Cd2+ + 2e
Cd(s)
Right hand electrode (reduction half cell) reaction is
Cu2+ + 2e
Cu(s)
The cell reaction is
Cd2+(aq) + Cu(s)
Cd(s) + Cu2+(aq)
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

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 +

C +

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
E = Eo

aC aD
RT
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.
E = Eo

aC aD
RT
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
E = Eo

[C] [D]
RT
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,
E = Eo

RT
ln K.
nF

This equation is known as Nernst equation.


E = Eo 2.303

RT
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
Mn+

For an oxidation half-cell reaction when the metal electrode M gives


ion,
M

Mn+ + ne
112

...(1)

the Nernst equation takes the form


E = Eo

[M n+ ]
2. 303 RT
log
... (2)
[M]
nF

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

2. 303 RT
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
E = Eo

0. 0591
log [Mn+]
n

... (4)

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
Zn2+ + 2e

Zn

The Nernst equation for the oxidation half-cell reaction is


E

Eo

0. 0591
log [Zn2+]
n

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


Substituting these values in the Nernst equation we have
E

0. 0591
(2)
2

0.763

0.763 + 0.0591 = 0.8221 V


113

Calculation of Cell potential


The Nernst equation is applicable to cell potentials as well. Thus,
Eocell

Ecell =

0. 0591
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

Anode

Zn

Cell

Zn + 2Ag+

2Ag

Eo = + 0.80

Zn2+ + 2e

Eo = 0.76 V

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
Eocell

Ecell =

0. 0591
log K
n

[Zn2 + ]
0. 0591
1.56
log
[Ag + ]2
2

[103 ]
0. 0591
1.56
log
[101 ]2
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
Ecell
or

= Eocell

log K =

0. 0591
log K
n

n Eocell
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


log K =
0 =
1.56 2 =
log K =
K =

n Eocell
0. 0591

2 1.56 0.03 log K


0.03 log K
1.56 2
= 52.79
0. 03

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

Ecell =

Eocell

[Ag]2 [Zn2 + ]
RT

ln
[Ag + ]2 [Zn]
nF

(since concentrations of solids are taken as unity)


=

Eo

[Zn2 + ]
cell ln [Ag + ]2

Substituting the various values in Nernst equation, we have


Ecell =
=

1.56

2. 303 8. 314 298


2 96495

log

0.1
(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
ZnO22 + Hg(s) + H2O

Zn(s) + HgO(s) + 2OH


(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


2Hg(l) + 2H+ + 2Cl

Hg2Cl2(s) + H2

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


Ecell

Eocell

aZn 2 + aCu
RT

ln
aZn aCu2 +
2F

Eocell

aZn 2+
RT

ln a 2+
2F
Cu

(Since activity of a pure metal is unity)

Eocell

0.337 ( 0.762) = 1.099 V

Ecell

1.099

0. 0591
0.1
log
2
0. 01

1.099

0. 0591
log 10
2

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 equiv1)


= 206.4 kJ mol1

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
0.44 V respectively.

Fe(s) as + 0.771V and

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)

At cathode :

Fe3+ + e

Ag+ + 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

At equilibrium, Ecell = Eocell n F ln


118

aAg + aFe 2+
aFe 3+

Since activity of solid silver is 1.0.


n = 1 and Keq =
Eocell =

aAg + aFe 2+
aFe 3+

0. 0591
log Keq
n
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
(d) nEo = 0.0591 log K
(c) nE = 0.0951 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
is + 0.15 V. Calculate the free energy change of the reaction.

Sn2+

[Ans. 28.95 kJ]


2. Write the Nernst equation for the half cell Zn2+(aq) / Zn(s).
o
[Ans. E Zn2+ / Zn = E Zn2+ /Zn RT ln [Zn2+]

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]
[Hint : ECu2+/Cu = EoCu2+/Cu

1
0. 0591
log
]
[Cu2+ ]
2

6. If E1 = 0.5 V corresponds to Cr3+ + 3e


Cr(s) and E2 = 0.41 V
3+
2+
corresponds to Cr + e
Cr reactions, calculate the emf
2+
(E3) of the reaction Cr + 2e
Cr(s)
[Ans. 0.955V]
[Hint : E3 =

3E1 E2
]
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 :
Fe2+ + Ag+ is 0.335, at 25oC. Calculate the standard
Ag(s) + Fe3+
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.
[Hint : Ecell =

Eocell

[Zn2 + ]
RT
n F ln
[Ag + ]2
121

[Ans. 1.648 V]

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

CH3

I CH3
H
Cis isomer

H3C II H
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

CH2CH3

CH2CH3

C
H

C
CH3

H3C

Cis

H
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
-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

COOH

COOH

COOH

HOOC

Cis
[Maleic acid]

Trans
[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-IngoldPrelog 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

H3C

H3C

C
Z-isomer

E-isomer

C
H3CCH2
1

C
CH3
2

H3CCH2
2

125

CH2CH2CH3
1

H3C

H3C

Cl
C

E-isomer

Z-isomer

Cl

CH2CH3
1

Dipolemoment studies is one of the best methods of identifying cistrans 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=CHCH=CH2
This molecule can exist in two forms.
CH2 = CH
|
CH = CH2
and
I

CH2 = CH
|
CH2 = CH
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 CC. In order
to indicate that, this cis-trans isomerism is due to restricted rotation about
CC 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 CC single
bond are called conformers. Free rotation about CC 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 CC 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

Cyclopropane
[Planar conformation]

Cyclo butane
[non planar conformation]

Cyclo pentane
[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 Baeyers
strain (i.e., the valence bond angle is 109o28']
a

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 CH bonds.
Types of CH bonds

Axial
[Six CH bonds parallel
to the axis of the
molecule]

Equatorial
[Six CH bonds subtending
an angle of about 70o
and 110o with the axis

3-axial bonds
facing upward
-axial

3-equatorial
bonds facing
upward
-equatorial

3-axial bonds
facing downward
-axial

3-equatorial
bonds facing
downward
-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
H

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

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


waves vibrating in
all planes.

Nicol
prism

Emergent light consisting


of wave vibrating in
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
direction

Anti-Clockwise
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 dextrorotation 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 laevorotation 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, CH3CHBrCH=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
C
H

(ethanol-symmetric
molecule)

C
OH

OH
H

CH3

OH
D

(deuterated ethanolasymmetric 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 -amino acids (except glycine) have chiral centres (chiral carbon)
and are optically active.
CH3

CH3

R
H

C*

H2N
-amino acid

OH

HO

COOH
COOH

COOH

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
H

COOH
OH

HO

OH

HO

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

HO

COOH

OH

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

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 superimposable 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


separated into two optically
active forms.

It is a single compound and


hence cannot be separated.

2. Optically inactive due to


external compensation.

Optically inactive due to


internal compensation.

3. Molecules of isomers
present are chiral.

Molecules are achiral.


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
magnitude but different sign of
optical rotation.
2. They have configuration with
non-super imposable object mirror
image relationship.
3. Enantiomers are identical in all
properties except the sign of
optical rotation.
4. Separation of enantiomers is a
tedious process.

Differ in the magnitude of


optical rotation.
They are never mirror images.

Diastereomers differ in all


physical propeties.
Separation from the other
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 Fischers projection formulae.
CHO
H

CHO
OH

CH2OH

CH2OH

Sign of rotation : d or (+) glyceraldehyde


Designation of
configuration

HO

l or () glyceraldehyde
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, Xlie 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

R1

R1

R2 = Oxidised group - COOH, CHO, CO...


R1 = Reduced group CH3, CH2OH ...
X = a heteroatom or a group with hetero atom

(In the projection formula, the broken


lines indicate the bonds that are going
below and thick lines, the bonds
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
R1

R1

Thus D and L lactic acids are


COOH
H

COOH
OH

HO

CH3

CH3

L
136

and tartaric acid - (R-stands for the remaining half portion of the molecule)
COOH
H

OH

HO

D-configuration

COOH

HO

OH

H
COOH

COOH
HO

COOH

R = CH(OH)COOH
R
H

L-configuration

COOH

OH

HO

OH
COOH

COOH

This system of designating configuration is of limited applicability.


In Fischers projection formula any two exchanges of groups attached
to the asymmetric carbon atom, are allowed, then the configuration is not
changed.
i.e.,
R

HO

Exchange
H by OH

R
OH

COOH

Exchange
H by COOH

COOH

OH

COOH

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 = 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
benzene

Meta dichloro
benzene

Para-dichloro
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

Cl

Cl

CH3
O2N

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

Cl

and

Cl

CH3

(OR)

CH3

NO2

and
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 = 60o

= 120o

= 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 ?
(b) CH2Br
(a) CH3CH=CHBr
CH2I
C=C
H3C

(c) (CH)3C = CHC2H5

CH2Br

(d) CH3CH = CHCHO

3. Give E/Z-designation for


(a)

CH3

CH2CH3

(b) BrCH
2

C=C
H

CH3
C=C

H3C

140

CH2CH3

CH3

(c)

(d)

C=C
Cl

H
C=C

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) HOH2CCH = 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

(a)

Cl
C=C

OHC

H
C=C

(c)

Cl

(b)

C=C
H

COOH

(d)
CHO

Br

C=C
H

COOH

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


(a) ClCH2C CCH3

(b) ClCH2CH = CHCH2Cl

(c) CH2 = CHCHO

(d) CH2 = CCH2CH3


|
CH3
141

9. Label the following as, E, Z isomers.


CH3

CH2OH
CH3

C
(a)

C=C

(b)
C

CHO
C=C

CH3

COOH

HOCH2

(c)

Cl

(d)
CH2Cl

H
C=C

Br

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


CONFORMATION
1. Which among the following can have different conformations ?
(b) CHCl3
(c) CH3COOH
(d) CH3CH2OH
(a) CH4
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 CH 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) CH3CH2CH2CH(OH)CH3
2. (d)

CH3
|
CH3CHCOOH

3. (d) sp3 carbon


4. (a) CH3CH2CH (CH3)CH2 CH2 CH3
(b) CH3CH2CH (CH3) CH=CH2
(c)

CH3
|
CH3CH2CH CCH

(d) CH3CH2 CH (OH) CH3


(e) CH3CH2CH (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 nonsuperimposable 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 ROH.
R can be (i) aliphatic saturated
(ii) unsaturated
(iii) aralkyl

ethyl alcohol
allyl alcohol
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 CH2OH

CHOH
R

Primary
1o

Secondary
2o

R
R
R

COH
Tertiary
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
name

Carbinol
name

CH3CH2OH

ethyl alcohol

methyl carbinol

ethanol

CH3CH2CH2OH

n-propyl alcohol

ethyl carbinol

1-propanol

CH3CHOHCH3

isopropyl alcohol

dimethyl carbinol

2-propanol

CH3CH2CHOH
|
CH3

secondary butyl
alcohol

ethyl methyl
carbinol

2-butanol

148

IUPAC
name

CH3CHCH2OH
|
CH3

Isobutyl alcohol

isopropyl carbinol

2-methyl1-propanol

CH3
|
H3CCOH
|
CH3

tert-butyl alcohol

trimethyl carbinol

2-methyl2-propanol

C6H5CH2OH

Benzyl alcohol

phenyl carbinol

phenyl methanol

CH3CH2CHOHCH2CH2CH3

---

ethyl, propyl carbinol 3-hexanol

CH3 CH3
|
|
CH3 C C CH3
|
|
H OH

----

dimethyl isopropyl
carbinol

2,3- dimethy1-2
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
(linear chain)

2-methyl-1-propanol
(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) Markownikoffs addition of water to olefins in presence of dilute
sulphuric acid.
CH3CH = CH2 + H2O

H2SO4

CH3 CHOH CH3

propylene

Hydration normally proceeds by protonation of olefins to form


carbocation, followed by nucleophilic attack by water.
R CH = CH2

H+

R CH CH3

H2O

OH2
|
R CH CH3
H+

OH
|
RCHCH3
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.
C2H4 + H2SO4

353K

H2O : + C2H5 HSO4

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
XMg R

H
C=O

H OH

R CO MgX

RCH2OH + Mg

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
C=O

H2/Pt

R
RCH2OH ;

C=O

H2/Pt

R2CHOH

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


R
C=O

LiAlH4

R
CH2 ;

C=O

HO

NaBH4

R
CHOH
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.
RX + NaOH

H2O

RX + AgOH

ROH + NaX
ROH + AgX

(b) Aliphatic primary amines react with Nitrous acid forming alcohols.
Diazonium ion is formed as an intermediate.
RNH2 + HONO

H2O

[RN=N+]
unstable

151

H2O

N2 + ROH

The nucleophile is water and the leaving group is Nitrogen molecule.


(c) Hydrolysis of esters by either acid or alkali.
R'COOR + H2O

H+

R'COOH + ROH

OH

R'COOR + NaOH

R'COONa + ROH

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.
+

ROR + HI

RO R
|
H

ROH + RI

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

2
C2H5OC2H5
2C2H5OH + H+
|
H
Protonation of ether oxygen, followed by nucleophilic displacement of
ethyl alcohol by water.

C2H5OC2H5 + H2O

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.
RH

HOH

ROH

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
|
|
OH ......OH

R
H
|
|
OH .....OH

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
in water

insoluble
in water

soluble
in water and
slightly soluble
in hydro carbon.

insoluble 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.
ROH + Na

RONa + 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.
ROH + CH3MgBr

ROMgBr + CH4
154

Hence alcohols cannot be used as a solvent for Grignards 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

ROH

H
|
ROCOR'
+

R'COCl

Cl

H+
ROCOR'

H
|
R O COR' + R' COO()
+

COR'
ROH +

O
COR'

H+
H+ + ROCOR'
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
||
H+
ROH
+
H

OCR'
ROCOR' + H2O
..
C2H5OH + CH3COOH

H+

CH3COOC2H5 + H2O
(ethyl acetate)

2. Alcohols form alkyl chlorides. When treated with anhydrous zinc


chloride and hydrogen chloride.
ROH + HCl

ZnCl2

155

RCl + H2O

This reaction involves protonation of the alcohol followed by nucleophilic


attack by chloride ion. Protonation weakens the CO 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
3o alcohol

(CH3)3 CCl + H2O

anhyd. ZnCl 2

(Turbidity appears immediately)


at room temperature

con.HCl

(CH3)2 CHOH

anhyd. ZnCl2

2o alcohol

(CH3)2CHCl + H2O

(Turbidity appears after 5-10 minutes)


at room temperature
Conc. HCl

CH3CH2OH
1o alcohol

anhydrous ZnCl2

CH3CH2Cl + H2O
(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

RCH2OSOCl

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

RCH2OSO Cl

RCH2Cl + SO2

This reaction belongs to SNi (Nucleophilic substitution internal)


4. Alcohols are converted to their halides by the action of phosphorous
halides.
ROH + 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
+

RCH2 O
Cl

R CH2Cl + POCl3 + HCl


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.
C2H5OH + H2SO4

410K

C2H5 . HSO4 + H2O

C2H5 HSO4

C2H5 O

+
C2H5

C2H5OH
157

HSO4

H
+
C2H5 O

C2H5OC2H5

H+

C2H5
(b) Intramolecular dehydration takes place leading to the formation of
olefins. This reaction involves -elimination. It is E1 reaction and the
intermediate is carbonium ion.
(CH3)3 COH

H+

(CH3)3 C

(CH3)3 C+

(CH3)2 C = CH2

H2O
+

H+

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


shown.
HCH2CH2HSO4

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.

CH3CH2OH

Al2O3
620 K

CH2=CH2

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


catalyst at 633 K to form mixture of amines.

ROH

NH3

Al2O3
633 K

RNH2

ROH

Heated alumina removes the water formed.

158

R2NH

ROH

R3N

16.3.2 Methods of distinction between three classes of alcohols


(1o, 2o and 3o)
Reaction involving hydrogen - to the OH group.
Since primary, secondary and tertiary alcohols differ in the number of
-hydrogen atoms, these reactions can be used to distinguish them.
1. Oxidation
Oxidation of alcohols with acidified potassium dichromate gives different
oxidation products.
(O)
CH3CHO + (O)
|
|
H H

H2O

CH3CH=O

CH3COOH

aldehyde

(primary alcohol)

CH3
|
CH3 C O
| |
H H

(O)

H2O

CH3
|
CH3C=O
(Ketone)

(O)

CH3COOH

(acid with lesser


carbon atoms)

(secondary alcohol)

CH3
|
H3C C OH
|
CH3

H+

CH3
|
CH3 C = CH2

(tertiary alcohol)

(O)

CH3COCH3 + HCOOH

CH3COOH

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


oxidation also decreases.
Hence the presence of -hydrogen is essential for normal oxidation
reactions of alcohols.
159

Acidified potassium permanganate oxidises the alcohols directly to the


carboxylic acid.
(O)

CH3CH2OH

(O)

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
Ethyl alcohol

CH3CHO

H2O

H2O

Acetaldehyde

Secondary alcohols are oxidised to ketones.


CH3
CHOH

CH3

(O)

CO

CH3

CH3

Isopropyl alcohol

Acetone

Tertiary alcohols do not undergo this reaction because it does not contain
-hydrogen which is involved.
The carbonyl compounds formed undergo further chlorination forming
chlorinated aldehydes and ketones.
CH3CHO
CH3COCH3

Cl2

Cl2

CCl3 CHO (chloral)


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.
C2H5OH

I2/KOH

CH3CHO

I2/KOH

CH3CHOHCH3

I2

CH3COCH3

KOH

CI3CHO
I2

CI3COCH3

CHI3 + HCOOK

KOH

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.
CH3 CH O
|
|
H
H

Cu/573K

CH3CHO

H2

CH3
|
CH3 C = O

H2

(aldehyde)

Primary alcohol

CH3
|
CH3 C O
|
|
H H

Cu/573 K

(acetone)

Secondary alcohol

CH3

OH
C

CH3

CH3

CH3

Cu/573K

C=CH2

dehydration

H2O

CH3

Tertiary alcohol

Isobutylene

Absence of -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

CH3CH2OH

CH3CH2I

primary alcohol

KOH

CH3 C=NOH
|
NO2
(Nitroxime or nitrolic acid)

AgNO2

CH3C H2O = NOH


|
NO2

CH3C=NOK+
|
NO2

Potassium salt of nitrolic acid


(red colour)

(b) Secondary alcohol :


CH3

CH3

P/I2

CHOH

CHI

CH3

CH3

Secondary alcohol

CH3

NO2

CH3

NO2
C

CH3

+ HON=O
H

KOH

C
CH3

AgNO2

No Reaction but blue colour


remains.

N=O

(Pseudo nitrol)
blue colour

(c) Tertiary alcohol :


CH3
CH3 C OH
CH3

CH3
P/I2

CH3
AgNO2

CH3 C I

CH3 C NO2

H3C

HNO2

No reaction

CH3
Nitro compound
colourless

Absence of -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
|
H

CH3 C = O
|
H

+ H2O

Gemdiol

CH2OH
|
CH2OH

CH2OH
|
CH2
|
CH2OH

1,2 ethane diol

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
CH2(OH)CH2CH2OH

propane-1,2-diol
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 Baeyers 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.
RCH = CH2 + O2

RCHCH2
O
164

H3O+

R CH CH2
|
|
OH OH

Thus ethylene forms ethylene epoxide.


Ag

CH2 = CH2 + O2

CH2 CH2

473-673 K

O
This is hydrolysed to ethylene glycol by dil. HCl or sulphuric acid at
333 K.
CH2 CH2

H3O+

CH2OH CH2OH

O
This reaction proceeds via the nucleophilic attack by water on the
protonated epoxide.

H2O :

CH2 OH
H+
+
|
H2O CH2

CH2 +
|
OH
CH2

CH2OH
|
CH2OH

(c) Olefins are converted to chlorohydrins and are then hydrolysed with
milk of lime. Ethylene glycol itself is prepared as follows :
CH2
||
CH2

+ HOCl

CH2OH
|
CH2Cl

Ca(OH)2

CH2OH
|
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
|
CH2Br

H2O
Na2CO3

CH2OH
|
CH2OH

2 NaBr

CO2

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
|
CH2NH2

2HNO2

CH2OH
|
CH2OH

2N2

2H2O

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 BouveaultBlanc 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
|
COOC2H5
CHO
|
CHO
glyoxal

4 (H)

8(H)

CH2OH
|
CH2OH
CH2OH
|
CH2OH

2 (H)

2 C2H5OH

CHO
|
CH2OH

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
|
CH2OH

Na
323 K

CH2ONa
|
CH2OH
Monosodium
glycolate

Na
433 K

CH2ONa
|
CH2ONa
Disodium
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
|
CH2OH

H+

HX

X CH2
+
|
CH2OH

CH2 O
|
CH2OH

H2O

Ethylene glycol reacts with hydrogen chloride gas as follows :


CH2OH
|
CH2OH

HCl / 433 K
H2O

CH2Cl
|
CH2OH

CH2Cl
|
CH2Cl

HCl / 473 K
H2O

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
|
CH2OH

2HNO3

H2SO4

CH2 O NO2
|
CH2 O NO2

+ 2H2O

(iii) Ethylene glycol reacts with organic acids like acetic acid in presence
of mineral acid, forming glycol mono and diacetate.
CH2OH
|
CH2OH

+ CH3COOH

H+
-H2O

CH2OCOCH3
CH3COOH
|
H+
CH2OH
glycol monoacetate

CH2OCOCH3
|
CH2 OCOCH3
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[CH2CH2OCO

COO]n H + (2n 1) H2O

(v) With phosphorous halides


Ethylene glycol forms ethylene chlorohydrin and ethylene dichloride with
either PCl5 or PCl3.
CH2OH
|
CH2OH

CH2Cl
|
CH2OH

CH2Cl
|
CH2Cl

Similarly PBr3 forms mono and dibromide.


CH2OH
|
CH2OH

CH2Br
|
CH2OH

CH2Br
|
CH2Br

ethylene bromohydrin

ethylene dibromide

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


to form ethylene.
CH2OH
|
CH2OH

CH2I
|
CH2I

CH2
||
CH2

-I2

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
|
CH2 OH

H2O
773K

169

CH2
|
CH2

(ii) When heated with anhydrous zinc chloride, ultimately acetaldehyde


is formed. This involves -elimination.
H
|
H C OH
|
H C OH
|
H

ZnCl2
H2O

H
|
COH
||
CH2

H
|
C=O
|
CH3

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

HO CH2 CH2 OH

O
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
HOCH2CH2 OH

H2SO4

H OCH2CH2

CH2CH2

H2SO4

O
HO CH2CH2

O
CH2CH2

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 CC bond
forming formic acid.
CH2OH
|
CH2OH

3(O)

HCOOH
+
HCOOH

+ H2O

(b) Periodic acid is a specific reagent to bring about such a CC bond


cleavage by oxidation.
CH2OH
HCOOH
3(O)
|
+
+ 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
aldehyde

glyoxalic
acid

COOH
|
CH2OH

glycollic acid

171

oxalic
acid

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

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'
|
CH2OCOR"

R, R' and R" can be same or different.

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
|
CHOCOR + 3NaOH
|
CH2OCOR

CH2OH
|
CHOH +
|
CH2OH

3RCOONa
(soap)

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
|
+ 3H2O
CHOCOR
|
CH2OCOR

CH2OH
|
CHOH
|
CH2OH

H2SO4
Steam

3RCOOH
(solid)

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
||
CH
|
CH3

Cl2
773 K

propylene

CH2
||
CH
|
CH2Cl

Na2CO3
773 K/12 atm

allyl chloride

CH2
||
HOCl
CH
|
CH2OH

allyl alcohol

CH2OH
|
CHOH
|
CH2OH
173

CH2OH
|
CHCl
|
CH2OH

glycerol
chlorohydrin
NaOH

+ NaCl

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
|
CHOH
|
CH2OH

Na

CH2ONa
|
CHOH
|
CH2OH

Na

CH2ONa
|
CHOH
|
CH2ONa

2. Reaction with hydrogen halides :


Glycerol reacts with hydrogen chloride at 383 K to give both and
-mono chloro derivative.
CH2OH
|
CHOH
|
CH2OH

HCl
383K

CH2Cl
|
CHOH
|
CH2OH

glycerol
-chlorohydrin

174

CH2OH
|
CHCl
|
CH2OH
glycerol -chlorohydrin

With excess of hydrogen chloride, , ' - and , dichlorohydrins


are obtained.
CH2Cl
|
CHOH
|
CH2OH

CH2OH
|
CHCl
|
CH2OH

Excess
HCl

CH2Cl
|
CHOH
|
CH2Cl

CH2Cl
|
CHCl
|
CH2OH

-' dichlorohydrin

,- 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
|
CHOH
|
CH2OH

HI or

PI3 or I2

CH2I
|
CHI
|
CH2I

CH2
||
CH
|
CH2I

-I2

With excess of the reagent allyl iodide further reacts giving ultimately
isopropyl iodide.
CH2
||
CH
|
CH2I
I Step

HI

CH3
|
CHI
|
CH2I

I2

CH3
|
CH
||
CH2

HI

propylene
III Step

II Step

175

CH3
|
CHI
|
CH3

isopropyl
iodide

The first and the third step involves Markownikoffs addition of HI to


the carbon-carbon double bond. The second step involves -elimination of
iodine.
5. With a well cooled mixture of concentrated sulphuric acid and
fuming nitric acid, nitroglycerine is formed.
CH2OH
|
CHOH + 3HONO2
|
CH2OH

conc.H2SO4

CH2ONO2
|
CHONO2
|
CH2ONO2

3H2O

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
|
CHOH
|
CH2OH
Glycerol
Monoacetate

CH2OCOCH3
|
CHOH
|
CH2OCOCH3
Glycerol
Diacetate

CH2OCOCH3
|
CHOCOCH3
|
CH2OCOCH3
Glycerol
Triacetate

6. Dehydration :
When glycerol is heated with potassium bisulphate or conc. sulphuric
acid or phosphorous pentoxide dehydration takes place. Two -elimination
reaction takes place to give acrolein or acrylic aldehyde.
H CH OH
|
H C OH
|
H CH OH

KHSO4

CH2
||
C
||
CHOH

CH2
||
CH
|
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
|
|
CHOH +
CO OH
|
CH2OH

CH2 O C = O
|
|
decarboxylation
CHOH
COOH
|
CH2OH
CO2

383K

monooxalate

CH2OCOH
|
CHOH glycerol mono formate
|
CH2OH
This on hydrolysis gives formic acid.
CH2OCOH
|
CHOH
|
CH2OH

CH2OH
|
CHOH
|
CH2OH

HCOOH
formic acid

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
|
HOCO
CHOH +
|
|
HOCO
CH2OH

533K

CH2 O CO
|
|
CH O CO
|
CH2OH

CH2
||
CH + 2CO2
|
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 Fentons 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 :
CH2OH

[O]

primary alcohol

[O]

CHO

COOH

aldehyde

acid

[O]

[O]

CHOH

> C=O

Secondary alcohol

Ketone

COOH + CO2
etc.

Oxidation reaction of glycerol

CH2OH
|
CHOH (O)
|
CH2OH

CHO
|
CHOH (O)
|
CH2OH

COOH
|
CHOH (O)
|
CH2OH

CH2OH
|
(O)
CO
prolonged
|
CH2OH

COOH
|
CO
|
COOH

dihydroxy acetone

mesoxalic acid

glyceraldehyde

glyceric acid

(O)
2 CO2 + H2O

(O)

178

COOH
|
+ CO2
COOH
oxalic acid

COOH
|
CHOH
|
COOH

(O)

tartronic acid

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.
C6H5CH3
Toluene

Cl2

HCl

C6H5CH2Cl

NaOH

Benzyl chloride

C6H5CH2OH + NaCl
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
C6H5CHO

C6H5CH2OH
+
C6H5COOH

+ H2O

Benzyl alcohol
Benzoic acid

(simple)

(ii) C6H5CHO
HCHO

+ H2O

C6H5CH2OH
+
HCOOH

OH

Benzyl alcohol
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. Grignards synthesis
Since benzyl alcohol is a primary alcohol, it is prepared by the action of
phenyl magnesium bromide on formaldehyde.
H
C6H5MgBr +

C6H5
C=O

ether

H
C

O MgBr

C6H5
CH2 OH
Br
+ Mg
OH
180

H3O+

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
HI
Iodine is removed by phosphorous.

C6H5CH3 + I2

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.
C6H5CH2 OH + H OCOCH3
C6H5CH2 O H
+
CH3CO Cl

HCl

Acetylchloride

H+

C6H5CH2OCOCH3

H2O

benzyl acetate

C6H5CH2OCOCH3

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.
C6H5CH2OH

Pb(NO3)2
or Cu(NO3)2

C6H5CHO

H2O

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
Na2CO3/KMnO4

Benzaldehyde

C6H5COOH
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
Cl

CH2OH

SO3H

Conc.

Cl2

CH2OH

CH2OH

+
H2SO4

Cl

SO3H

o- and p- chloro
substituted compounds

o- and psulphonic 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 [CH3C6H4OH].
Classification and Nomenclature
1. Phenols may be classified as monohydric, dihydric and trihydric
according to the number of hydroxyl groups.
(i) Monohydric phenols :
CH3
OH

CH3

CH3
OH

OH
Hydroxy benzene
(Phenol)

o-hydroxy toluene
(o-cresol)

m-hydroxy toluene
(m-cresol)

OH
p-hydroxy toluene
(p-cresol)

(ii) Subsituted phenols :


These are named as derivatives of phenol or as hydroxy compounds.
183

CHO
OH

OH
OH

O2N

COOH
NO2

NH2
o-aminophenol

o-hydroxy
benzaldehyde

NO2

OH

2,4,6-trinitro
phenol

p-hydroxy
benzoic acid

(iii) Dihydric phenols :


OH

OH

CH3

OH

OH

HO

OH

OH

OH
1,2-dihydroxybenzene
or
ortho dihydroxy
benzene
or
Catechol

1,3-dihydroxybenzene 1,4-dihydroxybenzene 3,5-dihydroxytoluene


or
or
or
meta dihydroxy
p-dihydroxy
Orcinol
benzene
benzene
or
or
Resorcinol
p-quinol

(iv) Trihydric phenols :


OH

OH

OH
OH

OH

OH

HO

OH

OH
1,2,3-trihydroxybenzene
(Pyrogallol)

1,2,4-trihydroxybenzene
(Hydroxy quinol)

1,3,5-trihydroxybenzene
(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.
Ar-Cl +

NaOH

C6H5 Cl + NaOH
Chloro benzene

623K

300 atm.
623K
300 atm.

ArOH

NaCl

C6H5OH + NaCl
phenol

This reaction is an example of aromatic nucleophilic substitution.


The replacement of nuclear halogen is difficult because of the stronger CCl
bond compared to that in alkyl halides. Yet, this reaction is used for the large
scale preparation and is known as Dows process.
2. Phenol is also manufactured by heating chlorobenzene with steam
in presence of silica as catalyst.
C6H5Cl + H2O

SiO2

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 + 2NaOH

ArSO3Na + H2O
573 K

Ar ONa + Na2SO3
Sodium phenoxide

ArONa

+ HCl

ArOH + NaCl

4. By boiling weakly acidic aqueous solution of diazonium chloride,


phenol is formed.
C6H5N2Cl

Benzene diazonium
chloride

H2O

H+

C6H5OH + HCl + N2

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

COONa

+ Na2CO3

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.
CH

AlCl3

CH3
CH3

+ CH3CH=CH2
Cumene

This is oxidised to hydro peroxide by oxygen of the air.


CH(CH3)2
O2

CH3
|
H3C COOH

Cumene hydro peroxide

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


CH3
|
H3C COOH

OH
H+

CH3
+ O=C

H2O

CH3
Phenol

186

Acetone

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 +

2C6H5ONa + H2

2Na

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.
O

OH
H2O

H3O+

Phenol

Phenolate ion

Resonance in phenolate ion


O

()

()

()

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


RCH2O()

RCH2OH

Presence of I, M groups in benzene ring enhances its acid strength.


OH

OH

>

>

NO2

OH

OH

Cl

>
CHO

At para position the resonance effect effectively operates.


OH

OH

>
NO2

188

CH3

Resonance in p-nitrophenol and its anion


+
OH

:OH

etc.
N+

N
O()

()O

O()

etc.
N+
O

N+
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

>
CN

NO2

OH

>

OH

>

CHO

CH3

Reaction with zinc dust


Phenols on distillation with zinc dust give aromatic hydrocarbons.
ArOH

ArH

Zn

C6H5OH + Zn

ZnO

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

C6H5 OH + CH3COOCOCH3

OH

C6H5OCOCH3 + HCl
C6H5OCOCH3 + CH3COOH

The reaction of phenols with benzoyl chloride in presence of sodium


hydroxide to form benzoates is known as Schotten-Baumann reaction.

190

C6H5OH + C6H5COCl

NaOH

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()

ArO() + R X
C6H5OH + (CH3)2 SO4

Dimethyl sulphate

C6H5OH + C2H5Br

+ X

ArOR
NaOH

OH

Na+

C6H5OCH3 + CH3OSO2OH
Anisole

Methyl hydrogen sulphate

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.


C6H5OH

OH

+ CH2N2

C6H5OCH3

diazomethane

N2

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

C6H5OH

NH3
+

ArNH2
ZnCl2/473 K

NH3

C6H5NH2

Phenol

H2O
+

H2O

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
Br

2 Br2

+ 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

298 K

NO2

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
HNO3

OH
NO2

+
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
Sulphonic acid

Para hydroxy benzene


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.
N=NCl + H

OH

OH

N=N

273 K
(Benzene diazonium chloride)

(p-hydroxy azobenzenea red orange dye)

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


194

OH

Kolbe schmidt or Kolbes 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

CO2

400 K
4 - 7 atm

HCl

COONa

OH

+ NaCl
COOH

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
CHCl3

NaOH

OH

+
CHO

OHC
Ortho
Para
(Hydroxy benzaldehyde)

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


OH

OH

CCl4

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
C

OH

C=O
H

OH
C

OH

OH
Phenolphthalein

Oxidations
Phenol undergoes oxidation to quinone on treatment with chromyl
chloride (CrO2Cl2).
OH + 2 ( O)

CrO2Cl2

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

+ HCHO

HO

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
------H2C

OH
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

(a)

(b)

N
+

N
()O

O()

O
O

(c)

(d)

N
+
O

O()

198

N
+
O

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
(c) CH3(CH2)2OH

(b) (CH3)2CHOH
(d) CH3CH2OH

15. When phenol is distilled with Zn dust it gives


(a) benzaldehyde
(c) toluene

(b) benzoic acid


(d) benzene

16. A compound that undergoes bromination easily is


(a) benzoic acid
(c) phenol

(b) benzene
(d) toluene

17. Isomerism exhibited by ethylene glycol is


(a) position isomerism
(c) functional isomerism

(b) chain isomerism


(d) both (a) and (c)

18. Ethylene diamine is converted to ethylene glycol using


(a) Na2CO3 solution
(c) NaHCO3 (aqueous)

(b) nitrous acid


(d) Baeyers reagent

19. Ethylene glycol forms terylene with


(a) adipic acid
(c) terephthalic acid

(b) phthalic anhydride


(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
(c) Nitro benzene

(b) Nitro glycerine


(d) Trinitro toluene

25. The reaction of ethylene glycol with PI3 gives


(a) ICH2CH2I
(c) CH2 = CHI

(b) CH2 = CH2


(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 Meyers 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
CC bond cleavage takesplace.
(c) Glycerol on dehydration forms CH2=CHCHO
(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.
C2H5OH

NH3

Al2O3
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-methylpropan-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 Kolbes 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.
OH + HNO3

con.H2SO4

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 Dows process.

202

31. Identify the product A and B.


OH
CHCl3

Ag+

NaOH

CH3

Ans.
OH

OH

COOH

CHO

A=

B=
CH3

CH3

32. Identify C and D.


ONa
CO2

403 K
6 atm

dil. HCl

Ans.
OH

OH
COONa

C=

33. Identify the product.


CH3
CHOH
CH3
Ans.

COOH

D=

A and B
[O]

[O]

prolonged

A = CH3 C CH3
||
O

[O]

203

CH3 COOH
B

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 Meyers 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) Kolbes 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.
CH3CH2OH

Al2O3

CH2 = CH2

620K

cold alkaline
KMnO4
(Baeyers reagent)

CH2 CH2
|
|
OH OH
2. Give the IUPAC names of
(i) CH3CH(OH)CH2OH
(ii) HOCH2CH2OH
(iii) CH3CHCOOH
|
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) CH3CHCH2OH and CH3CH2CH2CH2OH
|
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.
(i) CH CH

dil.H2SO4

[O]

SOCl2

HgSO4

Ans.

A = CH3CHO
B = CH3COOH
C = CH3COCl

(ii) C2H5OH

PCl5

KCN

H2O/H+

sodalime

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
206

+ LiAl(OCH3)4

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

manganese dioxide
(brown precipitate)

CH3CH2CH2CH2 OH +
1-butanol

+ 2MnO2 + 3 (O)

2(O)
room temp.

CH3 CH2 CH2 COOH + H2O


butanoic acid

7. Write the conversion of acetic acid to t-butyl alcohol.

Ca(OH)2

CH3COOH

(CH3COO)2Ca
calcium acetate

CH3COCH3
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).
CH3CHO

NaOH

CH3CHOHCH2CHO

(D)

aldol

heat
H2O

CH3 CH = CH CHO
2-butenal (E)

Compound E on catalytic hydrogenation gives butyl alcohol.


CH3 CH = CHCHO

H2

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
CH3CH2CH2COOCH2CH3

LiAlH4

CH3CH2OH + CH3CH2CH2 CH2OH


ethyl alcohol

(B)

butyl alcohol

(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
and (iii)

Ans.

CH2OH

(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)3CCH2OH

(c) (CH3)2 C OH
|
C6H5

(d) BrCH2CH2 CH C (CH3)3


|
OH

(e) CH2 = CHCHOHCH3

(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 +and 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
(ii) glycerol

KHSO4

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 :
(i)

C2H4

(ii) glycerol

O2/Ag

H2SO4/H2O

523 K

473K

HNO3

HNO3

(O)

(iii) Allyl chloride

(O)
Na2CO3/H2O

HOCl

5. Convert the following :


(i) glycol

Formaldehyde

(ii) glycerol

TNG

(iii) glycerol

Glycerol Triacetate
211

NaOH

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

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 ROR, where oxygen atom is linked
to both sides by either saturated, unsaturated or aromatic carbon. Their
general formula is ROR'.
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
dimethyl ether

C2H5 O C2H5
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
C6H5OCH3
C6H5OC6H5
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
CH3OCH3 is dimethyl ether CH3OC2H5 is ethyl methyl ether.
215

IUPAC name - Here ethers are named as alkoxy derivatives of alkanes.


Formula

IUPAC name

Common name

CH3 O CH3
CH3 O C2H5
CH3 O CH2CH2 CH3
CH3 O CH CH3
|
CH3

Methoxy methane
Methoxy ethane
1-methoxy propane
2-methoxy propane

Dimethyl ether
Ethyl methyl ether
methyl n-propyl ether
methyl iso propyl ether

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

C3H8O

Ethers

Alcohols

CH3OCH2CH3

CH3CH2CH2OH

ethyl methyl ether

n-propyl alcohol

CH3 CH CH3
|
OH
isopropyl alcohol

C4H10O

CH3CH2OCH2CH3

CH3CH2CH2CH2OH

diethyl ether

n-butyl alcohol

CH3OCH2CH2CH3

CH3CHCH2OH
|
CH3

methyl-n-propyl ether

isobutyl alcohol

CH3OCHCH3
|
CH3

methyl isopropyl ether

CH3CH2CHCH3
|
OH
sec.butyl alcohol

CH3
|
CH3COH
|
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 O CH2CH2CH3

CH3CH2OCH2CH3

methyl-n-propyl ether

diethyl ether

CH3
|
CH3OCHCH3
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.
ROH + H OR

H2SO4

C2H5 O H + H O C2H5

413K
con. H2SO4

R O R + H2O
C2H5 O C2H5

This reaction proceeds by a nucleophilic substitution mechanism. The


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

C2H5
|
O+ H
|
H

C2H5 O C2H5

+ H+ + H2O

Dehydration can also be brought about by passing vapours of alcohol


over heated Alumina or Thoria.
2C2H5OH

250oC
Al2O3

C2H5 O C2H5

+ H2O

2. Williamsons synthesis
This is the most important method. It consists of heating alkyl halides
with sodium or potassium alkoxide.
217

RX

+ NaOR'

ROR' + NaX

C2H5Br

+ NaOC2H5

C2H5 O C2H5

CH3Br

+ NaOC2H5

CH3 O C2H5

methyl bromide

sodium ethoxide

+ NaBr
+ NaBr

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.
RX

+ Ag2O +

XR

C2H5 I + Ag2O + I C2H5

ROR

+ 2AgX

C2H5 O C2H5 + 2AgI

Mixed ethers can be prepared by taking different alkyl halide with dry
silver oxide.
CH3I

+ Ag2O + I C2H5

methyl iodide

R O Ag

CH3 O C2H5 + 2AgI

ethyl iodide

ethyl methyl ether

Silver alkoxide may be an intermediate.

4. Using Grignard reagent.


Using Grignard reagent lower halogenated ether may be converted to
higher ethers.
R O CH2R' + MgX2
R O CH2 X + X Mg R'
Br
CH3OCH2Cl + BrMgCH3

CH3OCH2CH3 + Mg

monochloro dimethyl ether

ethyl methyl ether

218

Cl

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 CO bond which is not as stable as CC 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 -hydrogen is substituted more
readily.

R O CH2 CH3

C2H5 O C2H5

Cl2

Cl
|
R O CH CH3
-chloro ether

Cl2

dark

CH3 CHCl O CH2CH3

Cl2

-chloro diethyl ether

CH3CHCl O CHCl CH3


, '-dichloro diethyl ether

In sunlight, substitution is complete. Thus diethyl ether forms perchloro


diethyl ether.
219

C2H5 O C2H5 + 10Cl2

light

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.
..
..
ROR+O:
..
..

..
RO
.. R or

ROR

: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 X

..
ROR+HX

..
C2H5 O C2H5 + HCl

C2H5 O C2H5
|
H

diethyl ether

diethyl oxonium chloride

220

Cl

H
|
(R O R) HSO4

R O R + H2SO4

dialkyl oxonium hydrogen sulphate

H
|
(C2H5 O C2H5) HSO4

C2H5 O C2H5 + H2SO4

diethyl oxonium hydrogen sulphate

(iii) Reaction with Lewis acids.


Similarly with Lewis acids like BF3, AlCl3.
..
R O R + BF3

O BF3

R
(Boron trifluoride etherate)

C2H5
O : BF3

C2H5 O C2H5 + 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
2R2O + R'MgX

OR2
Mg

R2O

X
CH3

2 C2H5OC2H5 + CH3MgI
diethyl ether

O(C2H5)2
Mg

methyl magnesium
iodide

221

O(C2H5)2 I

Hence ether is used as a solvent for Grignards reagent.


3. Reaction involving CO bond : Hydrolysis
(i) Ethers on boiling with water in presence dilute acids are hydrolysed to
form alcohols.
H+

ROR + HOH

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.
C2H5 O CH3

HI

C2H5OH + CH3I

(iii) With excess hot concentrated hydroidic acid, alkyl iodides are formed.
CH3 O C2H5

2HI

CH3I

+ C2H5I

+ H2O

This reaction also follows the mechanism mentioned in the previous


reaction.
222

This reaction is used in the Zeisels 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
C2H5OC2H5+ 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 ArOR or ArOAr.
Nomenclature :
Formula

Name in common
system

Name in IUPAC
system

C6H5OCH3

methyl phenyl ether


(or)
anisole

methoxy benzene

C6H5OC2H5

ethyl phenyl ether


(or)
phenetole

ethoxy benzene

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 CH3 + N2
C6H5 O
. . H + CH2 N2
diazomethane

3. Manufacture of ether :
Large scale methylation of phenol is carried out using dimethyl
sulphate in presence of sodium hydroxide.
C6H5OH

(CH3)2SO4

NaOH

C6H5O + CH3 O SO2 OCH3

C6H5OCH3

CH3.HSO4

C6H5OCH3 + OSO2OCH3

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

..
C6H5OCH3

AlCl3

|
C6H5 O CH3
+

BF

..
C6H5OCH3

BF3

|
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
HI
anisole

I + CH3 O+ C6H5
|
H

I CH3 + HOC6H5
phenol

(protonated ether

Here iodide is the nucleophile and the leaving group is phenol.


Because of the strong CO bond in anisole, cleavage of the CO 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
3

OCH3
NO2

OCH3

con. HNO3

con.H2SO4

NO2

225

Bromination yields ortho bromo anisole and p-bromo anisole.


OCH3

OCH3
Br

Br2

OCH3

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
(Anisole)

Aliphatic ethers
(Diethyl ether)

1. Comparatively high boiling


liquid.

Volatile liquid

2. Used in perfumery.

Used as anaesthetic.

3. Not used as solvent.

Used as a solvent.

4. Can not be used as


a substitute for petrol.

Mixed with alcohol, used as


a substitute for petrol.

5. On heating with HI
forms phenol and CH3I only.

It forms C2H5OH, and C2H5I.

6. With nitrating mixture


forms nitro anisoles.

Nitration does not take place.

7. Does not form peroxide


easily.

Forms peroxide in air.

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)2O+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
C2H5OH

250oC

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
H3C OH

Reduction

(Oxidation state
2 in alcohol)

O
||
H C OH

Oxidation

C
||
O

(Oxidation state
+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

Example
CH3

CH3
C=O
H

C=O
H3C

(Acetaldehyde)

(Acetone)

231

The general formula can be


R
C=O
H

R
C=O
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

Acetic acid

Acetaldehyde

C4H9CHO
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

Isobutyraldehyde

2-methyl propanal

CH3
|
CH3 CHCHO
CH2 = CHCHO

Acrolin or acraldehyde 2-propenal

CH3 CH = CH CHO

Crotonaldehyde

2-butenal

C6H5CHO

Benzaldehyde

Phenyl methanal

C6H5CH = CHCHO

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
O
||
CH3 CCH2 CH = CH2 Allyl methyl ketone

2-pentanone

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

butanal

CH3
|
CH3 CH CHO
2-methyl propanal

(ii) CH3 CH2 CH2 CH2 CHO

CH3
|
H3C C CHO
|
CH3

Pentanal

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
||
CH3 CH2 CH2 C CH3

O
||
CH3 CH C CH3
|
CH3 3-methyl-2-butanone

2-pentanone

234

Positional Isomerism :

The carbonyl group may occupy different positions in the carbon chain
to give Positional Isomers.
O
||
CH3 CH2 C CH2 CH3

O
||
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
|
| +
H
H
(O)

CH3 CH = O + H2O
acetaldehyde

primary alcohol
ethyl alcohol

(CH3)2 C O
| |
H H

K2Cr2O7/H+

(CH3)2 C = O + H2O
(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.
CH3 CH2 OH

(CH3)2 CHOH

O2/Ag
520K

O2/Ag

CH3CHO
acetaldehyde

(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.
RCH O
|
|
H H

573 K

RCH = O + H2

Cu

aldehyde

1o alcohol
573K

CH3 CHOH
|
H

CH3 CHO + H2

Cu

acetaldehyde

Ethyl alcohol

R2 C O
|
|
H
H

573 K
Cu

R2C = O + H2
ketone

2o alcohol

CH3
CH3

C O
|
|
H
H

573K
Cu

Isopropyl alcohol

CH3
C = O + H2
CH3
acetone

2. Dry Distillation. By the distillation of calcium salt of fatty acids with


calcium formate - aldehyde is formed.
CH3COO

OCOH

Ca + Ca
CH3COO

OCOH

Calcium acetate

Calcium formate

236

CH3
|
2 HC=O + 2CaCO3
Acetaldehyde

By the distillation of calcium salt of fatty acid, ketone is formed.


CH3COO

CH3
|
+ CaCO3
CH3 C = O

Ca
CH3COO
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
|
Cl +
CH3 C = O + H2
|
Cl

Pd

HH
Pd
BaSO4

acetyl chloride

BaSO4

RC=O
|
H

CH3 C = O
|
H

HCl

+ HCl

acetaldehyde

As formyl chloride is unstable at room temperature, formaldehyde cannot


be prepared by this method.
This is called Rosenmunds 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.
RC=O
O=CR
|
Cd
|
Cl
Cl
R'
R'

2R C = O
|
R'

237

CdCl2

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.
CH3 CH

Cl
+ 2 NaOH
Cl

CH3CH

OH H O
2

CH3CHO

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
C

CH3

+ 2 NaOH
Cl

HOH

CH3

OH
C

CH3

CH3

H2O

C=O

OH

2,2-dichloro propane

CH3
acetone

5. By ozonolysis :

Ozone forms addition product with olefin called ozonide, which on


reductive cleavage gives aldehyde or ketone.
O
RCH = CHR' + O3

RCH CHR'
O

Zn/HCl

(Ozonide)

RCH + R' CH
||
|| + H2O
O
O
(Aldehyde)

O
R2C = CR'2 + O3

R2C

CR'2

O
O
(ozonide)
238

Zn/HCl

R2C + R'2 C + H2O

||

||

(ketone)

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.
CC bond in 1,2-diols is cleaved by periodic acid.
R-CHOH
...................
|
R'-CHOH

RCHO + R'CHO

HIO4

Aldehydes

CH3 CHOH
...................
|
CH3 CHOH

HIO4

2CH3CHO
acetaldehyde

butane-2,3-diol

R2 C OH
...................
|
R'2C OH

HIO4

R2CO + R'2CO
(ketone)

(CH3)2 C OH
...................
|
(CH3)2 C OH

HIO4

2CH3 COCH3
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
H2
(Propyne)

H+
Hg2+

CH3CHO (acetaldehyde)

CH3C CH
H+

O H2

Hg2+

239

CH3COCH3 (acetone)

8. Stephens reaction :
Aldehyde can be prepared by Stephens 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
HH
methyl cyanide

O H2
CH3 CH = NH.HCl

Hydrolysis

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

Nu

C O
|
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 -hydrogen atom.
H CH2

CH2
C=O

C=O

BH

(Deprotonation of -hydrogen forming carbanion)


-hydrogen is the hydrogen attached to the -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
C=O

R
C=O

Most reactive

C=O
R

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 -hydrogen atoms are more easily replaced than in
ketones.
241

CH3CHO

+ 3Cl2

CCl3 CHO

(Acetaldehyde)

CH3COCH3

+ 3HCl

(Trichloro acetaldehyde)

+ 3Cl2

CCl3 COCH3 + 3HCl

(Acetone)

(Trichloro acetone)

This reaction proceeds with the formation of carbanion.

CH3
C=O

CH2

H+

Cl Cl

C=O

Cl
|
CH2

R
(carbanion)

(ketone)
(b) Addition reactions.

C = O + Cl

R
(-chloroketone)

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

OSO2Na

acetaldehyde bisulphite compound

CH3
C = O + HOSO2Na

CH3

H3C

OH
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 -hydrogen atom is removed as a proton


by the base.
CH3 C = O
|
H

OH

CH2 C = O
|
H

+ H2O

Step 2 :

The carbanion attacks the carbonyl carbon of another unionised aldehyde


molecule.
H
|
CH3 C = O

H
|

CH3 C O
|
CH2 CHO

CH2 CHO

alkoxide ion

Step 3 :

The alkoxide ion formed is protonated by water to give aldol.


H
|
CH3 C O
|
CH2CHO

H
|

CH3 C OH + OH
|
CH2CHO

H OH

Aldol

Acetone also undergoes this type of condensation as shown.


CH3 C = O
|
CH3

CH2 C = O
|
CH3

OH

Acetone

Carbanion

243

+ H2O


CH3 C O

CH3 C = O
|
CH3

CH2 COCH3

CH3
CH2COCH3

(Nucleophilic attack)

CH3 C O

CH3

H2O
Protonation

CH3
CH2COCH3

OH
C

CH2COCH3

CH3

When an aldehyde and a ketone react in the same way it is called crossed
aldol condensation.

CH3 C = O
|
H

OH

CH2 C = O
|
H

H3C

+ H2O

CH3

C = O

C O

H3C CH2 CHO

CH3

CH2CHO

CH3
H2O

C
H3C

H3C

CH2CHO

OH
C

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
|
|
OH H

CH3 CH = CH CHO

H2O

Crotonaldehyde

(v) This reaction is characteristic of carbonyl compounds having hydrogen atom. If there is no -hydrogen atom in the carbonyl compound,
aldol condensation does not take place.
HCHO,

C6H5CHO,

Formaldehyde, Benzaldehyde

C6H5COC6H5.
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
C=O

OH
C

HCN

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
+ H+

CN

CN
Cyano hydrin

Like other nitriles cyanohydrin can be hydrolysed to give carboxylic


acid.
CH3 CH CN
|
OH

H+/H2O

CH3 CH COOH
|
OH

Acetaldehyde cyanohydrin

Lactic acid

This is a very efficient method of preparing lactic acid and other


-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
C = O + R MgX

H3O+

OMgX

+ Mg
OH

OH

Formaldehyde gives primary alcohol and other aldehydes give secondary


alcohol with Grignard reagent. Ketones give tertiary alcohol.

(i)

H C = O + CH3 MgI
|
H

CH3
|
HO
H C OMgI 2
|
H

formaldehyde

CH3
|
H C OH
|
H
primary alcohol
(ethyl alcohol)

246

CH3

(ii)

|
CH3 C OMgI
|
H

CH3 C = O + CH3MgI
|
H

H2O

acetaldehyde

CH3
|
CH3 C OH
|
H
Secondary alcohol
Iso propyl alcohol

CH3
|
CH3 C OMgI
|
CH3

(iii)
CH3 C = O + CH3 MgI
|
CH3
acetone

H2O

CH3
|
CH3 C OH
|

CH3
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
C=

OH

O + HNH2

H2O

CH3CH = NH
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
|
CH2
|
N

H2C

CH2

CH2

CH2

N
CH2
247

Benzaldehyde undergoes condensation reaction with ammonia to form


hydrobenzamide.
C6H5 CH = O
+
C6H5CH

H2 N H
+

= O

O = CHC6H5

C6H5CH= N

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 C = O

+ HNH2

CH3
|
CH3 C OH
|
NH2
acetone ammonia

CH3
|
CH3 C OH + CH3 C CH3
|
||
NH2
O

CH3
|
high temp
CH3 C CH2 C CH3
H2O
|
||
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

CH3CH = NOH
acetaldehyde oxime

248

(b)

OH

C6H5CHO + HNHOH
..

C6H5CH = NOH

NHOH

benzaldehyde

CH3

H2O

C6H5 CH

CH3

OH

C = O + HNHOH
..
CH3

Benzaldoxime

H3C
H2O

C
CH3

NHOH

C = NOH
H3C
Acetone oxime

2. Reaction with hydrazine (NH2NH2)


Aldehydes and ketones react with hydrazine to form hydrazones.
CH3

CH3 OH
C = O + NHNH2

CH3
H2O

C
H

NHNH2

acetaldehyde

CH3

H
acetaldehyde hydrazone

CH3

OH

C = O + H NHNH2
CH3

C = NNH2

CH3
H2O

C
CH3

C = NNH2

NHNH2

CH3

Acetone

Acetone hydrazone

3. Reaction with phenyl hydrazine C6H5NHNH2


Aldehydes and ketones react with phenyl hydrazine to form phenyl
hydrazones.
C6H5

C6H5
C = O + HNHNHC6H5

(a)

OH
C

H2O

C6H5
C = NNHC6H5

NHNHC6H5 H

benzaldehyde

CH3

CH3
C = O + HNHNHC6H5

(b)

CH3

C
CH3

acetone

249

OH
H2O

CH3

NHNHC6H5

benzaldehyde
phenyl hydrazone

C = NNHC6H5
CH3
acetone phenyl
hydrazone

4. Reaction with semicarbazide NH2NHCONH2


Aldehydes and ketones react with semicarbazide to form semicarbazone.
(a)

CH3

CH3
C = O + HNHNHCONH2

OH
C

acetaldehyde

NHNHCONH2
H2O

CH3
C = NNHCONH2
H
acetaldehyde semicarbazone

(b)

C6H5

C6H5
C = O + HNHNHCONH2

OH
C

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
C=O

H2/Pt

CHOH

H
250

Ketone on catalytic reduction gives secondary alcohol.


R

Pt

C=O
R H H
CH3

Pt
H2

C=O
CH3 HH

R2CHOH
CH3
CHOH
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
C=O
H

NaBH4

CH3

C O

H+

CH3

OH
C

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
C = O + 4 (H)
H3C

Zn/Hg
HCl

CH3
CH2

+ H2O

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
C=O
H

CH3

N2H4
C2H5ONa

CH2 + N2 + H2O
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 Tollens reagent and Fehlings solution oxidise
aldehydes to monocarboxylic acids having the same number of carbon atoms.
(O)

RCHO
Aldehyde

RCOOH
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

Popotts Rule :

During oxidation of unsymmetric ketones with oxidising agent which


brings about the cleavage of CC 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

CH3CH2CH2COOH

CO2 + H2O

n-butyric acid

CH3COOH
acetic acid

minor products

CH3CH2COOH
propionic acid

major produts

Because aldehydes are easily oxidised, they are reducing agents. They
reduce ammonical silver nitrate (Tollens reagent) to metallic silver and
Fehlings solution (copper sulphate, sodium potassium tartrate) to red cuprous
oxide.
CH3CHO + 2Ag+ + 3OH
Acetaldehyde

CH3COO + 2Ag + 2H2O


Acetate ion

CH3CHO + 2Cu2+ + 5OH

(silver mirror)

CH3COO + Cu2O + 3H2O

(blue)
cupric ion

(red precipitate)
cuprous ion

Aliphatic aldehydes restore the original colour (red-pink) of the Schiff's


reagent. (when SO2 is passed through intensely pink coloured Schiffs 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
|
C=O
|
H

H
|
CO
|
H
n

(ii) Acetaldehyde polymerises to a cyclic structure called paraldehyde


when a drop of concentrated sulphuric acid is added to it.

3CH3CHO

CH3
|
CH

con.H2SO4

CH3CH

CHCH3
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) Tollens reagent only
(b) Tollens 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 :
CH3CHO

OH

CH3CHOH CH2CHO

H2O

CH3CH = CHCHO

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

Salicylaldehyde

2-hydroxy
benzaldehyde

Cinnamaldehyde

3-phenyl prop-2-enal

CHO
OH

C6H5CH = CHCHO

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.
C6H5CH3
Toluene

(O)

C6H5CHO

air/V2O5 Benzaldehyde
773K

255

+ H2O

2. Benzyl chloride is oxidised by aqueous lead nitrate.


H2O

Pb(NO3)2

HNO3

C6H5CH2Cl
Benzyl chloride

HNO3
C6H5CHO
Benzaldehyde

3. By the hydrolysis of benzal chloride. (gem dihalides)


OH

2H2O

C6H5CHCl2

C6H5CH

H2O

C6H5CHO

OH
(unstable)

Distillation of calcium benzoate with calcium formate gives benzaldehyde.


C6H5COO

OCOH
Ca + Ca

C6H5COO

OCOH

Calcium benzoate

(calcium formate)

2C6H5CHO + 2CaCO3

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 -hydrogen atom indicates that a carbanion cannot be
generated at the -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 Fehlings 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
C6H5CH=O + RNH2

C6H5CH

NHR
OH

C6H5CH=O + C6H5NH2

C6H5CH

[H2O]

[H2O]

NHC6H5

C6H5CH=NR

C6H5CH=NC6H5

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
|
|
H Cl Cl
Cl

HCl

8. Cannizaro reaction : Benzaldehyde undergoes Cannizaro reaction


because of the absence -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
|
C6H5 C = O

OH

H
|
C6H5 C O
|
OH

Nucleophilic attack by OH ion on carbonyl carbon.


II step.

.H|.

H
|
C6H5 C = O + C6H5 C O
|
|
H
OH

C6H5 C O + C6H5 C = O
|
|
OH
H

Transfer of hydride ion from the anion to carbonyl carbon of another


molecule.
III step.

H
|
C6H5 C = O + C6H5 C OH
|
|
O
H

H
|
C6H5 C = O + C6H5 C O
|
|
OH
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
, unsaturated aldehyde or ketone.
NaOH

CH3CHO

CH2CHO (Carbanion)
H+

NaOH

C6H5CH = O
()CH

C6H5

2CHO

CHO

C6H5CHOH
|
CH2CHO

|
CH2CHO

(Nucleophilic attack)

C6H5 CH OH
|
CH H
|
CHO

C6H5 CH
||
CH CHO

-elimination
H2O

(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 -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 -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
||
C6H5CH = O + H C C6H5

alc
KCN

259

O
||
C6H5CHOH C C6H5
(Benzoin)

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 3COOCOCH3
Acetic anhydride

C6H5CH = CHCOOH
Cinnamic acid

+
CH3COOH
Sodium acetate is the base that generates a carbanion at the -carbon in
the acetic anhydride. This brings forth nucleophilic attack on the carbonyl
carbon forming -hydroxy acid, water gets removed from this by
-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
Conc. H2SO4

CH=O
H

N(CH3)2
CH
N(CH3)2

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
a condensation product

gives simple
addition product.

3. With alkaline
solution

undergoes Cannizzaro
reaction

undergoes aldol
condensation.

4. With phenol

forms thermosetting
plastic-bakelite

does not form


resin.

5. With RMgX

forms RCH2OH

RCHOH is formed.
|
CH3

Comparison of Aliphatic aldehyde and aromatic aldehyde

Reactions

CH3CHO

C6H5CHO

1. Heating with
gives a red precipitate
Fehlings solution.

no reaction.

2. With ammonia

forms simple addition


product.

forms complex
condensation
product.

3. With caustic
soda

undergoes Aldol
condensation

undergoes Cannizzaro
reaction.

4. With primary
amines

does not
form Schiffs base

forms Schiffs base.

5. With chlorine

does not
form acetyl chloride

forms benzoyl
chloride.

6. Polymerisation

undergoes
polymerisation.

does not polymerise.

7. Electrophilic
substitution.

does not
undergo.

undergoes at the
meta position.

8. With Schiffs
reagent.

gives pink colour


in cold.

gives pink colour.

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
| |
H H

(O)

(CH3)2C = O
K2Cr2O7/H+

2. Dry distillation of calcium acetate.


CH3 COO
Ca
CH3COO

(Calcium acetate)

CH3

Distillation

H3C

C = O + CaCO3
(Acetone)

263

3. Passing the vapours of isopropyl alcohol over heated copper - catalytic


dehydrogenation takes place.
(CH3 )2 C O
|
|
H H

573 K

(CH3 )2 C = O

Cu

H2

Acetone

(Isopropyl alcohol)

4. By the hydrolysis of isopropylidene chloride.


CH3

Cl

2 NaOH

CH3

C
CH3

OH
C

CH3

Cl

(Isopropyl alcohol)

OH

(Unstable)

H2O

CH3
C=O
CH3
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 Tollens reagent and
Fehlings solution. It does not restore the colour of Schiffs 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
H3C
LiAlH4
C=O
CHOH
H3C
H3C
264

H3C

LiAlH4

C=O
H3C

H()

H3C
H3C

CO
|
H

H2O

H3C
H3C

alkoxideion

COH
|
H

isopropyl alcohol

Lithium aluminium hydride donates hydride ion (a nucleophile).


4. Clemmenson reduction or Wolff-kishner reduction converts acetone
to propane.
H3C
C=O
H3C

Zn/Hg/HCl (or)

H3C

N2H4/NaOC2H5

H3C

CH2

(Acetone)

(Propane)

5. Haloform reaction
The compounds having CH3CHOH or CH3CO group undergoes
haloform reaction.
It undergoes halogenation at -carbon atom.
CH3COCH3 + 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,
NH2NH2, C6H5NHNH2, NH2 NHCONH2.
7. With ammonia its forms an addition product.
H2O

CH3C = O
|
CH3

+ HNH2 (Ammonia)
HCH2COCH3

NH2
CH3CCH2 COCH3
|
CH3
(Diacetone amine)

265

8. With chloroform acetone forms an addition products.


CH3
|
CH3 C + HCCl3
||
O

KOH

CH3
|
CH3 C CCl3
|
OH

(Chloretone)

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

C = O + H2CHCOCH3
H3C

C = CHCOCH3

H2O

H3C

H3C
H3C

Mesityl oxide
4-methyl pent-3-ene-2-one

CH3

C = CHCOCH3 + O = C
H3C

CH3

H3C

CH3
C=CH.COCH=C

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

3CH3COCH3

+
CH3

3 H2O

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 Fehlings
solution.

gives a red
precipitate

does not react.

2. With Tollens
reagent.

gives silver mirror. no silver mirror.

3. Oxidation

gives acetic acid

gives acetic acid


with loss of one
carbon atom.

4. Reduction with
NaBH4

ethanol (primary
alcohol)

isopropyl alcohol
(secondary alcohol)

5. With NH3

simple addition
forms complex
product is formed. ketonic amine.

6. Iodoform
reaction

forms iodoform
and formic acid.

7. Polymerisation

forms paraldehyde forms condensation


products.

8. With Schiffs reagent.

pink colour
appears in cold.

no pink colour in
cold.

9. Warming with
NaOH

a brown resinons
mass.

no resinous mass.

forms iodoform
and acetic acid.

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

+ ClCOCH3

COCH3

AlCl3

+ HCl

Acetyl chloride
Acetophenone

Benzene

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

C6H5COO

CaCO3+ C6H5COCH3

COOCH3

(Calcium acetate)

Acetophenone

(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.


C6H5COCH3

(O)

C6H5COCOOH

(Acetophenone)

Phenyl glyoxalic acid

C6H5COOH+CO2
benzoic acid

2. Reduction : Reagents like sodium and ethanol, sodium borohydride,


lithium aluminium hydride reduce acetophenone to phenyl methyl carbinol.
(a)

C6H5COCH3

2(H)

C6H5CHOHCH3

(b) Clemmenson reduction or Wolff-kishner reduction converts aceto


phenone to ethyl benzene.
C6H5COCH3

4(H)

C6H5CH2CH3 + H2O
268

Halogenation :

At 273 K bromine in ether reacts with acetophenone to form phenacyl


bromide.
One -hydrogen is removed as a proton to the remaining carbanion,
bromine addition takes place.
C6H5COCH2H + 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

NaOH

CHCl3

C6H5COONa

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.
AlCl3

ClCOC6H5

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 +

Benzophenone

Phosgene

+ Benzene

Thus involves two Friedel crafts acylation reactions.


3. By the dry distillation of calcium benzoate.
C6H5COO
Ca
C6H5COO

Distillation

C6H5COC6H5 + CaCO3
Benzophenone

(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.
C6H5COC6H5
Benzophenone

(O)

C6H5COOH
Benzoic acid

270

5. Reduction with sodium amalgam and water or lithium aluminium hydride,


diphenyl carbinol is formed.
C6H5COC6H5

2(H)

Benzophenone

C6H5CHOHC6H5
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 H

C6H5 COOK
Potasium benzoate

C6H6
Benzene

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 Fehlings solution
(b) the iodoform test
(c) the Schiffs test
(d) the Tollens 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. Tollens 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) RCH = NNH2
(b) RC N
(c) R C NH2
(d) RCH3
||
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
|
CH3 C OH
|
CH3

(d) CH3 CH2 CH2 OH

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 Rosenmunds 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
||
CH3 C CH3

(A)

LiAlH4

(B)

SOCl2

(C)

alc.KOH

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

(D)

Answers :

O
||
H CH

CH3MgBr
H2O/H+

CH3CH2OH

K2Cr2O7

ethyl alcohol

H2SO4

CH3CHO
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
||
CH3 CH2 CH2 C CH3 + 4 NaOH + 3 I2
2-pentanone

O
||
CH3 CH2 CH2 C ONa
+ CHI3 + 3H2O + 3NaI
Iodoform
(yellow precipitate)

16. How will you synthesise acetone from acetaldehyde ?


Answers: O
||
CH3 C H

CH3MgI

acetaldehyde

OH
|
CH3 CH CH3
isopropyl
alcohol

K2Cr2O7

H2SO4

O
||
CH3 C CH3
acetone

17. Give the IUPAC names of


(i)

CH3 CH C CH OCH2 CH3


|
||
|
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

and

18. An organic compound, C2H4O gives a red precipitate when warmed


with Fehlings 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
CH3CHO + CH3CHO

NaOH

CH3COO + 2Cu+ + 2H2O


H
|
H3C C CH2CHO
|
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.

Answers: (i) HCCH + H2O

Hg2+

Ethyne

OH

CH3CHO
Ethanal

CH3 CH CH2 CHO


|
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 ?


CH3CHO
(a) CH3COCl
(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
(b) CH3C N
(c) CH3COCH3
(d) CH CH

CH3COOH
CH3CH2CH3
CH3CH2CH3
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 CH3C6H4OH (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 Fehlings solution, Tollens 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 -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 -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 -hydrogen - uses.
Name reactions
Rosenmund reduction
Clemmenson reduction
Wolff-kishner reduction
Aldol condensation
Cannizaro reaction
Fehlings test
Tollens 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

Organic compounds containing the carboxyl group,

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
HCOOH
CH3COOH
C3H7COOH
C4H9COOH
C11H23COOH

Source
Red ant (formica)
Vinegar (acetum)
Butter (Butyrum)
Root of valarion plant
Laurel oil

Trivial name
formic acid
acetic acid
butyric acid
valeric acid
lauric acid

In case of substituted acids the position of the substituent is represented


by , , , etc. Thus

CH3 CH CH2 COOH


|
CH3
-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) , ,
, ...
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
CH3
|
1
CH3 CH2 CH COOH
4

2-methyl butanoic acid (IUPAC)


-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

propanoic acid

methyl acetate

HCOOC2H5

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.
RCH2OH
R
CHOH

(O)

(O)

C=O

R
(i)

RCOOH

(O)

RCOOH

R
CH3CH2OH

(O)

ethyl alcohol

(ii)

(O)

RCHO

CH3
CHOH

CH3CHO

(O)

CH3COOH

acetaldehyde

(O)

CH3

acetic acid
(O)

C=O

CH3

CH3

Isopropyl alcohol

acetone

CH3COOH + CO2
acetic acid

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.
RCN

(i)

R C NH2
||
O

O H2
alkyl cyanide

CH3 C N

RCOOH

amide

CH3 C NH2
||

H2O

methyl cyanide

H2O

H2O

CH3COOH + NH3

O
acetamide

HCN

H2O

Hydrogen cyanide

HC=O
|
NH2

H2O

H C OH + NH3
||
O

Formamide

(ii)

O
||
R C NH2

H2O

RCOOH

NH3

HO H
Example,
O
||
CH3 C NH2

O
||
CH3 C OH + NH3

H2O

acetamide

(iii)

O
||
R C OCH3
ester

H+

or

O
||
R C OH

CH3OH

O
||
CH3 C OH

CH3OH

OH

HO H
Example,
O
||
CH3 C OCH3
methyl acetate

HOH
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
RC X
X

OH
R C OH
OH

3KOH

H2O

unstable

CH3 CCl3

OH
CH3 C OH
OH

3KOH

trichloro ethane

H2O

RC=O
|
OH
CH3 C = O
|
OH

3. From Grignard reagent :


O
||
R C OMgI

RMgI + CO2

+H2O

O
||
OH
RCOH + Mg
I

Methyl magnesium iodide with carbondioxide gives acetic acid.

CH3MgI + CO2

O
||
H2O
CH3 C OMgI

O
||
OH
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.
CH3OH
HCHO

3(O)

(O)

HCOOH
HCOOH

286

5. From glycerol
By heating glycerol with oxalic acid at 373 K 383 K
CH2 OH
|
+ HO C = O
CHOH
|
|
COOH
CH2OH
O
||
CH2 O CH
|
CHOH
|
CH2OH

CH2 O CO COOH
|
CO2
CHOH
|
CH2OH

383 K

CH2OH
|
CHOH +
|
CH2OH

H2O

glycerol monoformate

HCOOH
formic acid

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

HO

RC

CR
O

OH

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

(sodium acetate salt)

287

H2O

2 HCOOH

+ 2Na2CO3

2 HCOONa
(sodium formate)

+ H2O + CO2

2. They liberate hydrogen, when react with electropositive metals like zinc
or magnesium.
2CH3COOH

Zn

(CH3COO)2 Zn

H2

H2

(zinc acetate)

2HCOOH

Mg

(HCOO)2 Mg
(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

(methyl formate)

H2O

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


CH3 CO OH

H+

CH3 CO O
H

288

Step 2. Attack by nucleophile.


H
+

CH3 CO O

H
|+
O C2H5
H
| +
CH3 C O
|
H
O

..
C2H5 OH

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
+
CH3 CO OH

P2O5

CH3 CO
O
CH3 CO
(Acetic anhydride)

HCOOH on dehydration forms carbon monoxide.


H
C=O

Con. H2SO4

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
||
HCOH

HC=O
|
Cl

Cl PCl3 Cl

POCl3

CO

HCl

formyl chloride

HC=O

HCl

Cl
The carboxyl group is involved in resonance.
O()

O
C

C
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.
R C OH
||
O

H2/Ru-pressure
or

R CH2 OH

LiAlH4

(ii) Heating with HI/P converts the carboxylic acid to alkane.


CH3COOH

HI/P

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

sodium acetate

methane

Na2CO3

Formic acid gets decarboxylated on heating.


H
C=O

160oC

H2

CO2

HO
H+

O()

R
C

RH

CO2

alkane

O
Carboxylate anion

8. Halogenation :
(i) Fatty acids having -hydrogen atoms, can be converted to -halo acids
by halogen in presence of halogen carrier like red phosphorous.
Br2/P

CH3CH2COOH
propionic acid

CH3CHBr COOH

-bromo propionic acid

CH3CBr2COOH

, , 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

RCH2COOH

H2O

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.
RCOOH + NH3

RCOONH4
(Ammonium Salt)

HCOOH + NH3

HCOONH4

H2O

RCONH2
(Amide)

(Ammonium formate) H2O

P2O5

RCN

H2O (Cyanide)

HCONH2
(Formamide)

10. Kolbes electrolytic reaction : Electrolysis of concentrated aqueous


solution of sodium salt of acids gives hydrocarbon.
Electrolysis

CH3 COO Na

CH3
|
+ 2CO2 + 2Na
CH3
sodium

CH3 COO Na

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
CH3 COO

CH3COCH3 + CaCO3

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
Fehlings 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 (Tollens reagent)
to metallic silver.
HCOOH + Ag2O

H2O + CO2 + 2Ag (metallic silver)

(b) Formic acid reduces Fehlings solution. It reduces blue coloured cupric
ions to red coloured cuprous ions.
HCOO

CO32 + Cu2O + 3H2O

+ 2Cu2+ + 5OH
(blue)

(red)

(c) On the otherhand when sodium formate is heated to 360oC it decomposes


to hydrogen and sodium oxalate.
H COONa

360oC

H COONa

COONa
|
COONa

Sodium formate

Sodium oxalate

H2

Problems for Practice


Formic acid gives a red precipitate when heated with Fehling solution
but acetic acid does not - reason out.
Answer.
Formic acid has

C = O group an aldehyde group but acetic acid

has no aldehydic group. Hence formic acid reduces - Fehlings 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
-hydroxy propionic acid
(or) lactic acid

CH2(OH)CH2COOH
-hydroxy propionic 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.
C12H22O11
cane sugar

C6H12O6

BAL

H2O

C6H12O6
(glucose)

2CH3COCHO
Methyl glyoxal

294

+ C6H12O6
(fructose)

2CH3CHOHCOOH
Lactic acid

(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.
2C + H2

electric

CHCH

Arc

1%Hg
80
dil. HCl

CH3CH(OH)CN

dil. H2SO4

CH3CHO

HCN

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

CH3CH = CH2

dil/NaOH

CH3CHCl CH2Cl

propylene

CH3CH(OH)CH2OH

1,2-dichloro propane
(O)

propane 1,2-diol

CH3CH(OH)COOH
lactic acid

(d) Hydrolysis of -bromo propionic acid :


Hydrolysis of -bromo propionic acid using moist Ag2O gives lactic
acid.
2CH3CH(Br)COOH

-bromo propionic acid

Ag2O
H2O

2CH3CH(OH)COOH
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 Fentons reagent Fe2+/H2O2 forms pyruvic
acid with lactic acid
CH3CH(OH)COOH

(O)

CH3COCOOH

H2O2/Fe2+

Lactic acid

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)

CH3CH(OH)COOH

CH3COCOOH

I2

pyruvic acid
NaOH

CHI3 +

iodoform

CI3COCOOH
tri iodo pyruvic acid

(COONa)2

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

OH H O

CHCH3
O
lactide

296

Uses of lactic acid :


1.
2.
3.
4.
5.

In tanning industry.
In soft drinks.
In the treatment of digestive disorder in children.
Preparation of lactates, ethyl lactate as a solvent.
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)2COOH

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.
C12H22O11 + 18 [O]

HNO3
V2O5

COOH
|
COOH

+ 5H2O

The CHOHCHOH - 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
sodium formate

NaOOC COONa
sodium oxalate

H2

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
|
COONa

COO
|
Ca +
COO

+ Ca(OH)2

sodium oxalate

2 NaOH

calcium oxalate

COO
|
Ca + H2SO4
COO

COOH
|
COOH

+ CaSO4

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
|
CH2OH

[O]

COOH
|
COOH

glycol

4. From Cyanogen :
By passing cyanogen through an aqueous solution of acid or alkali.
CN
|
CN
cyanogen

2H2O

CONH2
|
CONH2
oxamide

298

2H2O

COOH
|
COOH

Succinic acid, Butanedioic acid HOOCCH2CH2COOH


Preparation : Succinic acid is prepared from ethylene dibromide by
treating with sodium cyanide and subsequent hydrolysis of ethylene dicyanide.
CH2Br
|
CH2Br

2NaCN

Ethylene
di bromide

CH2CN
|
CH2CN

H2O

HCl

ethylene
dicyanide

CH2COOH
|
CH2COOH

succinic acid

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
|
+ NaOH
COOH
oxalic acid

(ii) CH2COOH
|
+ NaOH
CH2COOH

COONa
|
COOH

COONa
|
COONa

NaOH

mono sodium
oxalate

CH2COONa
|
CH2COOH

Succinic acid

mono sodium
succinate

disodium
oxalate
NaOH

CH2COONa
|
CH2COONa
disodium succinate

2. With ammonia : Dicarboxylic acid gives ammonium salts first which


then loses water molecule to give amide.

299

COOH
|
COOH

COONH4
|
COONH4

+ 2NH3

CONH2
|
+ 2H2O
CONH2

ammonium
oxalate

oxamide

Succinic acid forms its ammonium salt. On strong heating it forms


succinimide.
CH2COOH
|
+ 2NH3
CH2COOH

CH2COONH4
|
CH2COONH4

Succinic acid

Ammonium succinate

CH2CO
|
NH
CH2CO

Succinimide

3. With PCl5 :
With PCl5, these form the acid chlorides.
(i) COOH
|
+
COOH

COCl
|
COCl

PCl5

oxalic acid

CH2COOH
|
+
CH2COOH

oxalylchloride

POCl3

CH2COCl
|
+
CH2COCl

PCl5

H2O

phosphorous
oxy chloride

POCl3

H2O

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
|
COOH

473K

HCOOH
formic acid

+ CO2

(ii) Succinic acid on heating to 300oC loses a molecule of water to form


anhydride.
CH2 COOH
|
CH2 COOH

300oC

CH2 CO
|
O
CH2 CO

H2O

succinic anhydride (a cyclic compound)

300

5. Oxidation : On warming oxalic acid with acidified potassium


permanganate, it is oxidised to carbon dioxide.
COOH
|
COOH

2CO2

+ [O]

+ H2O

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 CC
H CC
H CC

|
O
|
O
|
OH
H
H
H
Acid

Anion

+ H3O+
When the bonding pair of electrons between oxygen and hydrogen in
OH 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
|
C
|
H

Cl

O
C
O

Thus the strength of the chloro acetic acids varies.


O
Cl3C C

O
>>

Cl2CHC

OH

O
>

ClH2C

OH

Trichloro acetic acid

OH

Dichloro acetic acid

Monochloro acetic acid

On the other hand comparing the strength of carboxylic acids they vary
as follows :
CH3CH2 COOH <
propionic acid

CH3COOH

<

acetic acid

HCOOH
formic acid

Since alkyl groups are +I groups, they increase the strength of the
OH 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

O2N

COOH

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

COOH

OH
COOH

Benzoic acid

o-toluic acid

NH2
COOH

salicylic acid
(o-hydroxy benzoic
acid)

COOH

anthranilic acid
(o-amino benzoic
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.
CH2CH3

CH3

Toluene

Ethyl
benzene

CH2Cl

Benzyl
chloride

CH2OH

Benzyl
alcohol

Benzaldehyde

The underlined portion indicates the side chain.


Toluene is oxidised by acidified KMnO4.
(i) C6H5CH3

H+/KMnO4

C6H5COOH

NaOH

(ii) C6H5CH2Cl

C6H5CH2OH

H+/KMnO4

(iii) C6H5CHO

C6H5COOH

303

Benzoic acid

(O)
KMnO4

CHO

C6H5COOH

2. Hydrolysis of phenyl cyanide :


C6H5CN

H+

H+

(C6H5CONH2)

H2O

Benzamide

C6H5COOH

H2O

3. Carbonation of Grignard reagent followed by hydrolysis.


C6H5
C6H5MgBr + O = C = O

H2O
C=O

BrMgO

Br
C6H5C = O + Mg
|
OH

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)

C6H5COOH + NH4OH

C6H5COONH4
(Ammonium benzoate)

H2O

C6H5CONH2

(b) It forms esters with alcohol in presence of catalytic amount of


Con. H2SO4.
C6H5COOH + C2H5OH

H+

C6H5COOC2H5
(ethyl benzoate)

304

+ H2O

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.
C6H5COOH

NaOH
CaO
soda lime

C6H6

CO2

4. Reduction :
Lithium Aluminium hydride reduces Benzoic acid to Benzyl alcohol.
O
C6H5C

LiAlH4

LiAlH4

[C6H5CHO]
OH

C6H5CH2OH
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

COOH

Fuming
H2SO4

SO3H
m-sulphonyl benzoic acid

19.6.3 Uses of benzoic acid :


1.
2.
3.
4.

Benzoic acid is used as an urinary antiseptic


Sodium benzoate is used as food preservative
Benzoic acid vapours are used to disinfect bronchial tube.
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
OH
benzoic acids.
OH

OH
COOH

COOH
(o-hydroxy benzoic acid)

(m-hydroxy benzoic acid)

COOH
(p-hydroxy benzoic acid)

19.7.1 Preparation :
Salicylic acid can be prepared by heating phenol with NaOH to get
sodium phenoxide.
306

OH

ONa

NaOH

This is heated with carbondioxide at 403K under pressure to form sodium


salicylate.
ONa

OH

CO2
403K/pressure

COONa

Mechanism :
O

O
||
C
||
O

OH

C
O

This reaction is called Kolbes reaction. The sodium salt on treatment


with dilute hydrochloric acid gives salicylic acid.
OH

OH
COONa

COOH

HCl

+ 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.
O

OH

+OH

C
O
Br

Br Br

OH

+OH

+ Br

Br

+ CO2

O
Br

OH
Br

Br

OH
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

Br2

COOH

Br

Br2

OH
Br

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

+ CO2

+ NaHCO3
COOH

H2O

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

COOH

H2SO4

+
COOCH3
(Methyl salicylate)

309

H2O

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 :

The general formula is


Y

O
||
RCY

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
(ii) 3CH3COOH + PCl3

CH3COCl + POCl3 + HCl


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

O
H

+
OH

HCl
(gas)

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

(ii) C2H5OH
..

(iii)

O
||
+ Cl C CH3

CH3
..
C6H5 OH +
Cl

O
||
C2H5OCCH3 + HCl
ethyl acetate

C=O

CH3COOC6H5
Phenyl acetate

2. Friedel Crafts Acetylation :


In presence of anhydrous Aluminium chloride acetylation of benzene
takes place with the formation of acetophenone.
311

COCH3

+ CH3COCl

anhy. AlCl3

+ HCl

It is an aromatic electrophilic substitution reaction.


The Lewis acid AlCl3 generates the electrophile from acetyl chloride.
The electrophile is the acetyl cation CH3C+ = 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

(Acetyl chloride)

+ CH3COONa
(Sodium acetate)

CH3COOCOCH3 + NaCl
(Acetic anhydride)

2. From acetic acid


By the action of dehydrating agent on acetic acid.
CH3CO OH

P2O5

CH3COO H

CH3CO
O + H2O
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

CH3CONH2+ CH3COOH

(Ammonolysis)

(Acetamide)

CH3CO

.. +
H 2N H
ammonia

2.

CH3CO

CH3COOH + CH3COCl

O + H Cl

acetyl chloride

CH3CO

(with dry hydrogen


chloride)

CH3CO
O
CH3CO

Cl
|
PCl3
|
Cl

2CH3COCl + POCl3
acetylchloride

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.
CH3COOH + CH3OH

H2SO4

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.
CH3COOCH3

H+/H2O

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
This is called trans esterification.

CH3COOC2H5 + CH3OH

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.
CH3COOCH3

C2H5ONa

CH2COOCH3 +

CH3

H+

CH3
C=O

C=O

CH3O

CH2COOCH3

+ OCH3

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.


CH3CN

H2O2

CH3CONH2

NaOH

19.11.1 Physical Properties


It exists as a dimer due to hydrogen bonding.

H
|
HN

CH3 C

C CH3
NH
|
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.
(a)

CH3CONH2

H+

CH3COOH + NH3

H2O

(b)

CH3CONH2

(acetic acid)

NaOH

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.


CH3CONH2

P2O5
H2O

CH3CN

4. It undergoes Hoff manns reaction with Br2/NaOH forming methyl


amine.
CH3CONH2

Br2
NaOH

CH3NH2 + CO2

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
(c) C6H5OH

(b) CH3COOH
(d) ClCH2COOH

2. Weakest acid among the following is


(a) Acetic acid
(c) Water

(b) Phenol
(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
(c) aceticacid

(b) ethane
(d) benzene

5. The acid which reduces Tollen's reagent is


(a) acetic acid
(c) formicacid

(b) benzoic acid


(d) oxalic acid

CH3
|
6. The IUPAC name of CH3 CH2 CH COOH is
(a) -methyl butric acid
(c) 2-methyl butanoic acid

(b) 3-methyl butanoic acid


(d) Iso pentanoic acid

7. The Isomerism exhibited by CH3CH2COOH and CH3COOCH3 is


(a) metamerism
(c) chain

(b) position
(d) functional

8. The acid that cannot be prepared by Grignard reagent


(a) acetic acid
(c) butyric acid

(b) formic acid


(d) benzoic acid
317

9. Which order of arrangement is correct interms of the strength of the acid


(a) CH3CH2COOH > CH3COOH < HCOOH < ClCH2COOH
(b) ClCH2COOH < HCOOH < CH3COOH < CH3CH2COOH
(c) CH3CH2COOH < 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
(b) HCOOH
(a) CO + H2O
(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 ?


(b) HOOCCH2COOH
(a) CH3CH2COOH
(c) CH3CH(OH)COOH
(d) Cl2CHCOOH
18. CH3CH(OH)COOH
? The product is
H2O2/Fe2+

(a) CH3COCOOH
(b) CH3CH2COOH
(d) COOHCH2COOH
(c) CH3CHOHCHO
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.
(i)

(ii)
(iii)

COOH
|
COOH

glycerol

COOH
|
COOH
CH2 COOH
|
CH2COOH

383 K

NH3

NH3

320

11. How are the follwing conversions carried out ?


aspirin
(i) Salicylic acid
(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 - -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 -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 : RNO2
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

R
R
R

2o

3o

RCH2NO2
1o

CHNO2

C NO2

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


|
CH3

1-Nitro-2-methyl propane

CH3
|
CH3 C CH2 NO2
|
CH3

1-Nitro-2,2-dimethyl propane

CH3
|
CH3 C CH3
|
NO2

2-nitro, 2-methyl propane

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


|
CH3

(branched chain)

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

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.

RX

+ AgNO2

CH3CH2Cl +

AgX + R NO2

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
CH4

methane

HONO2

+ HONO2

400oC

nitric acid

C6H13NO2

+ H2O

CH3NO2 +

H2O

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)

326

(Aci form)

The aciform contains replaceable hydrogen atom. Hence it dissolves in


alkali solution forming salt like compounds.
+

CH2 = N

+
CH2 = N O

NaOH

+ H2O

O Na+

OH
This anion exhibits resonance.
O

CH2 = N

CH2 N
O

CH2 N
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 -position in presence of alkali.
O
Br2

CH3CH2N

NaOH

Br
|
CH3 CH N

O
Br2
NaOH

O
Mono bromo
nitro ethane

Br
|
CH3 C N
|
Br

di bromo
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.
CH3NO2 + 3Cl2

NaOH

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

HCHO + CH3NO2

dil. NaOH

CH2OHCH2NO2
2-nitro ethanol

CH3CHO + CH3NO2

dil. NaOH

CH3CHOHCH2NO2
1-nitro-2-propanol

CH3COCH3 + CH3NO2

dil. NaOH

(CH3)2COHCH2NO2
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]

CH3 NO2 + 6 [H]

RNH2
Sn/HCl

2H2O

CH3NH2

2H2O

Methylamine

(ii) Reduction under neutral conditions using Zn/NH 4Cl or Zn/CaCl2hydroxyl amines are formed.
RNO2

+ 4 (H)

Zn/NH4Cl

RNHOH

+ H2O

Hydroxyl amine

CH3 CH2NO2

Zn/NH4Cl

+ 4 [H]

(Nitro ethane)

CH3CH2NHOH

+ H2O

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
acetic acid

328

NH2OH

hydroxylamine

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 -hydrogen and that reacts with HNO2.
(c)

CH3
|
CH3 C CH3
|
NO2

has no -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.
NO2

CH3

NO2

p-nitro toluene

NO2

NO2

NO2

NO2
Nitrobenzene

CH3

O2N

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

CHNO2

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.

+ HNO3

Conc.
H2SO4

NO2

330K

H2O

Sulphuric acid generates the electrophile NO2+, nitronium ion-from


nitric acid. This is an example of aromatic electrophilic substitution reaction.
H

NO2

NO2
H

330

NO2

The generation of nitronium ion.


H
|
H O NO2

H2SO4 + HONO2

HSO4

H
|
H O NO2

H2O

+ NO2

To the nitronium ion (being an electron deficient specie) the bond of


benzene, donates a pair of electrons forming a -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

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.
C6H5NO2 +

6 [H]

Sn/con.HCl
or
Fe/con.HCl

C6H5NH2

2H2O

Aniline

(b) Neutral medium


When reduced with a neutral, reducing agents like zinc dust and aqueous
ammonium chloride, aromatic nitro compounds form aryl hydroxylamines.

C6H5NO2

4 [H]

Zn/NH4Cl

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

C6H5NO2

azoxy benzene

SnCl2 + NaOH

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.
C6H5NO2
C6H5NO2

LiAlH4

C6H5NH2 [Aniline]

H2/Ni
Catalytic
hydrogenation

C6H5NH2

(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

NO2

O2N

1,3,5-Trinitro benzene

2. Chlorination
Chlorine in presence of anhydrous ferric chloride generates positively
charged species. Chlorination takes place at meta position.
Cl

NO2
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. -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.

..
HNH
|
H
Ammonia

..
CH3 NH
|
H
Aliphatic amine

335

..
C6H5 N H
|
H
Aromatic amine

Amines are basic in nature. They accept protons forming alkyl or aryl
ammonium ions.

H+

..

+ RNH2

R NH2

|
Proton

H alkyl ammonium ion

Alkyl amine

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 N H

R
|
R N H

Primary

Secondary

1o

Tertiary

2o

Primary amine has


Secondary amine has
Tertiary amine has

R
|
R N R
3o

NH2 group (two hydrogen atoms


bonded to nitrogen)
NH group (only one hydrogen bonded
to nitrogen)
N group (No hydrogen atom bonded
to nitrogen)

Generally the strength of the base is in the order.


3o amine

>

2o amine
336

>

1o amine

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

CH3 NH2

amino methane

methyl amine

CH3 CH CH3
|
NH2

2-amino propane

isopropyl amine

CH3CH2CH2NH2

1-amino propane

n-propyl amine

CH3 CH CH2 NH2


|
CH3

1-amino-2-methyl
propane

isobutyl amine

CH3
|
CH3 CH CH CH3
|
NH2

2-amino-3-methyl
butane

isopentyl amine

CH3NH CH2 CH3

(N-methyl amino)
ethane

ethyl methyl
amine

CH3NH CH CH3
|
CH3

2-(N-methyl amino) methyl isopropyl


propane
amine

CH3 N CH CH2 CH3


|
|
CH3 CH3

2-(N,N-dimethyl
amino) butane

337

Common name

dimethyl sec.butyl
amine

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.
(a)

CH3 CH2 NO2

3H2/Ni or Pt

CH3CH2NH2

Nitro ethane

+ 2H2O

Ethylamine

(b)

CH3 CH2 NO2

(c)

CH3NO2

Sn (or) Zn/HCl

LiAlH4

CH3CH2 NH2

+ 2H2O

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.
(a) CH3CONH2 +

4 [H]

Na/C2H5OH

(Acetamide)

CH3CH2NH2 + H2O
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.
(a) CH3C N
(b) CH3C N

4 [H]

LiAlH4

Na/C2H5OH

CH3CH2NH2

CH3CH2NH2

Ether

(c) CH3C N

H2/Ni

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

Methyl isocyanide

CH3 N C

CH3NHCH3

Dimethylamine
LiAlH4

CH3NH CH3

ether

5. From amides
By elimination reaction - primary amine is prepared.
Hoffmans hypobromite reaction or Hoffmans bromamide reaction
CH3CONH2

Br2/KOH

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

methylamine

H2 O
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.
CH3CH2OH

+ NH3

Al2O3

(CH3CH2) NH2

723K

1o

CH3CH2OH + (CH3CH2)2 NH

Al2O3

+ H2O

amine

(CH3CH2)2NH +
2oamine
diethyl amine

CH3CH2OH + (CH3CH2)2NH

Al2O3

(CH3CH2)3 N + H2O
3o amine
triethylamine

340

H2O

In both of the above methods, pure amines cannot be prepared. Only


mixture of amines are obtained.
7. Gabriels phthalimide synthesis of primary amine.
CO

CO

NH

KOH

CO

CO

NK

RX

NR

CO

phthalimide

CO
N-alkyl phthalimide

potassium 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 ..... NH
|
|
|
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
341

>

Tertiary amine

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 nitrogens 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.
CH3NH2

CH3Br

1o amine

CH3NHCH3

CH3Br

(CH3)2 NCH3

2o amine

3o amine

CH3Br

(CH3)4 N+Br
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

[CH3N=N OH]

primary amine

CH3OH + N2

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

Tertiary amine

(CH3)3 NH+ NO2


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

Carbondisulphide

methyl isothiocyanate

+ H2S

7. Formation of Schiffs base


Primary amines condense with aromatic aldehydes forming Schiffs
bases.
C6H5CHO

+ H2N CH3

C6H5CH = NCH3
Schiffs base
(benzal-N-methyl amine)

344

20.3.4 Distinction between primary, secondary and tertiary amines


Primary amine
RNH2

Secondary amine
R2NH

Tertiary amine
R3N

1. With HNO2 forms


alcohol.

forms N-nitroso
amine.

forms salt.

2. With CHCl3/KOH
forms carbylamine

No reaction.

No reaction

3. With acetyl chloride


forms N-alkyl
acetamide.

form N,N-dialkyl
acetamide.

No reaction

4. With CS2 and HgCl2


alkyl isothiocyanate
is formed.

No reaction

No reaction

5. With Diethyl oxalate

Forms N,N-dialkyl
oxamic ester, a liquid.
CONR2
|
COOC2H5

No reaction

With two molar


proportion of
alkyl halide,
quaternary
ammonium salt
is formed.

With only one


molar proportion
of alkyl halide
quarternary
ammonium salt
is formed.

COOC2H5
CONHR
|
2RNH2 |
CONHR
COOC2H5

dialkyl oxamide, a
solid at room
temperature is
formed.
6. With three molar
proportion of alkyl
halide, quarternary
ammonium saltcrystalline
compound
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

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

H3C

Benzyl amine

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.
C6H5C N

H2/Ni

C6H5CH2NH2

Benzonitrile
LiAlH4
H2/Pd

C6H5CONH2

C6H5CH2NH2

Benzamide
LiAlH4

346

2. From benzylbromide
By the action of alcoholic ammonia on benzyl bromide.
C6H5CH2 Br

+ HNH2

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
+
benzyl ammonium
chloride

benzylamine

2. Substitution at Nitrogen
N-alkylation : With alkyl halide it forms secondary amine, tertiary amine
and finally quaternary ammonium salt.
C6H5CH2NH2

CH3Br

C6H5CH2NHCH3
+

CH3Br

C6H5CH2 N (CH3)3 Br

C6H5CH2 N (CH3)2

CH3Br

N-Acetylation :
With acetyl chloride or heating with acetic anhydride N-benzyl acetamide
is formed.
C6H5CH2 NH2 +

ClCOCH3

C6H5CH2 NH2 + (CH3CO)2O

C6H5CH2NHCOCH3 + HCl
N-benzyl acetamide
C6H5CH2NHCOCH3 + CH3COOH
N-benzyl acetamide

3. With nitrous acid


With nitrous acid it forms benzyl alcohol.
C6H5CH2NH2 + O = N OH
347

C6H5CH2OH

+ N2

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
o-Toluidine

Aniline

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
(H)

348

2H2O

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.
C6H5Cl + 2NH3

CuCl2

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

KOH

C6H5NH2

+ CO2

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

C6H5NH3 Cl

+ HCl

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.
C6H5NH2 + CH3I

C6H5N (CH3)2

C6H5NHCH3

CH3I

C6H5N (CH3)2

2o amine
3o amine
(N-methyl aniline) (N, N-dimethyl aniline)
+

CH3I

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.
C6H5NH2

+ ClCOC6H5

NaOH

benzoyl chloride

C6H5NHCOC6H5
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 Schiffs base.
C6H5NH2

+ O = CHR

C6H5N = CHR
(Aldimine or Schiffs 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=NOH

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.
NH2

O
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
C=O + 2HCl

Carbonyl chloride

C6H5NH
S-diphenyl urea

(S stands for symmetric)


8. With carbondisulphide, S-diphenyl thiourea is formed. Phenyl
isothiocyanate is formed in the first step. (C6H5N=C=S)
2C6H5NH2 +

CS2

C6H5NH
C=S + H 2 S

carbondi
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

H2SO4

353K

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
HNO3
H2SO4

NH2

NO2+

NaOH

(HNO3 + H 2SO4)

NO2

NO2

(m-nitroaniline)

p-nitro aniline is prepared in the following three stages.


NHCOCH3

NHCOCH3

NH2
CH3COCl

NH2

H3O+

HNO3/H2SO4

NO

2
20.4.6 Uses of aniline
1. For preparing dyes and dye intermediates.

+ CH3COOH

NO2

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, Nacylation, formation of Schiffs 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

354

RH

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

HCN

Hydrogen cyanide

CH3CN

Methyl cyanide

Acetonitrile

Ethane nitrile

CH3CH2CN

Ethyl cyanide

Propionitrile
(or)
propiononitrile

Propane nitrile

isopropyl
cyanide

isobutyronitrile

2-methyl-propane
nitrile
(or)
2-cyano propane
(as a substituent)

CH3CHCH3
|
CN

As acid nitrile
Formonitrile

355

IUPAC name
Methane nitrile

20.5.1 Uses of Nitriles


It is an important synthetic reagent to prepare, aldehydes, acids, amides,
esters, amines alcohols etc.
Acrylo nitrile (CH2=CHCN) 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

CN 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

C6H5NH2 + HNO2 + HCl

273 278 K

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.
C6H5 N2 Cl
H
H

H3PO2
Cu+

C6H6 + N2 + HCl

Cuprous salts catalyse this reaction.


(b) Replacement by OH
When the aqueous solution is boiled, phenol is obtained.
357

C6H5 N2 Cl
HO

C6H5OH + N2 + HCl

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
CH3O
H

C6H5OCH3

[Alcohol is the nucleophile]

Aromatic ethers
(anisole)

C6H5 N2 Cl

C6H5OCOCH3

CH3COO

+ N2 +

HCl

+ N2 + HCl

Phenyl acetate
(ester)

[Carboxylate ion is the


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

C6H5N2Cl

HCl

C6H5 Cl

N2

Cu2Cl2

C6H5N2Cl

HBr
Cu2Br2

C6H5Br

+ N2

(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.
C6H5N2Cl

C6H5N2Cl

Cu
HCl

Cu
HBr

C6H5Cl + N2

C6H5Br + N2

3. Replacement by cyanide group :


The diazonium salt solution when treated with cuprous cyanide /
potassium cyanide mixture, phenyl cyanide is formed.
C6H5 N2 Cl
NC

Cu2(CN)2

C6H5CN

+ N2 + HCl

Treatment of diazonium chloride with KCN solution in presence of


copper, also gives phenyl cyanide.
C6H5N2Cl

+ KCN

Cu

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

C6H5N2Cl

+ C6H6

NaOH

C6H5 C6H5
Biphenyl

+ N2

+ HCl

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 +

C6H5N = N

OH

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+ +

C6H5N2

+
OH

OH
H
+
OH

C6H5N=N

N2Cl +

OH

N(CH3)2

+ H+

N=N

N, N - dimethyl aniline

N(CH3)2

p-dimethyl amino azo benzene

Reaction with primary amine takes place in a different way :


(I)
N2Cl + H2N

N=NNH
Diazoaminobenzene
(Substitution at Nitrogen)

(II)

N=NNH

HCl
[Rearrangement]

N=N

NH2

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
(c) C2H5Ag + NaBr

(b) C2H5ONO
(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