C

120 273= +
Hence
393 - 318 75393K 249
393
Hence maximum 3930.1908
5.7 efficiency of a steam engine = L19,08 %
CONCEPT ENTROPY OF
IN THERMODYNAMICS
"Entropy the
is
of the system." W
When
entropy of the system hassystem quantitmoves
ativemfrom
measurement
ordered(eLLA) of randomness(74)
When a solid is
ions
inmelted,
creased.thereFor example, state to disordered state, then we say that the
find more places to
be happens a net increase of entropy. The atoms, molecules or
OCcupied as
compared
particle are fixed to when
in their
accommodat
the ed (u3z)
substances in the is
in the same volume
solid. state. In the
system is less. positions. So, we say that the
entropy or the
solid state, the
randomness of the
(1) When the liquid is
atoms, ions
the
or evaporized,
molecules are
there happens increase of entropy. In the
more vapour state, the
molecules of the gaseous substances disordered as compared to the liquid state.
can roam about in a It means that
5.7.1
Entropy As AState Function better way.
The basic definition of entropy
change (i):
AS = Total
AS =
T (1Lbeots+t) is,
change in entropy, when we go fronm initial state to
"It means that the entropy the final state.
isothermally, when we go from initialchange
state
is
to
the ratio of total heat abs orbed
reversibly and
result of entropy change is þased on Carnot cycle, infinal state and the absolute temperature." This
that which heat is absorbed reversibly. So, we can say

AS = Srev
It means that the entropy change depends upon the
state function, a small change in its value can be inital and the final states and being a
represented by dS.
-tssfiersiS. t/li AS
dS

5.7.2 Entropy Change For AReversible Process Is Zero:

When 'g'is the amount of heat absorbed by the system reversibly, then heat lost by the
Surrounding will also be qrev'
Entropy change of the system is given by,
 250 ILMI Physical Chemistry
ra
ASystem T

Entropy change of the surrounding

ASguounding T
The total entropy change for the combined system and suroundings will be,
aystem t+ AS'surrounding = 0

5.7.3 Entropy Of the Universe Increasing (e-u4be:

AI he processes 0curing in nature are themodynamically ireversible (sLbsbLe).
Alhese processes are accompanied by increase of entropy. So, we can say that entropy of the
universe is increasing.
Ifwe keep in mind the first and second laws of thermodynamics, then we can say that the
energy of the universe is constant ( e ß y while the entropy of the universe is
continuously increasing (svodsbet) and tends to a maximum value.
5.74 Entropy For Irreversible Process:
Let us suppose that the total loss of heat by the surroundings ( ) is q' irreversibly. This
heat is to be absorbed by the system. There happens a change in the entropy of the system
(4zessoL This entopy change does not depend upon the heat which is
actualy absorbed, but it depends upon the heat absorbed reversbly. In other words,it depends upon',:
In the case of isothermal absorption of heat by the system at absolute temperature 'T, the
entropy change of the system will be
Orey
ASystem
Now, we also suppose that the loss of heat 'q,e by the surroundings takes place very very
slowly, because the surroundings are much bigger in size as compared to the system. The entropy
change of the surrounding is given by
4S,Psurrounding T

So, ASysiem Asuounding T

We know that
Wey Winey
Intermal energy 'E'is the state function (nK4¯S). The value of 'AE is same
whether the process is carried out reversibly or irreversibly.
AE = rev -W
qreyWirev
Hence, we reach the conclusion is that.
 Chemvica Therimodynamics
251

Hence T T
Grev
T >0
|4S,System AS

It means that all the

surrounding
entropy spontaneous processes
). are accompanied by net increase of
57.5 Entropy Of Melting:
"If we take the ratio of
melting pointof the substance, enthalpy
then it is which
is required to melt one mole of asubstance at the
called entropy of melting."
AS =
AH,
m
Tm
AHm = Amount of heat
required to melt one mole of the
substance. It is also called latent heat of melting.
T = Melting point of the
substance.
57.6 Entropy Of Vapourization:
If we take the ratio of enthalpy which is required to
and the boiling point of a substance, then it is called vapourize one mole of a substance
entropy of vapourization.
AH,
AS, =
AH, Amount of heat required to vapourize one mole of the
substance. This is also called latent heat of vapourization
= Boiling point of the substance.
When a gaseous substance is converted into the liquid state, then evolution of heat takes
place. Hence 'AH, is negative, and 'AS, is negative. It means that there is decrease of entropy.
Similary, when a liquid is solidified, 'AH is negative and 'AS is also negative.
|Sample Problem (5.7)
One mole of solid "S" at it melting point is changed into the liquid at the same
lemperature. The entropy change of 26.4 J K take place. Calculate the melting point of the
solid if its enthalpy of fusion is 0.1 kJg and molar mass of solid is 46.
Solution:
Ihe entropy change of the substance is represented by AS.
AS = 26.4 J Kl mol1
Molar mass of solid = 46g mol"1
Enthalpy of fusion = 0.1kJg1 = 100Jgi
252 ILMI Physical Chemistry
So, AH =100 Jgx 46 gmolt = 4600 Jmol1
AH
Since AS =

So
AS
4600 J mol1
26.4 J K1 moli =174.24 K
5.7.7 Entropy Change For An ldeal Gas In Terms Of Temperature And Volume
In order to have arelationship between entropy change and the change of temperature and
volume we take the help of fundamental definition ( S ) of eDtropy change and first law of
themodynamics.
Consider one mole of an ideal gas, enclosed in a cylinder. There is frictionless piston
( n t ) i n the cylinder. Now, supply asmallamount of heat 8q reversibly and isothermaly
at temperature 'T, then the entropy change is given by the following equation.
dS = (1)
The expression for Sq, according to first law of thermodynamics is
Sq = dE +Sw (2)
If frst law of themodynamics is applied under the reversible conditions, then
Grey (3)
Let the work done is due to the expansion of the gas, then
= PdV
Hence, equation (3) can be written as
qey
rev
dE +PdV (4)
Now,put equation (4) in (1), to get the value of change of entropy.
dE +PdV
dS = T
Rearranging this equation
TdS = dE + PdV (5)
According to the definition of heat capacity at constant value (Cy), we have
dE
dT
dE = C,dT (6)
The general gas equation for one mole of an ideal gas is
PV = RT

P =
RT .....

V
Now,put equation (6) and (7) is equation (5)
 253
Chemical Thermodynamics
TdS = RT
Dividing this equation by 'T
(8) the value of smal change of
This equation is very important because we are calculating
entropy'ds in terms of small change of change of volume 'dV. If we want
temperature 'dT and smallterms of appreciable changes of
to calculate the appreciable changes of entropy that is
temperature and volume, then we should 'AS, in
proceed follows.
as
Suppose uiat volume changes from V,' to V' when the temperature change from l '2
then the equaton (8) should be integrated between these limits to get the change of entropy 'Aom
S, to Sz.
T
Jds

Keep it in mind that 'Cy is thought to be constant when the temperature change takes place
from T, to T,. Actually 'C,' is not constant for appreciable change of temperature.
Performing integration

Putting the limits

$,-S, = Cn T, -In T,) +R(-n V, in V)
Applying the formula of In

AS =C, In |+RIn (9)

With the help of equaion (9), we can calculate the entropy change ( y ) ,
when the temperature of one mole of an ideal gas is increased from "T to T2' and consequently the
volume çhanges from VTo V2. It is clear from this equation (7), that if T2>T and V> V then '4S'
is positivè.
But if T, > T, and V> Ve, then 'AS' is negative. It means that by heating the gas, the entropy
Change is positive and by cooling the gas, entropy change is negative.
Sample Problem (5.8)
Calculate the change in entropy by one mole of an ideal gas when it expands from a
volume of 10 dm³ at 50°C to a volume of 15 dm' at 150°C (C = 32.97 J K mol, R= 8.314 J
K mol).
 254 ILMI Physical Chemlstry
Solution:
The entropy change due to the simutaneous variation in temperature and volume is given by
AS = +nR in y
r
AS = 2.303 nC, log T +2.303 nR log V
Data:
T1 50°C + 273 = 323 K
T2 = 150 +273 = 423 K
Vi = 10dm3
V2 = 15 dm
n = 1
Cp = 32.97 J K mol1
R= 8.314 J K molt
Putting values,
AS = 2.303 x 1 x 32.97 x log n423 +2.303 x 1x 8.314 x log
323
AS = 75.92 log 4232+19.147 log 10
15
= 75.92x0.117 +19.147 x 0.176
= 8.88 +3.369
AS = 12.24 J K1|
5.7.8 Entropy Change In Terms Of Temperature And Pressure:

We can use the general gas equation and substute the term V, in equation (9) of 5.7.7. For
one mole of an ideal gas,
P,V, = RT,
P,V, = RT,
Divide these two equations
P,,
P,V,
or
V, TP, (10)
Put equation (10) in (9) of 5.7.7
AS =
(11)
 255
hemtcatThermodynamics
from R.H.S. of
In order to make the two terms In
together, from two separate factors
take the help of C, and Cy
n(11)we
equation
Since, Cp-Cy Rso, C = Co-R
Put this value of Cy in equation (11)
AS =

00ening the brackets and using the formula of log system, we get
T.
AS =

P.
AS =Cp In (12)
an ideal gas when the
Equation (12) tells us the change of entropy for one mole of
(emperature changes trom'T to'T, and the pressure change from'P,' toP:
Similarny
If T,>and P> P then 4S is positive and there happens an increase of entropy.
,and P, >P then entropy change is negative.
s79 Entropy Change For lsothermal Process:

In isothermal process, there is no change of temperature so,

We know that the change of entropy in terms of temperature and volume is given as,
AS = (13)

The process is isothermal, so T, =T, hence In of unity is always zero.

In = In 1=0.
AS =
of pressure and temperature, is as follows.
We also know that the change of entropy in tems
T P.
AS =

zero.
On similar grounds, we can prove that In i s

P, (14)
So, AS RinP
wokdoneby
CASJS
son,this themodynanlc uyAste0d ewotuncton.
b's Free Energy
The mathematical definition of the Gibb's free energy
theterm TS. energy 'G sin term of entheoy of the
and
G = H-TS

The thermoaynams
'G'
parameter (2Ls H. T nd "s are state unclone
physcal
. 1 S 4 ) SO should also be a state funcion. In order to understand he
sgniñcance (e s of 'G let us consider an isothermal change taking place at a temperature T.
Furthersuppose that, the enthalpy changes from Hto 'H and the entropy changes from S; bS-
is that the Gibb's free energy change from 'G to'G, can be written as,
resultis
So.the net to 'G
G= H-TS,
G, = H,-TS,
Subtracting these two expressions
G,-G = (H-H) -T(S,-S,)
AG = AH-TAS (2)
equation (2) the change of Gibb's free energy is the diference of enthalpy
"According to
term'TAS is also afom of energy.
change 'AH and the term TAS. The
According to the definition of entropy,
258 ILMI Physical Chemistry
AS =

So, TAS = v (3)

When the pressure is constant, then
AH AE +PAV (4)
Putting the equation (3) and (4) in (2),
AG (AE +PAV)-9rey
AG = (AE-q)+ PAV (5)
According to first law of themodynamics,
rev = AE+ W.max
AE-re =-W.max (6)
Puting equation (6) in equation (5)
AG -WmtPAV
or -AG = Wmay -PAV ()
Equatlon (7) gives real significance of Gibb's free energy change. This is the amount of
energy evolved, when certain quantity of the pressure volume work 'PAV is subtracting from
"Wmax
'PAV is the work of expansion. So, W-PAV stands for the maximum work other than the
work for expansion and is called maximum useful work available from the process.

-s(useftul work done)lalens)Rg4GÀn)PANW

So, a process occurring at constant temperature and pressure has a decrease in Gibb's
free energy equal to the maximum useful work obtained from the process.
5.8.1 Variation Of Work Function With Temperature And Volume:

If we want to determine the change of work function with respect to volume and with respect t
temperature, then we should take into consideration the basic definition of work function 'A', that
entropy change and mathematical definition of first law of thermodynamics.
The work function 'A' is related to 'E, T and 'S, as
A = E-TS
(1)
Now, diferentiate this equation,considering that there happen a change in Adue to change
'ET and 'S. Let these changes be 'dA, 'dE,'dS' and 'dT.
So, dA = dE- TdS-SdT (2)
We also know that entropy change is
dS = T
According to first law of thermodynamics
 260

(8)
function 'A', with respect to temperature
According to equation (6), rate of change of work
at constant volume is the negatlve value of entropy.
Born February 11, 1839, New Haven, Connecticut
Residence United States
Fields Physics, chenistry, mathematics
Institutions Yale University
|Alma mater Yale
Known for Statistical mechanicS, Statistical ensemble, Gibbs
entropy, Phase space, Gibbs free energy, Phase
rule, Gibbs paradox, Vector calculus, Cross product,
Gibbs phenomenon, Gibbs-Helmholtz equation,
Gibbs-Duhem equation, Gibbs algorithm, Gibbs
ceasure, Gibbs state, Gibbs-Thomson effect, Gibbs J. Willard Gibbs
isotherm, Gibbs-Donnan effect, Gibbs lemma
Notable awards Rumford Prize (1880), Copley'Medal (1901)
|Died April 28, 1903 (aged 64)
5.8.2 Variation Of Gibb's Free Energy With The Temperature And Pressure:

lf we want to determine the change of Gibb's free energy with respect to temperature and
pressure, then we should take into consideration the basic definition of Gibb's free energy 'G, that of
entropy change and the mathematical definition of first law of thermodynamic. The work function
G is related to 'H', 'T and 'S' as follows.
G = HTS .... (1)
Since, H = E+PV
So, G E+ PV-TS (2)
Now, differentiate equation (2) considering that there happens change in 'G' due to the
changes in 'E, "P, V, T and 'S.
Let these changes be 'dG, 'dE, 'dV, 'dP, dT and 'dS.
dG = dE +PdV + VdP-TdS- SdT (3)
dE + PdV
Since, dS T T
So, TdS dE + PdV (4)
Put equation (4) in (3),
dG = dE +Pd + VdP- dE-Pd-SdT
dG = VdP- SdT
(5)
According to equation (5), the change in the Gibb's free energy dG depends upon the change
of pressure and the change of temperature. If there is
simultaneously (, ) change of
temperature and pressure, then equation (5) is useful but we want to deduce two equations by
Considering temperature and pressure constant one by one.
 ChemicalThermodynamics
261
At Constant Temperature:
If dT =0, in equation (5)
thenit can be written as,
(dG), =V(dP), =V(dP),
Since G IS changing only with respect to pressure
constant,then when the temoerature is thougnu

(6)
It means that the rate of
change of Gibb's free energy with respect to pressure
constantttermperature is equal to the volume of
AtConstant Pressure:
the system.
If dP =0, in equation (5) then it can be
writern as,
Since, G IS changing with respect to the temperature. when the pressure is thought to be
Constant, then

with respect to
According to this equation (7), the rate of change of free energy
termberature at constant pressure is equal to negative entropy.
58.3 Change of Free Energy Under lsothermal Condition (bafasjel »):
In the previous article we have derived that,
dG = VdP- SdT
When the conditions are isothermal, then temperature is constant and so dT =0
Hence, (de), =V(dPr
Suppose that under these isothermal conditions, pressure changes from P. to 'P
P2
(1)
(AG),
P4
the general gas equation will be
If we have 'n' moles of an ideal gas, then
PV = nRT
nRT (2)
V
P

Put equation (2) in (1)

P2
(DRT
dP
(AG}, P
P of integration sign.
constants, so taken out
nRT is a collection of
 262
ILMI Physical Chemistry
P2
(AG), : nRT P
P

The integration ofis hP.

(AG), nRT [n P]
Putting limits
(AG), nRT (In P,-In P,)
Applying the formula of In.
P2
nRT Inp, (3)
(AG), 1
"T, at which the process is being
So, if we know two pressures 'P and 'P and temperature
calculated. If P> P(AG) =+ve,
carried out, then free energy change at constant temperature can be expands and is a spontaneOus
gas
then process is not spontaneous. If P, < P AG = -VC, the
process.
to Boyle's law,
We also know that under the isothermal conditions according
P,V, = P,2
P (4)
P,
Puting equation (4) in (3),
(4G], =nRTIin ....5)
terms of change
Equation (5) can help us to understand the Gibb's free energy change in
of volume from V, to V, at a given termperature.
If V, >V, AG =+ve, V,<Vy AG=-ve
Sample Problem (5.9)
What is the free energy change, which oCcurs when 5 moles of an ideal gas expands
dm,
reversibly and isothermally at 298 Kfrom initial state of 1dm to 10
Solution:
Data:
n = 5 moles
T= 298 K
Initial vol. (Vi) = 1 dm3
Initial vol. (V2) = 10 dm
R = 83143 J K- mol1
Substituting the values in the equation
 (AG)r = 143× 298 x\log 10)
28530.27 log (1O"1) = -28530.27 J
(AG)r = -28.53 kJ.
A
5.8.4
Gibb's-Helmholtz Equation (tf:
Gibb's-Helmholtz equation is the relationshio between Gibb's free energy change, enu
change, and the rate of change of Gibb's free energy change with respect to temperature

ALSASat)0sSAS)etbeileu)ts inal shaga is

AG
ÜT P
In order to derive this equation, we proceed as follows.
According to definition of Gibb's free energy.
G H-TS (1)
For isothermal process, the equation can be written as,
AG = AH-TAS (2)
equation (2), to get the final equaton.
Now, we want to get the value of 'AS' and substitute in
H = E + PV (3)
Since,
Putting equation (3) in (1),
G = E+PV TS
Differentiating this equation. .... (4)
-TdS-SdT
dG = dE + PdV + VdP
dE +PdV
Since, (5)
TdS = dE + PdV
TdS' in equation (4) from (5), we get
Putting the value of (6)
SdT
dG = VdP- equation,then dP =0,
constantin the above
is kept
Ifthepressure -S (dT)p
So, (dG),
say that
or we can
 264 ILMI PhyslcalChemistry
-S| (7)
aTP
According to equation (7), the rate of change of free energy with respect to temperature
at constant pressure s negative entropy of the system. Let us say that, at the iniial and final states
of the system.

= -S,

-S
Subtracting these two equations,
={S,- S,) =-4S
or

(aAG) ***..8)

Putting equation (8) (2), we get

4G =AH+OAG) (9)
ÜTP
Equation (9) is the most common fom of Gibb's-Helmholtz equatlon. Thls equation is
applicable in allthe processes, which occur at constant pressure.
This equation can be converted in another useful form
Divide this equation (9) with 'T on both sides.
AG

Let us rearange this equation and bring the differential term on the L.H.S.
AG

AAGIN
OT P
AH|
T2 (10)
This equation (10) can be used to calculate the enthalpy 'AH' at constant pressure, if value of
free energy change at two different temperatures are known.
5.8.5 Applications Of Gibb's-Helmoltz Equation:
It is very useful equation and it has the following applications.
() If we know the Gibb's free energy values at any two temperatures, then the enthalpy
change in that process can be calculated.
ChemicalThermodynamics 265
(2) The electrical energyY produced in a Galvanic cell is Bqual tothe decrease in the free
energy AS accompanied in a cell reacton, The decrease in fre0 eneng
-AG = nEF
Where n number of electrons lost or (1)
.

E EMF of the gained the cell reacuo

in
cell.
F = 1Faraday =
96,500 coulombs
Since, AG
AH +T[246)
EF = AH

nEF -AH +nFTE

\OTp

coeffient
ftafint LM-A7qaE) EMFUL
If we know the temperature co-efficient of the EMF of the cell, which is then we can
OT
calculated 'AH. is Zero, then nEF =-AH, which is the enthalpy change of thesystem.
5.8.6 Gibb's-Helmholtz Equation In Terms Of Internal Energy And Work Function:
On similar grounds, the required equation to be deived is,
AA = AE+

We know that,

Apply this relation to the change of work function.

AA= A,-Ay
(aAA) = -AS (1)
ÜT
The relationship of Helmholtz work function with intemal energy and entropy is,
A = E-TS
AA = AE + TAS (2)
Putting the equation (1) in equation (2),
AA = AE + T|
 ILMI Physical Chemistry
266

5.9 THERMODYNAMICS OF EQUILIBRIUM OR VANT

HOFF'S ISOTHERM

5.9.1 The Free Energy Change of a Reaction

Consider a general reaction
aA + bB CC+ dD
a, b, G, dare their number of moles in balanced equation.
reactants.
ne ree energy change is the diterence of free energies of products and
So, AG =Free energy of products - Free energy of reactants
In terms of chemical potentials of reactants and products, the free energy change is give by
the following equation
AG= GProducts -GReactants
AG= (CHc t+d 4)-(a 4a +b ¡)
Wnere Ha Hg He and 4, are the chehical potentials of A, B, Cand Drespectively.
5.9.2 Standard Free Energy Change of a Reaction
When all the reactants and products of a chemical reaction are taken in their standard state,
Ue iee energy change accompanying the reaction is called standard free energy change. It is
represented by AG°. Thus,
AG° =Gproducis GReacants
In tems of chemical potentials, we can write it in the form

Here Ha He and H, are the standard chemical potentials of A, B, Cand Drespectively.

5.9.3 Free Energy Change as a Criterion of Spontaneity
The change in free energy can be used as a criterion of feasibility of a process. There are
three situations.
() AG<0, the process is spontaneous in forward direction.
AG >0, the process is non-spontaneous in forward direction. In fact it will proceed in
backward direction i.e., products will get converted into reactants.
(ii) AG =0, the reaction will be at equilibrium.
Consider a reversible reaction of the type
Reactants Products
Let us take the example of free energy changes that take place when the reaction is in
progress are depicted in Fig. (5.6)
N,O, (9) 2NO, (9)
In the beginning the concentration of reactants is maximum, therefore, the free
2ssociated with them is also maximum while the free energy associated with products is minimum.energy
 Chemical Thermodynamics
The
variation of free 267
temperature and
pressure is energy of N,O, and NO2 versus the extent of reaction at constant
representsthe standard free shown in Fig. (5.6). At
energy of the reactant. point Aonly the reactant N0, s present and it
energy’
Free 8
2 moles
aG+
:+5.40 ky of NO

mole of NO4
Akee

AG°T0.84 kJ
A83.45 NO2
16.6% N,Ð,JAG® =0
1
Fig. (5.6) Graph of0.75 0.5 0.25
free energy of system
0.0
of forward as well as
backward
showing spontaneity
At point B, only products i.e., 2 reaction.
standard iree energY Of products. PointC moles of NO, are present and point Btherefore represents
is the eguilibrium state where
NO, exist togene. At hisi point the AG = 0, 16.6% of N,O, and 83.4070
The difference between the standard free
Droducts (point B)and the standard free energy of energy o
reactants
energy of equilibrum mixture (point C) is 0.84 kJ lower than (point A) is AG° = +5.40 kJ. Ihe ree
N,O, (g) changes into equilibrium mixture, the value of AGO point A. That implies that when one mole or
=-0.84 kJ. Similarly when 2 moles of NO
change into equilibrium mixture, the value of AG° is 5.4 kJ.
Thus, we find that in both the cases the value of AG° is
processes are spontaneous. negative. Therefore both the
There are threerelations to determine the free energy change of
1. AG° = AH° - TASO is arelationship of standard free energy reactions.
and entropy changes. change with standard enthalpy
Heat of reaction AH° is detemind experimentally and entropy change AS° is
the absolute entropies of the reactants and products, using the relation calculated from
ASO =2S° (Products) - ZS° (Reacants)
2 AGO =-RT In K, or AG° =-RT In Ke.
Relates equilibrium constant and standard free energy change. Knowing the value of K, or Ke
it is possible to calculate standard free energy change using the above relationship.
3
AG° =EAG° (Products)-E AG° (Reactants)
Standard free energy of formation is defined as the free energy change accompanying a
reaction in which one mole of substance in its standard state is formed from its elements in their
Standard states. Free energy of formation of an element in its standard state is taken as zero.
4
Free energy change AG of a gaseous reaction, at constant temperature can also be obtained,
using the following relation
268 I MI Physlcal Chemlstry

AG =n RT in
where P and P2 are initial and final pressures respectively.
9.5.4 Problems Based on Calculation of Standard Free Energy Change
Sample Problem (5.10)
Calculate the standard free energy change for the converslon of COg) to CO20) and
predict whether the reaction is feasible or not.
AH° = 270 kJ mol-1
coo.) CO2 (g)
Standard entropies of CO, COand O, are 205, 190and 200 JK- mol respectively.
Solution:
Standard change in entropy AS° is given by
AS°= 2S° (Products)-zS° (Reactants)
or

Substituting the values, we have

AS° =205-190 +* 200= -85 JIK- mol
Apply the relation
AG° = AHO-TASO
Here AH° = -270kJ mol-1 =-270000 J mof-1
T= 25 +273 = 298 K
ASO =-85 JK- mol-1
AG° =-270000 J mot-1 298 K(-85 JK- mol-)
=-244670 J=-244.67 kJ
Since AGO is negative, hence the reaction is feasible.
5.9.5 Thermodynamic Derivation of the Law of Chemical Equilibrium
Derivation of relationship of standard free energy change and equilibrium constant of a
reaction. Consider a general reversible reaction,
aA + bB cC + dD
Here the reactants and products are taken to be ideal gases. Let a Hg Ho Ho are the
chemical potentials of A, B, Cand Drespectively at constant temperature and presSure.
Total free energy of reactants =GReactanks au + bug
Total free energy of products =Gproducs =Cç +dub
At constant temperature and pressure, the free energy change of the reaction is given by
AG =GProducs - GReaclants
AG=(CAc +duo)-(aHA big) ...0)
 chemicalThermodynamics
When the
systembeis in 269
writ eequi
n aslibrium state at constat
shereforeequation (1) can
(CHC +duo)- (aua+ lemperature and pressure, AG =0,
or ba) =0
Chemical potential of . any
...()
where p is the
t component
RT In p
in the ideal gas
mixture is given by the relation
i state
standard ie., at 1 atmpartial pressure of the ...(i)
Substituting the pressure. °
values of ufromdepends (i)
component
only on and ° is the chemical potential in the
c(et RTInP+d equation intotemperat
equationure.(ü) we get
Opening the
brackets and (Ho+RT
bringing
In p,) =a
like (u+
terms together.
RTI In p) +b(H + RT In p)
RT (C In P +d in
p)+ (cutdug) =RT ((a ln p +bIn p) +(au +b)
RT (n P;+ In p) +(CHc+
Taking terms involving RT on L.H.S dy) =RT In P+Inp)
RT (n P+in po)- (In p +In
pl=(a +bu-(c+d
Applying formula of log| log x-log y=
C logand putting
or RT In aPc .Po
PA PB
Rearranging R.H.S
Gaeactants -

=-(Gproducis -GReacantl)-AG
Taking RT on R.H.S
C d

or
Pc Po -AGO
RT . (iv)
PA Pg
The quotient on L.H.S is equal to K, when
C d
reaction has attained equilibrium position.
Pc - Po
So, a bConstant (Kp) .()
PA PB
Equation (iv) can be written as
|AGO =-RT In Ko ... (I)
Molar Concentration
If molar concentrations are taken in place of partial pressures, the
j of a component may be chemical potential equation
expressed as
H°+RT In C
 270 ILMI Physical Chemistry
where Cis the molar concentration of the given component in the reacion mixure and u° is
state.
the chemical potential of the substance in the standard
C

bConstant (K)

or
[CE. D.=Ke
IAP. (B
So, we can obtain a relation between AG° and Ke as under
AG° =-RT InKe ..(vi)
To derive the law of equilibrium in terrns of activities, we write the chemical potential of each
component as
*p°+RT In a
where a is the activity of the component and u° depends both on temperature and pressure.
C

B=Constant (Ka)

Hence, AGO =-RT In K¡l ...(vii)

By knowing, AG° of the reaction we can calculate Kp, Kç or Ka and vice versa. K, = Ke only
when the number of moles of reactants and products are equal. Therefore, the value of AG° obtained in
equations (vi) and (vii) are different.
Sample Problem (5.11)
The value of Kp, for the water gas reaction
C0+ H,0 CO, + H
is 1.06 x 105 at 25°C. Calculate the standard state free energy change (AG°) of the
reaction at 25°C. (R =8.314 JK- mol)
Solution:
The expression is ion
AGº =-RT in Kp =-2.303 RT log KÍ
Putting values
=2.303) (8.314 J K- mot) (298 K) log (1.06 x10*)
=-28673.6 J=-28.674 kJ

5.10 CLAPEYRON EQUATION

We know that when the temperature of the system changes then equilibrium present in the two
phases is affected. For example, a melting substance changes its equilibrium position with
change of temperature Similarly, the vapour pressure of liquid changes with the change of
temperature.
 Chemical
/ Thermodynamics 271

Now, we want to proceed to know that, how this task was handled mathematically
When asystem is in equilibrium, then the free energy change accompanying
processis zero. It means AG0. When the then
the pressure and temperature of a system change,
thefree
ener9y changes acoording to the following
dG =VdP- SdT equation.
(1)
Now, suppose nat we have a system at our disnosal which is
wophases are in equilibrium at temperature T and pressure 'P". Let usconsisting of two
suppose that thepnas
free energy ofof
thephase'A' is 'G' and that of phase 'B' is 'G,, Now change the temperature of the system from "T to
T+dT. Similarly, the pressure changes from 'P to P+ dP', Due to these changes, the coresponding
changesinthe free energy of the phase 'A'is
'dG,' and that of phase 'B' is dG
Look at the following diagram (5.7) to
understands this.
T T+ dT

B
G2 B GztdG2
A
Gi A GtdG
Fig. (5./) Equilibrium of two phases Aand Bat the two temperature Tand T+ dT.
Apply equation (1) on these two phases.
dG, = V,dP - S,dT (2)
dG, = V,dP - S,dT (3)
V, = Molar volume of a substance in phase A.
V, = Molar volume of the substance in the phase B.
S, = molar entropy in phase 'A'.
S, = Molar entropy in phase 'B'.
When phase 'A' is in equilibrium with phase 'B' then dG=0,
G, -G, = 0
When the temperature changes by 'dT' and pressure by dP", then
(G,+ dG,) -(G, +dG,) = 0
Since, G,-G, = 0

So, dG, - dG,= 0

or dG, = dG, (4)
Putting the value of 'dG,' and 'dG, from equaions (2) and (3) in the equation (4),
V,dP - S,dP= V,dP - S,dT
Rearranging and taking things as common.
(V,- V,jdP = (S,- S,jdT
 272 ILMI Physical Chemistry
Let (V,-V) = AV and (S,- S,) =AS
So, AVdP = ASdT

or
dP AS (5)
dT
AS = Molar entropy change, when the phase 'A' changes into phase 'B'. lf this change occurs
at temperature 'T, then
AS = (6)
This temperature T at which the change takes place, is the melting point of the
substance or boiling point of the substance. In both cases, AH is latent heat of transformatlon

Putting equation (6) in (5)

dP AH (7)
dT TAV
This equation (7) tells us the rate of change of vapour pressure with respect to
temperature in terms of heat of transformatlon 'AH, temperature of change of phase T, and
change of volume 'AV. This equation was first of all derived by Clapeyron in 1934 and is called
Clapeyron equation.
Application of Clapeyron Equation:
This equation can be applied to various physical equilibra like melting, vapourization
(Che) and sublimation (tekby).In these processes, there happens a phase change

5.10.1 Clapeyron Equation And Melting Equilibrium:

When a solid and liquid are in equilibrium at its melting points, then
AH = AHn

AH = Latent heat of melting.

= Melting point of the substance.
Equation (7) is modified into,

Here dP
dT TAV
Where AV = V,-V,
V, = Molar volume of liquid.
V, = Molar volume of solid.
dP AHn (8)
Hence,
dT T-V)
According to the equation (8), we know the rate of change of vapour pressure with resp
to temperature. This equation can also be witen as,
 chemical ThermOdynamics
273

AH
This equation (9) gives us (9)
variation of meltng polnt with the pressure.
5102 Clausius-Clapeyron Equation:
f one mole of a liquid is
In vapour of the same iquid, the
Capeyronequaton ((8) can be
witen forequilibrium with one mole of the
that as follows.
dP
aH,
T,-V)
In equaton (10) the vaDous
(10)

of theliquid. parameters on the R.H.S. are related with the liquid and the
Napour
I, = Boiling point of liquid
V, = Molar volume of liquid
V, = Molar volume of
vapour
AH, = Latent heat of
vapourization.
Equabon (10), can be sinplified (e-obw) by consideing that the volume of one mole of
Squid IS Very very small as compared to volume of one mole of thé vapours V. So, let us ignore
y'nthe denominator off equation (10),

dP AH,
=
(11)
Where, T = Boiling point of the liquid.
Now, assume that vapours of the liquid are behaving like an ideal gas then,
PV, = RT
RT
P
Putting this value of V, in equation (11),
dP AH,
RrP
Rearranging this equation,
1dP AH,
PdT RT²
witen as folows.
The L.H.S. of this equation van be
d In P AH, (12)
dT RT?
 274 ILMI Physical Chemistry
This equation (12) is the rate of change of log of vapour pressure of the lquid with
respect to temperature and this is in terms of vapourtzatlon of the liquids. This equation is
called Clausius-Clapeyron equation because this equation was derived by Clausius, when he
did a detailed study of Clapeyron's equatlon.
5.10.3 Integration Of Clausius-Clapeyron Equation:
Clausius-Clapeyron equation (12) becomes more useful in its integrated form.
din P AH, (12)
dT RT2
Let us do the separation of variables, by taking the dT on the R.H.S.
d In P =
R T2
We will do the integration within limits by considering that at temperature "T, the vapour
pressure is P and at temperature 'T, the vapOur pressure is P. Then
P2
Sd in P
P1 T
The integration of dih Pis In Pand of is

Putting the limits

In P,-In P, =
P, AH,(T,-T,
In P R (13)

This equation (13) give us of the chance to calculate heat of vapourization if we know two
vapour pressures at two temperatures of a liquid.
Born 2January 1822
Köslin, Province of Pomerania, Prussia
(present-day Koszalin, Poland)
Nationality German
Fields Physics
Known for Thermodynamics and originator of the concept
of entropy
Died 24 August 1888 (aged 66) Rudolf Clausius
phemica
275
/SampleProblem (5.12)
The vapour
respectlvely. pressures of a quld at
Calculate Ahy of llquld at this 85°C and 96°C are 560 torr and 650
torr
Solution:
temperature range (R 8.3143 JK mor.
pata:
I =85°C +273 =
358 K
T2 = 96°C +273 = 369 K
Pi = 560 torr
P2 = 650 torr
n = 8.3142 JK moli
The integrated form of Clausius - Clapeyron
P2 AHy
equation is
log p,2.303 R
Substituting the values, we get
650 AHy 369358
log 560 2.303 x 8.314 369 x 358
AHy 11
log (1.16) = 19.148* 132102
log (1.16) 0.0000043 AHy = 4.3x 107% AHy
0.0647 = 4.3 × 10 AHy
0.0647
AHy = 4.3 x 108 =0.0150 x 10+6
molt|Ans.
AHy = 15 x 10-3J moli = 15 kJ
Equation (jibelbw:
5.10.4 Application of Clausius-Clapeyron a number of applications. particular temperature can
is very important and has
This equation liquid, then vapour pressure at a
AH, of the another temperature.
(1) If we know the vapour pressure at we
know the be calculated, if
be calculated, if we
of vapouization (ok) 'AH' can
(2) The latent heat ( ì )
and tWo vapour
pressures:
then the tboiling
know two
temperatures particular pressure,
known at some latent heat of
boiling point of the liquid is calculated provided that the
(3) If the other pressure can be
point at any
is known. the depression of
the liquid
vapourization of Clausius-Clapeyron equation to understand
coligative properties.
the
We can use ( E I )ofa solution,as one of the
(4) the elevation of boilino point
freezing point understanding
also finds its uses for state.
This equation solventinthesolution Equation:
(5) oz6J)ofa IsochoreAnd| Cilausius-Clapeyronequilibrium constant with
(Cb Hoff change of log of proportionaf tothe square
Of Van't rate of
5.10.5 Comparison conveys the ideathatofthereaction, and inversely
This equationproportionalto AH value
lemperature is directly