MSCCH 503

MSCCH-503
M. Sc. I Semester
PHYSICAL CHEMISTRY-I
SCHOOL OF SCIENCES
DEPARTMENT OF CHEMISTRY
UTTARAKHAND OPEN UNIVERSITY
MSCCH-503
PHYSICAL CHEMISTRY-I
SCHOOL OF SCIENCES
DEPARTMENT OF CHEMISTRY
UTTARAKHAND OPEN UNIVERSITY
Phone No. 05946-261122, 261123

Toll free No. 18001804025
Fax No. 05946-264232, E. mail info@uou.ac.in
htpp://uou.ac.in
Expert Committee
Prof. B.S.Saraswat Prof. A.K. Pant
Department of Chemistry Department of Chemistry
Indira Gandhi National Open University G.B.Pant Agriculture, University
Maidan Garhi, New Delhi Pantnagar
Prof. A. B. Melkani Prof. Diwan S Rawat

DSB Campus, Delhi University
Kumaun University, Nainital Delhi
Dr. Hemant Kandpal Dr. Charu C. Pant

Assistant Professor Academic Consultant
School of Health Science Department of Chemistry
Uttarakhand Open University, Haldwani Uttarakhand Open University,
Board of Studies
Prof. A.B. Melkani Prof. G.C. Shah
DSB Campus, Kumaun University SSJ Campus, Kumaun University
Nainital Nainital
Prof. R.D.Kaushik Prof. P.D.Pant

Department of Chemistry Director I/C, School of Sciences
Gurukul Kangri Vishwavidyalaya Uttarakhand Open University
Haridwar Haldwani
Dr. Shalini Singh Dr. Charu C. Pant

Assistant Professor Academic Consultant
School of Sciences School of Science
Uttarakhand Open University, Haldwani Uttarakhand Open University,
Programme Coordinator
Dr. Shalini Singh

Assistant Professor
Department of Chemistry
Uttarakhand Open University
Haldwani
Unit Written By Unit No.
1. Dr. K. B. Melkani 01, 02, 03 & 04
Retd. Professor
DSB Campus Kumaun University, Nainital
2. Dr. Renu Loshali 05, 06, 07 & 08
Department of Chemistry,
Govt. Degree College, Bazpur
3. Dr. Mahesh Arya 09 & 10
Assistant Professor
DSB Campus Kumaun University, Nainital
Course Editor
Dr. M.G.H. Zaidi
Professor & Head,
Department of Chemistry,
College of Basic Sciences and Humanities
G.B. Pant University, Pantnager
Title : : Physical Chemistry-I

ISBN No.: :
Copyright : Uttarakhand Open University
Edition : 2021
Published by : Uttarakhand Open University, Haldwani, Nainital- 263139
CONTENTS
BLOCK- 1 THERMODYNAMICS
Unit 1 Classical Thermodynamics-I 1-27

Unit 2 Classical Thermodynamics-I 28-57
Unit 3 Statistical Thermodynamics 58-74
Unit 4 Applications of Statistical Mechanics 75-102
BLOCK-2 KINETICS AND CATALYSIS
Unit 5 Theories of Reaction Rates 103-120

Unit 6 Solution Kinetics 121-137
Unit 7 The Fast Reaction Kinetics 138-156
Unit 8 Catalysis 157-178
BLOCK-3 ELECTROCHEMISTRY
Unit 9 Electrochemistry-I 179-201

Unit 10Electrochemistry-II 202-236
PHYSICAL CHEMISTRY-I MSCCH-503
UNIT- 1- CLASSICAL THERMODYNAMICS-I
CONTENTS:
1.1 Introduction
1.2 Reversible and irreversible process
1.2.1 Reversible process
1.2.2 Irreversible process
1.3 Thermodynamic work
1.4 Work Reversible Cycle Process
1.5 First law of thermodynamics
1.6 Internal energy
1.7 Mathematical formulation of first law of thermodynamics
1.8 Enthalpy
1.9 Calculation of Cp-Cv Thermodynamically
1.10 Joule’s law
1.11 Joule Thomson Effect
1.12 Joule-Thomson coefficient in ideal gas
1.13 Joule-Thomson coefficient for a real gas
1.14 Second Law of Thermodynamics
1.15 Cyclic Process
1.16 Entropy: Nature of dq and dq/T
1.17 Physical Significance of Entropy
1.18 Entropy of a Perfect Gas
1.19 Change of entropy with temperature
1.20 Entropy of mixing
1.21 Work function or Helmholtz free energy A and Gibbs free energy or Gibbs potential G
1.22 Change in A and G with the parameters of the system
1.23 Maxwell’s relations
UTTARAKHAND OPEN UNIVERSITY Page 1

1.1 INTRODUCTION
Thermodynamics is the branch of chemistry that deals with energy transformation in all type
of physical chemical and biological processes. Thermodynamics leads with three
fundamental laws which are purely based on human experiences. These are the first, second
and third law of thermodynamics. These laws provide numerical approach of prediction of
spontaneity and feasibility of various processes under prescribed set of conditions.
Thermodynamic principles allow deriving most of the important laws of the physical
chemistry such as vant Hoff’s law, phase rule and distribution law.
Thermodynamics is applicable to the microscopic system consisting of matter in bulk and not
to microscopic systems of individual atoms or molecules. It does not bother about the time
factor. That means it does not tell anything regarding the rate of a physical change or a
chemical reaction. It is concerned only with initial and final states of the system.
Thermodynamic principles correlate different observable properties of system without
providing their magnitudes.
A thermodynamic system is said to be in a certain state when all its properties are fixed. The
fundamental properties which determine state of a system are Pressure (P), temperature (T),
volume (V), mass and composition. Change in magnitude of such properties alters the state of
system. For such reasons, these parameters are regarded as state variables or state functions
for a system. A change in system from the initial state to final state will accompanied by a
change in state variables. However, it is not necessary that all the state variables under
specified set of conditions may completely define a system. The relation among state
variables is defined as equation of state. For an ideal gaseous system, the equation of state PV
=nRT, where R=gas constant may be isolated through implication of the fundamental
approach based on Boyles and Charles laws.
Binary relation of state variables under specified set of conditions liberates thermodynamic
properties of a system. Such thermodynamic properties are internal energy (E) enthalpy (H),
entropy (S), Gibbs free energy (G), Helmholtz function(A), chemical potential (µ ), heat
capacity etc. For example, at fixed mass of an ideal gas, at constant volume, H
=f(T,P).Similarly other thermodynamic properties such as internal energy and entropy may
be defined as E=f(T,V) and S=f(E,V) respectively.

1.2 REVERSIBLE AND IRREVERSIBLE PROCESS
1.2.1 Reversible process:

Reversible processes proceed from the initial to the final state of a system through an
infinite series of infinitesimally small stages. At each of stages, the system remains in the
state of equilibrium.
1.2.2 Irreversible process:

An irreversible process proceeds when system goes from initial to final state in a single step
in such a way that it cannot be reversed.
In this process the system remain in the state of equilibrium at initial and final stages,
however, such equilibrium conditions are not well maintained the intermediate stages.
Let us consider specific quantity of a gas in a cylinder with a weightless and
frictionless piston. The expansion of the gas can be carried out by two methods as shown in
fig.1.1. Let the pressure applied on the piston be P which equal to the external pressure of the
gas. Since the external and internal pressure are exactly
Fig.1.1 Work in reversible (a) and irreversible process (b)
Counter balanced, the piston remains stationary and there is no change in the volume of the
gas. Now suppose the pressure on the piston is decreased by an infinitesimal amount dP, thus
the external pressure on the piston being P-dP, the piston moves up and the gas will expend
by an infinitesimal small amount. The gas will therefore be expended infinitely slowly
(reversible process). At all stages in the expansion of the gas, dP being negligibly small the

gas is maintained in a state of equilibrium throughout. If at any point of the process the
pressure is increased by dP, the gas would contract reversibly fig.1.1 (a).
Now on the after hand, the expansion is irreversible, if the pressure on the piston falls
suddenly, it moves upward rapidly in a single operation fig.1.1 (b).the gas is in equilibrium
state in the initial and final stages only, the expansion of the gas, in this case, takes place in
an irreversible manner.
1.3 THERMODYNAMIC WORK
Reversible and irreversible work:

Thermodynamic work, often called as P-V work is the work done in expansion (or
compression) of a gas. Let us consider a gas contained in a cylinder fitted with a frictionless
piston. Pressure (P, which is force per unit area) of the gas, exert a force on the piston
fig.1.2. This can be balanced by applying an equal but opposite pressure from out- side on the
piston. Let it be designated as Pext. It is a external pressure which is used in evaluating work.
This is true whether it is expansion or contraction.
Fig.1.2 Pressure volume work of a system
If the gas expands at constant pressure, the piston will move to a distance l. Since,
Work = force distance
=ƒ l ……………….1.1
and pressure is force per unit area
=Pext
or f =Pext A ………………..1.2

Here A is the cross- section area of the piston.

From equation 1.1and 1.2 we have
Work = =Pext . A.l
= Pext . V ..…….………1.3
Work is done at the expense of internal energy, hence the internal energy decreases and work
done bears a negative sign. Work may be expressed in dynes-centimeter, ergs, joules. PV
work as well be expressed as the product of pressure and volume units e.g., litre /
atmospheres.
If the initial volume is V1and final volume is V2 then work in this case will be
W= -Pex (V2 –V1)
It is to be noticed that the work done by the system is not a state function, it depends
upon the path of transformation. In the case just cited above pressure the piston is decreased
as volume changes from initial volumeV1 to final volume V2, this is irreversible work.
Consider a system in which an ideal gas is confined in a cylinder with a frictionless piston
fig.1.3.
Fig.1.3 Isothermal reversible expansion work
Suppose it expands reversibly from V1to V2 at a constant temperature. The pressure of the gas
is successively reduced from P1to P2. Let us reduce the pressure P1 by an infinitesimal
amount p, i.e., let the pressure be P1- p and the volume increases be , then the work
done by the system would be ( P1 - p) P1

As p is very small, will also be very small, and the multiplication of these two will be
very small quantity and can be neglected. Then the new pressure is again reduced
infinitesimally and a little more expansion involving again P work would be available. In
this way by infinitely large number of successive steps we can expend the gas from
volumeV1 to V2. Let the equilibrium pressure attained by the gas, when the volume becomes
V2 be P2. The total work done by the gas during expansion would be summation of all these
minute quantities, i.e.,
W= dV
………………………1.4
Here dP. will be very small quantity and can be neglected. We must remember that P has
also been changing during the expansion continuously. If the system contains n gm.moles of
the gas and the gas be supposed ideal one, then
W= =nRT ln
For one mole of an ideal gas the expression work will be
W =RT ln ………………………..1.5
as =
W = RT ln ………………………..1.6
Since the change has been carried out in successive stages of infinitesimal amount and
therefore it is reversible process. The work in the isothermal reversible expansion of one
mole is
W =RT ln = RT ln ………………………1.7
This work is the product of force and displacement. The displacement in this case is
specified, namely (V2 – V1). Hence greater the magnitude of the force or pressure, the greater

would be magnitude of the work. If the pressure over the piston were made greater than (P1 -
) there obviously would be no expansion.
Therefore if we want to have expansion as desired, (P1 - ) is the maximum that could be
applied. So the work obtained in the equation (1.7) is the maximum. That could be applied. If
the pressure over the piston were made appreciably less, instead of infinitesimally smaller
than the gas pressure, the work would be evidently less than obtained above and the process
also would be more irreversible. Hence we conclude that the work in the reversible process is
the maximum and is greater than that in the irreversible process.
It can be proved in the following manner.
For this we carry out the expansion of the same gas in two ways. Firstly, we change
the volume as before until the pressure is P2, the process is reversible work.
Wr =RT ln = RT ln ………………………..1.7
Secondly, we reduce the pressure over the piston at once to P2, which would be equilibrium
pressure of the gas when the volume is V2, then the gas would immediately expands against a
constant pressure P2 the process is irreversible work is
Wir = P2 (V2-V1) = P2 ( -
= RT (1 - )
Wr –wir = RT ln - RT (1 - )
= RT ( ) – RT ( )
= RT ( – )( - )
= RT ( )( )
= RT ………………..1.8
This is positive quantity whatever be the value of P1 and P2,

i.e. Wr Wir

1.4 WORK IN REVERSIBLE CYCLE PROCESS
We know that when gas has expanded to volume V2 the gas pressure has come down to P2. If
the pressure is increased by infinitesimal amounts in successive stages the volume becomes V1
and therefore, pressureP1. The work done in the system will be
W` = 2. V=
= RT ln = - RT ln ………………….1.9
Here the work term becomes the same with reversal of sign. Thus if the complete reversible
cycle of expansion and contraction is carried out at constant temperature then the net work
would be zero.
= W + W` = RT ln - RT ln =0
Or in an isothermal reversible cyclic process,

=0 …………………1.10
1.5 FIRST LAW OF THERMODYNAMICS
All class of physical, chemical or biological transformations into one another are assumed to
facilitate at the cost of conservation of energy and matter. The transformations and conservation
of energy during processes are studied under the first law of thermodynamics. According to this
law, the energy transformations in all the processes are purely conservative and proceed without
any creation or loss of energy. Such kind of statements however doesn’t hold when Einstein’s
relation inter-conversions of energy and matter are considered as below:
E= mc2 ………………..1.11
Where E is energy associated with matter of mass ‘m’ and ‘c’ is the velocity of light in vacuum,
a constant. In our present discussion, we shall have no occasion to consider this inter conversion
of energy and matter and we shall take the first law to be strictly true.

1.6 INTERNAL ENERGY

Thermodynamically, internal energy of a system of a fixed mass is the unique function of
temperature and volume as expressed below:
E = f (V, T )
Any change in internal energy, may be expressed through following exact differential:
dE = ( )V dT +( T dV
The internal energy of a system is determined by the state of a system and is dependent of the
path by which it is obtained. Hence the internal energy of a system is a state function.
1.7 MATHEMATICAL FORMULATION OF FIRST LAW OF

THERMODYNAMICS
Suppose a system is in state A having energy EA and undergoes a change to another state B with
energy EB . During this change, absorption of a small quantity of heat q at stage A , will impart
net amount of energy to system as EA+q. This will allow the system to perform work, with
final energy of EB+w. From the law of conservation of energy this follows that:
EA+q =EB+w
or E = q-w …………………1.12
For small changes

dE = q – w
Here E is state function hence its change is dE and q and w are not state functions, they depend
upon the path, hence, q and w.
1.8 ENTHALPY
Suppose the change of state of a system is brought at constant pressure P. In that case there will
be change of volume from VA to VB. Under such conditions, system may execute the work
done (w) as below:

w = -P (VB – VA) …………………1.13

Substituting the value of work from 1.13 to 1.2 will result
E = q – P (VB –VA)
EB-EA = q –P (VB – VA)
Rearranging above expression will result
(EB+PVB) – ( + PVA) = q …..…………….1.14
The quantity E + PV is known as total energy stored and thermodynamically termed as enthalpy
(H) of the system
H = E + PV ..………………1.15
In this equation E, P and V are all state functions, thus H, the value of which depends upon the
value of E, P and V must also be the function of state. Hence the value is independent of the
path by which the state of the system is changed.
From equation 1.14 and 1.15 are have
HB-HA = H …………………1.16
Since HA and HA are definite quantities, it is evident that H, like E is a definite
quantity depending upon initial and final states. We can write
H= +P V …………………1.17
Here V is increase in the volume under gone by the system.
For a fixed mass of system H=f(T,P), that represents the following exact differential
1.9 CALCULATION OF CP-CV THERMODYNAMICALLY
Heat capacity is defined as the quantity of heat required to raise the temperature of the
system from the lower to the higher temperature divided by the temperature difference. If q

calories are the heat absorbed by mass m and the temperature rises from T1 to T2, the heat
capacity is given by the expression
c= …………………..1.18
For unit mass say restricted to 1 gm, heat capacity is called the specific heat of the system.
However, if mass of the system is one mole, then the heat capacity is called molar heat capacity
(C). Heat capacity varies with temperature; hence the true molar heat capacity is defined by the
equation
C= …………………..1.19
Molar heat capacity is defined as the amount of heat required to raise the temperature of
one mole of substance or system by 1K.
Since heat is not the state function, it is necessary to fix either of a thermodynamic
variable such as P or V at which the temperature of system is raised by one degree. This
generates two different kinds of the heat capacities. First kind of heat capacity is defined as
“heat capacity at constant volume (Cv)” and another one is the “heat capacity at constant
pressure (Cp)”.
From first law of thermodynamics we know
dq = dE + PdV
Hence = + …………………….1.20
at constant volume dV= 0 hence =( V
Cv =( )V ……………………..1.21
From equation 1.20
Cv = +P )P .……………………1.22
and H = E+ PV
Hence ( )P = ( P +P )P .……………………1.23
Comparing 1.22 and 1.23
CP = ( )P

Now Cp –Cv = ( )P - ( )V
Since H = E+ PV
Cp –Cv =( P +P )P - ( )V ………………..1.24
We know E = f (V, T )
dE = ( )V dT +( T dV
Dividing both sides by dT and keeping pressure constant
( P =( )V +( T( )p .……………….1.25
Putting this value of ( P in equation 1.24
Cp –Cv = ( )V +( T( )p + P )p - ( )V
=( )p {( +P}
For an ideal gas ( T =0
Hence Cp –Cv = P )P = P.
Since PV=RT and )P =
Cp –Cv = R …………………1.26
1.10 JOULE’S LAW

Joule carried out experiments to find out change in internal energy of a gas. The
arrangement for the experiment is shown in fig. 1.4
Let us consider two containers A and B connected by a stop cock at the middle and placed in a
water bath. The temperature of the bath was noted. The stop cock was then opened and the
temperature was again recorded. No temperature change was found. Since ideal gas expends
against vacuum without work and does not exchange heat with the surroundings that keeps the
temperature of water bath to be constant. Thus from the first law of thermodynamics.

Fig.1.4 Joule’s Experiment

dq = dE +d
or dE = dq – d = 0 both dq=0 and dw=0,
hence dE=0
but dE = T dV + v dT
Since dT = 0
dE = T dV = 0
as dV since the gas which was occupying one container, now occupies both the containers
Hence T =0 …………………..1.27
We can write T = T T
Since T so T =0 ..…………………1.28
We know H = E + PV
T = T +
T = 0 ………………….1.29
1.11 JOULE THOMSON EFFECT

The phenomenon of producing lower temperature when a polar gas is made to expend
adiabatically from the region of high pressure into a region of low pressure is known as Joule
Thomson effect. Non polar gases such as Hydrogen and Helium are warmed up under similar
circumstances. The temperature below which a gas becomes cooler on expansion is known as
the inversion temperature.

Experimental Details:
The experiment performed by Joule and Thomson to measure the temperature change on
expansion of a real gas is illustrated in fig 1.5
Fig.1.5 porous plug experiment

A tube of non conducting material filled with a porous plug in the middle and two
frictionless piston A and B on the side is taken. Let a volume of V1 of a gas at pressure P1 be
forced through the porous plug by the slow movement of piston A. the gas on right hand
chamber is allowed to expand to volume V2 and pressure P2 by moving the piston B outward.
The change in temperature is found by taking reading on the two thermometers.
Work done on the gas = P1V1
Work done by the gas = P2V2
Net work done by the gas = P2V2-P1V1
Since the expansion of the gas is done adiabatically, the system is not in a position to absorb
heat from the surroundings. The system thus does work at the expense of the internal energy.
Hence the internal energy decreases from E1 to E2
P2V2 – P1V1 = E1-E2
or P2V2 +E2 = P1V1+ E1
or H2 = H1 .…………….1.30
or H =0
This reveals that Joule-Thomson expansion of a gas takes place at constant enthalpy. Hence
this kind of expansion is also called isoenthalpic.
The rate of change in temperature with pressure when enthalpy remains constant is
called Joule-Thomson coefficient.
……….……..1.31
Since such flow through porous plug, usually the gas runs into lower pressure, i.e., dp
is negative. Hence will be positive if dT is also negative, i.e., if temperature falls. Except

Hydrogen and Helium at ordinary temperature almost all gases cool down in passing through
porous plug. For Hydrogen and Helium .
We know
in the above experiment dH =0

so =-
or
……………..1.32
1.12 JOULE-THOMSON COEFFICIENT IN IDEAL GAS

We know H=E+PV, so equation 1.32 can be Written as
……………1.33
In this equation of a gas is usually positive quantity, while for any gas is
always a negative quantity. As a result the first term is always positive. The magnitude of
second term may be negative or positive. At low temperature the value of this
term is negative under these conditions both the term are positive, has positive value. That
means cooling will take place.
For ideal gases PV is constant and first term is zero hence the =0.
1.13 JOULE-THOMSON COEFFICIENT FOR A REAL GAS

Joule-Thomson coefficient for a real gas can be calculated with the help of van der
Waals equation. Since, both a and b are small, the term in the equation can be
neglected provided pressure is not too high. The Von der Waal equation can be written as
………………1.34
Replacing V by we have
………………1.35
Differentiating the equation with respect to temperature at constant pressure, we get

………………1.36
Rearranging equation 1.34, we have
Dividing both sides by PT we get

..…..…………1.37
Substituting the value of R/P from equation 1.36 in equation 1.35 we get
The well known thermodynamic relation is:

………………1.38
From equation 1.38, equation 1.31 becomes

……..………..1.39
From equation 1.37 and equation 1.39 we get
…….…………1.40

From this equation it is clear that Joule – Thomson coefficient is positive as long as is
greater than b. This is the case when temperature is low. At high temperature hence
s negative. Since a, b and R are constant, it is evident that the magnitude and sign of Joule
Thomson coefficient depends only upon the temperature at which the gas is allowed to
expand.
The temperature at which the Joule – Thomson coefficient changes sign is known as
the inversion temperature ) At this temperature J.T. is zero so that
or = ………………….1.41
Here represents inversion temperature. This inversion temperature depends upon the van
der Waals constant a and b of the gas.
1.14 SECOND LAW OF THERMODYNAMICS

Foundation of the second law of thermodynamics was laid by German scientist Rudolf
Clausius in 1850 though examining the relation between heat transfer and work. First law of
thermodynamics although states the rule of conservation of energy but doesn’t intimate about
the direction through which the process is going on. Realizing directional nature of the
process, Clausius proposed that:
“Heat always flows spontaneously from hotter to colder region, and never the reverse, unless
external work is performed on the system”.
Heat cannot spontaneously flow from cold regions to hot regions without external work being
performed on the system, which is evident from ordinary experience of refrigeration, for
example. In a refrigerator, heat flows from cold to hot, but only when forced by an external
agent, the refrigeration system.
In another approach, Lord Kelvin proposed that:
“It is impossible, by means of inanimate material agency, to derive mechanical effect from
any portion of matter by cooling it below the temperature of the coldest of the surrounding
objects”.
Just like first law, the second law of thermodynamics is also truly a law of experience
gathered from observations of nature. Any such experience which would determine the
criteria for the direction for the occurrence of a change will be the basis of second law.

1.15 CYCLIC PROCESS

Cyclic process represents revival of original state of a system after completing a series of
changes. An isothermal cycle is one that complete at constant temperature. At the same time
if changes are carried out reversibly it is called reversible cycle. Although the reversible
cyclic processes are purely theoretical and imaginary, the concept to demonstrate maximum
conversion of heat into work.
Efficiency of a machine or engine is defined as the fraction of heat absorbed by a machine or
engine which it can convert into work.
.………………1.42
Where Q1 is heat absorbed at temperature T1 and Q2 the heat rejected at temperature T2.
1.16 ENTROPY: NATURE OF DQ AND DQ/T

Rudolf Clausius in the early 1850s observed that irreversible process proceed with dissipation
of small amount of heat energy δQ across the system boundary. Clausius has coined the term
entropy (S ) to explain such loss of energy during irreversible processes. Entropy is a state
function; it depends only on the state of a system and not on the past history. Presently,
entropy is recognized as a thermodynamic quantity representing the unavailability of a
system's thermal energy for conversion into mechanical work, often interpreted as the degree
of disorder or randomness in the system. Thermodynamically, for a fixed mass of system,
entropy is expressed as S=f(E,V) for that the exact differential is expressed as:
The amount of heat absorbed or evolved in a process carried out reversibly at temperature T
may be evaluated through application of Carnot cycle.
Suppose a system changes from one to another state, the heat dq is either absorbed or
evolved. The value of dq depends upon path of transformation and hence it is not a perfect
differential. From Carnot cycle we know the efficiency of an engine is given by the relation
=
or .………………1.43
The above equation may be written in general form as

Where qrev is the amount of heat absorbed or evolved in a process carried out reversibly at
temperature T. The term qrev/T denotes a definite quantity or a state function, called entropy
change of the system.
If we assign positive sign to the heat absorbed (q2) and negative sign to heat given out q1 the
equation 1.43 can be written as
or ....…………..1.44
Fig. 1.6 demonstrates a reversible cycle ABA to be made up of large number of Carnot cycles
and adiabatic curves under isothermal conditions.
Fig 1.6 Entropy change in a cyclic process

The lines slanting horizontally stand for adiabatics and those slanting vertically stand for
isothermals. Starting from A and going along the Carnot cycles successively, the whole of
cycle ABA can be covered. Now the cycle ABA which is reversible one, consists of a series
of Carnot cycles for each of which the following expression will hold good.
=0 …………….1.45
The cycle ABA can be regarded as comprising of two paths, i.e., from A to B and back from
B to A, thus
…….1.46

The integral is the summation of all the terms when the system changes from A to B
along the path I and similarly integral is the summation of all the terms when the
system returns from B to A, i.e., initial state along the path II

Thus it is clear that
(path I) = (path II)
or (path I) (path II) ........……1.47
From equation 1.47 it is clear that is a definite quantity independent of path taken for
the change and depends only on initial state and final state. In other words it is a perfect
differential. The function is called entropy and is denoted by symbol S first proposed
by Clausius (1854). If SB be entropy in state B and SA entropy in state A then change in

entropy is given as
………………..1.48
Generally the equation is written as
For a very small change
It is not easy to define the actual entropy of a system. However it is easier to define change of
entropy during a change. It is clear from equation 1.48 that when heat is absorbed by the
system dq is positive. T is always positive. Thus is positive. That means entropy of the
system increases by the absorption of heat. Hence, evolution of heat by the system means
entropy decreases.
Since the entropy change is expressed as heat absorbed or evolved per unit temperature,
entropy data are numerically expressed in terms of joules per degree per mole (JK-1). This is
known as entropy unit, e.u.
In isothermal reversible expansion of an ideal gas, there will be no change in internal energy
dE=0. In that case from first law
or
If the gas is expanding from volume V1 to V2 for n moles

………………1.49
Entropy of one mole of a substance in pure state at 250C and one atmospheric pressure is
defined as standard entropy of that substance and is denoted by S0: During the reaction, each
reactant and each product are in their standard state.Under such conditions; the overall
entropy change may be evaluated as:
1.17 PHYSICAL SIGNIFICANCE OF ENTROPY
When a system is left to itself it will gradually pass into a state of equilibrium. This is
common experience. The state of equilibrium means a state of maximum disorder or chaos. If
we let loose a quantity of yellowish green chlorine gas at corner of the floor of the room, the
gas would spread in all directions until it would be most chaotically distributed into the entire
room and the equilibrium will be reached. If we arrange a number of red and black balls in a
tray in a particular pattern and then shake the tray, the balls will be mixed up in the most
disordered fashion. These are all natural processes and we never find the opposite to happen
in nature. These processes are irreversible and thus lead to entropy increase. The more the
system reaches equilibrium, the greater is the disorder and irreversibility, and when the
equilibrium is reached, it has the maximum disorder. Hence the entropy also goes on
increasing and reaches its maximum at the equilibrium state. In other words, entropy is the
measure of the disorder of the system.
Now if we attempt to bring order to system entropy decreases. Suppose we have a gas in
equilibrium confined in a cylinder with a piston. The piston is now some what raised upwards
increasing the volume slightly. All the molecules, in whatever direction those might be
moving, are subjected now to a tendency of motion in the direction of piston. This is
indirectly an attempt to bring some order. In consequences, the gas is cooled and the entropy
decreases. So in the crystalline state of pure substances the entropy becomes the least as there
is perfect order or least chaos.
1.18 ENTROPY OF A PERFECT GAS
From first law of thermodynamics, it is possible to express entropy of a perfect gas.

We know,
dq=dE+PdV
Dividing both the sides by T, we get
(for one gm. mol)
or ………….1.50
on integrating ….……….1.51
is constant of integration.
rearranging (putting we get
…………..1.52
1.19 CHANGE OF ENTROPY WITH TEMPERATURE
We know
or ……………..1.53
Since

or ……………..1.54
1.20 ENTROPY OF MIXING
When two or more gases are brought in contact, they immediately diffuse into one
another and mix up irreversible. Such a spontaneous process would lead to increase in
entropy. If the gases are ideal we can drive the relation for mixing.
Let one mole of gas A and one mole of gas B are mixed together at constant
temperature T and pressure P. Before mixing the entropies are
After mixing, the final pressure remaining constant, the partial pressures of A and B may be
denoted by PA and PB such that P=PA+PB the entropies of two gases in the mixture are
Total entropy change is given as
….………..1.55
Since PA/P or ln PB/P is negative quantity

Hence, , that means mixing of two or more gases is a irreversible process.
1.21 WORK FUNCTION OR HELMHOLTZ FREE ENERGY A

AND GIBBS FREE ENERGY OR GIBBS POTENTIAL G

Till now we have studied only three thermodynamic functions, viz. the internal energy (E),
enthalpy (H) and entropy (S). In addition to these three thermodynamic functions there are
two additional thermodynamic functions which also depend only on initial and final states of
system. These functions are work function and free energy functions represented by A and G
respectively. These functions are such that they utilize entropy in their derivation. With these
functions the entropy change can be determined more conveniently.
……………………1.56
…………………...1.57
We know E, H and S depend on the state of the system, it is clear that both A and G
also depend upon the state only. The exact nature of these functions will be clear from the
following discussion.
Let us consider that a thermodynamic system changes from initial state to final state at
constant temperature. Let A1, E1 and S1 be the work function, internal energy and entropy in
the initial state and A2, E2 and S2 are the values of these functions in the final state
respectively then,
A2=E2-TS2
A1 = E1- TS1
Subtracting second equation from first equation
We get +
or ………….………1.58
From first law of thermodynamics and from entropy equation
or
…....…………….1.59
i.e. decrease in work function A in any process at constant temperature gives that maximum
work that can be obtained from the system during the change this function, A is therefore
termed as work function this is also referred as Helmholtz free energy or Helmholtz function.
Similarly, from free energy function we get

or
In this equation PV signifies the work done against pressure. Hence gives the maximum
work obtainable from the system other than pressure volume work. This is known as net
work.
1.22 CHANGE IN A AND G WITH THE PARAMETERS OF THE

SYSTEM
If a closed system undergoes a change, the only work involved being mechanical against the
pressure, the infinitesimal reversible changes of A and G. would be
………………1.60
and
………………...1.61
From equation 1.60

…..….………..1.62
And from equation 1.61

....…………….1.63
From equation 1.62 and 1.63 different forms of Gibbs Helmholtz equation can be derived by
substituting these values of in their respective equations of work function and Gibbs free
energy.

1.23 MAXWELL’S RELATIONS
We know E is internal energy,

and . Then
...………….1.64
……………1.65
…………….1.66
………….…1.67
From equation 1.64
and
and
So
Similarly
………….1.68
and

These are four Maxwells relations. The last two relations give us the isothermal dependence
of entropy on volume and pressure.
SOURCE OF STUDY MATERIAL
1. Thermodynamics : By P.C. Rakshit
2. Advanced Physical Chemistry : By J.N. Gurtu & A. Gurtu
3. Principles of Physical Chemistry : By Puri, Sharma & Pathania
4. Essentials of Physical Chemistry : By B.S. Bahl, Arun Bahl, G.D. Tuli
5. Physical Chemistry : By Walter J. Moore

UNIT –2 CLASSICAL THERMODYNAMICS-II
CONTENTS
2.1 Introduction
2.2 Partial Molar Quantities/Chemical Potential
2.3 Gibbs Duhem Equations
2.4 Variation of Chemical Potential
2.4.1 Variation with Temperature
2.4.2 Variation of Chemical Potential with Pressure
2.5 Clapeyron Equation
2.6 Clasius Clapeyron Equation
2.7 Fugacity
2.8 Physical Significance of Fugacity
2.9 Thermodynamic Derivation of Law of Mass Action
2.10 Free Energy Change (G) in Chemical Reactions
2.11 Activity Concept
2.12 Activity Coefficients of Electrolytes
2.13 Changes in Gibbs free energy (G) in Chemical Reactions
2.14 Standard Value of Gibbs Potential
2.15 van’t Hoffs Equation and van’t Hoffs Isochore
2.16 Feasibility of a Reaction
2.1 INTRODUCTION
This unit deals with thermodynamics of open system, phase equilibria, fugacity and
derivation of law of mass action.
2.2 PARTIAL MOLAR QUANTITIES/ CHEMICAL

POTENTIAL
Internal energy (E), enthalpy (H), work function A, Gibbs free energy G, and entropy
(S) are all extensive properties. The value of these thermodynamic properties varies with
energy and matter content of the system. This is quite possible that the system may
exclusively exchange energy with surroundings, keeping material content to be constant. This

class of system is defined as closed system. Thermodynamically, a closed system is defined

as:
X=f (P,T) dV=0
Y=f (P,V) dT=0
Z= f (T,V) dP=0
However, if a system is capable to exchange the energy and matter with surroundings, this is
called open system. This class of system is defined as open system. Thermodynamically, an
open system is defined as:
X=f (P,T,n1,n2,--------) dV=0

Y=f (P,V, ,n1,n2,--------) dT=0
Z= f (T,V,n1,n2,--------) dP=0
Where, , etc, are the quantities (g mol) of 1st, 2nd and onwards components of the
system.
In order to ascertain the effect of change in X with reference to mass and thermodynamic
variables, let us consider any one class of the class of an open system
X=f (P,T,n1,n2,--------) dV=0
For small change in temperature pressure and number of moles of components, the change in
thermodynamic property of an open system is represented as,
The term is called partial molar property for the first component. This is more
often represented as 1 which denotes the rate of change of X on addition of one mole of the
first component keeping other variables unchanged.
For change in the mass of system, at constant temperature and pressure, we have
= 1dn1+ 2dn2+ 3dn3 ……………2.2
It may be noted that X stands for any extensive property.
Thus for ith component in a system,
Partial molar internal energy = = i

Partial molar enthalpy = = i
Partial molar volume = =Vi
So partial molar volume of 1st component-

= i …………………..2.3
The most important partial molar property is partial molar free energy.
The change in the thermodynamic potential (Gibbs potential G) at a constant
temperature and pressure can be expressed as
……. ………………2.4
The partial molar free energy is given by =
J.W. Gibbs proposed that for component of an open system, chemical potential is
represented as .
Hence = i= …..……………2.5
That means equation 2.4 can be written as
…..……………2.6
It must be noted that is independent of the mass of system but not independent of
composition of the system.
2.3 GIBBS DUHEM EQUATIONS
Suppose at constant temperature and pressure, all the molar concentration of components are
increased in the same proportion of their initial amounts. This implies to increase of first

component as of the second component as , etc. For component, similarly

increase will be expressed as . Hence
,
Since G is an extensive property, the increase, from equation 2.5
…………
…………
or …….. ....………..……2.7
Total differential of G of equation 2.6 is written as

……
………) + + +…….) .….2.8
Subtracting equation 2.6 from eqn. 2.8 we get

+ + ……………=0 …………..2.9
Thus we have three useful relations for chemical potential with the composition of the
system.
(i) + + …………………=0
(ii) ………….= …..…. 2.10
(iii) …………..= …………….2.10
These are commonly known as Gibbs Duhem relations.

Now consider a solution having two components in equilibrium with their vapours at constant
temperature and pressure. If a binary system undergoes an infinitesimal change of the
composition, Gibbs Duhem equation takes the form:
+ =0 ……………..2.11
Here n1 and n2 are number of moles of the two components and and are respective
chemical potentials. Dividing the above equation by n1+n2 we get

or =0 ……..………2.12
Where is mole fraction of constituent 1 and mole fraction of constituent 2. We can
write equation 2.12 in the following form
+ =0 ..…………….2.13
We know
or -
Substituting the value of in equation 2.13 we get
- =0
or = =0 ………….…2.14
This is alternative form of the Gibbs Duhem equation.
2.4 VARIATION OF CHEMICAL POTENTIAL
2.4.1 Variation with Temperature:
We know chemical potential by definition is give by

= ……….……. 2.15
Differentiating this equation with respect to temperature at constant pressure we get
= …..………….2.16
We know =S …..…………2.17

Hence differentiating this equation with respect to at constant temperature and pressure we
get
= ..…………….2.18
Comparing equation 2.16 with 2.18 we get
= = i …….………..2.19
This is partial molar entropy by definition. This equation gives variation of chemical
potential of any constituent i with temperature.
2.4.2 Variation of Chemical Potential with Pressure:
We know =
Differentiating above equation with respect to pressure at constant temperature
= ………………2.20
We know =V
Differentiating above equation with respect to at constant temperature and pressure we get
=(
Now, suppose there is a system containing a mixture of ideal gases at constant temperature T,
we get
n= n1+n2+n3 + …………………….. + ……..
and
Differentiating the above equation with respect to ni (moles of compound i) at constant

temperature and pressure (all n’s remaining unchanged).

or partial molar volume i = RT/P
Substituting this value of partial molar volume in equation 2.21

We get = Vi
or =
But we know partial pressure of the component,
For a system ni and n are fixed that is constant, hence
so
or ( being constant of integration)
If only a pure substance is present then .
The constant Z depends on temperature and nature of gas. At standard state chemical
potential is denoted by
Then RTln+ or = …..………..2.22
This is the relation connecting chemical potential with pressure of a component in an ideal
gas mixture.
We know where molar concentration of component is .
Hence
Also we know Ni being the mole fraction of the component

Thus we have
……………2.23
Since all gas laws of ideal gases also extended to ideal solution, the equation 2.23 will hold
true for ideal solutions also.
2.5 CLAPEYRON EQUATION
Consider two phases A and B in equilibrium of the same component with each other
at constant temperature (T) and pressure (P). If the two phases are in equilibrium then free
energy in both the phases should be same, i.e.,
Where is free energy in phase A and free energy in phase B. now temperature
is raised to and pressure is raised to P+dP then free energy in phase A will be
(suppose) and in phase B will be . Since the
system is in equilibrium, then …………..2.24
From equation 2.23 we have …………..2.25

We know
Hence
and
Putting these values in equation 2.25

=
Rearranging the term we get
is change in entropy
We know from our earlier knowledge
At equilibrium G=0, so H= S
or =
So we get H/ ……………2.26
In this equation H is change in enthalpy taking place at temperature T. VB and VA
are molar volumes of the component in B and A phases respectively and represents rate of
change of temperature with pressure.

Equation 2.26 relates the change in equilibrium pressure with temperature T occurring
in a system having two phases of the same component. This equation is named as
Clapeyron’s equation.
For solid liquid equilibria, H represents molar heat of fusion, VB represents molar
volume in liquid phase and VA represents molar volume in solid phase. The equation is
helpful in determining effect of pressure on boiling point.
For liquid vapour equilibria, H represents molar heat of vaporisaton, represents
molar volume in vapour phase and represents molar volume in liquid phase, T represents
boiling point of the liquid. For such equilibria clapeyron equation can be written as
.……………..2.27
Since quantity (since volume in vapour phase is always greater than

volume in liquid phase) hence boiling point increases with pressure.

2.6 CLASIUS CLAPEYRON EQUATION
In equation 2.27, since volume in vapour phase is much greater than volume in liquid
phase; hence. Substituting with , the equation 2.27 is
reduced as
Assuming that the system behaves ideally, the above equation may modified through
substituting
or
or …………….. 2.28
This is is Clausins Clapeyron equation

On integrating this equation between limits P2 at T2 and P1 at T1
we get
The above equation is defined as Clausius Clapeyron equation. This equation has following
applications
1. In determining heat of vaporization

2. In determining effect of pressure on boiling point
3. In studying thermodynamics of elevation in boiling point
4. In studying thermodynamics of depression in freezing point.
2.7 FUGACITY

The actual behavior of real gases is different from behavior of idea gases. Lewis
introduced concept of fugacity for representing actual behavior of real gases. The fugacity, in
substituting for pressure, will include in it the imperfections of the real gases and yet
retaining the form of equation. Thus, fugacity is a sort of fictitious pressure “which is used to
order to retain for real gases simple forms of equations which is used for ideal gases only.”
For ideal gases or

For real gases or .…….… 2.29
Equation 2.29 evidently, gives the free energy of real gases at temperature T and pressure P at
which fugacity can be taken as f.
so for real gases (for n moles) ……………2.30
Integrating the equation 2.30 for fugacities and at constant temperature T gives
……………. 2.31
If P is actual pressure, the ratio approaches to unity, when P approaches to zero, in that case
a real gas approaches to ideal behavior. The fugacity can be defined as
P
At low pressure fugacity is equal to pressure. But at high pressure the two terms differ
materially.
Now
Differentiating this equation will respect to pressure at constant temperature and constant
number of moles of the various constituents. i.e., in a closed system, we get.
(As is constant quantity)
we have ……………. 2.32
At a definite temperature equation 2.32 can be written as
…………… 2.33

The departure from ideal behavior can be written as
for an ideal gas , V is volume of real gas
From equation 2.32 the above equation can be written as
Integration this equation between pressure 0 and P we get

………..2.34
………. 2.35
The value of the integral of equation 2.35 can be evaluated experimentally:
Fig. 2.1 Determination of fugacity
Now as given in the above equation can be determined at different pressures. These values
are plotted against corresponding pressure as shown in fig. 2.1. The shaded area under the
curve between pressure P=0 and any given pressure P, gives the value of the integral
f (fugacity) can be evaluated at any given pressure P of the gas through substituting
this value in equation 2.35,. Since departure from ideal behavior ( ) can be both positive as
well as negative. Thus, the fugacity of the gas can be less than the pressure or more than the
pressure. It is clear from above figure the area and hence the value of is positive at low
pressure and more than P at high pressures.

2.8 PHYSICAL SIGNIFICANCE OF FUGACITY
If a system or a part of system be at higher temperature than that of its surroundings,

then heat energy will escape from the former to latter. The higher the temperature the greater
the tendency of the heat escapes. Let us consider a system consisting of liquid water in
contact until its vapour. Water molecules in liquid phase will have a tendency to escape into
vapour phase by evaporation while those in the vapour phase will have a tendency to escape
into the liquid phase by condensation. At equilibrium the two escaping tendencies will be
equal. It is accepted that each substance in a given state has a tendency to escape from that
state. This escaping tendency was termed as fugacity by Lewis.
2.9 THERMODYNAMIC DERIVATION OF LAW OF MASS

ACTION
van’t Hoff deduced the law of mass action thermodynamically by using an equilibrium box in
which all the systems were in equilibrium with each other at constant temperature.
This box is simply hypothetical and it has following properties
(a) The walls of the box are rigid having indefinite dimensions.
(b) The walls may be suitably made permeable to various components.
(c) The various components present are in equilibrium with each other.
(d) The working substances are ideal gases.
(e) The box is assumed to have large dimensions so that there is no change in
concentration or pressure (partial) of any component, if a small amount of those is
added or removed from it.
(f) The temperature of the box remains constant.
Now let us consider a chemical change at constant temperature

Consider two equilibrium boxes 1 and 2 in which components A,B,C and D are in
equilibrium, Suppose PA,PB,PC and PD are partial pressures of the A, B, C and D and CA, CB,
CC, and CD are the concentrations for box no. 1 similarly PÀ, P` B, P`C and P`D are partial
pressures of A, B, C and D and CÀ, C`B, C`C, and C`D are corresponding concentrations in the
box no. 2.
(a) Let us calculate the work done in transferring one mole of A. By means of the piston
moving outwards infinitesimally slowly, one mole of A is removed from box (1) so that
the partial pressure of A (which is Pa) remains constant. The amount of work done is
PAVA. Where VA is the volume of one mole of A under pressure PA.
(b) As the partial pressure is different in two boxes, that the removed gas from box(1) is
changed isothermally and reversibly from PA to PÀ by working the piston.
The amount work done is
(c) The gas is now ready to be put in the box no. (2) by compressing the gas infinitesimally
slowly by working the piston, so the partial pressure of A in the box (2) (which is PÀ)
remains constant. This will be put in box no. 2.
The work done in the process is PÀVÀ where VÀ is volume of one mole of A under a partial
pressure of PÀ
Total work done in this process is
(since ) ….………… 2.36
We know partial pressure is proportional to concentration
….…………. 2.37
Similarly one mole of B is transferred from box-1 to box-2, the work done will be
……………….2.38

At the same time one mole of C and one mole of D are transferred from box(2) to box(1),
they interact to produce A or B to maintain the equilibrium the work done will be
…………… 2.39
…………… 2.40
When one mole of C and one mole of D are transferred from box(2) to box(1) they interact to
produce A and B to maintain the equilibrium.
For such an isothermal cyclic process total amount of work done is zero, as the system
remains always in equilibrium.
Here
or ln
Similarly ……………2.42
Equation 2.41 and 2.42 are the two forms of law of mass action.
2.10 FREE ENERGY CHANGE (G) IN CHEMICAL REACTIONS
Suppose at a given temperature T and at a given set of arbitrarily chosen pressure (or
concentration) one mole of A reacts with one mole of B yielding one mole of C and one mole
of D, i.e.,
The change in free energy in a system due to chemical reaction at constant

temperature and pressure would be

2.11 ACTIVITY CONCEPT

The chemical potential equation is
Since the absolute value of chemical potential is not known, it is not possible to
evaluate the value of of a substance. The function fugacity was introduced into the
expression of the thermodynamic potential to cover the departure from ideal behavior of the
system.Lewis introduced another function called activity or relative fugacity, denoted by ‘a’.
If and denote the fugacities of a substance in a given state and in a standard state,
arbitrarily chosen, then the activity ‘a’ is the ratio of two fugacities,
……………… 2.43
It is obvious that in the standard state activity is
From the above it is clear that activity of a substance in any given state is defined as the ratio
of the fugacity of the substance in that state to the fugacity of same substance in standard
state.
The difference between chemical potential of a substance in any state and that in the
pure state is given by
So ..……………2.44
Since activity is the ratio of fugacity, its numerical value will depend upon the standard state,
which may be arbitrary fixed. Since, activity and the fugacity are numerically the same. For
gases and vapours, at standard state, fugacity is unity. Thus a=f/f0=f/1=f
For an ideal gas fugacity and pressure are equal and the same is also true for other gases at
low pressures. Hence in all such cases
For pure liquids and solids activities in pure state under one atmospheric pressure are taken as
unity at each temperature. But in solutions it is not always convenient to assume the pure
state as the standard for unit activity. It is necessary to consider the activities of solutes and
solvents separately.
Let us consider a reaction to take place in solution

The equilibrium constant for this reaction is written as
………………….2.45
Where aA aB, aC and aD represent the ideal concentrations in terms of molality (m) or activities of
the respective constituents A, B, C and D. If ‘a’ represents the ideal concentration and ‘c’ or
‘m’ the real concentration, the ratio a/m is known as activity coefficient ( ). Activity
coefficient is the measure of extent to which an ion or molecule departs from ideal behavior.
The ionization of a uni-univalent electrolyte of type AB can be represented as
The equilibrium constant K is written as
where a+ is the activity of cation (A+), a-, the activity of anion (B-) and a2 is the
activity of the undissociated electrolyte (AB).
The mean ionic activity of the two ions (a ) may be regarded as the geometric mean of the
activities of the respective ions
a- =
The activity coefficient of cation is and that of anion is . The mean activity
coefficient of the two ions is regarded as the geometric mean of the activity
coefficients of the respective ions.

Where
2.12 ACTIVITY COEFFICIENTS OF ELECTROLYTES
The concept of activity coefficient generally applicable to all cases. Because of the
ionic dissociation in solution of electrolyte the expression require certain modification. At a
given temperature under unit pressure the standard state of an ionic species is such that at
infinite dilution, the activity becomes equal to its concentration. The concentration is
generally expressed in molality or molarity. Then
Lt m 0 Lt c 0
In molal units in molar units
+ Sign refer to cations and – signs refer to anions. Now let us consider a simple case
of uni-univalent electrolyte AB, which ionizes in solutions as:
Suppose and are the chemical potentials of the electrolyte molecule, cation and
anion respectively. Then
Where terms are constant, representing corresponding chemical potentials at the standard
state.

Assuming the electrolyte dissociates completely, as in the case of strong electrolytes or

solutions at infinite dilution, then
And also at standard state
i.e.,
we can write RTln
or
is called mean ionic activity
Therefore
If we take a multivalent electrolyte in general, which dissociate as
Assuming complete dissociation
We can write
or
This is mean ionic activity of a multivalent electrolyte.
2.13 CHANGES IN GIBBS FREE ENERGY IN CHEMICAL

REACTIONS

Let us consider a general reaction in which a mole of A are reacting with b moles of B
to produce c moles of C and d moles of D at a given temperature T,
The change in thermodynamics potential (Gibbs potential) in the system due to the chemical
reaction at constant temperature and pressure, is given by
= (d )
Where is chemical potential
We know
We have
G = d(RT + +c(RT
-a(RTln
= RTln(
= RTln ( ...……….. 2.46
where Z is a constant
In this expression and are the activities of the components in the arbiturary
choosen conditions for the reaction.
It must be kept in mind that this relation is valid for any chosen state and therefore
would also be valid it we start with components in the equilibrium state. Now, using o for
denoting equilibrium conditions,
= RTln +
But at equilibrium =0

Then …………….2.47
Then for any equilibrium reaction, the change in the thermodynamic potential would be
…………….2.48
As this expression is derived at constant pressure this relation is commonly known as van’t
Hoff’s reaction isotherm.
In terms of fugacity
In terms of concentration
=- ....………….2.49
In terms of pressure
= .……………2.50
The importance of this reaction isotherm lies in the fact that can predict the feasibility of the
reaction. It is well known fact that when a reaction precedes spontaneously, the Gibbs
potential gradually diminishes until it becomes minimum at equilibrium. This means that for
spontaneous reactions is negative. That is in equation 2.49. should be less than
ln If the conditions are so chosen that becomes greater than ln then the reaction
will not occur. If we reduce the concentrations (or pressures) of the products and increase
those of reactants, then would diminish and the possibility of the reaction in the
desired direction improves. Thus we can determine the direction of a chemical change.
2.14 STANDARD VALUE OF GIBBS POTENTIAL
The value of change in Gibbs potential is given by the relation, as we have deduced above.

If the reaction is carried out in such a condition that all the reactants and products are at unit
activity, under these conditions the change in thermodynamics potential is called the standard
change in Gibbs potential (G) and is denoted at , so,
Because then
Then the equation for Gibbs potential change is given by
…………….2.51
For ideally behaving systems the corresponding relations are,
and
Then
and
2.15 VAN’T HOFFS EQUATION AND VAN’T HOFFS

ISOCHORE
van’t Hoff reaction isotherm is given by the relation
Differentiating this equation with respect to temperature at constant pressure
We know is a fixed quantity as pressure of the components is arbitrarily chosen,

hence

Multiplying both the sides by T, we have
Rearranging the term we have
From Gibbs- Helmholtz relation we know
So
Hence ………….. 2.52
This equation is commonly known as van’t Hoff equation.
We know,
Substituting the this value in equation 2.52
We get

…...…….2.53
In this expression is the energy change at constant volume, i.e., heat change at
constant volume. This relation for the variation of equilibrium constant with temperature
at constant volume is commonly mentioned as van’t Hoff isochore.
2.16 FEASIBILITY OF A REACTION
Free energy (G) and work function (A) are useful in determining feasibility of a
reaction or its attainment of equilibrium. We know that entropy remains unchanged in
reversible change, but irreversible changes are accompanied with increase in entropy,
therefore
For reversible change
Now suppose there is a system with its surroundings. Let ds and ds` be the entropy-
change in the system and surroundings respectively. Therefore
(i) For reversible change ds+ds`=0
(ii) For irreversible change ds+ds`>0
Combining the two change we may write
………….2.54
If we regard the change in the surrounding as reversible and suppose the surroundings supply
heat dq reversibly, then
If dE is internal energy increase of the system and w be the work done by the system, then
from the first law,

Now
Then
Herein, symbols in this equation refer to the system only.
Hence,
(a) For a real process to occur in nature

…………2.55
(b) At an infinitesimal reversible change of system
…………2.56
This condition is valid once the system is at equilibrium. Now suppose the work is
mechanical i.e., w=PdV, we can write the above equation in the following form
……………2.57
(i) If E and V are constant, then
The inequality sign for real changes and the equality sign for condition of equilibrium.
This means at equilibrium S becomes maximum and
…….………2.58
(ii) From the definition of work function
Substituting this value of dA in eqn 2.57
We get,
or
In isothermal process, if system does not produce any work,

……………..2.59
For real processes i.e. free energy diminishes. When equilibrium is attained
free energy becomes minimum and
(a) For equilibrium
(b) For spontaneous change

(iii) Gibbs free energy equation is
Substituting this value of dG in equation 2.57
We get,
or ……………..2.60
In an isothermal process at constant pressure
For real process Gibbs free energy decreases . When equilibrium attained, Gibbs free
energy is minimum,
For a process to occur spontaneously , in other words Gibbs free energy change
should be negative. Every process tends to attain equilibrium, so G will diminish
gradually and at equilibrium it will attain the minimum value, i.e.,
For a spontaneous process
and at equilibrium

The possibility of spontaneous occurrence of a chemical process is determined by

ascertaining whether the Gibbs free energy change is negative for the change under the
given conditions.
Since
, ..………..2.61
The Gibbs free energy change can be determined if we can find the change in enthalpy
and the change in entropy ( for the reaction.
The enthalpy change is obtained from the measurement of the heat of reaction
or it may be calculated from the bond energies in the molecules of reactants and products.
The entropy change is obtained from the individual entropies of reactants and
products, or from other measurements such as e.m.f. etc. The entropy increases whenever as a
result of the reaction the randomness increases. It is generally true that when a solid reactant
gives gaseous products, the entropy increases, i.e., is positive. In gaseous reactions the
sign of the entropy-change is determined from the number of product and reactant molecules.
If the number of product molecules be larger, will be positive. All dissociation processes
are attended with an increase in entropy.
The variation of entropy-change with temperature and variation of enthalpy-change with

temperature are not very large. The approximate estimations, and may be determined
at a convenient temperature may be used for reactions at other temperatures without an
appreciable error. But the change in Gibbs free energy varies considerably with
temperature.
From equation 2.60 it is clear that (i) the more negative is more negative and (ii) more
positive the more negative is . This shows that the system at constant pressure and
temperature would try to move to the state of maximum entropy and minimum enthalpy.
In processes where is negative and is positive, we have negative value of , such

processes would occur spontaneously.
Example -1

Here for the dissociation of is -2000 cal and is 18 cal/degree. Hence at C
The dissociation of would be spontaneous.
Example -2
This reaction is endothermic. This reaction will proceed if is positive and greater
than . Here entropy increases, as reactant C has least disorder, cal/degree. The
enthalpy change was found to be +31400 cal.
Hence at 250C
But if temperature is 12000K then
Therefore the reaction will not occur at 2980K but will be spontaneous at 12000K.
This also shows the profound influence of temperature on .
TERMINAL QUESTION
Short Answer type questions

1. Describe energy of activation. How can energy of activation be determined?
2. Derive the relation (∂P/∂T)V = (∂S/∂V)T
3. Derive the law of mass action thermodynamically.
4. Derive the relation for entropy of a perfect gas.

5. At NTP, 2.8 litre of oxygen were mixed with 19.6 litre of hydrogen. calculate the
entropy change.
6. Derive Gibbs-Deeham equation.
7. Define chemical potential. What is its physical significance?
8. Show that reversible work is always greater than irreversible work.
9. Establish for one mole of a perfect gas :
S = CV ln P + Cp lnV + constant
10. Establish the relation : RT ln (f/p) = (V-Vi)dP
Long answer type questions:
1. (a) Starting from the limitation of Gibbs-Helmholtz relation, discuss Nernst heat
theorem. What are the limitations of Nernst heat theorem? Discuss third law of
thermodynamics.
2. (a) Define fugacity. How can fugacity be determined in the laboratory?
(b) Derive two important forms of Gibbs-Helmholtz relation.
3. (a) Write a note on Maxwell-Boltzman statistics.
(b) Discuss Duham-Murgules equation.
(c) Write a note on chemical potential.
4. (a) Define partition function.
(b) Derive the relation for internal energy, entropy, pressure and heat capacity in
terms of partition function.
5. (a) Discuss partition function and different types of energies

(b) Establish Debye’s T3 law for heat capacity of solids.

UNIT-3 STATISTICAL THERMODYNAMICS
CONTENTS
3.1 Introduction
3.2 Probability
3.3 Boltzmann Distribution
3.4 Partition Function
3.5 Partition Function and Thermodynamic Functions
3.5.1 Internal energy
3.5.2 Entropy
3.6 The Third Law of Thermodynamics
3.7 Bose – Einstein Statistics
3.8 Fermi – Dirac Statics
3.9 Molar Partition Function
3.10 Terminal question
3.1 INTRODUCTION
Statistical mechanics provides a link between quantum mechanics and classical

thermodynamics. The classical thermodynamics is based on empirical laws in which
variables, pressure temperature, energy are regarded as function of state. In the derivation of
various relations of thermodynamic function, it is not necessary at any point to take account
the constitution of the material system, i.e., the constitution of the material system ignored.
The experimental observations support the laws; the drawback of the classical
thermodynamics is that we cannot calculate the absolute value of the thermodynamic function
of a substance directly. Classical Thermodynamics gives no indication as to the possible
origin of the laws. In order to overcome, this new method of approach has been developed
which is known as statistical thermodynamics.
In statistical thermodynamics the matter is pictured as composed of innumerable particles in
motion. The physical behavior of the particles is governed by the laws of classical
thermodynamics subject to quantum mechanical principles. Even in the smallest system, the
number of particles is so large that it is impossible to follow the behavior of every individual

particle. Statistical methods are essentially employed to express the property of the system,
particularly to find out what fractions of the molecules have a given energy.
Statistical mechanics can be applied easily to simple ideal systems such as monoatomic gases
and diatomic gases. For applications to interacting systems such as liquids (where strong
intermolecular forces exist), the details of the intermolecular potential energy, which is not
accurately known, have also to be taken into account. That is why statistical mechanics of
liquids is a difficult but fascinating subject. Gases under high pressure too are difficult to treat
statistically since they deviate strongly from ideality. In recent years statistical methods have
been applied successfully to simple liquids and dense gases. It is easier to find out the value
of entropy, free energy, enthalpy, heat capacity etc. from spectroscopic data by using
statistical method.
3.2 PROBABILITY
If we toss a coin, either head or tail will come up. We cannot predict whether head or
tail will come up in a particular toss. But we can reasonably say that in any toss there is a
fifty percent chance of the head being up. That is desired probability of the event is one in
two. Let us take another case. If a single card is drawn out from a well-shuffled deck of cards,
the probability or chance of drawing a heart is one in four, the probability of drawing a king
is one in thirteen, and the probability of drawing a king of hearts is one in fifty two.
If there are n equally likely and mutually exclusive ways of occurrence of an event in
a given set of conditions, then out of these n ways m are favorable to an event A, then the
mathematical probability of A is m/n. We may define this in another way. If a occurrence
succeeds in p ways and fails in q ways, all the ways being exclusive and equally likely, then
the probability of the event succeeding is p/(p+q). For example if we want to hit in color out
of the four colors, then we can hit at any particular color in one way, i.e., p=1, we may hit at
any of the three color, i.e., equally likely cases of failure is 3, i.e., q=3. Hence the probability
of succeeding is given by
Hence the probability of an event

There are two simple theorem of probability:

(i) If several events occur exclusively, then the total probability of their occurrence is the sum
of the probabilities of their separate occurances.
When two events occur and the probability of first event be w1 and the second event
w2 then total probability of both first and second occurring is w1+w2
Suppose we have two dice and they are tossed. We intend to find out the probability
of obtaining a total of 8 points. There are only the following five different ways of securing 8
points.
1st die 6 5 4 3 2
nd
2 die 2 3 4 5 6
Now let us consider the first combination (6 and 2), there is only one way out of six in
which six will come at the top of the first die, and also there is only one way for a two to
come at the top of second die. Thus the probability of obtaining eight by first combination is
thus
This is true for every other four remaining combinations. Hence the total probability of
getting an eight is
(ii) The probability of the simultaneous occurrence of two events A and B, is given by the
product of the probability of event A and the (conditional) probability of B, when the event A
has occurred.
If wA is the unconditional probability of A and wB is probability of B when A has
already occurred, then the probability of their simultaneous occurrence (wAB) is given by
WAB = wAwB
Suppose from a well shuffled deck of cards we intend to draw the king and queen of hearts.
The probability of obtaining king of hearts by a single draw is 1/52. If the king of hearts has
been received, the probability of securing the queen of hearts from the remaining is 1/51. The
total probability of simultaneously obtaining the pair is

Now let us discuss some other cases. Let us toss two different coins a large number
of times and count the number in which
(i) The two tails fall uppermost t1t2

(ii) The two heads fall uppermost h1h2
(iii) Tail of first coin and head of second coin uppermost t1h2
(iv) Head of first coin and tail of second coin uppermost h1t2
Where t denotes tail and h denotes head and suffix 1 and 2 indicate the first and second coin.
Now there are two possible events for first coin and two possible events for second
coin. Hence total possible events will be (t1+h1)(t2+h2) =2x2=4. Obviously any one of the
four cases can occur. The probability of each of the four equally like cases is ¼.
If we have four coins, the total possible cases by simultaneous toss of the four coins is
(t+h)4 = 24 =16. There are, however, five possible combinations or states. These are
tttt, ttth, tthh,thhh, hhhh
Now we select any one of these combinations say tthh (two tails and two heads
upwards)
tthh thht thth htth htht hhtt
That is there are six ways in which two tails and two heads be upwards from 4 coins. For th3
there are four possible ways to obtaining the same.
The total possible event is given by (t+h)4.
Expending this binomially we get
(t+h)4 = t4 + 4t3h + 6t2h2 + 4th3 + h4. In this equation the exponents of t and h indicate the
number of tails and heads upwards in a given combination. If you examine the equation the
coefficient of the term indicate the number of ways the particular combination would occur,
the total is 24 or 16. Thus probability of t2h2 is or 6x2-4 This is mathematical probability
of t2h2.
The same result can be obtained as follows. Total number of possible events is (t1+h1)
(t2+h2) i.e. 4. The total permutation of these four is 4! But this number also includes the
permutation of two events of first coin and two events of second coin for t2h2 which is 2! x 2!.

Hence the real number of micro states or possibilities of complextion would be

The same result we obtained above.
Now if number of individuals be n and these are accommodated in several houses or

cells, such that n1 are in cell 1, n1 in cell 2 n3 in cell 3 etc; the number of microstates for a
given combination or macrostate is given by
Where denotes product of terms following it. Again we have taken the case of coins.
Suppose we have n identical coins tossed as described earlier. Following our usual method to
all the n coins. The total number of cases or macrostate that can occur is given by (t+h)n=2n
The possible combinations or microstates are
tn, tn-1h, tn-2h2 …………tptq hn-1, hn
when p+q=n
The coefficient of the terms tphq in the binomial expansion of the above is
This is the total number of complexions or microstates that would arise when p coins have
tails and q coins have heads upwards. This can be done nCp ways.
The mathematical probability of the occurrence of tphq is therefore
W= nCp/2n = ……………3.1
Plank introduced the term thermodynamic probability or statistical probability

denoted by P to indicate the total number of possible complexions or microstate for any given
combination.
Thus it is different from mathematical probability
Thermodynamic probability
Mathematical probability
Where each individual item of the system can give rise to c-cases.

It is clear from these two probabilities that because total number of possible cases (Cn)
is constant, thermodynamic probability (W) is proportional to mathematical probability (P)
3.3 BOLTZMANN DISTRIBUTION

Let us consider a system of constant energy E, composed of n identical particles at
temperature T which has the following characteristics.
(a) Particle do not attract or repel each other.
(b) Each particle is distinguishable from the other.
(c) No restriction on assigning various energy levels to the particles is being imposed.
All these assumptions lead to the classical Boltzmann distribution law. All the
particles are not in the same energy level. Let there be n particles such that n, particles in
energy level 1, n2 particles in energy level 2 and so on. Irrespective of this distribution,
total number of particles and energy of the system is constant i.e.,
……………..3.2
E= …………….. 3.3
The allowed energy levels are fixed by quantum mechanical principles. As the
occupation number n1, n2 etc in different energy levels change the distribution also changes
there are obviously number of ways of distribution, similar to the arrangement of n boys in p
rooms, so that n1, in one room, n2 boys in other room and so on. This number is given by
………………..3.4
Thus the thermodynamic probability of a distribution is equal to number of ways of

realizing the distribution. This equation is used to determine the probability for all
distributions of all the molecules in a given molecular system in different energy levels at a
constant total energy.
In equation 3.4, is the total number of molecules and the summation is over all the
energy levels. It is possible to realize a given energy level in more than one way i.e., more
than one quantum has the same energy. When this happens, the total energy is said to be
degenerate. Let be the degeneracy (or multiplicity) of the energy level . This means if
there is one particle in each energy level there are ways of distributing. For two particles in

the level, there are possible distribution. Thus for particles in ith level, there are gini
possible distribution. Hence the thermodynamic probability for the system of particles is
given by
…………….3.5
We know from Boltzmann equation

or ……………..3.6
The probability must be maximum for an equilibrium state, so at equilibrium
We are thus interested in finding the distribution that will make W a maximum.
It is more convenient to maximize the logarithm of P. It is known from calculus that
at the maximum the derivative of function vanishes.
Now we confine our investigation to a closed system of independent particles, it
would meet the following two requirements:
(i) Total number of particles is constant i.e.
………..…….3.7
(ii) Total energy, E of the system is constant i.e.,
………………3.8
Since total number of particles is constant
…………..…..3.9
and total energy is also constant
….…….…..3.10
Taking logarithms of both the sides of equation 3.5 we have
Using Stirling’s formula for factorials of large numbers:
…………..3.11

..…………3.12
Differentiating equation 3.12 and keeping in mind and are constants
…..…………3.13
As …..………..3.14
At equilibrium
……………..3.15
If the system were open then would vary without restriction and the variation
would be independent of one another. It would then be possible to solve the equation 2.15 by
setting each of the coefficients of the terms equal to zero. But our system is closed one
end since is constant, the value of are not independent of one another, as it is seen in
equation no 3.14.
To solve the equation 3.15 we apply the Lagrange’s method of undetermined
multipliers. We can write equation 3.15 in the following form
……………….3.16
Now multiply 3.9 by and 3.10 by and subtract the addition from equation 3.16
…..…………..3.17
The variable etc is independent of each other, so that the equation 3.17 to
hold each term in the summation must be zero.

…..………….3.18
Now
or …………….. 3.19
………………3.20
Dividing equation 3.18 by equation 3.20 we get
………………3.21
This is general form of Boltzmann distribution law
3.4 PARTITION FUNCTION

The denominator in the equation 3.21, is sum of the factor over all
energy levels. It is called partition function and is represented by f.
Then Boltzmann distribution law can be written as.
….…………3.22
Qualitatively speaking, the partition function is a measure of available energy levels

and it indicates how the particles are distributed among the various energy states.
3.5 PARTITION FUNCTION AND THERMODYNAMIC

FUNCTIONS
3.5.1 Internal energy

The internal energy E of a system of n particles is given by the equation
(substituting g=1)
but
So
Hence ………….3.23
For a gm mole
…………….3.23 (a)
The average energy of each molecule
………..3.24
3.5.2 Entropy:
The relation between entropy and probability W is given by the relation.
…….…….3.25
We know W is proportional to the thermodynamics probability (P)
(B is a constant)
(S-B)/k =

Since
…………..3.26
From Plank’s arbitrary assumption and
Similarly, Pressure P, Gibbs free energy G, work
function A, heat capacity , enthalpy H can be represented in terms of partition function.
3.6 THE THIRD LAW OF THERMODYNAMICS
Statistical formulation of third law can be made in the following way. We know.
……………..3.27
At very low pressure .
Hence
and
so
Hence is molar partition function
dT
(by differentiating partially)
Equating temperature independent terms we get

Here is statistical weight factor of the lowest energy state. For a perfect crystal at 00 K
there is only one arrangement, which means . Hence the entropy which is third
law
Now ………3.28
In general we can write
………….3.29
This is the expression for entropy at any temperature T.
3.7 BOSE – EINSTEIN STATISTICS
In classical distribution of particles are distinguished from one another. If two particles
interchange their positions (or energy states) a new complexion would occur. But in Bose –
Einstein statics we start will identical particles which are indistinguishable. Therefore the
interchange of two particles between two energy states will not give rise to new complexion
or micro-state.
For example, suppose then are four particles distributed between two cells, say x and y, three
in x cell and one in Y cell. Then would give rise to four complexions if
cell x Abc abd acd bcd aaa
cell y d c b a a
Boltzmann Bose Einstein

They are distinguishable (Boltzmann) and only one complexion, if indistinguishable (Bose
Einstein)
Suppose there are indistinguishable particles. Consider with energy with degeneracy
These particles have to be distributed among states, we shall need partitions
to place the particles in sections, each section corresponding to an energy state. It means
is the degeneracy of the level. The problem is to distribute particles into sections
without any restrictions. The permutation of particles and partitions simultaneously
is given by But this includes the permutations of particles and
partions amongst themselves also, as both these groups are internally
indistinguishable.
Hence the actual number in which particles may be allocated in states is given by.
The thermodynamic probability is then given by.
…………..3.30
Using sterling’s formula and neglecting unity as compared to (since is very large) we
get
hence
As at the maximum
We have

As deduced in Boltzmann law, we have
……………..3.32
………….….3.33
Multiplying eqn. 2.32 by and eqn. 2.33 by and substract eqn. 2.31 from their sum we get
Since we have
……………3.34
Equation 2.34 is Bose – Einstein distribution law.
3.8 FERMI – DIRAC STATICS
In classical statics or in Bose-Einstein statistics there was no restriction to the number of

particle present in any energy state. On applying this concept to particles like electrons the
Pauli’s exclusion principle is invoked. Pauli’s exclusion principal says that two particles in an
atom cannot be in the same energy level. It means that not move than one particle can be
assigned to a particular energy state.
Suppose there be particles of energy in which there are gi energy states. If all the
particles are assumed to be identical and that only particles can be identical and that number
of ways ni particles can be distributed among gi states in that group can be written as
The thermodynamics probability is given by after considering all the groups in the
macrostate.

Hence,
Since is constant
At the maximum
or ……..…..3.35
From the derivation of Boltzmann distribution law we know
……………..3.36
…………..3.37
Multiplying eqn. 3.36 by , 3.37 by and substracting eqn. 3.35 we get
Since and and are arbitrary constants, the terms with in each of the parantheses
would equate to zero.
so,
or …………….3.38

Equation 2.39 gives Fermi-Dirac distribution law. Non or is large, both Bose-Einstein
and Fermi-Dirac distribution are rendered into the form
This is same as Boltzmann distribution law.
3.9 MOLAR PARTITION FUNCTION:
In the above discussion we have considered systems in which there are n distinguishable
particles distributed in different energy levels and f represents the molecular partition
function. But we have to deal with large scale systems, in which quantities are taken in gm-
moles.
Let us take a system which may be supposed to be constituted a large numbers of smaller
ones each with a gm-mole of the substance. That is, the individual unit here is not a molecule
but a mole. Let the energy levels allowed for the whole system (each one mole) be ,
…… and let there be such systems in all. In each of these systems there are, of course N,
Avogadro number of molecules. Then, the average energy E, of each such unit is
If Z is partition function of these systems, then
Now applying the same procedure in equation 3.24 the energy of the system will be
…………….3.39
From equation 2.23 (a) we have energy of one mole is
This is the relation we have in equation 3.39. Hence

The entropy then can be written as
This equation is useful for calculating entropy of the system, provided partition function is
known.
3.10 TERMINAL QUESTIONS
1. Define probability?
2. Derive Boltzmann Distribution equation.
3. What is Partition function.
4. Give the relation between partition function and thermodynamic functions.
5. Define the third law of Thermodynamics.
6. Define Bose-Einstein statistics.
7. Define Fermi – Dirac statics.
8. What is molar partition function?
9. Derive third law of Thermodynamics.

UNIT: 4 APPLICATIONS OF STATISTICAL

THERMODYNAMICS
CONTENTS
4.0 Introduction
4.1 Various Types of Partition Functions
4.2 Partition Function for Translational Energy
4.3 Internal Energy of a Monoatomic Gas
4.4 Sackur Tetrode Equation
4.5 Partition Function for Diatomic Gas Molecules
4.5.1 Rotational Partition Function
4.5.2 Vibrational Partition Function
4.6 Electronic Partition Function
4.7 Equipartition of Energy
4.8 Relation between Partition Function and Thermodynamic Functions
4.8.1 Partition Function and Internal Energy
4.8.2 Partition Function and Entropy
4.8.3 Partition Function and Work Function (A)
4.8.4 Partition Function and Pressure
4.8.5 Gibbs Function and Partition Function
4.8.6 Enthalpy and Partition Function
4.8.7 Heat capacity ( ) and Partition Function
4.8.8 Equilibrium Constant and Partition Function
4.9 Heat Capacity of Solids
4.10 Quantum Theory of Heat Capacity of Solids
4.11 Residual Entropy
4.12 Terminal questions
4.0 INTRODUCTION

Statistical thermodynamics analysis is facilitated through the use of the partition function.
This is great analytical tool. It is a fact that most often the molecules are associated with
energy of different types. In expressing the partition functions, all these forms of energy must
be taken into account.
4.1 VARIOUS TYPES OF PARTITION FUNCTIONS
Let us take a system containing molecules of identical physical nature with

different forms of energies. Such energies may include translational, rotational, vibrational
etc. Let the different types of energy be label t, r, v……….
The allowed energy-levels of the t types are , , …….., for r type are , ,
………., and so on for other types.
The Boltzmann distribution will be represented by.
Where , , …. etc. are partition functions appropriate to t, v, and r types of energy.
The total energy E of the system is
E= …………..
= ……….
= ….….…..4.1
If is the net molecular partition function, when every molecules is capable of freely taking
any number of types of energy, we can write

E= In f ………..4.2
Comparing equation 4.1 and equation 4.2 we have
f= , , …….. …...…..4.3
Now we can state that net partition function is the product of the separate partition functions
in respect of different types of energy independently associated with the molecules.
4.2 PARTITION FUNCTION FOR TRANSLATIONAL ENERGY
Let us consider motion of the particle along x- direction. The molecular partition function
due to translation in that direction is given by.
= .………..4.4
Here is statistical weight factor which is unity in this case for each translational level and
is the translation energy of molecule in x-direction.
So =
The translational energy is also quantized, though the differences in energy levels are quite
small. The particle would exhibit periodicity in translational motion only due to impacts on
the walls of the container. Consider a cube having length l. The molecules moving along x-
direction will repeat its motion each time it complete a path 2l. If is the wavelength
associated with the matter wave, we have
Where is an integer. The translational energy ( ) along the - axis is given by

Here is velocity and is momentum associated with the moving particle.
According to de Broglie, there is associated with any particle of mass moving with a
velocity in a single direction, a wavelength
Therefore
Hence
……………….4.5
Substituting the value of in equation 4.4
We get
……………4.6
Since energy levels are very close, the variation of energy may be taken to be continuous and
hence the summation may be replaced by integration.
Put

The value of
So …………..4.7
If we consider the translational motion in all the three directions (x, y and z), the molecular
partition function for translation would be
Since volume of the cube
V ..…………..4.8
In case of monoatomic gas, the molar partition function is
From Stirling’s formula
So,

……………4.9
4.3 INTERNAL ENERGY OF A MONOATOMIC GAS
Internal energy of a monoatomic gas can be obtained by making use of equation 4.9. In the
case of monoatomic gas, rotational and vibrational energies are absent and volume V is
constant.
We have from equation 4.8
Taking log of both sides of equation, we get
……………..4.10
Now

4.4 SACKUR TETRODE EQUATION
This equation evaluates the entropy of monoatomic gas
The translational entropy from entropy equation is
Since , we have
or ….……….4.11
The equation 4.11 is known as Sackur Tetrode equation.

4.5 PARTITION FUNCTION FOR DIATOMIC GAS MOLECULES
4.5.1 Rotational Partition Function
The rotational energy for diatomic molecules considered as rigid rotator is given
by
for jth quantum level – here
= moment of inertia
The partition function for rotational energy of a diatomic molecule is given by
As axis of rotation is defined by two coordinates, which means that there are two
rotational degree of freedom. Each quantum level of rotational will bring in two possible
modes of distribution of rotational energy. Thus the statistical weight factor ( ) in the
rotational level j is given by (2j+1). Hence the rotational partition function can be written as
……………….4.12
As the magnitude of I is comparatively large and the rotational levels are close we
may write equation 4.12 in the following form
….………..4.13
Where

Now suppose
Then
Then the equation 4.13 may be written as
…………..4.14
This value of is valid for hetero nuclear molecules like HCl, NO etc. For homo
nuclear molecules like O16 O16, N14 N14 etc where the molecules when reversed becomes
indistinguishable from initial state; in that case the partition function is to be divided by the
number of symmetry 2. That is
……………..4.15
That means when symmetry is the partition function is given by
…………………..4.16
Now the rotational energy of a mole of a diatomic gas is given by the relation
……………….4.17
4.5.2 Vibrational Partition Function
The partition function for vibrational energy of a diatomic molecule is given by

Where is statistical weight factor which is unity for vibration levels.
Hence …………………….4.18
The vibrational energy of diatomic molecule is given by
In this expression is fundamental frequency of vibration and n is an integer 0, 1,

2….. etc.
Now the vibrational partition function may be written as
……)
………………4.19
In this expression the quantity is very small and as a first approximation,
….………….4.20
4.6 ELECTRONIC PARTITION FUNCTION
Many monoatomic as well as polyatomic molecules have multiple electronic ground

states. In other words, in their normal states there are two or more electronic levels with
energies so close together that they may be considered as a single level with a statistical

weight factor greater than unity. In addition to this, there may be some excited electronic
states whose energy may be considerably greater than that of the ground states. As we
increase the temperature, such excited states become more and more occupied. Hence
electronic partition function is greater than unity and varies with temperature. The statistical
weight factor for each electronic level, normal or excited is equal to (2j+1), where j is the
resultant quantum number of the atom in the given state.
Now electronic partition function
Here is the energy of the electronic state is excess of the lowest state i.e., ground
state. In the ground state = 0 therefore become unity.
4.7 EQUIPARTITION OF ENERGY
According to law of equipartition of energy, the total energy of a molecule is divided

equally amongst the various degrees of freedom of the molecule, for each degree of freedom
of the molecule, for each for each per molecule or per mole.
The different kinds of energy possessed by a molecule are usually expressible in
squared terms for each degree of freedom. Thus the kinetic energy is of the form ,
rotational energy, , vibrational energy and so on. Let there be r

terms, associated with the energy of a molecule.
Then total energy E of the molecule is given as
…….
……………..+
The partition function of the molecule,
……………

………
Put
or
putting the value , etc…. in the above equation
we have
f= =
Hence . . . ………
. ……..)
.Q ………………4.21
Where ………)
It is to be remembered that etc and hence Q would not contain .
We know

Hence . )
………………….4.22
Equation 4.22 means that if the energy would be expressed as sum of r squared terms, the
average energy e is r x . Hence for each degree of freedom (square term) the energy is
This is principle of equipartition of energy.
But in some instances such conditions are not fulfilled. In the case of a gas in a
gravitational field. In this case the energy is not a square term but mgh, the mean
gravitational potential energy is not . Similarly in these cases where energy taken up is
quantised, the energy associated with them is not a linear function of temperature.
In the case of crystals, say of metals, the atoms have only vibration motion. The
vibration may occur in three directions and each mode has two degree of freedom. Hence
x 3 x 2=3kT
or …………….4.23
This is known as Dulong-Petit’s law. Equation 4.23 means heat capacity should be
independent of temperature. But considerable variation with temperature has been noticed.
That is, the principle of equipartition of energy has failed.

4.8 RELATION BETWEEN PARTITION FUNCTION AND THERMODYNAMIC

FUNCTIONS
4.8.1 Partition Function and Internal Energy
The internal energy of a system of n molecules is given by
……..
……………..4.24
But we know
Hence
So …………………4.25
From equation 4.25 equation 4.24 becomes
……………..4.26
For one mole, n may be replaced by Avogadro’s number N. hence

…………………4.27
The average energy of each molecule is then written as
…………..4.28
4.8.2 Partition Function and Entropy
The entropy equation is terms of partition function can be derived as follows.
The Boltzmann distribution law may be written as
Then ……………4.29
Now the relation between entropy and probability is
(W=mathematical probability)
We know thermodynamic probability (W is proportional to mathematical probability (P).
(where B is constant)
Since ……………..4.30
Substituting the value of from equation 4.29,
We have

As
……………….4.31
Differentiating equation 4.31 at constant volume
We get
Since
or
From first and second law of thermodynamics
We have

Hence
So ………………..4.32
So partition function can be written as
And
Now from equation 4.31
; As ..….…………..4.33
Substituting the value of E we get
4.8.3 Partition Function and Work Function (A)
We know that work function is defined as
By substituting the value of E and S
From above we get

Since ………………4.34
4.8.4 Partition Function and Pressure:
or
Since
So
………………….4.35
4.8.5 Gibbs Function and Partition Function
We know
4.8.6 Enthalpy and Partition Function
By definition

.…………..4.36
4.8.7 Heat capacity ( ) and Partition Function
By definition
Substituting the value of E in this expresstion
….…………4.37
4.8.8 Equilibrium Constant and Partition Function
The equilibrium constant of a chemical change can also be evaluated from the
partition function of the reactants and products.
We know from Gibbs potential
(As , the work function)
So
for a perfect gas
From our earlier discussion we know
…from equation ……………4.38
Hence

Since
Hence
……………….4.39
Now total energy of a molecule can be written as
In this expression is translational energy, is rotational energy, vibrational energy,

electronic energy and is zero energy i.e., the energy possessed by the molecule at the
ground state at . Usually the zero of energy to which all other energies are referred
is the energy of dissociated atoms infinite distance apart, at 0K. The molecule at 0K would
possess some energy which is zero-energy, .
Now molecular partition function of a gas is given by
0 0 0 0
x x x x
0
x x
0 0 0 0
Where and
0
Putting x =f`
We get

Substitute this value of partition function in equation 4.39,
………………4.40
Put and at standard state, where the value of G will be we have the
expression
……………..4.41
Now let us consider a general gaseous equation in which a moles of A and b moles of B
reacting to give c moles of C and d moles of D, we have,
cC+dD
In this equilibrium
Substituting the value of , , , and
As described in equation 3.40, we get
.
…..………..4.42
Here
and
but we know

……………..4.43
Hence equilibrium constant is given by the relation
….…………4.44
4.9 HEAT CAPACITY OF SOLIDS
We have discussed above that if the energy could be expressed as sum of r squared
terms, the average energy E is rx1/2KT. Hence, for each degree of freedom the energy is ½
KT. This is law of equilibrium of energy.
But in some instances such conditions are not fulfilled. For example in the case of gas
in gravitational field, where potential energy is not a squared term but mgh, the mean
gravitational potential energy is not ½ KT. Similarly, in these cases where energy taken up is
quantized, the energy associated with them is not linear function of temperature.
We have seen in our earlier discussions that in crystals, the atoms have only vibratory
motion. In that case vibration may occur in three directions and each mode has two degree of
freedom.
Hence
or
The above equation indicates that heat capacity is independent of temperature. However,
considerable variation in heat capacity of solids with temperature has been noticed, that
reveals the failure of the principle of equilibrium of energy.
4.10 QUANTUM THEORY OF HEAT CAPACITY OF SOLIDS
The atoms in the crystalline solids are arranged in one set pattern and have only
vibratory motion, the electronic levels are assumed to be excited. For each atom, there are
three vibrational degrees of freedom, therefore, for one mole of crystal of atoms i.e., one

gm. Mole, there are degrees of freedom. The vibrational motion is considered harmonic,
so that an oscillating atom at the nth level will have the energy,
Where is the fundamental frequency? Einstein (1907) proposed the quantum treatment of
the specific heat of solids. He considered that N atoms of the crystal were all independently
vibrating with common frequency . Then the partition function for the whole crystal is
given by,
Taking log of both the sides we get,
……………4.45
We have earlier calculated the vibrational energy of a mole of diatomic gas equal to
..…………..4.46
Then the heat capacity is given by

….…………4.47
This is known as Einstein’s equation. At fairly high temperature, it is clear from the above
equation that Cv=3R, which is classical result of Dulong and Petit’s. This led Debye to
produce certain modifications in the assumptions of Einstein.
Debye suggested that all the atoms were not oscillating with the same frequency as
suggested by Einstein. He pointed out that the atoms were vibrating with a spectrum of
modes of vibrations ranging from (frequency at ground state) to some maximum
frequency . The difference between and is so large that it may assume that is
practically zero. The modes of vibrations are limited in number.
The modes of vibration of a radiation between and + in volume V is given by
Here C is average velocity of elastic waves in the crystal. The total modes of vibration
in the crystal is 3N. Hence,
The total modes of vibration in the crystal are then
Then ….…..……..4.48
We have therefore

…....………..4.49
The vibrational partition function is given by
The paritition function of the whole crystal may be obtained by attaching to each
frequency the partition function of the single oscillation i.e.,
…..…..4.50
At very low temperature the second term is very small and can be neglected. We have then
…………….4.51
Now ..…….………4.52
Substituting the value from above in the energy equation we get

The heat capacity is then given by
……………4.53
Equation 4.53 is known as Debye’s specific heat relation at low temperature. Expressing
, the above equation becomes
…………….4.54
Since for a given substance the value of is constant, hence varies with at
low temperature. This law is known as Debye’s law.
4.11 RESIDUAL ENTROPY
Entropies calculated using third law of thermodynamics are called thermal entropy.
However statistical entropies are more rigorous. It is found that the thermal entropies are
smaller than the statistical entropies and deviate ranging from 3.1 to 4.83 JK-1 mol-1. We thus
conclude that entropies of substance (such as H2, D2, NO, N2O, H2O etc.) are not zero at 0K
in accordance to third law, but finite. These entropies are called residual entropies.
We know that S=klnW=kln1=0 which is true according to third law of

thermodynamics. The occurrence of residual entropy at 0K in the substances as mentioned
above, suggests that the lowest energy level in these systems is degenerate. This approach has
been used to explain the residual entropy. The existence of residual entropy is a crystal at 0K
is presumably due to the alternative arrangements of molecules in the solid. Such
arrangements are shown in fig. 4.1 for CO and N2O :
CO CO CO CO CO CO OC OC
CO CO CO CO CO OC OC CO
NNO NNO NNO NNO NNO NNO ONN ONN
NNO NNO NNO NNO NNO ONN ONN NNO
(a) (b)
Fig. 4.1 Alternative molecular arrangements (a) perfect crystal (b) actual crystal

Since both the arrangements are equally likely. From Boltzmann entropy equation,
S=klnW
But W=2N (N is Avogadro’s number)
We get
S=kln2N
=Nkln2
=Rln2
=(8.314JK-1 mol-1) (2.303) (0.3010)
=5.76K-1 mol-1.
As the residual entropies are found experimentally to be less than this value, it is
evident that the two alternative orientations of CO and N2O molecules in the solid state at 0K
are not completely random.
The occurrence of residual entropy in ice is also attributed to the molecular disorder at 0K. In
ice crystal, each ice molecule is tetrahedrally coordinated to four other water molecules by
hydrogen bonds. This enables that crystal to exist in many configurations at 0K. For H2 and
D2 the thermal entropies at 0K are less than the corresponding statistical entropies. The
calculation of the statistical entropy assumes that there exists equilibrium between ortho H2
and para H2 at all temperatures. The of ortho H2 and para H2 is found to be 18.37 JK-1
mol-1 in the vicinity of 0K. when this value is added to the thermal entropy (calculated from
heat capacity measurements), the agreement with the statistical entropy is very good.
1. Define various types of partition functions.

2. Give partition function for translational energy.
3. Give Sackur Tetrode Equation

4. Define partition function for diatomic gas molecules.

5. Give relation between partition function and thermodynamic functions.
6. Explain quantum theory of heat capacity of solids.

UNIT 5: THEORIES OF REACTION RATE
CONTENTS
5.1 Objectives Introduction
5.2 Introduction
5.3 Theories of rate of reaction
5.3.1 Collision theory of reaction rate
5. 3.1.1 Classical collision theory
5.3.1.2 Modified collision theory
5.3.1.3 Limitations of collision theory
5.3.2 Transition sate theory or activated complex theory
5.3.2.1 Statistical mechanics formulation of activated complex theory
5.3.2.2 Thermodynamic formulation of activated complex theory
5.3.2.3 Comparison of activated complex theory and collision theory
5.4 Theory of unimolecular reactions
5.4.1 Lindemann’s theory
5.4.2 Hinshelwood’s theory
5.4.3 RRKM theory
5.5 Potential energy surface
5.6 Summary
5.7 Self-Assessment Questions (SAQ)
5.8 Glossary
5.9 Answers to SAQ’s
5.10 References
5.11 Terminal Questions

5.1 OBJECTIVES
After reading this unit, you will be able to:
• Define rate of reaction.

• Explain collision theory of reaction rate along with its limitations.
• Describe the transition state theory that includes both its thermodynamical and
statistical formulation.
• Write Lindemann’s mechanism of unimolecular reaction.
• Give the concept of Hinshelwood’s treatment of the unimolecular reactions.
• Write short on potential energy surface.
5.2 INTRODUCTION
The present unit deals with theories of reaction rate that includes different theories like
collision theory, transition sate theory and theories of unimolecular reactions. Unimolecular
theories include Lindemann’s theory, Hinshelwood’s theory and RRKM theory. In addition
to these theories of reaction rate, we will discuss about potential energy surface.
5.3 THEORIES OF RATE OF REACTION
Rate of reaction is also known as reaction rate. It is defined as the rate of change of
concentration of reactants or products per unit time. As the reaction proceeds, the
concentration of reactant decreases while the concentration of the products increases.
Therefore the rate of reaction for a general reaction is given by:
A B
r = – d [A]/dt = + d[B]/dt
where (–) sign shows decrease in concentration of reactant A while the (+) sign shows
increase in the concentration of product B, infinitesimally small change in concentration is
represented by d. The rate of reaction is expressed in mole litre–1 time–1. Generally the time
–1
taken is in seconds hence the rate is expressed in mol l s –1. According to rate law, rate of
reaction is directly proportional to the concentration of the reactants, raised to some power.
For a general reaction:

A B
r = k [A]
where k = proportionality constant = rate constant or velocity constant of a reaction
The concentration terms in the rate law expression are raised to some power, this power is
known as order of reaction. This is the basic idea of chemical kinetics. Now let us discuss
different theories of reaction rate
5.3.1 Collision theory of reaction rate
The collision theory of reaction rate is developed by Arrhenius and van’t Hoff. According to
collision theory of reaction rate, reactant molecules must collide with each other that result in
a chemical reaction. There are two theories of collision: one is classical collision theory while
the other is modern collision theory. Let us discuss these theories one by one:
5. 3.1.1 Classical collision theory
According to classical collision theory, gaseous reactant molecules collide with each other
that result in a chemical reaction and the rate of this reaction is directly proportional to the
number of colliding reactant molecules. Let us consider a reaction in which reactant X and Y
reacts or collides to form product XY. Therefore according to classical collision theory:
X+Y XY
Rate of reaction is proportional to [X] [Y]
Where [X] and [Y] is the concentration of reactant X and Y. Let us consider a collision
between two gas molecules C and D. The number of collision occurring between two gas
molecules per second per centimeter cube is given by Z which is known as collision number.
Z for bimolecular collision is given by ZCD:
ZCD = nC nD (dCD)2 (8ΠRT/ µ)1/2 ………….. (1)
Where nC is the number of gaseous molecule (C), nD is the number of gaseous molecule (D),
dCD is the average collision diameter, R is gas constant, T is absolute temperature (in Kelvin)
and µ is reduced mass. The average collision diameter (dCD) is given by (dC + dD)/ 2 while the
reduced mass µ is given by mC mD/ mC + mD, where mC is molecular mass of gas C and mD is
molecular mass of gas D. Hence collision number Z can be written as:

ZCD = nC nD {(dC + dD)/ 2}2 {8ΠRT (mC + mD) / mC mD}1/2 ………… (2)
On applying chemical kinetics to bimolecular collision among gaseous molecule C and D,

rate constant (k) expression is given by:
k = Z e – E/ RT ………….. (3)
In order to check the validity of equation 3, reaction between hydrogen (H2) and iodine (I2) is
taken into consideration. It has been observed that at 556K, the rate constant which is
obtained experimentally is 3.7 × 10– 7. The value of rate constant using equation 3 is
calculated and is equal to 5.5 × 10– 7. The value of rate constant thus obtained is in good
agreement with the experimental value that proves the validity of the rate constant expression
for bimolecular collision between hydrogen and iodine. Similar agreement has also been
observed in case of reaction or collision between nitrogen and oxygen.
But in certain reactions like polymerization of 1,3-butadiene, polymerization of two

molecules of ethylene, it was found that the experimental rate constant is less than that
obtained from equation 3. Similarly there are certain reactions in which experimental rate
constant is much higher than obtained from equation 3 like in case of chain reactions. As it is
clear from above that rate constant given in equation 3 is not applicable to all reactions but
applicable only to simple gaseous reactions. Hence the classical collision theory needs
modifications and a collision theory known as modified collision theory is proposed.
5.3.1.2 Modified collision theory
Simple collision theory was modified by Arrhenius and a modified collision theory was
proposed. The theory considers several points:
• All collisions among the molecules are not responsible for causing a chemical
reaction. Only those collisions are effective (workable) which possess a minimum
amount of energy known as activation energy for a chemical reaction to occur. It has
been observed that when the colliding molecule possess energy equal to or greater
than activation energy then only the chemical reaction takes place otherwise not . It
means that when energy of colliding molecules is lower than the activation energy
then no chemical reaction takes place. Therefore in the rate expression for
bimolecular collision (equation 3), a new term called steric factor or probability
factor is introduced. Therefore equation 3 is written as:

k = PZ e – E/ RT ………… (4)
where P is the probability factor or steric factor having value from 1 to 10– 8. It has been
found that probability factor is related to entropy change by the expression:
P1/P2 = e ∆S/ R ……… (5)
Where P1 is probability factor for forward reaction and P2 is probability factor for backward
reaction (condition is that the reaction is reversible).
• The colliding molecules should must possess a proper orientation required for the
reaction to occur. In simple words, we can say that only effective collision (collision
having correct orientation) leads to a chemical reaction. The proper orientation means
that there must be direct contact among the atoms which are involved in bond
breaking and bond forming. This will become more clear by Figure 1 given below:
Figure 1. Diagram showing effective and ineffective collision
• In case of collision between same molecules, pre-exponential factor A is given by

expression:
A = (3.89 × 1029) P d2 (T/M) ½ ……… (6)
Where T is absolute temperature, M is molar mass (gram per mole), P is probability factor
and d is average collision diameter. Similarly for different molecules undergoing collision, d
is replaced by d12 which is given by (d1 + d2)/ 2 while M is replaced by M1M2/ M1+M2. For
this A is given by:
A = (2.75 × 1029) P (d12)2 (T/ µ) ½ …….. (7)
Therefore it is finally concluded that only those collisions are effective (leads to a chemical
reaction) in which colliding molecules must possess proper orientation and energy.
5.3.1.3 Limitations of collision theory
Though the theory is applicable in case of simple gas molecule but it suffers certain
limitations:

• Classical collision theory do not consider the internal motion of the molecules taking
part in a collision which leads to a chemical reaction.
• In order to relate the probability factor with the properties of the colliding reactant
molecules, several attempts were made but satisfactory results were not obtained.
• As modified collision consider the concept of classical collision theory which is based
on classical mechanics that require modifications.
• Only kinetic energy of the reactant molecules is considered not the vibrational or
rotational energy. The reason of not taking this energy is not clear.
5.3.2 Transition sates theory or activated complex theory
Transition state theory (TST) is also known as activated complex theory (ACT) or absolute
reaction rate theory. This theory was proposed by Pelzer and Minger but later on by Eyring,
Evans and Polanyi. As by using this theory, we can find the absolute value of rate constant by
using physical properties therefore the theory is also known by name absolute theory. This
theory considers the quantum mechanics instead of classical mechanics. According to
transition sate theory, collisions among the reactant molecules do not lead to chemical
reaction but there is change in potential energy of the reactants as it changes when reactants
approaches from infinite distance in order to react and then forms products. Reactants having
sufficient energy from infinite distance approach each other and form an activated complex
which further forms the products. The reaction is given below:
Reactants ↔ Activated complex → Products
For example, there are two reactants X2 and Y2, they reacts to form an activated complex
which together forms products.
Activated complex is a special molecule that possesses highest energy or most unstable
molecule that possesses three translational degree of freedom in which forth degree of
freedom is along the reaction coordinate. It has transient existence. In activated complex, as
the bond among the atoms are weak hence one vibrational degree of freedom is less than the
normal molecule. This vibrational degree of freedom changes to translational degree of
freedom hence possess forth degree of freedom (translational). On the basis of transition state
theory, energy profile diagram is given in Figure 2.

Figure 2. Energy profile diagram for exothermic reaction
It is clear from Figure 2 that energy of products is less than energy of the reactants, therefore
E products –E reactants is negative. This shows that change in energy is negative which indicates
that during the formation of products, some energy is released (exothermic). Figure 2 also
shows that activation energy (Ea) is the difference between the energy of the activated
complex and energy of the reactants. Similarly for endothermic reaction, the energy profile
diagram is given below in Figure 3.
Figure 3. Energy profile diagram for endothermic reaction
Now we will study the formulation of activated complex theory in terms of statistical
mechanism and thermodynamics. Let us discuss these formulations one by one.
5.3.2.1 Statistical mechanics formulation of activated complex theory
It is also known as statistical formulation of reaction rate. In order to show statistical

formulation of reaction rate, the following mechanism is considered.
Where X2Y2* represents activated complex. It is clear from the above mechanism that rate of
reaction (decomposition) is directly proportional to the concentration of the activated

complex [X2Y2*]. The rate of decomposition of activated complex also depends upon the
number of activated complex that cross the energy barrier per unit time. This is called
frequency of crossing the energy barrier and is given by the ratio of average velocity of
activated complex to the length (d) at the highest energy level (i.e. activated complex energy
state). According to kinetic theory of gas, the average velocity (vavg) is given by:
vavg = ( kT/ 2Πm )1/2 ……. (8)
where k is Boltzmann constant, T is absolute temperature, m is the mass of the activated

complex. Therefore frequency of crossing the energy barrier is given by: ( kT/ 2Πm )1/2 / d
In addition to concentration of activated complex and frequency of crossing the energy

barrier, the rate of reaction (decomposition) also depends upon the chance (probability) of
crossing the energy barrier by the activated complex. The probability is shown by expression:
d (2ΠmkT)1/2 /h
Therefore on multiplying all these factors, rate of reaction (decomposition) is given by rd:
rd= [X2Y2*] × ( kT/ 2Πm )1/2 / d × d (2ΠmkT)1/2 / h
rd = (kT/h) × [X2Y2*]
Here kT/h refers to universal frequency. Now it is clear that activated complex is formed
from reactants therefore rate of formation (rf) is directly proportional to the concentration of
the reactant X and Y. Therefore:
rf = kf [X] [Y]
As activated complex has transient existence or it is an intermediate therefore steady state

approximation is applied. According to steady state approximation, the rate of formation and
decomposition of an intermediate (in this case activated complex) is equal. Hence: rf = rd
kf [X] [Y] = (kT/h) × [X2Y2*]
kf = (kT/h) × [X2Y2*] / [X] [Y]
K* is equilibrium constant and is given by:
K* = [X2Y2*] / [X] [Y]
kf = (kT/h) × K* ……… (9)

On applying statistical mechanism: K* = (θ*/ θX θY) × e – ∆Eo / RT
Where θ*, θX and θY are the partition function of reactants X, Y and activated complex
respectively. – ∆Eo is the change in energy (zero point). On putting the value of K* in equation
(9), we obtain:
kf = (kT/h) × (θ*/ θX θY) × e – ∆Eo / RT ……. (10)
5.3.2.2 Thermodynamic formulation of activated complex theory
By using thermodynamics, we can express the rate constant of the reaction (mechanism)
which is according to activated complex theory. This expression of rate constant containing
thermodynamic functions is called thermodynamic formulation of reaction rate or activated
complex theory. On considering the general mechanism:
As discussed earlier that in statistical formulation of reaction rate, rate constant is given by:
kf = (kT/h) × K* ……. (11)
According to second law of thermodynamics, – ∆G = RT ln K
Where T is absolute temperature and R is gas constant. On applying this reaction isotherm on
first step of the mechanism given by activated complex theory we obtain:
– ∆G* = RT ln K* ……… (12)
From the definition of free energy, when there is change in the state of the system, change in
free energy is given by relation: ∆G = ∆H – T ∆S
Applying to activated complex theory at constant temperature: ∆G* = ∆H* – T ∆S*
On putting the value of ∆G* in equation 12, we obtain: – (∆H* – T ∆S*) = RT ln K*
ln K* = – (∆H* – T ∆S*) / RT
K* = e – (∆H* – T ∆S*) / RT
On putting the value of K* in equation 11, we obtain: kf = (kT/h) × e – (∆H* – T ∆S*) / RT
kf = (kT/h) × e – ∆H* / RT × e ∆S* / R

……… (13)

Equation 13 is known as Wyne- Jones and Eyring equation or simply Eyring equation.
Equation 13 represents thermodynamic formulation of reaction rate in which rate expression
contains thermodynamic functions. For gaseous reactions
ln kf = ln kT/h – ∆H* / RT + ∆S* / R
On differentiating the above equation with respect to temperature, we obtain:
dln kf /dT = ∆H* / RT2 + 1/T
dln kf /dT = (∆H* + RT )/ RT2 …… (14)
According to Arrhenius equation which shows the dependence of rate constant on

temperature is given by expression: k = A e– Ea/ RT
On taking log and differentiating with respect to temperature, we obtain:
dln kf / dT = Ea / RT2 …….. (15)
On comparing equation 14 and 15, we obtain: (∆H* + RT)/ RT2 = Ea / RT2
∆H* = Ea – RT
On putting the value of ∆H* in Eyring equation, we obtain: kf = (kT/h) × e – (Ea – RT) / RT × e ∆S*
/R
5.3.2.3 Comparison of activated complex theory and collision theory
From collision theory: kf = PZ e – E/ RT
On putting the value of kf in Eyring equation, we obtain:
Z e – E/ RT = (kT/h) × e – ∆H* / RT × e ∆S* / R
If ∆H* is approximately equal to E, then ∆H* ≈ E, therefore by replacing ∆H* by E, we

obtain:
PZ e – E/ RT = (kT/h) × e – E / RT × e ∆S* / R
∆S* / R
PZ = (kT/h) × e
∆S* / R
P = (kT/hZ) × e
The value of probability factor is found to be in between 10–5 to 10–10. The value of P is less
than the value obtained from collision theory which shows that reaction proceeds more

slowly on the basis of activated complex theory. ACT provides the physical significance of
probability factor by relating it to entropy of activation ∆S*.
It has been found that for reactions between simple molecules, both collision theory and
activated complex theory give same results but when reaction occurs in between complex
molecules, activated complex theory give satisfactory result while collision theory fails.
5.4 THEORY OF UNIMOLECULAR REACTIONS
Before coming to the theories of unimolecular reactions, let us discuss about the unimolecular
reactions. Reactions in which one reactant molecule forms the activated complex or one
reactant molecule forms the products. As the name indicate unimolecular which indicates one
reactant molecule. Unimolecular reactions are classified into two types: elementary
unimolecular reaction and free radical unimolecular reactions. Let us discuss these reactions
one by one:
• Elementary unimolecular reactions: The reaction in which products are formed from
reactants in a single step that involve a formation of an activated complex. For
example, formation of propylene from cyclopropane.
• Free radical unimolecular reactions: In these reactions as the name suggests, free
radicals are formed as an intermediate instead of single activated complex. Several
decomposition reactions comes under this category.
Now coming to theories of unimolecular reactions. Various theories are there which explain
the mechanism of unimolecular reactions which include Lindemann’s theory, Hinshelwood
theory and RRKM theory. We will now discuss all these mechanism or theories on by one:
5.4.1 Lindemann’s theory
This theory was proposed by F.A Lindemann and subsequently supported by Christiansen
According to Lindemann, the following mechanism is proposed for conversion of A into
Products
(i) A + A A* + A (Collisions causing activation of molecules): rate constant k1
(ii) A* + A A + A (Collisions causing deactivation of molecules): rate constant k2
(iii) A* Products (Formation of products or decomposition): rate constant k3

Here A is reactant molecule, A* is an energized or activated molecule having sufficient

energy to form products but A* is not an activated complex. According to Lindemann’s
mechanism, reactant molecules collide with each other and form A* by the process known as
activation which is shown by step one having rate constant k1. The energized molecule has
two possibility whether it forms products by the process of decomposition which is shown by
step three having rate constant k3 or may get deactivated to form back the reactant molecules
which is shown by step two having rate constant k2. As there is time gap between activation
process and decomposition process therefore in this time gap, deactivation of energized
molecules takes place. As A* is an intermediate therefore steady state approximation is
applied to it.
Rate of formation of A* = d[A*]/ dt = k1 [A]2 – k2 [A][A*] – k3 [A*]
On applying steady state: d[A*]/ dt = 0
Hence: k1 [A]2 – k2 [A][A*] – k3 [A*] = 0
k1 [A]2 – k2 [A][A*] – k3 [A*] = 0
k1 [A]2 = k2 [A][A*] + k3 [A*]
k1 [A]2 = [A*] (k2 [A] + k3)
[A*] = k1 [A]2 / k2 [A] + k3
We know that rate of reaction is proportional to the concentration of the energized molecule
as in this step formation of products takes place. Therefore:
r = k3 [A*]
On putting the value of [A*] from above expression we obtain: r = k3 k1 [A]2 / k2 [A] + k3
For reactions taking place in gaseous phase, the concentration term is replaced by pressure
terms. Hence: r = k3 k1 P2 / k2 P + k3
Two case arises:
• Case 1: At high pressure: P >> k3, therefore k3 can be neglected.

r = k3 k1 P2 / k2 P
r = k3 k1 P / k2

This expression shows that at high pressure, rate of reaction is directly proportional to
pressure of a gas raised to power one or we can say it obeys first order kinetics.
• At low pressure: P << k3, therefore k2 P can be neglected.

r = k3 k1 P2 / k3
This expression shows that at low pressure, rate of reaction is directly proportional to
pressure of a gas raised to power two or we can say it obeys second order kinetics.
Though the theory given by Lindemann is quite satisfactory in explaining the mechanism of
unimolecular reactions but there are some drawbacks:
• According to Lindmann, rate expression comes out to be: r = k3 k1 P2 / k2

P + k3
If reaction obeys first order kinetics: r = k [A]
k [A] = k3 k1 [A]2 / k2 [A] + k3
On taking reciprocal: 1/ k [A] = (k2 [A] + k3)/ k3 k1 [A]2
1/ k = (k2 [A] + k3)/ k3 k1 [A]
1/ k = (k2 [A] / k3 k1 [A]) + (k3/ k3 k1 [A])
1/ k = (k2 / k3 k1) + (1/ k1 [A])
Graph is plotted between 1/ k versus 1/ [A], result straight line with slope 1/k1 and intercept
k2 / k3 k1. But instead of straight line there is deviation from it. Lindemann’s drawback leads
Hinshelwood to put forward his theory. Let us now discuss Hinshelwood’s theory of
unimolecular reactions.
5.4.2 Hinshelwood’s theory
Hinshelwood on the basis of statistical mechanism determines the chance or probability of a

reactant molecule to become active by collision. Hinshelwood provides an analytical
formulation of Lindemann’s theory. According to Hinshelwood, the probability of
deactivation of energized molecule (A*) formed by collisions of reactant molecules (A) is
equal to one. According to Hinshelwood, rate constant (k) is given by expression:
k = {Z/(S–1)!} × (E/kT) S–1 e –E/kT

where Z is collision number, S is number of vibrational degree of freedom the value of which
is obtained by hit and trial method, k is Boltzmann constant , T is absolute temperature and E
is energy of activation. For the molecule having one vibrational degree of freedom, the above
expression of k reduced to:
k = Z e –E/ kT
It has been found that for large value of S, pre-exponential factor (A) depends strongly on the
temperature. Though the theory is successful but there are certain limitations:
• The theory does not show the dependence of pressure on rate constant.
• From Lindemann’s theory on which Hinshelwood theory is based, the variation of 1/
k versus 1/ [A] should be straight line but there are deviations in the curve which was
not explained by Hinshelwood.
5.4.3 RRKM theory
RRKM theory of unimolecular reaction stands for Rice- Rampsberger- Kassel- Marcus
theory. This is one of the most refined and successful theory of reaction rate. According to
RRKM theory which on the basis of activated complex theory considered all vibration of
energized molecule (A*) as vibrational frequency and all rotation of energized molecules as
rotational constant. RRKM proposed the mechanism which is as follows:
(i) A + A A* + A (Collisions causing activation of molecules): rate constant k1
(ii) A* + A A + A (Collisions causing deactivation of molecules): rate constant k2
(iii) A* A# (Conversion of energized molecule into activated molecule): rate constant

k3
(iii) A# Products (Formation of products or decomposition): rate constant k4
Here A* is energized molecule and A# is activated molecule. Activated molecule forms

product and possess minimum amount of energy known as activation energy. According to
RRKM theory:
dk1/k2 = N c(ɛc) e– ɛc / kT dɛc/ fc
Where N c(ɛc) is the energy density of the degree of freedom that contribute to bond
breaking, fc is the partition function where c represents critical energy contribution and ɛc is
critical energy of the activated complex which is more than zero point energy. The critical

energy ɛc is equal to the sum of energies of motion along the reaction coordinate and energy
associated with vibrations and rotations. It has been found that at high pressure, RRKM
theory give the same expression of rate constant as given by activated complex theory.
Therefore we can say that at high pressure, RRKM theory get reduced to transition state
theory or activated complex theory. At high pressure, thermal Boltzmann distribution is
maintained at all energies. At high pressure, the expression for rate constant is:
k = (kT/h) × (f#/fA) × e –E/kT
where f# represents partition function of activated complex and fA represents partition

function of reactants. This is all about the theories of reaction rate.
5.5 POTENTIAL ENERGY SURFACE
Potential energy surface is short is also known as PES. The concept of PES is applied to
several branch of science that includes physics, chemistry. The properties of structure
comprising of atoms are predicted by applying the concept of PES. This surface represents
the energy of a system which is generally based on the position of the atoms. Energy profile
diagram also refers to potential energy diagram or PES represents the variation of energy
with reaction progress. In potential energy diagram or curve, there is a point at which
potential energy is maximum along the reaction coordinate. This point is known as saddle
point which corresponds to transition state. There are stationary points in the curve that
represents stable chemical species or species with lowest energy. On the basis of bond length
extension in the activated complex in comparison to bond length of the reactants or product,
potential energy surface is classified into two types: attractive potential energy surface and
repulsive potential energy surface. In order to define these types, let us take a general
reaction: X + Y-Z X-Y + Z
The bond length of newly formed bond (rXY) is equal to the difference of the bond length of
XY in the transition state ((rXY)* and bond length of XY in the product molecule (r1XY) i.e.
rXY = rXY* – r1XY . In this reaction there is cleavage of Y-Z bond thus rYZ = rYZ* – r1YZ, where
r1YZ refers to bond length of Y-Z bond of the reactants. Potential energy surface is said to be
attractive when rXY > rYZ for those reactions in which heat is evolved. Here transition state is
achieved by bringing the reactants close to each other. For example, K and Br2 to form KBr
and Br. Potential energy surface is said to be repulsive when rXY < rYZ for those reactions in
which heat is evolved. Here transition state is achieved by the separation of the products. For

example, H and Cl2 to form HCl and Cl. The potential energy diagram is given in Figure 4 in
which AB represent lowest energy path. Point o gives the potential energy of these atoms X,
Y and Z which are well separated from each other.
Figure 4. Potential energy surface for reaction X + Y-Z X-Y + Z
For the reaction in which energy is absorbed, the PES is said to be attractive when
translational energy of the reactants is effective. The PES is said to be repulsive when
vibrational excitation of the reactants is effective. The concept of PES is very useful in
determining the geometry of a molecule and kinetics of a chemical reaction by considering
the position of the atoms.
5.6 SUMMARY
In this unit we have discussed the theories of rate of reactions that includes collision theory
and activated complex theory. Collision theory is discussed under two headings: classical
collision theory and modern collision theory. In activated complex theory, we discussed its
statistical and thermodynamical formulation of reaction rate. Then we move forward to
unimolecular reactions where we studied about the theories of unimolecular reactions which
include Lindemann’s mechanism, Hinshelwood mechanism and RRKM mechanism. In
addition to all these, we also studied about the potential energy surface that plays an
important role in determining the molecular structure.
5.7 SELF-ASSESSMENT QUESTIONS (SAQ)
Fill in the blanks:
1. According to collision theory, the molecules must undergo ……….

2. Rate of reaction in a collision process is directly proportional to the ………. of the

colliding reactant molecules.
3. The number of collision occurring among gas molecules (reactants) per second per
centimeter cube is given by ………
4. The value of probability factor or steric factor obtained from collision theory varies from
……….
5. Classical collision theory is applied to ………. gas molecules.
6. Probability factor is related to ………. change of the reaction.
7. For effective collision, molecules must have proper ……….
8. ………. and ………. developed the collision theory of reaction rate.
9. According to ACT, reactants before forming the products forms an intermediate known as
……….
10. The energy of the activated complex is ………. in the energy profile diagram.
11. The statistical formulation of reaction rate is given by ……….
12. The thermodynamic formulation of reaction rate is given by ……….
13. Reaction isotherm is given by the expression ……….
14. ………. theory explain the physical significance of probability factor.
15. The value of steric factor obtained from activated complex theory is in the range ……….
16. According to Lindemann’s hypothesis, at low pressure the unimolecular reaction obeys
………. order kinetics.
17. At high pressure, unimolecular reactions obeys ………. order kinetics according to
Lindemann.
18. The most successful theory that explains the mechanism of unimolecular reaction is
………. theory.
19. A* represents ………. molecule.
20. According to Hinshelwood, A* forms ………. molecule.
5.8 GLOSSARY
• Activated complex: Unstable molecule having highest energy in the energy profile
diagram.
• Potential energy surface: Surface associated with the position of atoms that
represents the energy of the system.
• Activation energy: Minimum energy that the reactants molecules must have in order
to form products.

• Steady state approximation: Rate of formation and rate of dissociation is same for
the intermediate.
5.9 ANSWERS TO SAQ’s

• Fill in the blanks:
1. Collision; 2. Concentration; 3. Collision number; 4. 1 to 10–8; 5. Simple; 6. Entropy; 7.
Orientation; 8. Arrhenius and van’t Hoff; 9. Activated complex; 10. Maximum; 11. kf =
(kT/h) × (θ*/ θX θY) × e – ∆Eo / RT; 12. kf = (kT/h) × e – ∆H* / RT × e ∆S* / R
; 13. – ∆G = RT ln K;
14. Activated complex theory; 15. 10–5 to 10–10; 16. Second; 17. First; 18. RRKM; 19.
Energized; 20. Activated molecule.
5.10 REFERENCES
1) Raj, G. (2017), Advanced Physical Chemistry, Goel Publishing House, Meerut.
2) Puri, B. R., Sharma, L. R. and Pathania, M. S. (2012), Principles of Physical
Chemistry, Vishal Publishing Co., Delhi.
3) Bahl, A., Bahl, B. S. and Tuli, G. D (2014), Essentials of Physical Chemistry, S.
Chand & Company Pvt. Ltd., New Delhi.
4) Gurtu, J. N. and Gurtu, A (2015), Advanced Physical Chemistry, Pragati Prakashan,
Meerut.

• Explain activated complex theory along with its statistical and thermodynamical
formulation of reaction rate.
• Describe different theories of unimolecular reactions including Lindemann,
Hinshelwood and RRKM theories.

UNIT 6: SOLUTION KINETICS
CONTENTS:
6.1 Objectives
6.2 Introduction
6.3 Rate of reaction
6.4 Factors affecting reaction rate
6.4.1 Concentration of reactant
6.4.2 Temperature
6.4.3 Catalyst
6.4.4 Intensity of light
6.4.5 Surface area of the reactant
6.4.6 Nature of the reactants
6.4.7 Pressure
6.4.8 Solvent effect
6.5 Factors affecting reaction rate in solution
6.5.1 Effect of dielectric constant
6.5.2 Effect of viscosity
6.6 Ionic strength
6.7 Salt effect
6.7.1 Primary salt effect
6.7.2 Secondary salt effect
6.8 Summary
6.10 Glossary

6.12 References
6.1 OBJECTIVES
After reading this unit, you will be able to:
• Define dielectric constant.

• Define ionic strength of a solution.
• Explain different factors that affect the rate of reaction occurring in solution.
• Explain the concept of primary and secondary salt effect.
6.2 INTRODUCTION
In the lower classes, we studied about the chemical kinetics which deals with the rate or
speed with which chemical reaction takes place. For example, corrosion is a very slow
process or have low rate of reaction. By using chemical kinetics, the mechanism of the
chemical reaction can be determined. There are several factors that affect the rate of chemical
reaction occurring in solution, gaseous phase or condensed phase. Solution as we know
consist of a solute and a solvent. A solute is present in small amount while the solvent is
present in large amount in the solution. For example, solution of sugar in water.
The present unit deals with the study of solution kinetics or the study of rate of rate with
which solute reacts with the solvent or kinetics of reactions in solution. In this unit, we will
discuss about different factors that affects the rate of reaction occurring in solution, the
concept dielectric constant, ionic strength followed with primary and secondary salt effect.
The chapter is quite interesting as it deals with the interaction of solvent with the solute in
solution thereby affecting the reaction rate. In order to understand the topic more clearly, we
will go through the entire chapter in order to study the factors affecting the kinetics of
reactions occurring in solution.

6.3 RATE OF REACTION
Rate of reaction is also known as reaction rate. It is defined as the rate of change of
concentration of reactants or products per unit time. As the reaction proceeds, the
concentration of reactant decreases while the concentration of the products increases.
Therefore the rate of reaction for a general reaction is given by:
A B
r = – d [A]/dt = + d[B]/dt
where (–) sign shows decrease in concentration of reactant A while the (+) sign shows
increase in the concentration of product B, infinitesimally small change in concentration is
represented by d. The rate of reaction is expressed in mole litre–1time–1. Generally the time
–1
taken is in seconds hence the rate is expressed in mol l s –1. According to rate law, rate of
reaction is directly proportional to the concentration of the reactants, raised to some power.
For a general reaction:
A B
r = k [A]
where k = proportionality constant = rate constant or velocity constant of a reaction
The concentration terms in the rate law expression are raised to some power, this power is
known as order of reaction. This is the basic idea of chemical kinetics. Now let us discuss the
factors that affect the rate of reaction.
6.4 FACTORS AFFECTING REACTION RATE
There are several factors that affect the rate of reaction:
6.4.1Concentration of reactants: From rate law, it is clear that rate of reaction is

directly proportional to the concentration of the reactants. Therefore more is the
concentration of reactant more will be the rate of reaction as more is the collision among the
reactants. According to collision theory, reaction occurs by the collision between the reactant
molecules.
6.4.2 Temperature

We know that temperature is directly proportional to average kinetic energy. More is the
kinetic energy, more is the speed of the reacting molecules and more is collision which
thereby increases the rate of reaction. It has been observed that for every 10oC rise in
temperature, the rate of reaction increases by a factor two or three. At two temperature that
differ from each other by 10oC, the ratio of the rate constant of a reaction is called
temperature coefficient of a reaction.The value of temperature coefficient is 2 or 3 as
discussed above.
Temperature coefficient = kT+ 10/ kT
Where k represents rate constant at two temperature that differ from each other by 10oC.
During the decomposition of HI, the rate of reaction increases by a factor of 1.7 when
temperature increases by 10oC.
6.4.3 Catalyst
These are certain substances that alter the rate of reaction. These substance generally
increases the rate of reaction without being consumed in the reaction and are termed as
catalyst. These substances remain unchanged in chemical composition and in amount at the
end of the reaction. The addition of a catalyst in a reaction increases the rate by lowering the
activation energy of the reaction due to which more number of reactant molecules cross the
energy barrier and form the products as there is an energybarrier between the reactant and the
product. Activation energy is the minimum amount of energy that the reactants molecules
must possess in order to form products. It is represented by Ea. For example, in the
decomposition of potassium chlorate, MnO2 (Manganese dioxide) acts as a catalyst which
speeds up the decomposition. The plot explaining the effect of catalyst on activation energy is
given in Figure 1.

Figure 1. Effect of catalyst on activation energy
6.4.4 Intensity of light
There are certain reaction that takes place in presence of light. Such reactions are called
photochemical reactions. In these reactions, photons are absorbed by the reactant molecules.
Hence, more is the no. of photons (light radiations) provided to the reactant molecules, more
is the energy to cross the energy barrier which results in the increase of reaction rate. For
example, the rate of photosynthesis increases when more photons are provided to the reactant
molecules or when day is sunny.
6.4.5 Surface area of the reactant
In case of heterogeneous reaction when reactants are not in same phase (like one reactant is in
solid phase and the other one is in gas phase), larger is the surface area of the reactant, more
will be the rate of reaction. This is because the reactions occur only at the surface of the
reacting species. For example, the rate of reaction for a lump of a solid is less than the rate
where it is present in powdered form as powder occupies more surface than the lump. The
rate of homogeneous reaction (both phase are same) is more than the rate of heterogeneous
reaction.
6.4.6 Nature of the reactants
Ionic compounds react with faster rate than the covalent compounds because the later require
energy to break the bond. For example, when silver nitrate (AgNO3) is added to sodium
chloride solution (NaCl), silver chloride (AgCl) is formed as a precipitate immediately.
NaCl + AgNO3AgCl (precipitate) + NaNO3
6.4.7 Pressure

If the reaction takes in gaseous phase, the increase in pressure increases the number of
collision among the gaseous molecules, thereby increasing the rate of reaction. As in case of
gaseous reaction, according to rate law, rate of reaction is directly proportional to the partial
pressure of the reactant species.
6.4.8 Solvent effect
In case of solution, we consider the effect of solvent on rate of reaction. The viscosity and
dielectric constant of a solvent affect the reaction rate. Before discussing its effect on reaction
rate, let us have some common knowledge about the viscosity and dielectric constant.
Viscosity of a liquid is defined as the resistance in the flow of liquid. Liquid consist of layers
of molecules that are arranged one over the other. This exerts resistance in the flow of a
liquid. Viscosity is inverse of fluidity. Fluidity is the ability of a liquid to flow. Viscosity is
represented by ƞ. The unit of viscosity is Poise (P). With increase in temperature, viscosity of
liquid decreases. Dielectric constant of a solvent is defined as the capacity of the solvent to
weaken the force of attraction (electrostatic) between ions (solute) and to separate them.
Dielectric constant is represented by ɛ.Water which is regarded as a universal solvent has
dielectric constant value equal to 79.8. Due to high value of dielectric constant, when solute
is added into the water, the water weakened the force of attraction by which solute molecules
are attached resulting in the free movement of ions (solute). Thus water is a strong
dissociating solvent. In vacuum, the value of dielectric constant is one for all the solvents.
6.5 FACTORS AFFECTING REACTION RATEIN SOLUTION
As we have discussed above that dielectric constant and viscosity affect the reaction rate in
solution. Each factor is discussed in detail below:
6.5.1 Effect of dielectric constant on rate of reaction
In order to show the effect of dielectric constant (ɛ) on rate of reaction, the theory of absolute
reaction rate also known as transition state theory has been undertaken into
consideration.According to this theory, ions undergoing the reaction in a medium of dielectric
constant (ɛ) are considered as a sphere. Let us consider an ionic reaction involving ions A and
B. Ionic reactions are those reactions that occurs in between the ions. Let rA andrBbe the
radius of two ions having charge ZAe and ZBe respectively. Initially these two ions A and B

are at an infinite distance. According to the activated complex theory, when these two ions
are brought together in order to form the activated complex, the work done (W) is given by:
W = (ZAe ) (ZB e) / ɛ dAB
Where ɛ is dielectric constant of the solvent, dABis the distance between two ions in an
activated complex.
W = ZA ZB e2 / ɛ dAB
If ions possess charges of same sign (both are either positive or both are negative), the work
is positive. If ions possess charges of different sign (one ion is positive while the other ion is
negative), the work is negative. This work is equal to electrostatic distribution. The free
energy of activation (∆G*) per molecule is given by the sum of free energy that contribute to
electrostatic distribution and non- electrostatic distribution (N.E.S.).
∆G*/ N = ∆G*N.E.S. / N + ZA ZBe2 / ɛ dAB …….. (1)
Where N is Avagadro’s number. On multiplying equation 1 by N, we obtain:
∆G* = ∆G*N.E.S. + ZA ZBe2 N / ɛ dAB …… (2)
From thermodynamics formulation of reaction rate (activated complex theory), rate constant
is related to free energy of activation (∆G*) by the expression:
k= e– ∆G*/RT
WherekT/h is universal frequency, k is Boltzmann constant, and T is absolute temperature

while h is Planck’s constant. On putting the value of ∆G* in the above equation, we obtain:
k= e– (∆G* N.E.S. + Z Z e2 N / ɛ d ) / RT
A B AB
k= e– ∆G* N.E.S./ RT e– ZA ZB e2 N / ɛ dAB RT
On taking natural log:
ln k = ln – ∆G* N.E.S. / RT– ZA ZB e2 N / ɛ dAB RT
Keeping – ∆G* N.E.S. / RT= k0 = another constant, we obtain:
ln k = ln k0– ZA ZB e2 N / ɛ dAB RT

When a graph is plotted between ln k versus 1/ ɛ, a straight line is obtained having slope ZA
ZB e2 N / dAB RTand intercept ln k0which is shown in Figure 2.
Figure 2. Variation of rate constant with dielectric constant
It is concluded that for an ionic reactions, with increase in dielectric constant of a solvent,
rate constant increases thereby increasing the rate of reaction while with decrease in dielectric
constant of the solvent, the rate of reaction decreases. This equation correlating rate constant
with dielectric constant is valid for a large number of ionic reactions.
6.5.2 Effect of viscosity
In order to show the effect of viscosity on rate of reaction, let us consider to reactant
molecules A and B having radii rAand rB respectively. The number of collision (encounters,
υ) between A and B per cubic centimeter is given by equation given below. One thing to be
noted here is that encounter word is used in place of collision. Collision word is used in case
of gases while for liquids and solids, encounter is used because here the solute molecules get
surrounded by the solvent molecules forming a cage.
υ = 4Π (rA+ rB) (DA + DB) nAnB cm–3 s–1 …… (1)
whereDA , DB are their respective diffusion coefficient and nA,nB are the number of molecules
per centimeter cube of A and B respectively.If each encounter leads to a chemical reaction
then the number of encounter is equal to rate of reaction.
υ/ N = 4Π (rA+ rB) (DA + DB) (nA /N)(nB / N)molcm–3 s–1
where N is Avogadro’s number.
υ = kDnAnB/ N ……. (2)
wherek D is diffusion- controlled rate constant. On putting the value of υ in equation 1.
kDnAnB/ N = 4Π (rA+ rB) (DA + DB) nAnB

kD / N = 4Π (rA+ rB) (DA + DB)
kD = 4Π N (rA+ rB) (DA + DB) ……. (3)
For spherical particles of a liquid, diffusion coefficient is related to radius (r) of the molecule
and the coefficient of viscosity (ƞ) by Stoke ‘s equation given below:
D = kT/ 6 Π ƞr
Where k is Boltzmann constant, T is absolute temperature. For reactant molecule A and B,
DA = kT/ 6 Π ƞrA; DB= kT/ 6 Π ƞrB
On putting the value of DA and DBin equation 3, we obtain:
kD = 4Π N (rA+ rB) (kT/ 6 Π ƞrA+ kT/ 6 Π ƞrB)
kD = 4Π N (rA+ rB) [kT/ 6 Π ƞ ( 1/ rA+ 1/ rB)]
kD = 4Π N (rA+ rB) [kT (rA+ rB)/ 6 Π ƞrArB ]
kD = 4Π N kT (rA+ rB)2 / 6 Π ƞrArB
kD = 2 R T (rA+ rB)2 / 3 ƞrArB (k = R/ N)
If rA= rB :kD = 8 RT / 3ƞ …….. (4)
Equation 4 is Debye- Smoluchowski equation. In this equation, diffusion -controlled rate

constant is inversely proportional to coefficient of viscosity (ƞ) of the solvent. This shows
that more is the viscosity of the solvent; less will be the rate of reaction. Therefore, viscosity
is inversely proportional to the rate of reaction.
6.6 IONIC STRENGTH
Ionic strength of a solution is defined as the measure of electrical intensity. This electrical
intensity is due to the presence of ions in the solution. Ionic strength is represented by I. The
expression of ionic strength for two ions in solution is given by:
I = ½ (m1Z12 + m2Z22)
Where m1 ismolality of ion 1 in solution, m2is molality of ion 2 in solution,Z1is valency of

ion 1, Z2is valency of ion 2. For example, in case of KCl (single electrolyte), there are two
ions, K+ and Cl–. In case of solution containing different ions (i), I is written as:

I = ½ ∑mi Zi2
6.7 SALT EFFECT
In case of salts, ions are formed. These ions exert force on each other. Ionic strength which
has been discussed above affects the rate of reaction. This is studied under topic salt effect.
The concept of salt effect was given by J. N. Bronsted and N. Bjerrum. Salt effects are
classified into primary salt effect and secondary salt effect. Let us discuss these effects one by
one:
6.7.1 Primary salt effect
This effect is seen in those reactions which do not involve catalyst. In case of primary salt
effect, the ions that act as a reactant first combine to form activated complex. Some of the
activated complex gives product while some of the activated complex becomes deactivated to
give back the ions (reactants). This mechanism is according to activated complex theory. The
reaction is shown below:
WhereA and B are the ions; ZA and ZB are their valencies respectively. AB is the activated
complex having valency ZA + ZB. According to rate law, rate of reaction is proportional to the
concentration of the activated complex.
r =k2[AB*] ………. (1)
It is clear from the reaction that there is equilibrium between ions and activated complex.
Therefore the equilibrium constant (K) is given by:
K = a*/ aAaB
Where a is the activity. We know that activity coefficient (ɣ) is equal to a/ c. Therefore:
a=ɣc
K = ɣ* [AB*]/ ɣA [A] ɣB [B]
[AB*] = K ɣAɣB [A] [B] / ɣ*

On putting the value of [AB*] in equation 1, we obtain:
r = k2 K ɣAɣB [A] [B] / ɣ*
r = k’ ɣAɣB [A] [B] / ɣ* ……. (2)
where k2 K = k’ = another constant. For the reaction in equilibrium: r = k [A] [B]
k = r / [A] [B]
Putting the value of r from equation 2 in above expression, we obtain:
k = k’ ɣAɣB [A] [B] / ɣ*[A] [B]
k = k’ ɣAɣB / ɣ*
On taking natural log: ln k = ln k’ + ln ɣAɣB / ɣ*
ln k = ln k’ + ln ɣA+lnɣB– ln ɣ* ……… (3)
For the solution of electrolyte, according to Debye- Huckel limiting law: ln ɣi = – AZi2 I1/2
Where I is the ionic strength of the solution, A is the constant for a particular solvent while
Ziis the valency of ith ion. Therefore:
For ion A: ln ɣA = – AZA2 I1/2
For ion B: ln ɣB = – AZB2 I1/2
For activated complex: ln ɣ* = – A (ZA+ ZB)2 I1/2
Now putting the value of ln ɣA, ln ɣBand ln ɣ*in equation 3, we obtain:
ln k = ln k’ – AZA2 I1/2– AZB2 I1/2– (– A (ZA+ ZB) 2 I1/2)
ln k = ln k’ – AZA2 I1/2– AZB2 I1/2+ A (ZA+ ZB) 2 I1/2
ln k = ln k’ – A I1/2 [ZA2 + ZB2 – (ZA+ ZB) 2]
ln k = ln k’ – A I1/2 [ZA2 + ZB2 – (ZA2 + ZB2+ 2 ZA ZB)]
ln k = ln k’ – A I1/2 (ZA2 + ZB2 –ZA2–ZB2 – 2 ZA ZB)
ln k = ln k’ – A I1/2 (– 2 ZA ZB)
ln k = ln k’ +2 A I1/2 ZA ZB

In case of water as a solvent, constant A possesses value 0.509. On putting this value on
above expression, we obtain:
ln k = ln k’ +2 (0.509) I1/2 ZA ZB
ln k = ln k’ +1.018 I1/2 ZA ZB ………. (4)
Equation 4 shows that the rate constant or rate of reaction depends on the valencies of ions as
well as the ionic strength (I) of the solution. This is primary salt effect and equation (4) is
called Bronsted- Bjerrum equation. On the basis of chemical reaction involved, different case
arises:
Case 1: If ZA ZB = positive
It means that both the ions undergoing the chemical reaction possess either positive charge or
negative chargethen only the product of ZA ZB is positive. It is clear from Bronsted- Bjerrum
equation that with increase in the ionic strength of the solution, rate constant increases
thereby increasing the rate of reaction. For example:
S2O32– + I– Products
[Co (NH3)5Br]2+ + Hg2+ Products
Case 2: If ZA ZB = negative
It means that one of the reactant (ion) possess negative charge then only the product of ZA ZB
is negative.It is clear from Bronsted- Bjerrum equation that with increase in the ionic strength
of the solution, rate constant decreases thereby decreasing the rate of reaction.For example:
H+ + Br–1 Products
Case 3: If ZA ZB = zero
It means that one of the reactant is non- electrolyte. It is clear from Bronsted- Bjerrum
equation that rate constant does not vary with ionic strength of the solution.For example:
ICH2COOH + CNS– Products
All these three cases are represented in Figure 3.

Figure 3. Variation of rate constant with ionic strength
6.7.2 Secondary salt effect
This effect is seen in those reactions that involve catalyst. In order to understand the
secondary salt effect, there must be change in the concentration of the catalyst involved. This
effect is shown by equation 5, given below:
ln k = ln k’ +1.018 I1/2
This equation shows that rate constant does not depend on the valency but it only depends
upon the ionic strength of the solution. With increase in the ionic strength of the solution, rate
constant also increases thereby increasing the rate of reaction.
6.8 SUMMARY
In this unit, we have discussed about the kinetics that takes place in a solution. The topic
consists of factors that affect the rate of reaction in solution that includes dielectric constant
and viscosity. Further an idea of ionic strength is given which is then correlated with the rate
constant which was explained under primary and secondary salt effect.
6.9 SELF- ASSESSMENT QUESTIONS (SAQ)

1. With increase in concentration of the reactant, rate of reaction ……….
2. Temperature coefficient is defined as the ratio of two ………. that differ from each other
by 10oC.
3. Catalyst ………. the rate of reaction by ………. the activation energy of the reaction.
4. The effect of pressure is considered, if the reaction occurs in ………. phase.

5. Dielectric constant is the property of a ……….
6. Rate of reaction ………. with increase in the dielectric constant of the solvent.
7. More is the viscosity of the solvent, ……. will be the rate of reaction.
8. Ionic strength of a solution is represented by ……….
9. Primary salt effect is seen in those reactions that involves ………. reactions.
10. In secondary salt effect,………. reactions are considered.
• Multiple choice questions:

1. When the product of valency of ions (ZAZB) is positive then the rate of reaction increases
due to:
a. Increase in ionic strength.
b. Decrease in ionic strength.
c. No effect
d. None of the above.
2. In Bronsted- Bjerrum equation, the value of constant A for water as a solvent is equal to:
a. 0.059
b. 0.509
c. 0.00509
d. 0.00
3. Bronsted- Bjerrum equation is written as:
a. ln k = ln k’ +2 A I1/2 (ZA+ ZB)
b.ln k = ln k’ +2 A I1/2 ZA ZB
c. ln k = ln k’ – 2 A I1/2 ZA ZB
d.ln k = ln k’ – 2 A I1/2 (ZA+ ZB)
4. Ionic strength of a solution containing two ion is given by formula:
a. I = ½ (m1Z12 + m2Z22+ m3Z32)

b. I = ½ (m1Z12 + m2Z22)
c. I = ½ (m1Z1 + m2Z2)
d. I = 2 (m1Z12 + m2Z22)
5. In Debye- Smoluchowski equation, the rate constant (kD) is:
a. Directly proportional to viscosity.
b. Inversely proportional to viscosity.
c. Independent of viscosity.
d. Depend on second power of viscosity.
6. Stoke’s equation is given by:
a. D = kT/ 6 Π ƞr
b. D = kTƞ / 6 Π r
c. D = kT2/ 6 Π ƞr
d. D = kT/ 6 Π ƞr2
7. Temperature coefficient is defined as the ratio of rate constant that differ from each other
by:
a. 20oC
b. 10oC
c. 30oC
d. 05oC
8. Catalyst increases the rate of reaction by:
a. Increasing the activation energy.
b. Decreasing the activation energy.
c. Increasing the concentration of the reactants.
d. None of the above.
• Short answer type questions:

1. How temperature affect the rate of reaction?
2. Show the effect of catalyst on rate of reaction?
3. Solvent affects the rate of reaction. Explain how in brief?
4. Define dielectric constant of a solvent.
5. Write Debye- Smoluchowski equation.
6. Write Bronsted- Bjerrum equation.
7. Define viscosity of a solution.
8. Write short note on activated complex theory.
6.10 GLOSSARY
• Dielectric constant - Capacity of the solvent to weaken the force of attraction present
in solute.
• Viscosity: Resistance in the flow of liquid.
• Ionic strength: Measure of electrical intensity.

1. Increases; 2. Rate constant; 3. Increases, lowering; 4. Gas; 5. Solvent; 6. Increases; 7. Less,
8. I; 9. Non- catalytic; 10. Catalytic
• Multiple- choice questions

1. a. Increase in ionic strength; 2. b. 0.509; 3. b.ln k = ln k’ +2 A I1/2 ZA ZB; 4. b. I = ½
(m1Z12 + m2Z22); 5. b. Inversely proportional to viscosity; 6. a. D = kT/ 6 Π ƞr; 7. b. 10oC; 8.
b. Decreasing the activation energy.
6.12 REFERENCES
Raj, G. (2017), Advanced Physical Chemistry, Goel Publishing House, Meerut.
Puri, B. R., Sharma, L. R. and Pathania, M. S. (2012), Principles of Physical Chemistry,

Vishal Publishing Co., Delhi.

Bahl, A., Bahl, B. S. and Tuli, G. D (2014), Essentials of Physical Chemistry, S. Chand &
Company Pvt. Ltd., New Delhi.
Gurtu, J. N. and Gurtu, A (2015), Advanced Physical Chemistry, PragatiPrakashan, Meerut.
• Describe in detail the various factors that affect the rate of reaction.
• Explain the effect of dielectric constant on the rate of reaction taking place in
solution.
• Viscosity of a solvent affects the rate of reaction in solution. Explain.
• Explain in detail the primary and secondary salt effect.

UNIT-7 THE FAST REACTION KINETICS
CONTENTS:
7.1 Introduction
7.2 Objectives
7.3 General idea of kinetics of fast reactions
7.3.1 Relaxation method
7.3.2 Flow method
7.3.3 Flash photolysis
7.4 Molecular reaction dynamics
7.5 Chain reaction
7.5.1 Kinetics of hydrogen –bromine chain reaction
7.5.2 Kinetics of hydrogen –chorine chain reaction
7.5.3 Pyrolysis of acetaldehyde
7.6 Enzyme reactions
7.6.1 Kinetics of enzyme reactions
7.6.1.1 Michaelis- Menten equation
7.6.1.2 Lineweaver- Burk equation
7.6.1.3 Eadie- Hofstee equation
7.7 Summary
7.9 Glossary
7.11 References
7.1 OBJECTIVES
After reading this unit you will be able to:
• Know about the kinetics of fast reactions.

• Describe various methods of studying the rate of fast reactions that includes relaxation
method, flow method and flash photolysis method.
• Write note on molecular reaction dynamics.
• Explain the kinetics of hydrogen-chlorine reaction and hydrogen-bromine reaction.
• Give the mechanism of pyrolysis of acetaldehyde that includes its kinetics also.
• Describe the kinetics of enzyme catalyzed reactions.
7.2 INTRODUCTION
In earlier chapters we have studied about chemical kinetics that deals with moderate
reactions. Moderate reactions are those reactions that occur not very fast or not very slow like
acid-catalyzed hydrolysis of esters. In fast reactions, reaction takes place so fast in such a
short time (few second or less) than required to mix the reactants. For these reactions, rate is
not obtained by conventional methods. Some other methods are used for determining the rate
which are mentioned below in further topics.
The present unit deals with kinetics of fast reactions in which we will go through various
methods for studying the rate of fast reactions that includes relaxation method, flow method
and flash photolysis. In addition to these, we will have a general idea of molecular reaction
dynamics. On moving forward, we will study about the kinetics of chain reactions that
includes hydrogen- chlorine reaction, hydrogen – bromine reaction and pyrolysis of
acetaldehyde. Finally we will conclude on the topic, kinetics of enzyme reactions.
The entire unit is quite interesting as after reading the unit we will be able to know how the
rate of fast reactions are determined that takes place in few seconds. We will also came to
know about the kinetics of reaction catalyzed by enzymes which are biological catalysts. Let
us now discuss these topics one by one.
7.3 GENERAL IDEA OF KINETICS OF FAST REACTIONS

As we have discussed earlier that fast reactions takes place in few seconds or even less than
this. Fast reactions are also known by name rapid reactions. For studying the rate of these
reactions, conventional methods (common method) for determining rate are not applied.
Methods used for determining the rate of fast reactions was given by Manfred Eigen (German
chemist) which are as follows:

7.3.1 Relaxation method
Relaxation method is one of the methods for determining the rate of fast reactions that takes
place in solution. Eigen and his coworkers put forward this method. In this method, there is a
sudden change in some of the physical parameter of a system that is in equilibrium. This
physical parameter includes temperature, pressure and electric field. Due to this change in the
system there is change in state of a system or we can say that there is change in temperature,
pressure or electric field. Relaxation is defined as a time required attaining the equilibrium
again after this change. It has been observed that there is a change in a solvent structure
which occurs quickly than the chemical reaction which is under consideration. By this
–10
method, reactions having half- life ranging from few seconds to 5 × 10 second are
measured. Let us now derive the rate constant expression by considering a reversible first-
order reaction:
Suppose at any instant, the total concentration of the reaction that consist of A and B is
represented by a while x be the concentration of B. As rate of reaction is defined as the
change in the concentration of reactant or product per unit time, therefore rate of formation of
product (r) is given by:
r = dx/ dt = k1 (a – x) – k2 x ………. (1)
where (a – x) is the concentration of A at any instant. If xe represents the equilibrium

concentration, the change in concentration (∆x) is given by: ∆x = x – xe or x = ∆x + xe
Now on putting the value of x in equation 1:
r = dx/ dt = d(∆x) /dt = k1 (a – ∆x – xe ) – k2 (∆x + xe)
d(∆x) /dt = k1 a – k1 ∆x – k1 xe – k2 ∆x + k2 xe ………. (2)
We know that at equilibrium: r = dx/ dt = 0 and x = xe
Hence equation (1) at equilibrium becomes: k1 (a – xe) – k2 xe = 0
k1 (a – xe) = k2 xe

On putting the value of k2 xe in equation 2: d (∆x) /dt = k1 a – k1 ∆x – k1 xe – k2 ∆x + k1 (a –

xe)
d(∆x) /dt = k1 a – k1 ∆x – k1 xe – k2 ∆x + k1 a – k1 xe
d(∆x) /dt = – k1 ∆x – k2 ∆x
d (∆x) /dt = – (k1+ k2) ∆x
d (∆x) /dt = – kr ∆x ; where (kr = k1+ k2)
Where kr is the relaxation rate constant which is equal to k1+ k2. Relaxation time (t) is a
reciprocal of relaxation rate constant, hence:
t = 1/ kr = 1/ k1+ k2
Relaxation time is obtained by different methods that includes pressure - jump method and
temperature- jump method which measures relaxation time of more than 10 –5 second whereas
for measuring relaxation time less than 10 –5 second, high electric field methods are there.
7.3.2 Flow method
This method is one of the commonly used method for determining the rate of fast reactions
and was the first method to be employed for studying the kinetics of fast reactions having
half-life in the range 10 to 10–3 seconds. This technique was proposed by Roughton and
Hastridge in 1923. There are various flow methods that include stopped-flow method,
continuous –flow method and quenched flow method. Out of these three methods, stopped-
flow method is commonly used method in comparison to continuous –flow method and
quenched flow method. Let us discuss these methods:
• Stopped- flow method: As discussed above, this is commonly used flow method. The
apparatus for this method is shown in Figure 1.
Figure 1. Apparatus for flow method

It is clear from Figure 1 that apparatus consist of two reservoir having reactants (reagents) R1
and R2. These two reservoirs is attached to a piston. By using piston, two reactants are
allowed to mix in a chamber known as mixing chamber indicated by M in Figure 1. From M,
the solution of two reagents then move through observation tube having light source in the
ultraviolet and visible region. After mixing the reagents, observations are made within a few
milliseconds. In this method, with different flow from the value of absorption, rate versus
time graph is plotted. In this method as the name indicates, the flow is stopped suddenly at a
particular point and the equilibrium rate is measured as a function of time by using absorption
data. One point to be noted is that in this method, measurements are done at a particular
point. For example, aqueous solution of Fe3+ and CNS– is studied by using this method.
• Continuous –flow method: In this method, absorption is recorded at different distance

from the mixing chamber. This method is more superior than stopped- flow method in
terms of time resolution but this method consume large amount of reagents
(reactants).
• Quenched flow method: In this method, the solution produced after mixing of
reagents passes into quenching solution where reaction stops. This method best suits
to those reactions which occur very fast like exchange reactions. Measurements are
made at various distance or at a different rate of flow of solution.
7.3.3 Flash photolysis
In this method, as the name indicates a strong flash of high intensity or energy of the order
105 J is allowed to fall on a sample for microseconds or 10–6 second. On the interaction of
high energy flash with the sample, almost all the molecules of the sample get excited that
results in the formation of free radicals (reaction intermediates). The concept of flash
photolysis was given by R. G. W. Norrish and G. Porter (1950). For this great achievement,
they were awarded by Nobel Prize. As free radicals are produced on the exposure of flash on
the sample therefore this photolysis is used from determining absorption spectra of free
radicals like •CH3, •Cl and •NH2 for studying reactions occurring in solution as well as in gas
phase. The apparatus for flash photolysis is shown in Figure 2.

Figure 2. Flash-photolysis apparatus
It is clear from Figure 2 that there is a high voltage supply that provide 10,000 volt to a
condenser. In the spark gap, a spark is generated by a trigger signal which is responsible for
passing current through the flash lamp above which sample is placed. Within few
microseconds, the condenser gets discharge resulting in the automatic stop of flash lamp.
Hence on exposure to flash, reactant or sample get excited and form free radicals. More is the
disappearance of excited molecules, more is the increase in transmitted light
(monochromatic). Figure 2 shows that transmitted light passes the oscilloscope which shows
the variation of the instantaneous signal voltage with time by means of graph. The
spectrometer is placed in such a way that the wavelength absorbed by the excited reactant
molecule or excited sample is same as the light the light passing through the condenser. In
this way absorption spectra is taken by using spectrometer. The rate of very fast reactions like
recombination of iodine atom, formation of chlorine atom in chlorine- oxygen reaction are
determined by flash photolysis.
7.4 MOLECULAR REACTION DYNAMICS

Molecular reaction dynamics is also known by name microscopic kinetics. D. R. Herschbach,
Y.T. Lee and J. C. Polanyi gave the concept of molecular reaction dynamics and won Nobel
Prize for this great work. Molecular reaction dynamics deals with the quantum state of
reactants and products along with intramolecular (within the molecule) and intermolecular (in
between the molecules) motions that take place during a simple chemical reaction
(elementary reaction). With quantum state we mean state of a quantized system having a
particular set of quantum number. By this dynamics, we can simply have a detailed

knowledge of basic chemical change. For studying molecular reaction dynamics, there is an
experimental method known as molecular beam method. In this method, a mono-energetic
beam of atoms or molecules is used. Molecular beam apparatus used in molecular beam
method is given in Figure 3.
Figure 3. Molecular beam apparatus
This apparatus is designed in such a way that narrow beam of reactants are produced in which
speeds of the molecules or atoms are controlled along with rotational, vibrational and
electronic states. In addition to this, apparatus also consist of a movable detector for detecting
the direction along with the speed of reactants and products. By this method, we can obtain
detailed information regarding the reaction product that deals with energy distribution,
distribution of angular momentum and quantum states of products and reactants. In old
molecular beam method, reactants are taken in a small container having opening (very small)
and beams are produced which are of very low intensity. In this method, there are differential
surface ionization detectors. It has been found that old molecular beam method is only for
alkali metals (first group elements). But in modern beam method, there is a use of supersonic
nozzle source that produces beams having more intensities (about third order of magnitude
than old beam method). For analyzing the scattered beam in modern beam method, mass
spectrometers are used in place of movable detector and all types of reactions are studied by
this modern beam method. It has been observed that on collision of reactant molecules, there
case of scattering arises. In first case, there is no transfer of energy among different degree of
freedom that refers to elastic scattering. In second case, there is no chemical reaction but
transfer of energy among different degree of freedom takes place. In third case, there is
transfer of energy along the chemical reaction.

7.5 CHAIN REACTION

As we know that reactions are classified into elementary and complex reaction. Elementary
reactions are those reactions that take place in a single step while complex reaction takes
place in two or more steps. These complex reactions are further classified into three types:
reversible reaction, consecutive reaction and chain reaction. Reversible reactions as the name
indicates, the rate of forward and backward reaction is same. In case of consecutive reactions,
steps take place one after another. Now coming to chain reaction, which is a type of complex
reaction in which highly reactive intermediates are formed which carry out a fast reaction for
a long time. Intermediates are short-lived chemical species formed during the conversion of
reactants into products. In place of short lived species we can also use a term transient
existence. In 1943, Frank O. Rice and Karl F. Herzfeld first studied the chain reaction. In the
mechanism of chain reaction, there are three steps: first is chain initiation, next is chain
propagation and last is chain termination. For studying the kinetics of chain reaction, we must
have knowledge of steady state approximation. According to steady state approximation, the
rate of formation of an intermediate is equal to the rate of its decomposition. Thus:
d[R]/dt = 0
where [R] is the concentration of intermediate. Several chain reactions that includes reaction
of hydrogen with halogens (chlorine and bromine), polymerization reaction, pyrolysis of
hydrocarbon, aldehydes. Let us now discuss the kinetics of reaction between hydrogen and
bromine.
7.5.1 Kinetics of hydrogen –bromine chain reaction
The reaction between hydrogen and bromine is given below along with its mechanism:
H2 (g) + Br2 (g) 2HBr (g)
Mechanism:
1. Chain initiation: (i) Br2 2 Br; rate constant: k1
2. Chain propagation: (ii) H2 + Br HBr + H; rate constant: k2
(iii) H + Br2 HBr + Br; rate constant: k3
3. Chain inhibition: (iv) H + HBr H2 + Br; rate constant: k4
4. Chain termination: (v) Br + Br Br2; rate constant: k5

In chain initiation step, bromine molecule acquire energy due to collision and form two
bromine atoms. Here H and Br are the intermediates.
Rate of formation of HBr is the rate of reaction which is given by:
r = d[HBr]/ dt = k2 [H2] [Br] + k3 [H] [Br2] – k4 [H] [HBr] ………. (1)
There are two intermediates, H and Br having rate of formation:
d[H]/ dt = k2 [H2] [Br] – k3 [H] [Br2] – k4 [H] [HBr]
d[Br]/ dt = 2 k1 [Br2] – k2 [H2] [Br] + k3 [H] [Br2] + k4 [H] [HBr] – 2 k5 [Br]2
On applying steady state, d[H]/ dt = 0; d[Br]/ dt = 0
k2 [H2] [Br] – k3 [H] [Br2] – k4 [H] [HBr] = 0 ………. (2)
2 k1 [Br2] – k2 [H2] [Br] + k3 [H] [Br2] + k4 [H] [HBr] – 2 k5 [Br]2 = 0 ………. (3)
From equation 2, k2 [H2] [Br] = k3 [H] [Br2] + k4 [H] [HBr]
k2 [H2] [Br] = [H] (k3 [Br2] + k4 [HBr])
[H] = k2 [H2] [Br] / (k3 [Br2] + k4 [HBr])
From equation 3,
k2 [H2] [Br] = 2 k1 [Br2] + k3 [H] [Br2] + k4 [H] [HBr] – 2 k5 [Br]2 = 0 ……….(4)
Now equation 2 can be written as:
k2 [H2] [Br] = k3 [H] [Br2] + k4 [H] [HBr] ………. (5)
On subtracting equation 5 from equation 4,
k2 [H2] [Br] – k2 [H2] [Br] = 2 k1 [Br2] + k3 [H] [Br2] + k4 [H] [HBr] – 2 k5 [Br]2 – k3 [H]
[Br2] – k4 [H] [HBr]
2 k1 [Br2] – 2 k5 [Br]2 = 0
k1 [Br2] = k5 [Br]2
[Br]2 = k1 [Br2]/ k5
[Br] = (k1 [Br2]/ k5)1/2

The expression for [H] contains [Br], hence on putting the value of [Br] in [H], we obtain:
[H] = k2 [H2] (k1 [Br2]/ k5)1/2 / (k3 [Br2] + k4 [HBr])
Now the value of [H] and [Br] in placed in equation 1,
r = d[HBr]/ dt = (k11/2 k2 [H2] [Br2] ½) / k51/2 + (k11/2 k2 k3 [Br2] [H2] [Br2] ½) / k51/2 (k3 [Br2] +
k4 [HBr]) – k11/2 k2 k4 [H2] [Br2] ½ [HBr] / k51/2 (k3 [Br2] + k4 [HBr])
r = d[HBr]/ dt = k11/2 k2 [H2] [Br2] ½ / k51/2 [1 + {k3 [Br2] / (k3 [Br2] + k4 [HBr])} – {k4 [HBr] /
(k3 [Br2] + k4 [HBr])}]
r = d[HBr]/ dt = k11/2 k2 [H2] [Br2] ½ / k51/2 (k3 [Br2] + k4 [HBr] + k3 [Br2] – k4 [HBr])/ (k3
[Br2] + k4 [HBr])
r = d[HBr]/ dt = k11/2 k2 [H2] [Br2] ½ / k51/2 [ 2 k3 [Br2] / (k3 [Br2] + k4 [HBr])] ………. (6)
Equation 6 shows the rate of formation of HBr or rate of reaction for hydrogen- bromine
chain reaction. It is clear from the above expression that with increase in time, the rate of
formation of HBr decreases.
7.5.2 Kinetics of hydrogen –chorine chain reaction
The reaction between hydrogen and chlorine is given as: H2 (g) + Cl2 (g) 2HCl (g)
Bodenstein and Nernst proposed the mechanism of reaction that occurs between hydrogen
and chlorine:
Mechanism:
1. Chain initiation: (i) Cl2 2 Cl; rate constant: k1
2. Chain propagation: (ii) Cl + H2 HCl + H; rate constant: k2
(iii) H + Cl2 HCl + Cl; rate constant: k3
4. Chain termination: (iv) Cl + wall ½ Cl2; rate constant: k4
Rate of formation of HCl is the rate of reaction which is given by:
r = d[HCl]/ dt = k2 [Cl] [H2] + k3 [H] [Cl2] ………. (1)
There are two intermediates H and Cl. The rate of formation of H is given by:
d[H]/ dt = k2 [Cl] [H2] – k3 [H] [Cl2]

Similarly rate of formation of Cl is given by:
d[Cl]/ dt = k1 Iabs – k2 [Cl] [H2] + k3 [H] [Cl2] – k4 [Cl]
where Iabs is the intensity of radiation absorbed. Applying steady –state approximation to
intermediates:
d[H]/ dt = 0; d[Cl]/ dt = 0
k2 [Cl] [H2] – k3 [H] [Cl2] = 0 ……… (2)
k1 Iabs – k2 [Cl] [H2] + k3 [H] [Cl2] – k4 [Cl] = 0 ………… (3)
On adding equation 2 and 3;
k2 [Cl] [H2] – k3 [H] [Cl2] + k1 Iabs – k2 [Cl] [H2] + k3 [H] [Cl2] – k4 [Cl] = 0
k1 Iabs – k4 [Cl] = 0
k1 Iabs = k4 [Cl]
[Cl] = k1 Iabs / k4
From equation 2, k2 [Cl] [H2] = k3 [H] [Cl2]
Now from equation 1, r = d[HCl]/ dt = k2 [Cl] [H2] + k2 [Cl] [H2]
r = d[HCl]/ dt = 2 k2 [Cl] [H2]
Now the value of [Cl] is placed in above expression of rate of reaction, we obtain:
r = d[HCl]/ dt = 2 k1 k2 [H2] Iabs / k4
The above expression shows that rate of formation of HCl for hydrogen- chlorine reaction is
directly proportional to the concentration of hydrogen gas taken as a reactant.
7.5.3 Pyrolysis of acetaldehyde
Pyrolysis means decomposition of a substance at high temperature. Here in this section, we

will study the pyrolysis of acetaldehyde or decomposition of acetaldehyde at very high
temperature at wavelength ranging from 2500 to 3100 oA. The reaction is given below:
CH3CHO CH4 + CH3CH3 + CO + other products
Mechanism:

(i) Chain initiation: CH3CHO CH3 + CHO; rate constant: k1
(ii) Chain propagation: CH3CHO + CH3 CH4 + CH3CO; rate constant: k2
CH3CO CO + CH3; rate constant: k3
(iii) Chain termination: CH3 + CH3 CH3 CH3; rate constant: k4
Rate of formation of intermediate, CH3CO and CH3 is given by:
d [CH3]/ dt = k1 Iabs – k2 [CH3CHO] [CH3] + k3 [CH3CO] – k4 [CH3]2
d [CH3CO]/ dt = k2 [CH3CHO] [CH3] – k3 [CH3CO]
On applying steady-state approximation to the intermediates, we have:
d [CH3]/ dt = 0 ; d [CH3CO]/ dt = 0
Hence: k1 Iabs – k2 [CH3CHO] [CH3] + k3 [CH3CO] – k4 [CH3]2 = 0 ………. (1)
k2 [CH3CHO] [CH3] – k3 [CH3CO] = 0 ………. (2)
On adding equation 1 and 2:
k1 Iabs – k2 [CH3CHO] [CH3] + k3 [CH3CO] – k4 [CH3]2 + k2 [CH3CHO] [CH3] – k3 [CH3CO]

=0
k1 Iabs – k4 [CH3]2 = 0
k1 Iabs = k4 [CH3]2
[CH3]2 = k1 Iabs/ k4
[CH3] = (k1 Iabs/ k4) 1/2
Now in order to find the concentration of CH3CO, we put the value of [CH3] in equation 2.
k2 [CH3CHO] (k1 Iabs/ k4) 1/2 – k3 [CH3CO] = 0
k2 [CH3CHO] (k1 Iabs/ k4) 1/2 = k3 [CH3CO]
[CH3CO] = k2 [CH3CHO] k11/2 Iabs1/2 / k3 k41/2
Now we know that the rate of reaction is the rate of formation of CO, therefore:
r = d [CO]/ dt = k3 [CH3CO]

On putting the value of [CH3CO] in above expression, we obtain:
r = d [CO]/ dt = k3 k2 [CH3CHO] k11/2 Iabs1/2 / k3 k41/2
r = d [CO]/ dt = k2 [CH3CHO] k11/2 Iabs1/2 / k41/2
r = d [CO]/ dt = k [CH3CHO] Iabs1/2 ……….. (3)
Where k = k2 k11/2/ k41/2, another constant. Equation 3 represents the rate expression for
pyrolysis of acetaldehyde. It is clear from above expression that rate of reaction is directly
proportional to the concentration of acetaldehyde.
7.6 ENZYME REACTIONS

Enzymes as we know are biological catalyst that catalyzes the reactions taking place in a
biological system. The catalysis by enzymes is known as micro- heterogeneous catalysis.
These are complex organic compounds (proteins) formed by living plants and animals.
Enzymes when dissolved in water forms colloidal solution. A particular reaction is catalyzed
by a specific enzyme like hydrolysis of maltose into two glucose is catalyzed by enzyme
maltase, similarly the enzyme zymase catalyze the conversion of glucose into ethyl alcohol
and carbon dioxide. Enzymes are used in small amount and increase the rate of reaction by
lowering the activation energy. Let us consider the kinetics of enzyme- catalyzed reaction.
7.6.1 Kinetics of enzyme reactions
There are three equations of enzyme- catalyzed reactions which are Michaelis- Menten
equation, Lineweaver – Burk equation and Eadie- Hofstee equation. Let us discuss these
equations one by one:
7.6.1.1 Michaelis- Menten equation
L. Michaelis and M. Menten in 1913 proposed the mechanism of enzyme- catalyzed

reactions. According to them, enzyme (E) combines with substrate (S) and form enzyme-
substrate complex (ES). This enzyme-substrate complex (ES) may form enzyme and
substrate or may form products (P). Here ES is an intermediate. The mechanismis as follows:
(i) E + S ES; rate constant = k1
(ii) ES E + S; rate constant = k2
(iii) ES Products + E; rate constant = k3

Rate of reaction is equal to rate of formation of products (P), therefore:
r = d[P]/ dt = k3 [ES] ………. (1)
Rate of formation of enzyme- substrate complex (ES) is given by:
d [ES]/ dt = k1 [E] [S] – k2 [ES] – k3 [ES]
Applying steady –state approximation: d [ES]/ dt = 0, Therefore:
k1 [E] [S] – k2 [ES] – k3 [ES] = 0 ………. (2)
If [Eo] represents the total enzyme concentration, then: [Eo] = [E] + [ES]
Where [E] is the concentration of free enzyme (enzyme without substrate) while [ES]
represents the concentration of enzyme- substrate complex.
[E] = [Eo] – [ES]
Now on putting the value of [E] in equation 2, we obtain:
k1 ([Eo] – [ES]) [S] – k2 [ES] – k3 [ES] = 0
k1 [Eo] [S] – k1 [ES] [S] – k2 [ES] – k3 [ES] = 0
k1 [Eo] [S] = k1 [ES] [S] + k2 [ES] + k3 [ES]
k1 [Eo] [S] = [ES] (k1 [S] + k2 + k3)
[ES] = k1 [Eo] [S] / k1 [S] + k2 + k3
Now the value of [ES] is placed in equation 1, therefore:
r = d[P]/ dt = k3 k1 [Eo] [S] / k1 [S] + k2 + k3
On dividing the numerator and denominator by k1, we obtain:
r = d[P]/ dt = k3 [Eo] [S] / [S] + (k2 + k3) / k1
r = d[P]/ dt = k3 [Eo] [S] / [S] + KM ………. (3)
Equation 3 is Michaelis- Menten equation where KM is Michaelis constant which is equal to

(k2 + k3) / k1. When all enzyme reacts with substrate then there will be no free enzyme or we
can say [Eo] = [ES]. In this case, rate of reaction is maximum and is represented by Vmax.
Vmax = k3 [Eo]

r = Vmax [S]/ [S] + KM
Three case arises:
• Case 1: When [S] >>> KM

r = Vmax (This shows that rate does not depend on the concentration of the substrate or we
can say that reaction obey zero- order kinetics).
• Case 2: When [S] <<< KM

r = Vmax [S]/ KM (This shows that with increase in concentration of substrate, rate of reaction
increases or we can say that reaction obey first order kinetics)
• Case 3: When [S] = KM

r = Vmax /2 (This shows that when rate of reaction is half the maximum rate, concentration of
the substrate is equal to Michaelis constant). All these three cases are given in Figure 4.
Figure 4. Michaelis- Menten plot
There is a term known as turnover number of an enzyme which is defined as the number of
molecules of reactants which forms the product in unit time by one molecule of an enzyme.
This number is represented by k3.
7.6.1.2 Lineweaver- Burk equation
This equation is reverse of Michaelis- Menten equation. This equation was proposed by
Lineweaver and Burk and is given by:
1/ r = (KM/ Vmax [S]) + (1/ Vmax)
This equation is Lineweaver- Burk equation, where KM is Michaelis constant, Vmax is

maximum rate, r is rate of reaction while [S] is concentration of the substrate. The plot is
given in Figure 5 which is known as Lineweaver- Burk plot.

Figure 5. Lineweaver- Burk plot
7.6.1.3 Eadie- Hofstee equation
This equation of enzyme- catalyzed reaction is given by Eadie and Hofstee which is given as:
r/ [S] = Vmax/ KM – r/ KM
This equation is Eadie- Hofstee equation, where KM is Michaelis constant, Vmax is maximum
rate, r is the rate of reaction while [S] is concentration of the substrate. The plot is given in
Figure 6 which is known as Eadie- Hofstee plot.
Figure 6. Eadie- Hofstee plot
7.7 SUMMARY
We have discussed about the kinetics of fast reactions in which we have studied various
methods like relaxation method, flow method and flash photolysis in order to find the rate of
fast reactions. Along with this, we have also discussed an elementary idea of microscopic
kinetics which is also known by name molecular reaction dynamics. Then we talked about

chain reactions that include mechanism and kinetics of several chain reactions like hydrogen-
chlorine, hydrogen- bromine and pyrolysis of acetaldehyde. After discussing the chain
reaction, we studied about biological catalyst i.e. enzymes in which its mechanism and
kinetics are studied by considering three equations: Michaelis- Menten equation, Lineweaver
– Burk equation and Eadie- Hofstee equation.
7.8 SELF- ASSESSMENT QUESTIONS (SAQ)

1. In old molecular beam method, beam produced possess ………. intensities.
2. In modern molecular beam method, beam produced are of ………. intensities.
3. Molecular reaction dynamics is also known by name ………. kinetics.
4. In molecular reaction dynamics, ………… states of reactants and products are considered.
5. ………. method is commonly used method for determining the rate of fast reactions.
6. In relaxation method, there is change in ………., ………. and ……….
7. For measuring relaxation time, the methods employed are ………. and ……….
8. Molecular reaction dynamics deals with ………. systems.
9. Chain reaction is a type of ………. reaction.
10. According to steady– state approximation, rate of disappearance of an intermediate is

………. to rate of appearance of an intermediate.
11. In hydrogen- bromine reaction, there are to intermediates, ………. and ……….
12. Br2 form two bromine atom by acquiring an energy which is due to ……….
13. In hydrogen- chlorine reaction, there are to intermediates, ………. and ……….
14. ………. is defined as the decomposition of a substance at high temperature.
15. Enzymes are ………. catalysts.
16. Enzymes catalysis is known as ………. catalysis.
17. The complex formed by enzyme with substrate is known as ………. complex.

18. Michaelis constant (Km) is equal to the concentration of the substrate when rate of
reaction is ………. the maximum rate.
19. When concentration of a substrate is greater than Michaelis constant, then reaction obeys
………. order kinetics.
20. When Michaelis constant is more than the concentration of a substrate, then reaction
obeys ………. order kinetics.
7.9 GLOSSARY
• Relaxation: Time required attaining the equilibrium after changing temperature,

pressure and electric field of a system.
• Catalysis: Process by which rate of reaction is changed.
• Enzymes: Biological catalysts that catalyze the reaction occurring in living plants and
animals.
• Pyrolysis: Decomposition of a substance at high temperature.
• Chain reaction: Highly reactive intermediates are formed which carry out a fast
reaction for a long time.

1. Low; 2. High; 3. Microscopic; 4. Quantum; 5. Flow; 6. Temperature, Pressure and Electric
field; 7. Temperature- jump method and pressure-jump method; 8. Quantized; 9. Complex;
10. Equal; 11. H and Br; 12. Collision; 13. H and Cl; 14. Pyrolysis; 15. Biological; 16.
Heterogeneous; 17. Enzyme- substrate; 18. Half; 19. Zero; 20. First.
7.11 REFERENCES

Gurtu, J. N. and Gurtu, A (2015), Advanced Physical Chemistry, Pragati Prakashan, Meerut.

• Describe various methods which are used for the determination of kinetics of fast
reactions.
• Explain kinetics of enzyme-catalyzed reaction by giving all the three equations:
Michaelis- Menten equation, Lineweaver- Burk equation and Eadie- hofstee equation.
• Discuss the kinetics of reaction between hydrogen-bromine and hydrogen–chlorine
reaction.

UNIT 8: CATALYSIS
CONTENTS:
8.1 Introduction
8.2 Objectives
8.3 Catalysis
8.3.1 Types of catalysis
8.4 Adsorption
8.4.1 Thermodynamics of adsorption
8.4.2 Types of adsorption
8.4.2.1 Physical adsorption
8.4.2.2 Chemical adsorption
8.4.3 Factors affecting adsorption
8.4.3.1 Nature of gas
8.4.3.2 Nature of adsorbent
8.4.3.3 Temperature
8.4.3.4 Pressure
8.5 Adsorption curves
8.6 Adsorption isotherm
8.6.1 Freundlich adsorption isotherm
8.6.2 Langmuir’s adsorption isotherm
8.6.3 Gibbs adsorption isotherm
8.7 B.E.T. equation
8.7.1 Determination of surface area
8.8 Catalytic activity at surface

8.9 Summary
8.11 Glossary
8.13 References
8.1 INTRODUCTION
As we know that there are some substances that change the rate of reaction either by
increasing the rate of reaction or by decreasing the rate of reaction without being used up.
These substances are refers to as catalyst and the process by which they change the rate of
reaction is called catalysis. Catalysis is further classified into various types like positive
catalysis, negative catalysis, auto- catalysis, homogeneous catalysis, heterogeneous catalysis.
All these types of catalysis are discussed in detail in upcoming sections.
The present unit deals with the concept of catalysis which is quite interesting. Unit also
contains several headings like types of catalysis, adsorption, types of adsorption, factors
affecting adsorption, adsorption isotherm that includes Freundlich adsorption isotherm,
Langmuir’s adsorption isotherm, Gibbs adsorption isotherm and B.E.T. equation. After going
through the unit it will be clear that how the process of catalysis works at the surface.
There is a catalytic converter in automobiles that contain platinum as catalyst. The platinum
that acts as catalyst convert toxic carbon monoxide into carbon dioxide thereby decreasing
the air pollution. There are several examples of catalysis that are eco- friendly (environment
loving) thereby making the chapter more and more interesting to the reader. Let us now
discuss the complete unit in detail.
8.2 OBJECTIVES
After reading this unit you will be able to:
• Define catalysis.

• Classify catalysis
• List the characteristics of catalyst.
• Explain the process of adsorption including its types.
• Write the factors that affect the phenomenon of adsorption.
• Describe adsorption isotherm, adsorption isobar, adsorption isostere.
• To determine the surface area by using the process of adsorption.
• Explain adsorption isotherm given by Gibbs known as Gibbs adsorption isotherm.
• Describe catalytic activity at a surface.
• List all considerations made by B.E.T.
8.3 CATALYSIS
As discussed above that there are certain substances that change the rate of reaction without
being consumed in the reaction. These substances are known as catalysts and the process or
phenomenon is known as catalysis. The term catalysis was coined by Berzelius. These
substances either increase the rate of reaction or decrease the rate of reaction. There are
several characteristics of catalyst which are discussed below:
• As said above that catalyst remains unchanged in the reaction. Catalyst remains
unchanged in terms of mass and chemical composition but it has been observed that
catalyst undergoes a physical change in which there is change in physical appearance
like if the catalyst is taken in a form of small pellets then at the end of the reaction, it
appears in a form of powder.
• Generally a small amount of a catalyst is needed to change the reaction rate. Like
finely divided (pore size is very small) platinum acts as a catalyst in the
decomposition of hydrogen peroxide. In certain like Friedel Craft’s reactions where
anhydrous AlCl3 is taken as a catalyst, the amount of catalyst is in large amount.
• Specific catalyst can catalyze a particular reaction. This shows that catalyst is specific
in its action. For example, when ethyl alcohol is passed over hot aluminum oxide
(Al2O3), dehydration occurs. Dehydration as the name indicates is the loss of water
thus ethyl alcohol loss water and form ethylene (CH2=CH2). On the other hand,
when ethyl alcohol is passed over hot copper, there is dehydrogenation (loss of
hydrogen molecule) which leads to the formation of acetaldehyde. (CH3CHO). This
shows that Al2O3is the catalyst that causes dehydration and copper is the catalyst that

causes dehydrogenation of ethyl alcohol which confirm that a particular catalyst

catalyze a particular reaction.
• Finely divided catalyst is more specific in its action in comparison to those that are
not finely divided. It has been observed that solid nickel in the form of lumps
possesses less catalytic activity than when it is taken in the form of powder.
• In case of reactions that exist in equilibrium or the reaction is reversible then catalyst
reduces the time needed to establish equilibrium but do not affect the final position
of the equilibrium. It means that the equilibrium can attained earlier by adding the
catalyst. For example, in Haber’s process of synthesis of ammonia, finely divided
iron is used as a catalyst by which equilibrium is attained earlier. The effect of
catalyst on equilibrium is shown in Figure 1.
Figure 1. Effect of catalyst on equilibrium

It is clear from the Figure 1 that with time, rate of forward reaction decreases while
that of reverse reaction increases. When the rate of both the reaction becomes equal,
then there is a state of equilibrium.
• Catalyst generally alters or changes the rate of reaction but do not start the reaction.
But there are certain reactions in which catalyst acts as initiator. There is no reaction
between hydrogen and oxygen at room temperature but in presence of catalyst
(platinum), they react.
• The catalytic activity of a catalyst can be increased by adding certain substance
known as promotors. As discussed above, in Haber’s process of ammonia synthesis,
finely divided iron is used as catalyst. Its activity is increased by adding
molybdenum which acts as promotor.
• There are certain substances that destroy the catalytic activity. These substances are
known as catalytic poisons. Catalytic poisons are also known as anti-catalysts. In

case of Haber’s process of ammonia synthesis, finely divided iron is used as catalyst
while hydrogen sulphide (H2S) destroy the activity of iron catalyst.
• Catalytic activity attains a maximum height or maximum rate at a particular
temperature. This temperature when catalytic activity is maximum is called optimum
temperature. For example, in case of an enzyme which acts as a biological catalyst,
the optimum temperature is 35oC to 37oC.
8.3.1 Types of catalysis
Now coming to the classification of catalysis, we have discussed earlier that catalyst
increases or decreases the rate of reaction. On this basis, catalyst is classified into two types:
• Positive catalysis: A catalysis in which there is increase in the rate of reaction is

known as positive catalysis and catalyst are known as positive catalysts. For example,
finely divided iron as catalyst in Haber’s process act as positive catalyst and the
process is called positive catalysis. Similarly in contact process of sulphuric acid
synthesis, finely divided platinum is used as a positive catalyst. Positive catalyst
lowers the activation energy thereby increasing the rate of reaction as given in Figure
2.
Figure 2. Effect of catalyst on activation energy
• Negative catalysis: A catalysis in which there is a decrease in rate of reaction is

known as negative catalysis and catalysts are known as negative catalyst. In some cases,
negative catalyst even stops the reaction. Negative catalysts are also known as inhibitors. For
example, in the decomposition of hydrogen peroxide (H2O2), dilute solution of acid (H+)
lowers the reaction rate. A very common example of negative catalyst is of TEL. TEL refers
to tetraethyl lead. This catalyst added to petrol which thereby decreases the rate of

combustion of petrol. In absence of catalyst, combustion takes place very rapidly. These
catalyst increases the activation energy thereby decreasing the reaction rate.
Another classification of catalyst depends on the phase of catalyst and reactant. A phase is
defined as a homogeneous part of a system that possesses same chemical and physical
properties. For example, mixtures of gases consist of one phase. It means that when gases are
mixed, we cannot differentiate individual gases which thereby form a homogeneous system
consisting of one phase. Practically, we all know that atmosphere contains several gases that
form one phase. Similarly when sugar is dissolved in water then a clear solution is formed
which is homogeneous and this solution consist of one phase. We say that water exist in three
phase solid, liquid and gas. On the basis of phase, catalysis is classified into two types:
• Homogeneous catalysis: As we know that a system that contains only one phase is
called homogeneous system. Here we are talking about catalysis, then homogeneous
catalysis is defined as a catalyst in which the reactant and catalyst are in same phase.
For example, when reactants and catalyst are in gaseous phase then catalysis is
homogeneous catalysis. When carbon monoxide gas (CO) combines with oxygen gas
(O2) in presence of nitric oxide (NO) as catalyst, there is a formation of carbon
dioxide (CO2). Here reactant CO, O2and catalyst NO are in gaseous phase. Similarly
sulphur dioxide combines with oxygen in presence of nitric oxide as catalyst to form
sulphur trioxide (gas).
2CO + O2+ NO 2CO2+ NO
2SO2 + O2+ NO 2SO3 + NO
As also discussed earlier that when sugar is added to water, it forms homogeneous system
having one phase. Therefore another example of homogeneous catalysis is reaction of cane –
sugar with water (hydrolysis of cane-sugar). In the hydrolysis of cane sugar, the catalyst used
is acid which may be sulphuric acid, hydrochloric acid, nitric acid etc. For this, cane-sugar is
dissolved in water making a clear solution, then acid is added which acts as catalyst. Acid
added is also in liquid phase. Thus we can say that the reactants and catalyst possess only one
phase. It has been found that rate of homogeneous catalysis is more than that of
heterogeneous catalysis.
• Heterogeneous catalysis: A system that consist of more than one phase constitute a
heterogeneous system. When reactants and catalyst possess different phase then the
catalysis is known as heterogeneous catalysis. The rate of this catalysis is less than

that of homogeneous catalysis. For example, when above reaction of sulphur dioxide
and oxygen (both in gaseous phase) reacts in presence of finely divided platinum as
catalyst (solid), then the phase of reactants and catalyst is different. Thus it constitute
heterogeneous catalysis. The chemical reaction is given below:
2SO2 + O2 + Pt 2SO3 + Pt
Another example of heterogeneous catalyst is
N2 + 3H2 + Fe 2NH3 + Fe
2 H2O2+ Pt 2 H2O + O2+ Pt
Here H2O2is present in liquid phase while catalyst, platinum is present is present in solid
phase. When the reactant is in solid phase and catalyst also in solid phase, then the catalysis
is heterogeneous catalysis as two solid constitute two different phase.
In addition to these types of catalysis, there is another type of catalysis known as enzyme
catalysis. Enzymes are large organic molecules produced by living plants and animals. These
are proteins having amino acid as a repeating unit. The catalysis carried by enzyme is called
enzyme catalysis. This catalysis is heterogeneous catalysis. For example, an enzyme diastase
catalyzes the hydrolysis of starch, similarly enzyme zymase convert glucose to ethyl alcohol
and carbon dioxide. Enzymes are considered as biological catalyst each having specific
function. Another type of catalysis is auto-catalysis. In this catalysis, one of the product
formed in the reaction itself acts as a catalyst. For example, when ethyl acetate
(CH3COOC2H5) reacts with water, there is formation of acetic acid (CH3COOH) and ethyl
alcohol (C2H5OH). Acetic acid thus formed acts as a catalyst.
8.4 ADSORPTION
Now the question arises that why solid acts as adsorbent. The reason is that in solid the
molecules are very close to each other or has compact arrangement of molecules having
strong intermolecular force of attraction. The molecules that are present towards the inner
side are attracted equally by other molecules surrounding it from all direction but the
molecules at the surface are attracted by other molecules that are present towards the inner
side. Therefore on the surface unbalanced residual forces are present. In order to balance
these residual forces, the solid surface attracts the molecular species (gas/ vapour / liquid)
towards itself that result in the process of adsorption. Solids with large surface area show
more adsorption. It means that powder of chalk is a better adsorbent than a piece of chalk.

The reverse of adsorption is known as desorption which is defined as a removal of adsorbate

from the surface of adsorbent. Adsorption is an important phenomenon having several
applications like we can remove color of cane-sugar by using animal charcoal (adsorbent),
play an important role in heterogeneous catalysis where reactant and catalyst are in different
phase, softening of hard water, chromatographic analysis. Plants receive nutrients from soil
which is due to adsorption. Certain adsorbent like activated charcoal is used in gas masks
which adsorb harmful gases and provide pure air to breath. Let us now discuss the
thermodynamics of adsorption.
8.4.1 Thermodynamics of adsorption
It is clearly explained above that when adsorption takes place, there is decrease in residual
force that results in the decrease in energy. This shows that during adsorption some energy is
released which is in the form of heat, hence adsorption is an exothermic process. In
exothermic process, energy in a form of heat is evolved hence ∆H is negative. ∆H represents
change in enthalpy which is a measure of heat content of a system. When one mole of
adsorbate (gas or vapour) is adsorbed on a surface of adsorbent, then the amount of heat
evolved or released is called molar enthalpy of adsorption. Now coming to another
thermodynamic function, entropy. Entropy as we know is a measure of randomness or
disorderness of the molecules present in the system. Suppose we have four numbers: 1,2,3,4.
If these are arranged like 1,2,3,4 in a proper order, we say that randomness or disorderness is
zero therefore entropy is zero. If these numbers are arranged like 1,3,2,4 then disorderness
occurs that results in increase of entropy. In adsorption, adsorbate (generally gas) adsorbed
on slid surface. So in adsorption there is decrease in entropy when gas (adsorbate)
accumulates on the surface of solid (adsorbent) as its randomness decreases. Before
adsorption the gas molecules are free to move (more entropy) but after adsorption the
molecules get attached on the surface thereby decreasing its disorderness or randomness.
Here ∆S is negative where S represent entropy and negative sign represents decrease in
entropy. Now coming to another thermodynamic function free energy (G). The relation
between ∆G (change in free energy), ∆H (change in enthalpy) and ∆S (change in entropy) is
given by: ∆G = ∆H – T∆S. As adsorption is a spontaneous process (process that takes place
naturally without any external help) so ∆G is negative. For this ∆H should be more negative
than ∆S.

8.4.2 Types of adsorption
On the basis of nature of interaction between adsorbate and adsorbent, adsorption is classified
into two types: physical adsorption and chemical adsorption.
7.4.2.1 Physical adsorption
Physical adsorption is known as physisorption or van der Waals adsorption. In this type of
adsorption, there is physical force of attraction between adsorbate and adsorbent which may
be due to polarization, dipole moment. The force that exists is weak van der Waals forces. In
this adsorption, more than one layer (multilayer) of adsorbate can form on the surface of the
adsorbent as the force is physical in nature. Therefore it can attract adsorbate molecules that
come under the influence of force. As the force between adsorbate and adsorbent is weak,
therefore heat evolved is low about 4 to 40 kJ mol–1. Physical adsorption is reversible in
nature it means that adsorbed gas or adsorbate can be easily recovered from the surface of the
adsorbent simply by lowering the pressure of a system at the same temperature at which the
adsorption occurs. As we know that desorption is reverse of adsorption, therefore small
amount of energy is required to remove the adsorbate from the surface of the adsorbent.
Hence we say that activation energy of desorption is very low. It has been observed that with
rise in temperature, physisorption decreases. For example, adsorption of gas (hydrogen) on
charcoal.
8.4.2.2 Chemical adsorption
Chemical adsorption is also known as chemisorption. In this type of adsorption, there is

chemical force of attraction between adsorbate and adsorbent that involve electrons. The
force that exist is a strong valence force. In this adsorption only one layer of adsorbate is
formed on the surface of the adsorbent as the force are chemical (ionic bond or chemical
bond) in nature. No multilayer is formed in chemisorption. As the force between adsorbate
and adsorbent is strong, heat evolved during adsorption is high about 40 to 400 kJmol–1.
Chemical adsorption is irreversible in nature it means that gas (adsorbate) once accumulate at
the surface cannot be removed by lowering the pressure of the gas at the same temperature at
which adsorption occurs. As the force is strong, hence activation energy of desorption is very
high. It has been observed that with increase of temperature, chemical adsorption increases.
For example, adsorption of hydrogen gas on the surface of nickel.

Another classification of adsorption is based on the amount of adsorbate on the surface of the
adsorbent. On this basis, adsorption is classified into positive adsorption and negative
adsorption. In positive adsorption as the name indicates, the amount of adsorbate on the
surface of adsorbent is more while in negative adsorption, the amount of adsorbate on the
surface of adsorbent is less. This is all about the classification of the adsorption.
8.4.3 Factors affecting adsorption
We know that as in adsorption, there is an adsorbate and adsorbent. Therefore adsorption

depends on the nature of adsorbate (gas generally) and nature of adsorbent (solid). In addition
to these two factors, adsorption also depends upon temperature and pressure. Let us discuss
these factors one by one:
8.4.3.1 Nature of gas (adsorbate)
It has been observed that gases which are easily liquefiable and readily soluble like NH3, SO2
are adsorbed more readily in comparison to permanent gases O2, N2 because easily
liquefiable gases possess more force of attraction than those gases that are not easily
liquefiable. Critical temperature of a substance is defined as a temperature at which vapour of
a substance cannot be liquefied (change to liquid) no matter how much pressure is applied. It
has been noticed that higher the critical temperature of a gas (adsorbate) more is adsorption.
8.4.3.2 Nature of adsorbent
Adsorption depends on the surface area of adsorbent. More is the surface exposed for
adsorption; more will be the process of adsorption. Hence adsorbent in powder form possess
more surface area resulting in more adsorption. Charcoal, silica gel in powder (porous) form,
finely divided nickel or platinum metal show more adsorption.
8.4.3.3 Temperature
The process of adsorption depends upon the temperature at which it takes place. As we know
that adsorption is an exothermic process, it means that in adsorption heat is evolved. We also
know that heat is related to temperature so with adsorption, temperature decreases. In short
adsorption is inversely proportional to temperature i.e. with increase of temperature,
adsorption decreases and vice-versa. It has been observed that when temperature dropped
from – 29oC to – 78oC, adsorption of nitrogen gas increases in case of coconut charcoal as an
adsorbent.

8.4.3.4 Pressure
The phenomenon of adsorption depends upon the pressure of gas (adsorbate). With
adsorption, pressures of gas decreases as gas molecules are notfree to move after adsorption.
Therefore more decrease in pressure leads to more adsorption while less decrease in pressure
leads to less adsorption.
8.5 ADSORPTION CURVES
We have discussed earlier that adsorption depends upon temperature and pressure. Therefore
adsorption is a function of temperature (T) and pressure (P).
a= f (P, T)
The commonly studied adsorption is adsorption of gas on solid. Here a represents adsorption
or amount of gas adsorbed. In the above expression, there are three terms P, T and a. By
keeping one term constant, a graph is plotted between other two terms. In this way we obtain
three adsorption curves which are discussed one by one below:
• Adsorption isotherm: In this curve, temperature remains constant therefore a graph is

plotted between pressure of a gas (P) and amount of gas adsorbed (a). The graph thus
obtained is called adsorption isotherm which is given in Figure 3.
Figure 3. Adsorption isotherm
• Adsorption isobar: In this curve, pressure remains constant therefore a graph is plotted
between amount of gas adsorbed (a) and temperature (T). The graph thus obtained is
called adsorption isobar which is given in Figure 4.

Figure 4. Adsorption isobar
• Adsorption isostere: In this curve, amount of gas adsorbed (a) remains constant
therefore a graph is plotted between temperature (T) and pressure of a gas (P). The
graph thus obtained is called adsorption isostere which is given in Figure 5.
Figure 5. Adsorption isostere
8.6 ADSORPTION ISOTHERM
Adsorption isotherm as discussed above is obtained by plotting a graph between amount of

gas adsorbed (a) and pressure of a gas (P) at constant temperature. Let us discuss the types of
adsorption isotherm.
8.6.1 Freundlich’s adsorption isotherm
Freundlich proposed an adsorption isotherm known as Freundlich’s adsorption isotherm. He

proposed an empirical equation that relates adsorption (a) with pressure of a gas (P) by a
relation:
a=kPn
where k and n are constant that depends on the nature of adsorbate (gas) and adsorbent.
According to Freundlich, the value of n lies in between zero and one. It means that with

increase of pressure of a gas, the amount of gas adsorbed do not increase to the same extent
as n is less than one. The plot of Freundlich’s adsorption isotherm is same as Figure 3. It is
clear initially with increase of pressure, adsorption increases but after a certain value of
pressure (high pressure), there is no adsorption. Here Freundlich fails as according to him
with increase of pressure of a gas, adsorption increases but the curve shows that at high
pressure, their dependency vanishes. Thus we say that Freundlich’s adsorption isotherm is
valid over a certain range of pressure only.
8.6.2 Langmuir’s adsorption isotherm
Langmuir proposed an adsorption isotherm known as Langmuir’s adsorption isotherm in

which gas is adsorbed in solid. Langmiur made the following assumptions:
• The adsorption is chemical in nature or chemisorption takes place which shows that
only one layer of adsorbate is formed on the surface of adsorbent (solid).
• The surface of adsorbent (solid) possesses equivalent sites that adsorb gas molecules
(one site adsorbs one gas molecule). Thus the surface of solid is homogeneous.
• Adsorbed gas molecules do not interact with each other.
• As the adsorption is chemical in nature, the adsorbed gas molecules do not move over
the surface of the adsorbent i.e. gas molecules are localized.
• There exist a dynamic equilibrium between the adsorbed gas molecules and free gas
molecules.
Langmuir’s adsorption isotherm is given in terms of θ which is thefraction of surfacewhere
adsorption takes place.
θ = KP/1 + KP
where K is constant which is the ratio of rate constant of adsorption process to the rate
constant of desorption process, P represents pressure of gas (G). Two conditions are applied
to the above expression:
• Case 1: When pressure is low: KP << 1, hence KP can be neglected: θ = KP

This shows that fraction of surface covered (θ) is directly proportional to pressure of the gas
raised to power one. Hence it obeys first order kinetics i.e. with increase of pressure θ
increases.
• Case 2: When pressure is high: KP >> 1, hence KP cannot be neglected : θ = 1

This shows that fraction of surface covered or adsorption does not depend on pressure of the
gas and the surface pf solid (adsorbent) is covered completely by monolayer. Both these
cases are represented in Figure 6.
Figure 6. Langmuir’s adsorption isotherm plot
At an intermediate pressure θ = K (P)n; where value of n is between zero and one. This
expression is same as Freundlich’s adsorption isotherm, thus we say that at an intermediate
pressure, Langmuir’s adsorption isotherm obeys Freundlich’s adsorption isotherm.
8.6.3 Gibbs adsorption isotherm
We have discussed earlier that a commonly studied adsorption is gas on solid. Now coming
to adsorption of a solute from a solution (liquid on solid). American physicist, J. W. Gibbs in
1878 proposed an adsorption isotherm called Gibbs adsorption isotherm where solute is
adsorbed from the solution. He relates adsorption with surface tension of a solvent which
changes on adding a solute. Let us consider a solution having two components (solute and
solvent), free energy (G) is given by:
G = n1µ1 + n2 µ2
Where n1is the number of moles of a solvent at the surface; n2 is the number of moles of a
solute at the surface, µ1 and µ2 are chemical potential of solvent and solute respectively.
Gibbs considers the adsorption of solute from the solution due to which there is change in
free energy. Thus:
G = n1µ1 + n2 µ2 + ɣ A ……. (1)
Where ɣ is surface tension and a represent surface area. On complete differentiation of

equation 1, we obtain:
dG = n1dµ1 + µ1dn1 + n2 dµ2 + µ2 dn2 + ɣ dA + A dɣ ………. (2)

It is clear from equation 2 that free energy (G) depends on n1, n2, A, T, P. Hence we can
write:
G = f (T, P, n1, n2, A)
dG = (∂G/ ∂T)P, n1, n2, A dT + (∂G/ ∂P)T, n1, n2, A dP + (∂G/ ∂ n1)T, P, n2, Adn1 + (∂G/ ∂ n2)T, P, n1, Adn2
+ (∂G/ ∂A)T, P, n1, n2dA
From thermodynamic relations:
1. (∂G/ ∂T) P, n1, n2, A = – S
2. (∂G/ ∂P) T, n1, n2, A = V
3. (∂G/ ∂ n1) T, P, n2, A = µ1
4. (∂G/ ∂ n1) T, P, n2, A = µ2
5. (∂G/ ∂A) T, P, n1, n2 = ɣ
dG = – SdT + VdP + µ1dn1+ µ2dn2 +ɣdA
At a particular temperature and pressure; dP = 0; dT = 0
dG = µ1dn1+ µ2dn2 +ɣdA ……… (3)
On comparing equation (2) and equation (3);
µ1dn1+ µ2dn2 +ɣdA = n1dµ1 + µ1dn1 + n2 dµ2 + µ2 dn2 + ɣ dA + A dɣ
n1dµ1 + n2 dµ2 + A dɣ = 0…….. (4)
According to Gibb’s Duhem equation: n1dµ1 + n2 dµ2 = 0
The above equation is for surface of solution which undergoes modifications during
adsorption. There is no change in the bulk phase of a solution as adsorption is a surface
phenomenon. Therefore in bulk phase n1orepresents number of moles of solvent and n2o
represents number of moles of solute. According to Gibb’s Duhem equation: n1o dµ1 + n2o dµ2
= 0 ……. (5)
On multiplying equation (5) by n1/n1o, we obtain:
n1dµ1 + n1n2odµ2 / n1o = 0
Now on subtracting from equation (4), we obtain:

n2 dµ2 – n1n2odµ2 / n1o+ A dɣ = 0
dµ2 (n2 – n1n2o/ n1o)+ A dɣ = 0
dµ2 (n2 – n1n2o/ n1o)= – A dɣ
– dɣ/ dµ2 = (n2 – n1 n2o/ n1o)/ A

The quantity on right side represents excess concentration of solute per unit area (A) of the
surface. This excess concentration is represented by Γ. As Γ is for soluteso we write Γ2 in
place of Γ.Thus
Γ2 = – dɣ/ dµ2……… (6)
The chemical potential of solute is given by: µ2= µ2o+ RT ln a2 ; where µ2ois the chemical
potential of the pure solute when it is in liquid state which is constant and a2is the activity of
the solute.
On differentiation: dµ2= RT d ln a2 ( dµ2o= 0), On putting the value of dµ2in equation (6), we
obtain:
Γ2 = – dɣ/ RT d ln a2
Γ2 = – 1/RT( dɣ/ d ln a2)
Γ2 = – a2 /RT(dɣ/ da2) ……. (7)
Equation 7 represents Gibb’s adsorption isotherm or equation. When graph is plotted between
ɣ and a2 (Figure 7), two case arises:
• Case 1: If dɣ/ da2= negative; Γ2= positive

This shows that excess concentration of solute on the surface increases or adsorption
increases which results in the decrease of surface tension. Here the solute is generally
organic compounds that are not ionized.
• Case 2: If dɣ/ da2= positive; Γ2= negative

This shows that excess concentration of solute on the surface decreases or adsorption
decreases which results in the increase of surface tension. Here the solute is generally
highly hydrated organic compounds or inorganic electrolytes.

Figure 7. Gibbs adsorption isotherm plot
In this way, Gibb’s relates adsorption with surface tension of a solvent that changes on
adding a solute. In case of dilute solution, activity is replaced by concentration. Therefore
equation 7 can be written as:Γ2 = – c2 /RT(dɣ/ dc2)
8.7 B.E.T. EQUATION
B.E.T. equation refers to Brunauer, Emmett and Teller. These are three scientists who
proposed an equation called B.E.T. equation. They consider physical adsorption that a result
in the formation of multilayer means that in addition to monolayer of adsorbate molecules,
bimolecular layer or trimolecular layer also form.B.E.T. consider Langmuir’s adsorptionbut
Langmuir considered chemical adsorption that results in the formation of monolayer of
adsorbate molecules while B.E.T. consider multi-molecular layer formation of adsorbate in
case of physical adsorption. They proposed different postulates:
• The surface of adsorbent is homogeneous (uniform) that contains sites over which
adsorbate molecules attached.
• There is no interaction among the adsorbed molecules.
• Adsorbate molecules form multi-layer on the surface of adsorbent.
• Between successive layers, there is a dynamic equilibrium.
On considering these postulates, B.E.T. derived an equation called B.E.T. equation which is
given below:
Where P is the pressure of gas, Pois saturated pressure of the gas;Vmono represents the volume
of gas adsorbed over the solid adsorbent when it is covered by monolayer of the gas

(adsorbate); Vtotalis the total volume of gas adsorbed when it forms unimolecular layer,
bimolecular layer, trimolecular layer and so on while C is a constant that depends on the
nature of gas. When P/ Vtotal (Po– P) is plotted against P/Po, we obtain a straight line having
intercept 1/ Vmono C and slope (C– 1)/ C Vmono. The graph thus obtained is called B.E.T.
graph or B.E.T. plot which is given below in Figure 8.
Figure 8.B.E.T. plot
Adsorption of nitrogen gas on silica gel (porous form) at –183oC obeys B.E.T. equation. It
has been observed that when P/Pois less than 0.05 or more than 0.35, B.E.T. equation fails.
By using B.E.T. equation we can determine the surface area of the adsorbent.
8.7.1 Determination of surface area
B.E.T. method of determining a surface area is easy. We know that B.E.T. equation is as
follows:
It obeys straight line having intercept 1/ Vmono C and slope (C– 1)/ C Vmono
Intercept + slope = 1/ Vmono C + (C– 1)/ C Vmono
Intercept + slope = 1/ Vmono [1/ C + (C – 1)/ C]
Intercept + slope = 1/ Vmono [1+ C – 1/ C ]
Intercept + slope = 1/ Vmono
Vmono= 1/ Intercept + slope
From this expression, Vmonois calculated by knowing the value of intercept and slope.

At NTP, 22400 ml of gas contains N molecules. Therefore, 1 ml of gas contains N/ 22400

molecules. Vmonoml of gas contains Vmono × N/ 22400 molecules.
Surface area of solid adsorbent = A × Vmono × N/ 22400
Where A is the area of each adsorbed gas molecule. From this expression, we can calculate or
determine surface area of solid adsorbent in which Vmonois calculated by using B.E.T.
equation. By knowing the surface area, we can also determine specific surface area which is
given by the relation: Specific surface area = surface area/ mass of adsorbent
8.8 CATALYTIC ACTIVITY AT SURFACE
Catalytic activity at surface refers to the activity of catalyst that occurs at the surface or that
involves process of adsorption that shows catalysts works at the surface. Catalytic activity at
surface refers to heterogeneous catalysis in which catalyst and reactant are in different phase.
There are free valencies on the surface of catalyst by which it allow the reactants to react
chemically on its surface. Catalyst activity at surface involves the following steps: suppose
we have two gaseous reactant X and Y. Now when these reactants come in contact with a
catalyst, they spread over the surface of the catalyst. This process is called diffusion (a). On
the surface of catalyst as we know free valencies are present due to these free valencies,
reactant molecules get adsorbed on the surface of the catalyst by forming a chemical bond
(b). Hence the adsorption is chemical adsorption. Now after adsorption, reactant molecules
(X and Y) interact with each other and form an activated complex (c). In activated complex
as we know that no bond is rigid and it is a state of high energy. Activated complex thus
formed decompose to give products which then diffuse from the catalyst surface by
desorption thereby regenerating the free valencies on the surface of the catalyst (d). All these
steps are consecutive i.e. takes place one after the other. The slowest step or rate determining
step in heterogeneous catalyst is the step in which products formation takes place. The
complete process is described below in Figure 9 by considering the reactant (X and Y) while
catalyst is finely divided metal.

Figure 9. Catalytic activity at surface
8.9 SUMMARY
In this unit, we have discussed about the concept of catalysis in detail that includes definition,
types of catalysis. Then we move to adsorption, factors affecting the adsorption, types of
adsorption and various adsorption isotherms that include Freundlich’s adsorption isotherm,
Langmuir’s adsorption isotherm, Gibb’s adsorption isotherm and B.E.T. equation.
8.10 SELF ASSESSMENT QUESTIONS (SAQ)

1. Positive catalyst ………. the rate of reaction.
2. Negative catalyst……… the rate of reaction.
3. The term catalysis was coined by ……….
4. Positive catalyst increases the rate of reaction by ………. the activation energy.
5. Negative catalyst decreases the rate of reaction by ………. the activation energy.
6. In Haber’s process of ammonia synthesis, finely divided ………. is used as a catalyst.
7. Catalytic activity increases by adding certain substances known as ……….

8. In homogeneous catalysis, both reactant and catalyst possess ………. phase.
9. In heterogeneous catalysis, both reactant and catalyst possess ………. phase.
10. Enzymes acts as ………. catalysts.
11. Adsorption is a ………. phenomenon while absorption is a ………. phenomenon.
12. Reverse of adsorption is ……….
13. Catalyst possess ………. on their surface in order to show the phenomenon of catalysis.
14. ………. adsorption isotherm relates adsorption with surface tension of a solvent.
15. B.E.T. equation was proposed by ………., ………. and ……….
8.11 GLOSSARY
• Catalysis: Phenomenon by which there is a change in the rate of reaction.

• Promotors: Substances that increases the catalytic activity.
• Inhibitors: Substances that decreases the catalytic activity.
• Positive catalyst: Catalyst that increases the rate of reaction.
• Adsorption: Phenomenon of accumulation of a substance on the surface of a solid.

1. Increases; 2. Decreases; 3. Berzelius; 4. Lowering; 5. Increasing; 6.Iron; 7. Promotors; 8.
Same; 9. Different; 10. Biological; 11. Surface, bulk; 12. Desorption; 13. Free valencies; 14.
Gibb’s; 15. Brunauer, Emmett and Teller
8.13 REFERENCES

Gurtu, J. N. and Gurtu, A (2015), Advanced Physical Chemistry, Pragati Prakashan, Meerut.

• Explain the phenomenon of catalysis in detail along with its classification.

• Define adsorption and discuss the various factors that affects the process of adsorption
along with its classification.
• Explain B.E.T. equation along with its application in determining the surface area of
the adsorbent.

UNIT 9- ELECTROCHEMISTRY-I
CONTENTS
9.1 Objectives
9.2 Introduction
9.3 Activity, activity coefficient, mean ionic activity and mean activity coefficient of
electrolytes, ionic strength of electrolytic solution
9.3.1 Activity and activity coefficient of electrolytes
9.3.1.1 Activity
9.3.1.2 Activity coefficient of a solution:
9.3.2 Mean ionic activity and mean activity coefficient of electrolytes
9.3.2.1 Mean ionic activity
9.3.2.2 Mean activity coefficient of electrolytes
9.3.2.3 Relation between mean activity and mean activity coefficient of electrolyte
9.4 Methods of determination of mean activity coefficient of electrolytes
9.4.1 EMF measurement method
9.4.2 Solubility method:
9.4.3. Freezing point depression measurement method
9.4.4 By Debye- Huckel limiting law
9.4.5 Ionic strength of electrolytic solutions
9.5 Drawbacks of Arrhenius theory and advent of Debye-Huckel theory
9.5.1 Drawbacks of Arrhenius theory
9.5.2 Debye-Huckel theory of strong electrolytes
9.6 Electrochemistry of solutions and Debye-Huckel treatment of dilute solutions
9.7 Summary

9.9 References
9.1 OBJECTIVES
After you have studied this chapter, you should be able to:
1. Describe the drawbacks of Arrhenius theory of weak electrolytes and need of a

theory to explain the behavior of strong electrolytes.
2. Define activity, activity coefficients of solutions and mean ionic activity, mean
activity coefficient of electrolytes.
3. Elucidate the need of mean ionic activity and mean activity coefficient for
electrolytic solutions.
4. Explain the concept of ionic strength and calculate the ionic strength of
5. List different methods to determine mean activity coefficient of electrolytes.
6. Describe different methods to determine mean activity coefficient of electrolytes
7. Describe the salient features of Debye-Huckel theory for electrolytic solution.
8. Explain ionic atmosphere of a given ion in electrolytic solution and its effect on
conductivity of electrolytic solutions.
9. Apply Debye-Huckel treatment to explain electrochemistry of dilute solutions. .
9.2 INTRODUCTION
Electrochemistry is the branch of chemistry which deals with the relationship between
electrical and chemical energy and their interconversion. Electrochemistry generally deals
with the electrical properties of electrolytes in their aqueous solutions. There are two types of
electrolytes, namely, weak and strong electrolytes. The weak electrolytes have low degree of
dissociation and furnish very few ions in their solutions. Strong electrolytes have high degree
of dissociation and give large number of ions in their aqueous solutions.
Arrhenius theory of electrolytes states that there is partial dissociation of electrolytes into
ions in their aqueous solution. There exists a dynamic equilibrium between the ions and
undissociated electrolyte. This theory is readily applicable to weak electrolytes but fails to
explain the behavior of strong electrolytes. There are several limitations of Arrhenius theory
out of which one is the Ostwald dilution law. This law is based on Arrhenius theory of
dissociation that holds good for weak electrolytes but fails to explain the dissociation of

strong electrolytes. The limitations of Arrhenius theory have originated the need of more
acceptable theory for strong electrolytes. Debye Huckel theory which assumes complete
dissociation of electrolytes in aqueous solution holds interionic interactions responsible for
the deviation of strong electrolytic solutions from ideal behavior. Before describing the
salient features and application of this theory, we shall discuss some of the basic
thermodynamic properties of the ionic solutions viz. ionic strength , activity, mean activity
etc. which will help us to understand the Debye Huckel treatment of the electrolytic solutions.
9.3 ACTIVITY, ACTIVITY COEFFICIENT, MEAN IONIC

ACTIVITY AND MEAN ACTIVITY COEFFICIENT OF
ELECTROLYTES, IONIC STRENGTH OF ELECTROLYTIC
SOLUTION
9.3.1 Activity and Activity Coefficient of Electrolytes
9.3.1.1 Activity
Thermodynamic properties of ideal solutions can be explained in terms of chemical potentials

and activities. Electrolytic solutions on the other hand differ from non electrolytic solutions
since electrolytes dissociate into ions in their solutions and there are strong interactions
among these ions. It results into deviation from the ideal behavior.
For ideal solutions, molal concentrations can be used to describe the activity of the solution
but for ionic solutions this approximation is correct only for very dilute solutions where ionic
interaction in the solution can be neglected. The term activity and activity coefficients
become significant in such cases.
Activity of a component of solution can be defined as its effective concentration. For an ideal
solution activity of a component is equal to its concentration whereas in case of non-ideal
solutions, activity (a) of a component is directly proportional to the concentration of the
component.
a= γ C where γ is called as activity coefficient of the component.
So, Activity of a component can be expressed in terms of molarity (M), molality (m) or mole
fraction (χ) of the component as
a=γ.M

a=γ.m
a=γ.x
For ideal solutions, γ=1, so a=C
9.3.1.2 Activity Coefficient of a Solution:
Activity coefficient is a factor used in thermodynamics to express the properties of non-ideal

solutions such as solutions of electrolytes. It can be defined as the ratio of activity of a
component and concentration of the non-ideal solution: γ = a/C , where C may be in terms of
molality, molarity or mole fraction . The value of γ is unity for ideal solutions so its values
other than 1 indicate the extent of deviation from the ideal behavior. Since activity coefficient
is a ratio it is a dimensionless quantity with no unit.
89.3.2 Mean Ionic Activity and Mean Activity Coefficient of Electrolytes
9.3.2.1 Mean Ionic Activity of Electrolytes
In case of nonelectrolytic solutions viz. solution of sugar in water, activity of solution refers
to the activity of its component i.e. sugar in the solution. In similar manner, activity of salt
present in solution refers to the activity of salt dissolved in the solution. Since dissolved salt
dissociates into ions, activity of solution should refer to activity of cations and anions. In
other words, activity of electrolytic solutions depends on activities of its ions but it is not
possible to measure the activities of individual ions due to following reason. Solutions of
electrolytes are electrically neutral. Any additions of cation or anions alone, if at all possible,
make the solutions electrically charged. The properties of ions in such a charged solution will
be different from that of electrically neutral situation. Since there is no way to measure
individual effect of cations and anions so it is not possible to measure the individual ionic
activity. So, activity of an electrolytic solution is defined in such a way that it includes the
equal contribution from cations and anions. This definition includes a term; Mean activity of
electrolytes (γ±).
Mean activity of electrolytic solution is defined as the geometric mean of the ionic activities.
Mathematically, for an electrolyte AxBy which dissociates as
AxBy xA+ +yB-
Where, total number of ions present in solution =x+y
Mean activity coefficient of electrolyte is expressed as:

γ±=[(a+)x.(a-)y] 1/x+y=(a±)x+y
(8.01)
Let us understand it in terms of chemical potential of a solute in a solution.
Chemical potential (µ) of a solute in an ideal solution is mathematically defined as,
µ real= µ0+RT In m (8.02)
Where, µ0 is standard chemical potential of solute and m is the molality of solution.
For non-ideal (real) solutions the chemical potential of a solute is expressed in terms of its
activity in the solution.
µ real= µ0+RT In a
µ real= µ0+RT In m. γ (Since a= m. γ )
Or, µ real= µ0+RT In m+RT In γ (8.03)
Substituting value from Equation No. 8.02 in Equation No.8.03,
µ real= µ ideal+RT In γ (8.04)
In the Equation No. 8.04,
µ real= µ ideal as
So, the deviation from ideality lies in the activity coefficient of solute.
For an electrolytic solution, components of solution include cations and anions. The total
molar Gibbs energy of an ideal solution of an electrolyte AX where A+ is univalent cation
and X- is univalent anion, is given by the expression
G ideal=µ+ideal+ µ-ideal
Where µ+ideal and µ-ideal are the chemical potentials of cation and anion respectively.
Similarly, total molar Gibbs energy of a non-ideal (real) solution is given by the expression
G real=µ+real+ µ-real (8.05)
From Equation No. 8.04,
µ+real= µ+ ideal+RT In γ+ (8.06)
And
µ-real= µ- ideal+RT In γ- (8.07)

Where, γ+ and γ- are activity coefficients of cation and anion respectively.
Substituting these values from Equation No.8.06 and 8.07 in Equation No.8.05
Greal=µ+real+RTlnγ++ µ-ideal +RT In γ-
Or Greal=µ+ideal+ + µ-ideal +RT In γ+γ-
Or Greal=µ+ideal+ + µ-ideal +RT In γ+γ- (8.08)
So, the total molar Gibbs energy of a solution of electrolyte depends on the activity
coefficients of cation and anion.
9.3.2.2 Mean Activity Coefficient of Electrolytes
An electrolyte undergoes dissociation in its aqueous solution. So the components of

electrolytic solutions include cations and anions. Theoretically, like a nonelectrolytic
solution, activity of an electrolytic solution should be the total contribution of activities of
cations and anions. But in an electrolytic solution, since cations and anions are inseparable, it
is not possible to measure their activity and activity coefficients separately.
So, for a real solution of electrolytes, a new term mean activity coefficient is introduced to
assign the nonideality of solution to the constituent ions. Mean activity coefficient is defined
as the geometric mean of the activity coefficients of cation and anion.
Mathematically, for a 1:1-electrolyte i.e. electrolyte having univalent cation and univalent
anion, the mean activity coefficient is defined as (γ+ γ-)1/2.In general, for an electrolyte AxBy
that dissociates in the aqueous solution as follows,
AxBy xA+ +yB-
The mean activity coefficient = [(γ+)x (γ-)]1/(x+y) (8.09)
9.3.2.3 Relation between Mean Activity And Mean Activity Coefficient Of Electrolyte
For an electrolyte AxBy this dissociates in the aqueous solution as follows,
Total number of ions=x+y
(8.10)
By definition of activity coefficient, and
Substituting it in Equation No 8.10,

Or, )
Or, (8.11)
As, the term in square bracket in Equation No. 8.11 is the geometrical mean of molality of
cations and anions, it can be written as mean molality of the solution
So the Equation No. 8.11 can be rewritten as,
(8.12)
9.4 METHODS OF DETERMINATION OF MEAN ACTIVITY

COEFFICIENT OF ELECTROLYTES
In order to ascertain whether a strong electrolyte in its solution behaves as an ideal or
showing deviation from ideality, it is important to know its activity. If its activity is equal to
its concentration it behavior is ideal. In case, if it deviates from this behavior it has activity
lower than its solution. It is easy to Calculate its activity if its activity is known to us. There
are several methods of determination of activity coefficients. Important among them are:
1. EMF measurement method

2. Measurement of Solubility of sparingly soluble salts
3. Freezing point depression measurement method
4. Debye- Huckel method
9.4.1 EMF Measurement Method
This method is explained taking the example of determination of activity coefficient of HCl.
A cell is setup by coupling Hydrogen electrode with Ag-AgCl electrode.

The hydrogen electrode contains the HCl solution for which activity coefficient is to be
determined. Both the electrodes are immersed in the same solution i.e. a cell without
transference is setup.
Representation of cell: Pt, H2 (g) (P= 1atm) // HCl (m1) AgCl(s) / Ag(s)
As the representation shows, hydrogen electrode acts as anode and Ag-AgCl electrode as
cathode.
Following half cell reactions take place in the cell:

At Anode: 1/2H2(g)=H+(aq)+e-
At Cathode: AgCl(s)+ e-= Ag(s)+Cl- (aq)
Cell Reaction: 1/2H2(g)+AgCl(s)=Ag(s)+H+(aq) Cl-(aq)
The emf of this cell can be given by Nernst equation as:
(8.13)
If pH2 then Equation (17) becomes,
Since,
For HCl, HC So, x =1 and y =1
So, Or,
So,
Or,
Since, And
Again for HCl, HC
m m m
So ,
Or,
Or,
Or,
So,

So,
Or,
(8.14)
The above equation is used to determine the mean activity coefficient of the electrolyte
Procedure:
A number of electrodes having different known concentration of HCl are setup and EMF of
each such setup is measured. A graph is plotted between and .
So,
Or,
Fig.8.01: Determination of mean activity coefficient by EMF method
9.4.2 Solubility Method:

Solubility of sparingly soluble salts depends on charge and concentration of ions in solution.
The mean activity coefficients of the sparingly soluble electrolytes can be determined by
solubility method.This method of determination of mean activity coefficient involves the
following principle.
When a sparingly soluble electrolyte AxBy is dissolved in water, it undergoes ionization.

There exists a dynamic equilibrium between undissolved salt and its ions in a saturated
solution. According to law of mass action,
(8.15)
Since activity of AxBy is assigned as unit, equation No. 8.15 becomes
K=(aA+)x(aB-)y
The constant K is known as activity product of electrolyte. Since a=γc
So, a+=γ+C+
And a-= γ-C-
So, K
Let S is the solubility of electrolyte
Or, K
Procedure:
For the experimental determination of mean activity coefficient by solubility method,

solubility of a given salt at various ionic strengths is experimentally measured. It is important
to know that solubility of sparingly soluble salts is the function of ionic strength.
Solubility values are plotted against square root of ionic strength .Plot results into a straight
line with positive slope (Fig. 8.02).
As,
So, at
Once the value of k is known, it is possible to calculate the value of

.

Fig. 8.02: Determination of mean activity coefficient by solubility product method
9.4.3. Freezing Point Depression Measurement Method

Activity coefficient of electrolytes can be calculated by measuring the depression in freezing
points of solutions of different strength. A detailed theory of the method is given below:
If in a binary solution,1 stand for solute and 0 for solvent, then its chemical potential given
by Gibbs-Duhem equation is,
nodµo+ n1dµ1=0 (8.18)
Where,
no = number of moles of solvent
n1=number of moles of solute
µo = chemical potential of solvent
µ1= chemical potential of solute
In general, chemical potential of a component A in a nonideal solution is given by the

expression,
µ (8.19)
Where, µoA is the Chemical potential of A in its standard state and aA is Activity of A
Equation No. 8.18 can be expanded by using Equation No 8.19,

(8.20)
According to Gibbs- Duhem equation, nodµo+n1dµ1=0, The Equation No.8.18 can be

rearranged as,

n1RTdlna1+noRTdlnao=0
Dividing this equation by RT, we get,
n1dlna1+nodlnao=0
(8.21)
The following expression correlates activity of solvent with temperature variation
(8.22)
Where ∆Hf , is the Latent heat of fusion.
Depression in Freezing point is given by ∆T= (To- T)
Where, To is the freezing point of pure solvent and T is freezing point of the solution.
On differentiation, d(∆T)= d(To- T) =-d(T), therefore equation (8.22) can be written as
(8.23)
Substituting value from Equation No. 8.23 into Equation No. 8.21 we get,
Since where MA is the molar mass of A
So,
(8.24)
By definition, activity where,
So,
(8.25)

Or,
Substituting value from Equation No.8.25 into equation No. 8.24
(8.26)
Let,
Then, on differentiation,
On rearranging the above equation,
On substituting value of x back,
(8.27)
Equating Equation No. 8.26 and 8.27,
On integrating the Equation
γ (8.29)
In the actual experiments, a number of solutions of electrolyte of known concentrations are

prepared and the depression in freezing point is determined for each of them. A graph is
plotted between x and molality. Area under this graph gives the value of
(Fig. 8.03).
This value is substituted in the Equation No 8.29 to get the value of .

Fig. 8.03: Determination of mean activity coefficient by Freezing Point method
9.4.4 By Debye- Huckel Limiting law

In 1923, Dutch chemist Peter Debye and German physicist Erich Huckel put forward a new
theory of strong electrolytes was which holds interionic forces responsible for deviation of
electrolytic solutions from ideality. A detail discussion of this theory will be given in Chapter
No.9.
Based on assumptions of complete dissociation of strong electrolytes at any concentration

and presence of extra free energy in solution due to interionic interaction, Debye and Huckel
arrived at an expression for mean activity coefficient of electrolytic solution with ionic
strength of solution as below:
γ±=-A│z+z-│√I (8.30)
Where, A is a constant. For water A = 0.509 at 298 K, γ± is the mean activity coefficient of
electrolyte. z+ and z- are magnitude of valence of cations and anions respectively and I is the
ionic strength of electrolytic solution.
This equation shows the value of mean activity coefficient of an electrolyte decreases with
increase in the ionic strength. The decrease is higher with increase in valence and decrease in
the dielectric constant of the solvent. This equation is called as a limiting law because while
deriving the equation it has been consistently assumed that these approximations are
applicable only when dilution approaches to infinity. So this equation is not expected to hold
good for concentrated solutions. Practically, this equation has been substantiated by the data
obtained for electrolytic solutions having concentration less than 1mmolkg-1 or with ionic
strength less than 0.001.
This equation can be used to determine mean activity coefficient of an electrolyte

experimentally in dilute solutions.

9.4.5 Ionic Strength of Electrolytic Solutions

Many of the properties of electrolytic solution depend upon the combined effect of
electrostatic field of various ions present in solution. Solubility of sparingly soluble salts,
activity coefficient of electrolytes, rate of ionic reactions are some of the properties which
depend on the total strength of ionic interaction in solution. For example CaSO4 is a sparingly
soluble salt but its solubility in sea water is much higher than that in fresh water. The reason
behind this fact is the ionic interaction in sea water is higher due to high concentration of
ions.
Lewis and Randall introduced a new function for electrolytic solutions in order to show the
dependency of properties of electrolytic solutions on the electrostatic interactions between
ions. This function of ionic concentration is known as Ionic Strength (I).
Ionic strength of a solution is defined by
I= (8.31)
Where, mi is molality of ith ion and zi is charge on ith ion.
Concept of ionic strength takes in consideration both the factors, concentration of charge and
magnitude (valence) of ion. In the above example, ionic strength of sea water is around
against 1 that of lake water. High ionic strength of
sea water can be attributed to high concentration of ions viz. concentration of
whereas it’s just in lake water. Other ions viz.
Mg2+, Ca2+, K+, Cl- etc. also add to ionic strength of sea water.
9.5 DRAWBACKS OF ARRHENIUS THEORY AND ADVENT OF

DEBYE HUCKEL THEORY
9.5.1 Drawbacks of Arrhenius Theory

Swedish chemist Svante August Arrhenius (1859-1927) proposed theory of electrolytic
solution in 1887. It was based on the findings of Kohlrausch Law and enthalpy of
neutralization data. As stated earlier in this chapter, Arrhenius theory of electrolytes states
that there is partial dissociation of electrolytes into ions in their aqueous solution and also,
there exists a dynamic equilibrium between the ions and undissociated electrolyte. The
dissociation increase with dilution accordingly equivalent and molar conductivity of solution

also increases with dilution. The reverse is also true which states, concentrated solutions of
electrolytes have lower degree of dissociation and thus lower molar and equivalent
conductivity. This theory is readily applicable to weak electrolytes but fails to explain the
behavior of strong electrolytes.
Main limitations of Arrhenius theory are:
(i). Ostwald Dilution Law which is an important outcome of Arrhenius theory, holds good for
weak electrolytes but fails miserably for strong electrolytes.
(ii). Degree of dissociation of strong electrolytes could be calculated from Kohlrausch Law
(i.e. α= ) and also from van’t Hoff factor. In actual, when calculated from these two
methods, values of degree of dissociation were far from concordant and varied to great
extent which raised doubts about following of Arrhenius theory by strong electrolytes.
(iii). Enthalpy of neutralization for the reaction between a strong acid and a strong base is
always constant(i.e.57.3 KJmol-1). It does not change with dilution. According to Arrhenius
theory, strong electrolytes (and therefore, strong acids and strong bases) have high degree of
dissociation (not completely dissociated!!!) so there should be some change, howsoever
small, in their degree of dissociation with dilution which should be reflected by change in
enthalpy of neutralization. But there is no such observation for neutralization reaction
between strong acid and strong base.
(iv). Danish physical chemist N J Bjerrum examined absorption spectra of solutions of many
strong electrolytes between 1909 to 1916 and he observed no evidence for the existence of
undissociated molecules of electrolytes in solution.
(v). Arrhenius theory gives no emphasis on the role of solvent in the behavior of strong
electrolytes in solution. In this theory solvent remains passive and merely plays as a medium
of ionic behavior.
These drawbacks rejected Arrhenius theory of strong electrolytes and posed a challenge
before the scientific community to devise a new theory that could explain the behavior of
strong electrolytes in solution, deviation of such solutions from ideality in more satisfactory
manner.
9.5.2 Debye Huckel Theory of Strong Electrolytes

Theory of strong electrolytes was put forward by Dutch chemist Peter Debye and German
physicist Erich Huckel In 1923, which addresses anomalies of Arrhenius theory. It’s a
mathematical treatment for the behavior of strong electrolytes in solution that holds interionic
forces responsible for deviation of electrolytic solutions from ideality.
Main postulates of Debye- Huckel theory are:
(i). Complete dissociation of strong electrolytes: Strong electrolytes are completely

dissociated into ions in their aqueous solutions. This is in contrast to the postulate of
Arrhenius theory which states about high degree of dissociation of strong electrolytes (but not
complete dissociation!!!).The 100% dissociation of strong electrolytes in aqueous solution is
in agreement with Bjerrum’s observation of spectroscopic studies of aqueous solution of
electrolytes.
(ii).Electrostatic interactions between ions in aqueous solution and ionic atmosphere: Ions
present in the solution exhibit electrostatic interaction. As a result, distribution of ions in
aqueous solution is not completely at random. In the immediate vicinity of a given central
ion, chances of finding a counter ion are more due to electrostatic attraction i.e. more anions
tend to be present around a cation and vice versa. Thus, on an average, a given central ion is
surrounded by ions of opposite charge. This results into formation of a screening layer of
oppositely charged ions around a central ion. This hallow of counter ions surrounding a given
central ion is termed as its ionic atmosphere. A pictorial representation of ionic atmosphere is
given in Fig. 8.01.
Ionic
Atmosphere
Central ion
Fig. 8.01: Symmetrical ionic atmosphere around a central ion
(iii). Reason for deviation from ideality: Though the strong electrolytes are completely
ionized in their aqueous solutions, they show nonideality in their behavior viz. fall in molar

conductivity. These deviations from ideality become more pronounced with increase in
concentration. There are two reasons behind this deviation:
(i) Asymmetry Effect (ii) Electrophoretic Effect

Let us understand these two terms one by one:
(i) Asymmetry Effect: For a stationary given central ion, its ionic atmosphere tends to be
spherically symmetrical around it. When the central ion moves towards its electrode under
the influence of applied electrical field, the ionic atmosphere still relaxes around it so the
symmetry of ionic atmosphere gets distorted. Though this decay in ionic atmosphere is
overcome by formation of new ionic atmosphere but there is a time lag between development
of asymmetry and regaining of symmetry in ionic atmosphere. As a result, ionic charge
density in the ionic atmosphere is more behind the moving ion than in front of it (Fig. 8.02).
This distortion of symmetry of charge density and accumulation of oppositely charged ions
more on back side of the ions exert a net backward electrostatic pull on the moving ion which
retards it. This retardation effect of distorted ionic atmosphere on the ionic velocity is known
as Asymmetry or relaxation effect. This effect is greater at higher concentration; thereby
retardation of ionic mobility is higher at higher concentration.
Debye-Huckel derived expression for force due to relaxation effect on the basis of theoretical
consideration of this effect.
According to them,
(8.32)
Relaxing ionic atmosphere
Direction of movement of central ion
Fig.8.02: Ionic atmosphere showing asymmetry effect

(ii) Electrophoretic effect: There is one more way by which the ionic atmosphere of a
given central ion hampers its motion and retards ionic mobility. The counter ions of ionic

atmosphere are solvated i.e. the ions are attracted to solvent molecules around them by ion-
dipole interactions. The ions of ionic atmosphere also move towards respective electrode
under the influence of applied electrical field (and of course it’s the direction opposite to the
direction of movement of central ion). These moving ions tend to drag the associated solvent
molecules with them. As a result, a moving central ion has to move against the stream of
these counter ions and solvent molecules which move along the counter ions present in ionic
atmosphere. This upstream movement further reduces the mobility of central ion. This
impediment of ionic mobility of central ion due to movement of solvent molecules bound
with counter ions of ionic atmosphere is termed as Electrophoretic effect.
Debye and Huckel derived expression for electrophoretic force acting on ith ion applying
Stokes law to the electrolytic solution. It comes out to be,
(8.33)
Various symbols used in the above Equation No.8.32 and 8.33 stands for,
ki=Frictional coefficient on ith ion due to solvent
e=Electronic charge
k=Reciprocal of thickness of ionic atmosphere
V=Potential gradient under which ith ion is moving
η=Coefficient of viscosity
a number defined by,
Where
As these two effects namely; asymmetry and Electrophoretic effect are more pronounced at
higher concentration, ionic mobility is adversely affected more at higher concentration. As a
result, even after complete ionization, strong electrolytic solutions show deviation from ideal
behavior viz. lower molar conductivity.
Theoretical treatment of ionic movement, led Debye and Huckel to calculate the retarding
forces acting on the central ion due to asymmetry and electrophoretic effect. This helped to
refine the concept of conductivity of strong electrolytes and led to another important
relationship in electrochemistry known as Debye-Huckel-Onsager equation. It has been
treated in detail in the next chapter.

Solvated ions of Ionic

atmosphere
Central ion
Fig.8.03: Electrophoretic effect
9.6 ELECTROCHEMISTRY OF SOLUTIONS AND DEBYE-

HUCKEL TREATMENTOF DILUTE SOLUTIONS
Debye-Huckel theory is quite successful in explaining electrochemistry of dilute solutions of
strong electrolytes. Debye-Huckel treatment considers complete ionization of strong
electrolytes in their aqueous solution at any concentration. Unlike Arrhenius theory, the
strong electrolytes are although completely ionized but not dissociated.The ions interact with
each other in the solution. This interionic interaction results into extra free energy in solution.
This is responsible in deviation of strong electrolytes solution from ideal behavior and
decreased observed molar conductivity.
According to it, under the influence of external electrical field when a given ion moves
through the solution towards its respective electrode its mobility is impeded by presence of
ionic atmosphere as well as solvation of ions of ionic atmosphere. As the ion moves to new
position, it tends to drag its ionic atmosphere. However, the ionic atmosphere still relaxes so
the symmetry of ionic atmosphere gets distorted. There is a time lag between development of
asymmetry and regaining of symmetry in ionic atmosphere. As a result, there is net increase
of ionic charge density behind the moving ion than in front of it. This accumulation of
oppositely charged ions exerts a net backward electrostatic pull on the moving ion which
retards it. This retardation effect on the ionic velocity is known as asymmetry or relaxation
effect. Apart from this, there is one more way by which the ionic atmosphere retards ionic
mobility. The counter ions of ionic atmosphere are solvated. The ions of ionic atmosphere
also move towards respective electrode under the influence of applied electrical field in a
direction opposite to that of central ion. These moving ions tend to drag the associated
solvent molecules with them. As a result, a moving central ion has to move against the stream

of these counter ions and solvent molecules which move along the counter ions present in
ionic atmosphere. This upstream movement further reduces the mobility of central ion. This
impediment of ionic mobility of central ion due to movement of solvent molecules bound
with counter ions of ionic atmosphere is termed as electrophoretic effect. Magnitude of
relaxation and electrophoretic effect increases with the concentration of the electrolytic
solution as well as with the charge of ions present in solution.
It is worth mentioning here, Norwegian-born American physical chemist Lars Onsager
modified this concept of conductivity of strong electrolytes later on. He proposed that moving
ions collide with the solvent molecules of which are almost of similar dimension to that of
ions. These collisions reduce the ionic mobility as this result into zigzag Brownian movement
of the ions. It can be considered as frictional resistance of solvent to the ionic mobility.
A moving ion, sooner or later, gains a steady state motion at which propelling electrical force
of forward motion is balanced by sum of opposing forces i.e. asymmetry force,
electrophoretic force and frictional force of solvent.
In case of weak electrolytes viz. ammonium hydroxide or acetic acid, only partial hydrolysis
takes place in their aqueous solution giving very few ions. These ions at normal concentration
are far from each other. The large distance between these ions rules out ionic interactions and
any effect such as electrophoretic or asymmetry effect arising thereby. There behavior in
aqueous solution can be explained by Arrhenius theory.
9.7 SUMMARY
Electrolytes are the substances which undergo ionization in their aqueous solution. As a result
electrolytic solutions are good conductor of electricity. Weak electrolytes undergo partial
dissociation in water and there exists a dynamic equilibrium between ions and undissociated
molecules. Conductivity and behavior of weak electrolytes can be explained on the basis of
Arrhenius- Ostwald theory. Strong electrolytes on the other hand ionize but not completely
dissociated at any concentration in their aqueous solution. This deviation from ideality is
measured in terms of their mean activity. Depressions in freezing point, EMF method,
solubility method, Debye-Huckel limiting law method are some of the methods to determine
the mean activity coefficient of electrolyte. Behavior of strong electrolyte and their deviation
from ideality can be explained by Debye-Huckel theory. This theory claims that ions are not
free even in solution and there exists interionic interactions in electrolytic solution. These
interactions lead to extra free energy in solution which can be held responsible for deviation

from ideality. Interionic interaction leads to formation ionic atmosphere around a given ion.
This ionic atmosphere impedes the ionic mobility of central ion by relaxation effect an
electrophoretic effect. This is why, strong electrolytes show lower molar conductivity than
expected even though they are completely ionized in their aqueous solution.

1. List four drawbacks of Arrhenius theory that forced scientist to develop new theory of
strong electrolytes.
2. What is meant by activity of a solution? Why is it necessary to use the term mean activity
instead of activity for electrolytic solutions?
3. What is meant by ionic strength of a solution? Calculate ionic strength of a solution which
is prepared by mixing 50ml of 0.1M NaCl and 50ml of 0.2M CaCl2?
4. List four methods to determine mean activity coefficient of electrolytes? Explain principle
of solubility method for determination of mean activity coefficient.
5. Explain principle and method of determination of mean activity coefficient of strong

electrolytes by EMF method.
6. Write short notes on the following:
(i) Ionic atmosphere (ii) Electrophoretic effect (iii) Relaxation effect
7. Account for the following:
(i) Strong electrolytes, though completely ionized show lower molar conductivity than
expected from their concentration.
(ii) It is better to use term ‘mean activity’ for electrolytic solution rather than ‘activity’.
8. Explain mechanism of conductivity of strong electrolytic solution in the light of Debye-

Huckel theory.
9.9 REFERENCES
1. Atkins, P. and de Paula, J. (2005).Physical Chemistry: 7th edition. Oxford University
Press.
2. Crow, D.R. (1974). Principles and Applications of Electrochemistry: 2nd edition. Chapman
and hall Limited.

3. Moore, W.J. (1976) .Physical Chemistry: 5th edition. Orient Longman Limited.
4. Glasstone, S. (1974) An Introduction to Electrochemistry: 4th edition. East- West Press

Private Limited.

UNIT 10 ELECTROCHEMISTRY-II
CONTENTS
10.1 Objectives 10.5.1 Main postulates of Debye-Huckel
theory
10.2 Introduction
10.3 Activity, activity coefficient, mean 10.5.2 Thickness of ionic atmosphere:
ionic activity and mean activity 10.5.3 Derivation of Debye-Huckel

coefficient of electrolytes, ionic strength of limiting law
electrolytic solution 10.6 Debye – Huckel- Onsager theory
10.3.1 Activity and activity coefficient of and Onsager equation
electrolytes 10.6.1 Main postulates of Debye –
10.3.1.1 Activity Huckel- Onsager theory:
10.3.1.2 Activity coefficient of a solution: 10.6.2 Derivation of Onsager equation:
10.3.2 Mean ionic activity and mean 10.7 Theory of conductivity of strong
activity coefficient of electrolytes electrolytes
10.3.2.1 Mean ionic activity 10.8 Decomposition potential and

overvoltage
10.3.2.2Mean activity coefficient of
electrolytes 10.8.1. Decomposition potential
10.3.2.3 Relation between mean activity 10.8.2. Overvoltage or over potential

and mean activity coefficient of electrolyte 10.8.2.1 Overvoltage: definition and
10.4 Methods of determination of mean explanation
activity coefficient of electrolytes 10.8.2.2 Types of overvoltage
10.4.1 Freezing point depression 10.8.2.2.1 Activation overvoltage
measurement method 10.8.2.2.2 Resistance overvoltage
10.4.2 EMF measurement method 10.8.2.2.3 Concentration overvoltage
10.9 Summary
10.4.3 Solubility method:
10.5 Debye - Huckel theory
10.11 References

10.1 OBJECTIVES
After you have studied this chapter, you should be able to:
1. Define activity, activity coefficient of components of solution.

2. Explain need for the new term mean activity and mean activity coefficient for
3. Define mean activity and mean activity coefficient of electrolytes.
4. Explain various methods of determination of mean activity coefficient of
electrolytes.
5. Explain salient features of Debye –Huckel theory of strong electrolytes including
ionic atmosphere.
6. Derive Debye- Huckel limiting law.
7. Derive the expression for thickness of ionic atmosphere.
8. Explain modification of Debye- Huckel theory by Onsager.
9. Derive Debye-Huckel-Onsager equation.
10. Explain theory of conduction of strong electrolytes.
11. Define overvoltage and its possible causes.
12. Define decomposition potential and its importance.’
10.2 INTRODUCTION
As we have studied in the previous chapter, weak and strong electrolytes behave differently in
their aqueous solutions. Weak electrolytes undergo partial dissociation and show low molar
conductivity at normal concentration. Their molar conductivity increases with dilution due to
increase in degree of dissociation. This fact can be explained by Arrhenius theory of weak
electrolytes. Strong electrolytes, on the other hand, undergo complete dissociation at any
concentration. Still their molar conductivities are also less than that of expected value. This is
expressed as their deviation from ideality. Debye-Huckel theory of strong electrolytes holds
interionic interactions in solution responsible for this deviation. This behavior of strong
electrolytes has been dealt in detail in the previous chapter in the light of Debye-Huckel theory.
This chapter will explore the mathematical aspects of Debye-Huckel theory, Debye-Huckel
limiting Law, its modification by Onsager and an important relationship between molar

conductivity and concentration of electrolytic solution i.e. Debye-Huckel-Onsager equation. At

the end we shall discuss two important concepts of electrode kinetics namely decomposition
potential and overvoltage. These two experimental observations help us to understand reversible
nature of standard EMF and deviation from it as some of the electrode processes take place
irreversibly. These two concepts will help us to explain formation of unexpected products during
electrolysis and role of electrode in deciding the product of electrolysis.
10.3 ACTIVITY, ACTIVITY COEFFICIENT, MEAN IONIC

ACTIVITY AND MEAN ACTIVITY COEFFICIENT OF
ELECTROLYTES, IONIC STRENGTH OF ELECTROLYTIC
SOLUTION
10.3.1 Activity and activity coefficient of electrolytes
10.3.1.1 Activity
Thermodynamic properties of ideal solutions can be explained in terms of chemical potentials

and activities. Electrolytic solutions on the other hand differ from non electrolytic solutions since
electrolytes dissociate into ions in their solutions and there are strong interactions among these
ions. It results into deviation from the ideal behavior.
For ideal solutions, molal concentrations can be used to describe the activity of the solution but
for ionic solutions this approximation is correct only for very dilute solutions where ionic
interaction in the solution can be neglected. The term activity and activity coefficients become
significant in such cases.
Activity of a component of solution can be defined as its effective concentration. For an ideal
solution activity of a component is equal to its concentration whereas in case of non-ideal
solutions, activity of a component is directly proportional to the concentration of the component.
Or, for a non-ideal solution, a=γC
For ideal solutions, γ= 1 so, a = C.

Where a is the activity of a component of solution, C is its concentration and γ is called as

activity coefficient of the component.
fraction (χ) of the component as a=γm, a=γM or a=γχ
10.3.1.2 Activity coefficient of a solution:
Activity coefficient is a factor used in thermodynamics to express the properties of non-ideal

solutions such as solutions of electrolytes. It can be defined as the ratio of activity of a
component and concentration of the non-ideal solution.
Since a= γ C where γ =a/C is called as activity coefficient of the component.
fraction (χ) of the component as γ =a/M ,γ =a/m or γ =a/x
The symbol γ in the above expressions is known as activity coefficient.
The value of γ = 1 for ideal solutions so its values other than 1 indicate the extent of deviation
from the ideal behavior. Since activity coefficient is a ratio it is a dimensionless quantity.
10.3.2 Mean ionic activity and mean activity coefficient of electrolytes
10.3.2.1 Mean ionic activity
The activity of nonelectrolytic solutions, such as solution of sugar in water, refers to activity of
its solute component. Similarly, activity of a salt present in solution refers to the activity of
cations and anions present in solution. Since there is no way to measure individual effect of
cations and anions so it is not possible to measure the individual ionic activity. So, activity of an
electrolytic solution is defined in such a way that it includes the equal contribution from cations
and anions. This definition includes a term; Mean activity of electrolytes (γ±).
Mean activity of electrolytic solution is defined as the geometric mean of the ionic activities.
Mathematically, for an electrolyte AxBy which dissociates as
AxBy xA+ +yB-
Where, total number of ions present in solution =x+y

Mean activity coefficient of electrolyte is expressed as:
γ±=[(a+)x.(a-)y] 1/x+y=(a±)1/x+y (9.01)
Let us understand it in terms of chemical potential of a solute in a solution.
Chemical potential (µ) of a solute in an ideal solution is mathematically defined as,
µ real= µ0+RT In m (9.02)
Where, µ0 is standard chemical potential of solute and m is the molality of solution.
For non-ideal (real) solutions the chemical potential of a solute is expressed in terms of its
activity in the solution.
µ real= µ0+RT In a
µ real= µ0+RT In m. γ (Since a= m. γ )
Or, µ real= µ0+RT In m+ RT In γ (9.03)
Substituting value from Equation No 9.02 in Equation No.9.03,
µ real= µ ideal+RT In γ (9.04)
In the Equation No. 9.04,
As Inγ tends to zero, µ real= µ ideal
For an electrolytic solution, components of solution include cations and anions. The total molar
Gibbs energy of an ideal solution of an electrolyte AX where A+ is univalent cation and X- is
univalent anion, is given by the expression
G ideal=µ+ideal+ µ-ideal
Where µ+ideal and µ-ideal are the chemical potentials of cation and anion respectively.
Similarly, total molar Gibbs energy of a non-ideal (real) solution is given by the expression
G real=µ+real+ µ-real (9.05)
From equation (9.04),
µ+real= µ+ ideal+RT In γ+ (9.06)
And

µ-real= µ- ideal+RT In γ- (9.07)
Where, γ+ and γ- are activity coefficients of cation and anion respectively.
Substituting these values from Equation No.9.06 and 9.07 in Equation No.9.05
Greal=µ+real+RTlnγ++ µ-ideal +RT In γ-
Or Greal=µ+ideal+ + µ-ideal +RT In γ+γ-
Or Greal=µ+ideal+ + µ-ideal +RT In γ+γ- (9.08)
So, the total molar Gibbs energy of a solution of electrolyte depends on the activity coefficients
of cation and anion both.
10.3.2.2 Mean activity coefficient of electrolytes
Theoretically, activity of an electrolytic solution should be the total contribution of activities of

cations and anions. Since cations and anions of electrolytes in solution are inseparable, it is not
possible to measure their activity and activity coefficients separately.
For such reasons, a new term mean activity coefficient is introduced to assign the nonideality of
solution to the constituent ions. Mean activity coefficient is defined as the geometric mean of the
activity coefficients of cations and anion.
Mathematically, for a uni-uni valent (1:1)-electrolyte i.e. electrolyte having univalent cation and
univalent anion, the mean activity coefficient is defined as (γ+ γ-)1/2.In general, for an electrolyte
AxBy that dissociates in the aqueous solution as follows,
AxBy xA+ +yB-
(γ+ γ-)1/2= [(γ+)x (γ-)y]1/(x+y) (9.09)
10.3.2.3 Relation between Mean activity and mean activity coefficient of electrolyte
For an electrolyte AxBy mean ionic activity coefficient is expressed according to

(8.01).Substituting the values of activity coefficients of cations (γ+m+) and anions (γ-m-) in
(8.01), the mean activity of electrolyte is expressed as:
a±=[(γ+m+)x(γ-m-)y ]1/x+y (9.10)
= γ± [(m+)x(m-)y ]1/x+y (9.11)

As, the term in square bracket in Equation No. 9.11 is the geometrical mean of molality of
cations and anions, it can be written as mean molality of the solution.
So the Equation No. 9.11 can be rewritten as,
a±=γ±m± (9.12)
10.4 METHODS OF DETERMINATION OF MEAN ACTIVITY

COEFFICIENT OF ELECTEROLYTES
In order to ascertain whether a strong electrolyte in its solution behaves as an ideal or showing
deviation from ideality, it is important to know its activity. If its activity is equal to its
concentration it behavior is ideal. In case, if it deviates from this behavior it has activity lower
than its solution. It is easy to Calculate its activity if its activity is known to us. There are
several methods of determination of activity coefficients. Important among them are:
5. Freezing point depression measurement method

6. EMF measurement method
7. Measurement of Solubility of sparingly soluble salts
10.4.1 Freezing point depression measurement method
Activity coefficient of electrolytes can be calculated by measuring the depression in freezing
points of solutions of different strength. A detailed theory of the method is given below:
If in a binary solution,1 stand for solute and 0 for solvent, then its chemical potential given by
Gibbs-Duhem equation is,
nodµo+ n1dµ1=0 (9.13)
Where, no is number of moles of solvent
n1is number of moles of solute
µo is chemical potential of solvent
µ1is chemical potential of solute
In general, chemical potential of a component A in a nonideal solution is given by the

expression,

µ = µA0+RT In aA (9.14)
Where, µoA is the Chemical potential of A in its standard state and aA is Activity of A
Equation No. 9.13 can be expanded by using Equation No 9.14,
Terms and of Equation No. 9.13 can be expanded by using Equation No. 9.14,
(µ1o+RT ina1)+nod (µoo+RT inao)=0 (9.15)
According to Gibbs- Duhem equation, nodµo+n1dµ1=0, The Equation No.8.18 can be rearranged
as,
n1RTdlna1+noRTdlnao=0
Dividing this equation by RT, we get,
n1dlna1+nodlnao=0 (9.16)
The following expression correlates activity of solvent with temperature variation
(9.17)
Where, ∆Hf , is Latent heat of fusion.
Depression in Freezing point is given by
Where, To is the freezing point of pure solvent and T is freezing point of the solution.
On differentiation, d (∆T)= d(To- T) =-d(T), therefore equation (8.22) can be written as
Or,
(9.18)

Substituting value from Equation No 9.18 into Equation 9.16 we get,
Since where MA is molar mass of A
So,
(9.19)
By definition, activity where,
So,
Or,
(9.20)
Substituting value from Equation No 9.20 into Equation No. 9.19
(9.21)
Let us suppose that
Then, on differentiation,

On substituting value of x back,
(9.22)
Equating Equation No. 9.21 and 9.22,
Or, (9.23)
In the above equation, as molality approaches zero and also x approaches zero.
So on integrating Equation No. 9.23
(9.24)
In the actual experiments, a number of solutions of electrolyte of known concentrations are

prepared and the depression in freezing point is determined for each of them. A graph is plotted
between x and molality. Area under this graph gives the value of .
10.4.2 EMF measurement method

A suitable cell is setup which includes the electrolyte for which activity coefficient is to be
measured.
This method is explained taking the example of determination of activity coefficient of HCl.
A cell is setup by coupling Hydrogen electrode with Ag-AgCl electrode.

The hydrogen electrode contains the HCl solution for which activity coefficient is to be
determined. Both the electrodes are immersed in the same solution i.e. a cell without transference
is setup.
Representation of cell: Pt, H2 (g) (P= 1atm) // HCl (m1) AgCl(s) / Ag(s)
As per representation, hydrogen electrode acts as anode and Ag-AgCl electrode as cathode.
Following half cell reactions take place in the cell:
At Anode: ½ H2(g) =H+ (aq)+e-
At Cathode: AgCl(s)+ e- =Ag(s)+Cl-(aq)
Cell Reaction: ½H2(g)+AgCl(s)=H+(aq)+Ag(s)+Cl-(aq)
The EMF of this cell can be given by Nernst equation as:
(9.25)
If PH2 =1 atm, Equation No. 9.25 becomes,
Since,
And for HCl, x =1 and y =1
So,
Or,
Since a=γm, then for HCl, the above equation may be simplified as

Or,
(9.26)
The above equation is used to determine γ± of 1:1 electrolytes
10.4.3 Solubility Method:
The mean activity coefficients of the electrolytes, particularly sparingly soluble electrolytes can
be determined by solubility method as follows;
In a saturated solution of sparingly soluble electrolyte AxBy following equilibrium exists,
According to law of mass action,
(9.27)
Or, k aAxBy =(aA+)x(aB-)y=K , where aAxBy=1
So Equation No. 9.27 becomes, K
The constant K is known as activity product of electrolyte.
Since activity a=γC
So, a+
And a-
So K
Or,
By definition,

So, (γ+x γ-y)= (γ±)x+y
So, K=(C+)x(C-)y (γ±)x+y (9.28)
Let S is the solubility of AxBy in water, then
Concentration of cation C+=xS
And Concentration of anion C-=yS
Or, K (9.29)
Procedure:
For the experimental determination of mean activity coefficient by solubility method, solubility
of a given salt at various ionic strengths is experimentally measured. It is important to know that
solubility of sparingly soluble salts is the function of ionic strength.
These solubilities are plotted against square root of ionic strength .Plot results into a
straight line with positive slope.
As,
So, at
Once the value of k is known, it is possible to calculate the value of

.
10.5 DEBYE - HUCKEL THEORY

In 1923, a new theory of strong electrolytes was put forward by Dutch chemist Peter Debye and
German physicist Erich Huckel which addresses anomalies of Arrhenius theory. It’s a
mathematical treatment for the behavior of strong electrolytes in solution which holds interionic
forces responsible for deviation of electrolytic solutions from ideality.
10.5.1 Main Postulates of Debye-Huckel theory

Main postulates of Debye- Huckel theory are:

(i). Complete dissociation of strong electrolytes: Strong electrolytes are completely dissociated
into ions in their aqueous solutions. This is in contrast to the postulate of Arrhenius theory which
states about high degree of ionization of strong electrolytes.The 100% dissociation of strong
electrolytes in aqueous solution is in agreement with Bjerrum’s observation of spectroscopic
studies of aqueous solution of electrolytes.
(ii).Electrostatic interactions between ions in aqueous solution and ionic atmosphere: Ions
present in the solution exhibit electrostatic interaction. As a result, distribution of ions in aqueous
solution is not completely at random. In the immediate vicinity of a given central ion chances of
finding a counter ion are more due to electrostatic attraction i.e. more anions tend to be present
around a cation and vice versa. Thus, on an average, a given central ion is surrounded by ions of
opposite charge. This results into formation of a screening layer of oppositely charged ions
around a central ion. This hallow of counter ions surrounding a given central ion is termed as its
ionic atmosphere.
(iii). Reason for deviation from ideality: Though the strong electrolytes are completely ionized
in their aqueous solutions, they show nonideality in their behavior viz. fall in molar conductivity.
These deviations from ideality become more pronounced with increase in concentration. There
are two reasons behind this deviation:
(ii) Asymmetry Effect (ii) Electrophoretic Effect

Let us understand these two terms one by one:
(iii) Asymmetry Effect: For a stationary given central ion, its ionic atmosphere tends to be
spherically symmetrical around it. When the central ion moves towards its electrode under the
influence of applied electrical field, the ionic atmosphere still relaxes so the symmetry of ionic
atmosphere gets distorted. Though this decay in ionic atmosphere is overcome by formation of
new ionic atmosphere but there is a time lag between development of asymmetry and regaining
of symmetry in ionic atmosphere. As a result, ionic charge density in the ionic atmosphere is
more behind the moving ion than in front of it. This distortion of symmetry of charge density and
accumulation of oppositely charged ions more on back side of the ions exert a net backward
electrostatic pull on the moving ion which retards it. This retardation effect of distorted ionic
atmosphere on the ionic velocity is known as Asymmetry or relaxation effect. This effect is

greater at higher concentration; thereby retardation of ionic mobility is higher at higher

concentration.
(iv) Electrophoretic effect: There is one more way by which the ionic atmosphere of a given
central ion hampers its motion and retards ionic mobility. The counter ions of ionic atmosphere
are solvated i.e. the ions are attracted to solvent molecules around them by ion- dipole
interactions. The ions of ionic atmosphere also move towards respective electrode under the
influence of applied electrical field (and of course it’s the direction opposite to the direction of
movement of central ion). These moving ions tend to drag the associated solvent molecules with
them. As a result, a moving central ion has to move against the stream of these counter ions and
solvent molecules which move along the counter ions present in ionic atmosphere. This upstream
movement further reduces the mobility of central ion. This impediment of ionic mobility of
central ion due to movement of solvent molecules bound with counter ions of ionic atmosphere
is termed as Electrophoretic effect.
As these two effects namely; asymmetry and Electrophoretic effect are more pronounced at
higher concentration, ionic mobility is adversely affected more at higher concentration. As a
result, even after complete ionization, strong electrolytic solutions show deviation from ideal
behavior viz. lower molar conductivity.
Theoretical treatment of ionic movement, led Debye and Huckel to calculate the retarding forces
acting on the central ion due to asymmetry and electrophoretic effect. This helped to refine the
concept of conductivity of strong electrolytes and led to another important relationship in
electrochemistry known as Debye-Huckel-Onsager equation.
10.5.2 Thickness of Ionic atmosphere:

As postulated in Debye-Huckel theory, strong electrolytes, though completely ionized in aqueous
solution, yet their ions are not entirely free. Interionic and ion-solvent interaction result in
impediment of ionic mobility which is observed as decrease in molar conductivity and deviation
from ideal behavior. A given central ion in strong electrolytic solution is surrounded by spherical
haze of counter ions which is known as its ionic atmosphere.
Let us take a small part of this system in which a given central ion with certain positive charge,
is present at point A and it is surrounded by ionic atmosphere in solution (Fig.9.01).

Let dv the small part of the volume of ionic atmosphere in the vicinity of central ion at distance r
from it and ψis the average electrical potential at this volume element. By definition, electrical
potential is the work done in bringing a unit positive charge from infinity to that point.
Fig. 9.01: Thickness of ionic atmosphere
So work done to bring unit positive charge from infinity to volume element=e+ ψ
Work done to bring unit negative charge from infinity to volume element= e-ψ
Where, e+ and e- are number of charges carried by cations and anions respectively
If N+ and N- are the number of cations and anions present in unit volume of electrolytic solution
then according to Boltzmann distribution law.
So,
And
Or
Electrical charge density (ρ) in this volume element can be defined as excess of positive charge
(or negative charge) present per unit volume.
Or,

(9.30)
For a 1:1 electrolyte, and
So, the Equation No. 9.30 becomes, (9.31)
Expanding the exponential terms by formulae,
And
As so higher term in the expansion can be neglected so Equation No. 9.31
becomes,
(9.32)
ρ=
There is a well established relationship in electrostatics, between electrostatic potential ψ and
charge density ρ at a point. It is given as Poisson equation, which can be expressed as,

Where, εo is the permittivity of vacuum (= 8.854 x 10-12 C2 N-1 m-2) and is Laplacian operator.
If is the dielectric constant or relative permittivity of the medium then absolute permittivity is
given as . Poisson equation, then becomes as,
For rectangular coordinates
As the electrostatic potential around central ion is spherically symmetrical, the above equation
can be expressed in terms of polar coordinates. Poisson equation, thus becomes
Using equation No 9.32, this equation becomes
Or,
Or,
Let
then the above equation becomes,

(9.33)
Since
And Ni , where Ci is concentration of ith ion and NAis Avogadro’s number.
So the above equation can be rewritten as
(9.34)
Or,
Or,
Since , the ionic strength of solution,
So (9.35)
Equation No. 9.33 is a differential equation. Its solution is given as:

Where A and A’ are the integration constants. In order to get the values of these constants, let us
consider a situation. For larger values of r, the above equation becomes,
(9.36)
For dilute solutions,
(9.37)
But at the same time, at infinite dilution, potential at a point at distance r from the central ion
will solely be the potential of central ion. It is given by,
(9.38)
Equating Equation No. 9.37.and 9.38 we get,
On substituting this value of A in Equation No. 9.36
(9.39)
In a very dilute solution, so Equation No. 9.39 becomes,
(9.40)
Above discussion brings forth the value of the electrical potential on central ion due to its ionic
atmosphere is,
(9.41)
10.5.3 Derivation of Debye-Huckel Limiting Law:

According to Debye-Huckel theory, there exists an interionic interaction in electrolytic solutions.

These interactions result into extra free energy of the solution which in turn leads to deviation
from ideal behaviour. This extra free energy is equal to reversible work done to give an ion
(central ion) of potential ψi (this is the potential at central ion due to its ionic atmosphere). The
extra free energy is measure of deviation from ideality and may be correlated with the ionic
activity.
The chemical potential of an ith ion (µi) in a solution is related to concentration mi as below:
µi (ideal) = µio (ideal) +RT in mi
In an electrolytic solution which is a non-ideal solution, chemical potential of ith ion (µi )
depends on its activity (ai) and can be given by
µi (electrolyte solution) = µio +RT in ai
Substituting ai=miγi may result
µi (electrolyte solution) = µio +RT in miγi
Since µi (ideal)= µio +RT in mi
Therefore µi (electrolyte solution) -µi (ideal) =RTinγi
The above difference in chemical potential is the extra free energy per mole. In other words, it is
the energy wise contribution of the ionic atmosphere to the total energy of the one mole of
central ion.
So, the extra free energy per ion (9.42)
Where kB is Boltzmann constant
The workdone (dw) to increase the charge of central ion by de at potential, ψi can be given by
w (9.43)
So, the reversible workdone w, to charge the ion from zero to zcθis given by
w (9.44)

According to equation 9.41, the value of the electrical potential on central ion due to its ionic
atmosphere is expressed as:
On substituting the value of ψi from Equation No.9.41 into Equation No. 9.44 results
(9.45)
As this work done is equal to the extra free energy per ion present in the solution, Equation No.
9.42 and 9.45 can be equated and thus, we get
(9.46)
On substituting the value of κ from Equation No. 9.35 to 9.46, and rearranging we get,
On substituting kB and further rearranging the above equation,
log γi =-A Zc2 (9.47)
Where,
(9.48)
The Equation No. 9.47 is one form of Debye-Huckel Limiting Law that correlates mean activity
coefficient of ith ion with its charge and ionic strength of the solution. In this equation A is a
constant for a given solvent at a given temperature.
Using equation 9.48, at 298K the value of A for water is 0.507

If one mole of electrolyte gives x cations and y anions then by definition of mean activity
coefficient,
On taking log of the above equation,
(9.49)
(9.50)
Dividing RHS of Equation No. 9.49 by y we get,
(9.51)
On substituting values in Equation No. 9.51 from Equation No. 9.50,
Or, (9.52)
Substituting log γi =-A Zc2 from Equation No. 9.47 into Equation No. 9.52,
or log γi =-A Z+ Z-
As, only the magnitude of the valence is considered for calculation, this equation can be written
as,
log γi =-A ΙZ+ Z-Ι (9.53)
This Equation No. 9.53 is known as Debye Huckel Limiting Law.

Practically, above equation has been substantiated by the data obtained for electrolytic solutions
having concentration less than 1mmolkg-1 or with ionic strength less than 0.001.In this equation,
A is a constant. For water at 298 K, A = 0.509. Other symbols have their usual significance
The general inference that can be drawn from this equation is that the value of mean activity
coefficient of an electrolyte decreases with increase in the ionic strength. The decrease is higher
with increase in valence and decrease in the dielectric constant of the solvent. This equation is
called as a limiting law because while deriving the equation it has been consistently assumed that
these approximations are applicable only when dilution approaches to infinity. So this equation is
not expected to hold good for concentrated solutions.
10.6 DEBYE-HUCKEL-ONSAGER THEORIES AND ONSAGER

EQUATION
Norwegian-born American physical chemist and theoretical physicist Lars Onsager (1903-1976)
improved Debye-Huckel theory in 1926. Debye and Huckel assumed the ionic movement in
solution in straight line. They neglected the fact that moving ions collide with the solvent
molecules and these collisions also affect their mobility along with electrophoretic and relaxation
effect. Onsager considered the effect of this collision and not only modified the Debye-Huckel
theory but also improved the expression derived by the former for relaxation effect.
10.6.1 Main Postulates of Debye – Huckel- Onsager Theory:
Lars Onsager modified the already proposed Debye-Huckel theory of strong electrolytes by
including the effect of ionic collisions with the solvent molecules. This version of Debye-Huckel
theory gets improved on adding Onsager’s modification and it can be called as Debye-Huckel-
Onsager theory of strong electrolytes. The main postulates of this theory are:
1. In electrolytic solution of strong electrolyte, ions moving towards respective electrode

under the influence of external electrical field collide with the solvent molecules. As a
result of these collisions, ions move not in straight line but in a zigzag Brownian
movement. This also reduces ionic mobility.
2. This effect of Brownian movement of ions should be taken into consideration while
deriving an expression for relaxation force acting on ion.

3. Three forces act upon moving ion opposite to direction of motion. These are;
(i)Relaxation force (ii) Electrophoretic force (iii) Frictional force of solvent
4. An ion moving with a steady velocity, experience zero resultant force as the force due the
external electrical force is exactly balanced by sum of these three forces acting on
opposite direction.
10.6.2 Derivation of Onsager Equation:
Onsager equation is an expression relating molar conductivity of strong electrolyte with

concentration. This can be derived by considering the three forces acting on an ion moving with
steady velocity in the direction opposite to external electrical field and equating sum of these
forces with force due to external electrical field.
Onsager derived the expression for Relaxation force acting on the ith ion making allowance for
Brownian movement.
According to it,
(9.54)
Debye and Huckel derived expression for electrophoretic force acting on ith ion applying stokes
law to the electrolytic solution. It comes out to be,
(9.55)
Frictional force of solvent is related to the ionic mobility as per the following relationship,
(9.56)
Various symbols used in the above Equations from 9.54 to 9.56 stands for,
th
Ki=Frictional coefficient on i ion due to solvent
k= ionic mobility (i.e. the steady velocity of the ith ion)
e= electronic charge
zi=valence of ith ion
V=potential gradient under which ith ion is moving
η=coefficient of viscosity

a number defined by,
Where
Let us understand value of w and q for NaCl.

For NaCl, valence of cation .
So
So,
At steady velocity of moving ion, sum of three opposing forces is equal to electrical force on it.
So, from Equation No. 9.54, 9.55, 9.56 and 9.57,
(9.57)
(9.58)
Let the ith ion is moving under the influence of unit potential gradient, i.e. then,
Equation No.9.58 becomes as,

(9.59)
Equivalent conductance of ith ion (λi ) is related to its ionic mobility (ui) by the following
expression
λi = ui F (9.60)
At infinite dilution, k=0, so the Equation No 9.59 may reduced to
(9.61)

Also at infinite dilution, limiting equivalent conductance of ith ion (λio) and its ionic mobility (uio)
are related as,
λio = uio F (9.62)
Equating Equations No 9.61 and 9.62,
(9.63)
On rearrangement, 9.63 is reduced to (9.64)
On substituting values from equation No (9.60) and (9.63) into (9.59) results
(9.65)
Substituting the value from Equation No. 9.64 into 9.65,
On dividing this equation by F we get,
(9.66)
Substituting the value of from Equation No. 9.35 in Equation No. 9.66 ,
On substituting the values of the constants and calculating, we get
(9.67)

Where Ci is the concentration of ith ion and zi is its valence. If Ci is replaced with C the
equivalent per litre , thenequivalent conductance of ith ion in electrolytic solution becomes
(9.68)
Since equivalent conductance of an electrolyte is the sum of equivalent conductance of its

constituent ions, it can be given from the above equation as,
(9.69)
Equation 9.69 is the general form of Debye-Huckel-Onsager equation for equivalent conductivity
of strong electrolyte.
For a 1:1 electrolyte z+ , and C, the equivalent conductivity can be

replaced by c, the molar conductivity as both are same for 1:1 electrolyte. Thus, the equation can
be simplified as,
(9.70)
Equations 9.68 to 9.70 are the various forms of Debye-Huckel-Onsager equation. It accounts for
the decrease in equivalent conductivity of strong electrolyte. First term in the square bracket
implies to electrophoretic force and the second term stands for relaxation force.
The above equation for 1:1 electrolyte can be represented in a simplified Debye-Huckel-Onsager
equation as,
Λ= (9.71)
Where, A and B are the constants which depend on nature of solvent and the temperature.
and

10.7 THEORY OF CONDUCTIVITY OF STRONG

ELECTROLYTES
Conductivity of strong electrolytes in a solution is explained on the basis of Debye-Huckel
theory in the light of Onsager’s modification. According to it, strong electrolytes are completely
ionized in aqueous solution at all concentrations. Oppositely charged ions thus formed, interact
in solution that leads to formation of spherically symmetrical ionic atmosphere of oppositely
charged ions around a given ion. So it can be said that ions are completely not free even in
solution. Under the influence of external electrical field, a given ion moves through the solution
towards its respective electrode. Ionic mobility is impeded by presence of ionic atmosphere as
well as solvent molecules around the given ion. As the ion moves to new position, it tends to
drag with it, its ionic atmosphere. However, the ionic atmosphere still relaxes so the symmetry of
ionic atmosphere gets distorted. There is a time lag between development of asymmetry and
regaining of symmetry in ionic atmosphere. As a result, there is net increase of ionic charge
density behind the moving ion than in front of it. This accumulation of oppositely charged ions
exerts a net backward electrostatic pull on the moving ion which retards it. This retardation effect
on the ionic velocity is known as asymmetry or relaxation effect.
Apart from this, there is one more way by which the ionic atmosphere retards ionic mobility. The
counter ions of ionic atmosphere are solvated. The ions of ionic atmosphere also move towards
respective electrode under the influence of applied electrical field in a direction opposite to that
of central ion. These moving ions tend to drag the associated solvent molecules with them. As a
result, a moving central ion has to move against the stream of these counter ions and solvent
molecules which move along the counter ions present in ionic atmosphere. This upstream
movement further reduces the mobility of central ion. This impediment of ionic mobility of
central ion due to movement of solvent molecules bound with counter ions of ionic atmosphere
is termed as electrophoretic effect.

Relaxing ionic atmosphere
Direction of movement of central
Fig.9.02: Relaxation Effect

The moving ion gets drifted towards the respective electrode under the continuous influence of
the external electrical field. But this movement is not in straight line as the moving ion gets
constantly collided with the solvent molecules which are almost of similar size. This results into
a zigzag Brownian movement of ion towards its electrode. This retarding effect on its motion is
termed as frictional force of solvent. A moving ion, sooner or later, gains a steady state motion at
which propelling electrical force of forward motion is balanced by sum of opposing forces i.e.
asymmetry force, electrophoretic force and frictional force of solvent.
10.8 DECOMPOSITION POTENTIAL AND OVERVOLTAGE

A lot of reactions take place at electrode surface. Rate of these reactions and are studied under
the branch electrochemical kinetics. Decomposition potential and overvoltage or overpotential
are the phenomena that deals with electrochemical kinetics.
10.8.1. Decomposition Potential

Le Blanc in 1893 set up an experiment in which he took an electrolytic cell and increased the
external EMF gradually and measured the current flowing through the cell and also the potential
across it simultaneously. Proceeding, in this manner, he plotted current density against potential
(cell voltage). Current density is defined as, magnitude of current per unit area of the electrode.
The graph thus obtained has been shown in Fig. 9.03.

Fig. 9.03: Decomposition potential
Such a graph of current density versus potential shows, potential keeps on increasing regularly
and rapidly but there is no appreciable increase in the current density. But there is a potential at
which there is sudden rise in the current density and beyond which the potential subsequently
changes by only a small degree. This potential is known as decomposition potential of the
solution. This potential can be obtained by extrapolation of the steeping part of the curve to the
potential axis. Theoretically, decomposition potential of a solution can be defined as the
minimum potential that must be applied between a pair of electrodes to pass the current of
appreciable strength.
When such experiments were performed with aqueous solutions of a number of acids and bases
taking smooth platinum as anode and cathode, following facts were evident:
1. Decomposition potential was almost constant irrespective of nature of electrolyte. It was

in the vicinity of 1.70 V.
2. Evolution of hydrogen and oxygen gases was observed with the passage of current in
each case.
These observations led le Blanc conclude that the same process takes place during the
experiment in all electrolytic solution under study. The only common process to these
electrolytic solutions could be the decomposition of water leading to formation of hydrogen and
hydroxyl ions. Their discharge at cathode and anode respectively form hydrogen and oxygen
gases. However, decomposition potential of solutions has no theoretical significance as it
depends on two individual electrodes, resistance of solution and concentration of solution.

10.8.2. Overvoltage or Over Potential
10.8.2.1 Overvoltage: definition and explanation
Le Blanc’s reveals decomposition potential for a number of aqueous solutions of acids and bases
remain around 1.70 V over platinum electrodes. The constant value of decomposition potential
attributes to the similar reaction i.e. decomposition of water and discharge of hydrogen and
hydroxyl ions in all the solutions.
The reaction that occurs during this electrolysis is,
Theoretical decomposition potential for this reaction can be calculated as follows:
Since, ∆G=-nFEo
Or,
On substituting the values, Eo = 1.23 V
This theoretical value of decomposition is quite different in fact quite lower than the observed
value that is 1.70 V.
German scientist Caspari in 1899 studied the dependence of decomposition potential on the
nature of the electrodes. Caspari performed the experiments similar to those of Le Blanc using
different metals as electrode and concentrated on the relation of potential at which evolution of
oxygen and hydrogen was actually observed with the nature of electrode.
The difference between the potential of the electrode when the gas evolution is actually observed
i.e. the observed decomposition potential and its theoretical reversible value is known as over
voltage or over potential. It is generally represented by η. Original word used by Caspari for this
difference in potential was ‘Uberspannung’ in German which was translated as “Overvoltage”.
In this case, for smooth platinum electrodes, Over voltage, η =1.70 V – 1.23 V = 0.47 V.

Caspari’s studies revealed that overpotential (overvoltage) value for the same reaction changes
with the change in nature of electrode. e.g. hydrogen overpotential at smooth platinum is 0.09 V
whereas at platinised platinum it is 0.00 V. It is as high as 0.78 V at mercury electrode.
10.8.2.2 Types of Overvoltage
Different types of overvoltage come across in the course of electrochemical reaction. These can
be classified as:
(i) Activation overvoltage (ii) Resistance overvoltage (iii) Concentration over voltage
Let us discuss them one by one.
10.8.2.2.1 Activation overvoltage
If a reaction at electrode is has high activation energy, it proceeds with slow transfer of
electrode. As a consequence, in order to get the product at electrode at an appreciable rate, extra
potential over the equilibrium potential is must be applied. This extra potential gives the
activation over voltage.
10.8.2.2.2 Resistance overvoltage

Electrolytic solution around an electrode is of limited conductivity and it resists the flow of
current. Therefore, there is drop of potential between two electrodes. It is known as resistance or
ohmic over voltage. It can also be caused by formation and deposition of a resistive film of
product on electrode.
10.8.2.2.3 Concentration overvoltage
It is caused by change in concentration around an electrode during an electrochemical reaction.
The imbalance in number of ions discharged and produced at an electrode cause decrease in
concentration in the vicinity of cathode or increase in concentration around anode. As a result
electrodes are said to be polarized and need extra potential to eliminate this polarization and
maintain current flow. This extra potential is known as concentration over voltage. Stirring the
solution around an electrode reduces the extent of concentration overvoltage.

10.9 SUMMARY
Arrhenius theory was unable to explain the behavior of strong electrolytes. This is because,
strong electrolytes, though completely ionized but remain in undissociated state at all
concentrations. Molar conductivity of the solution of strong electrolyte is lower than that is
expected. For such reasons, the concentration of strong electrolytes in solution is expressed in
terms of activity which is the effective concentration of a solution. The ratio of activity and
concentration of a component of solution is known as its activity coefficient. Since, failure of
Arrhenius theory, a new theory was put forward by Debye and Huckel and later on modified by
Onsager to explain the behavior of strong electrolytes through introducing the concept of
interionic attractions. The ionic interaction result into formation ionic atmosphere around a given
ion in solution. This ionic atmosphere predominantly consists of oppositely charged ions. It
impedes the mobility of central ion by relaxation effect and electrophoretic effect. The interionic
interactions are responsible for decrease in molar conductivity and deviations of solutions of
strong electrolytes from ideal behavior. Onsager further added to Debye-Huckel theory, the role
of ionic collisions with solvent molecules which result into Brownian movement of the ions and
further decelerate a moving ion. Relation between mean activity coefficient of solution with the
ionic strength and valence of the ions is expressed through -Huckel limiting law. At the last part
of the chapter, two basic experimental observations of electrolysis, namely decomposition
potential and overvoltage have been discussed. Over voltage of an individual electrode can be
the collective contribution from three overvoltage namely; activation, resistance and
concentration over voltage.
1. List four methods to determine mean activity coefficient of electrolytes? Explain principle of
determination of mean activity coefficient by depression in freezing point.
2. Explain salient features of Debye-Huckel theory. How is it different from Arrhenius theory?
3. Explain Onsager’s modification of Debye-Huckel theory of strong electrolytes.

4. Account for the following:
(i) Weak electrolytic solutions do not face electrophoretic and relaxation effect.
(ii) CaSO4 is a sparingly soluble salt but its solubility in sea water is several times higher than
that of in lake water.
(iii) During electrolysis of aqueous NaCl, Cl2 is liberated at anode instead of O2 though its E0
value is more positive than the later.
5. Derive expression for thickness of ionic atmosphere.
6. Derive Debye- Huckel Limiting law. Why is it called as limiting law?
7. Derive Onsager equation of molar conductivity of strong electrolyte.
8. What is meant by decomposition potential? What was Le Blanc’s explanation for its constant
value?
9. Define overvoltage. What are the reasons for overvoltage?
10. Explain mechanism of conductivity of strong electrolyte.
10.11 REFERENCES
1. Atkins, P. and de Paula, J. (2005).Physical Chemistry: 7th edition. Oxford University Press.
2. Crow, D.R. (1974). Principles and Applications of Electrochemistry: 2nd edition. Chapman and
hall Limited.
3. Moore, W.J. (1976) .Physical Chemistry: 5th edition. Orient Longman Limited.
4. Glasstone, S. (1974) An Introduction to Electrochemistry: 4th edition. East- West Press

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Phone No. 05946-261122, 261123

Prof. A. B. Melkani Prof. Diwan S Rawat

Dr. Hemant Kandpal Dr. Charu C. Pant

Prof. R.D.Kaushik Prof. P.D.Pant

Dr. Shalini Singh Dr. Charu C. Pant

Dr. Shalini Singh

Title : : Physical Chemistry-I

Unit 1 Classical Thermodynamics-I 1-27

BLOCK-2 KINETICS AND CATALYSIS

Unit 5 Theories of Reaction Rates 103-120

Unit 9 Electrochemistry-I 179-201

UNIT- 1- CLASSICAL THERMODYNAMICS-I

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1.2 REVERSIBLE AND IRREVERSIBLE PROCESS

1.2.1 Reversible process:

1.2.2 Irreversible process:

Fig.1.1 Work in reversible (a) and irreversible process (b)

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1.3 THERMODYNAMIC WORK

Reversible and irreversible work:

Fig.1.2 Pressure volume work of a system

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Here A is the cross- section area of the piston.

W= -Pex (V2 –V1)

Fig.1.3 Isothermal reversible expansion work

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For one mole of an ideal gas the expression work will be

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It can be proved in the following manner.

This is positive quantity whatever be the value of P1 and P2,

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1.4 WORK IN REVERSIBLE CYCLE PROCESS

Or in an isothermal reversible cyclic process,

1.5 FIRST LAW OF THERMODYNAMICS

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1.6 INTERNAL ENERGY

1.7 MATHEMATICAL FORMULATION OF FIRST LAW OF

For small changes

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w = -P (VB – VA) …………………1.13

Rearranging above expression will result

(EB+PVB) – ( + PVA) = q …..…………….1.14

1.9 CALCULATION OF CP-CV THERMODYNAMICALLY

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at constant volume dV= 0 hence =( V

From equation 1.20

Comparing 1.22 and 1.23

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Dividing both sides by dT and keeping pressure constant

Putting this value of ( P in equation 1.24

For an ideal gas ( T =0

Since PV=RT and )P =

1.10 JOULE’S LAW

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Fig.1.4 Joule’s Experiment

1.11 JOULE THOMSON EFFECT

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