REKHA G R

Lecturer in Chemistry

Heat engine

The machine used for the conversion of heat into work is called heat engine. In order to
bring about this conversion, the engine absorbs heat from a heat reservoir at a higher
temperature called the source, converts a part of it into work and returns the remainder to the
heat reservoir at a lower temperature, called the sink.

Efficiency of a machine

The fraction of the heat absorbed by a machine that it can transform into work is called the
efficiency of the machine. Thus if ‘Q’ is heat absorbed and ‘w’ is the work done then the
efficiency of the machine is given by

η = w/Q

Carnot cycle

A Carnot cycle is process in which a system returns to its original state after a number of
successive changes. A process conducted in this manner is called a cyclic process. Carnot’s
engine could perform a series of operations between temperatures T 1 and T2, so that at the
end of these operations the system was restored to the original state. This cycle of processes
which occurred under reversible conditions is referred to as the Carnot cycle. The medium
employed in operating Carnot’s engine was one mole of an ideal gas which could be
imagined to be contained in a cylinder fitted with a frictionless piston. The Carnot’s cycle
consists of four different operations which can be shown on pressure-volume diagram as
shown in the figure.

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i. Isothermal expansion
The cylinder containing one mole of the ideal gas, occupying a volume V 1 is placed in
contact with the source (i.e heat reservoir at temperature T2). The gas absorb heat q2
from the source and expands isothermally and reversibly till its volume has increased
to V2. Let q2 be the heat absorbed by the system at temperature T 2 and w1 be the work
done by the system on surroundings. Then
V2
−W1 = q2 = RT2 ln ( ) ………(i)
V1

ii. Adiabatic expansion

The cylinder is now removed from the source and placed in perfectly insulating
material so that the gas now expands adiabatically and reversibly. Work is done in the
expansion but since no heat enters or leaves the system, the temperature must fall. The
reversible adiabatic expansion is continued till the temperature has fallen to T 1 which
is the temperature of the sink. Suppose the corresponding volume becomes V3. The
path is shown by the adiabatic curve BC in figure. The work done w2 is given by
−W2 = Cv(T1 – T2)
Or –W2 = − Cv(T2 – T1) …………(ii)
iii. Isothermal compression
The cylinder is now removed from the insulating material and placed in contact with
the sink.(i.,e the heat reservoir at the lower temperature T 1). The gas is compressed
isothermally and reversibly till the volume decreases from V3 to V4 . The process is
represented by the path CD in figure. The work done on the system is taken as
positive and will be given by
V4
W3 = RT1 ln (
V3
) ………(iii)

During the operation, an amount of heat q1 exactly equal to w3 will be returned to the
sink at T1. According to sign conventions, q1 will be negative and w3 will be positive.
V4
−q1= W3 = RT1 ln ( )
V3
iv. Adiabatic compression
The cylinder is now removed from the sink and placed again on the insulating
material. The gas is then compressed adiabatically and reversibly along DA till this
initial state A is regained. The temperature of the gas rises from T1 to T2. The work
done on the system is positive and will be given by
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 W4= Cv(T2 – T1) …………(iv)
As a result of these four operations, the system has returned to its original state so that
a reversible cycle has been completed. The net work(w) done by the system will be
given by
W= ( − w1) + (− w2) + (w3) + (w4)
V2 V4
= RT2 ln ( ) − Cv(T2 – T1) + RT1 ln ( ) + Cv(T2 – T1)
V1 V3

V2 V4
W = RT2 ln ( ) + RT1 ln ( ) ……….(v)
V1 V3

V1 and V4 lie on one adiabatic curve and V3 and V2 lie on another, applying volume
temperature relationships, we have

𝑉4 γ−1 𝑇2
(𝑉 ) = ……….(vi)
1 𝑇1

𝑉 γ−1 𝑇
(𝑉3 ) 2
= ……….(vii)
𝑇1
1

Comparing equations (vi) and (vii), we get

𝑉 γ−1 𝑉 γ−1
(𝑉4 ) = ( 3)
𝑉
1 1

𝑉 𝑉
or (𝑉4 ) = (𝑉3 )
1 2

𝑉4 𝑉1
or =
𝑉3 𝑉2

substituting this value in equation (v), we get

V2 V1
W = RT2 ln ( ) + RT1 ln ( )
V1 V2

V V
= RT2 ln ( 2 ) − RT1 ln ( 2 )
V 1 V 1

V
W= R(T2 – T1) ln ( 2 ) ………(viii)
V 1

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Dividing equation (viii) by equation (i) , we get
𝑤 𝑇2 −𝑇1
=
𝑞2 𝑇2

This gives the efficiency of the Carnot cycle or engine.

Clausius- Clapeyron equation

When a system is in equilibrium, the free energy change accompanying the process
is zero.

i.e., ∆G =0 for a system in equilibrium …..(i)

The variation of free energy with temperature and pressure is given by the total
differential equation.

dG =VdP – SdT ……..(ii)

Consider the system consisting of two phases I and II in equilibrium at temperature

T and pressure P. under these conditions, suppose that free energy of phase I is G1
and that of phase II is G2. If the temperature of the system is changed from T to
T+dT and pressure from P to P + dP, suppose the corresponding change in free
energy of phase I is dG1 and that of phase II is dG2. Then according to equation (ii)

dG1 = V1dP – S1dT ……(iii)

And dG2 = V2dP – S2dT ……(iv)

Where V1 and S1 are the molar volume and entropy of phase I and V 2 and S2 are
the corresponding values for phase II

But when phase I is in equilibrium with phase II

∆G=0

i.e., G2 – G1 =0

where G1 is the molar free energy of phase I and G2 that of phase II at temperature
T + dT and pressure P + dP, we must have

(G2 + dG2) – (G1 + dG1) = 0

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But G2 – G1 =0

∴ dG2 – dG1 = 0

Or dG2 = dG1

substituting the values of dG1 and dG2 from equation (iii) and (iv), we get

V2dP – S2dT = V1dP – S1dT

Or (V2 – V1) dP = (S2 – S1)dT

Or ∆VdP = ∆SdT
𝑑𝑃 ∆𝑆
Or = ………..……(v)
𝑑𝑇 ∆𝑉

Where ∆V =V2 –V1 is the molar volume change and ∆S =S2 –S1 is the molar
entropy change where phase I changes into phases II. If this change occurs at the
temperature T and ∆H is latent heat of transformation, then
∆𝐻
∆S =
𝑇

Putting this value in equation (v), we get

𝑑𝑃 ∆𝐻
= ………….....(vi)
𝑑𝑇 𝑇∆𝑉

This equation is called Clapeyron equation.

For the vaporisation equilibrium i.e.,

Liquid ⇌ Vapour

The Clapeyron equation (vi) takes the form

𝑑𝑃 ∆𝐻𝑉
= …………..(vii)
𝑑𝑇 𝑇𝑏 (𝑉𝑣 −𝑉𝑙 )

Where ∆Hv = latent heat of vaporisation

Tb = boiling point of the liquid

Vl = molar volume of the liquid

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Vv = molar volume of the vapour

Volume of the liquid (Vl) is very small as compared to the volume of the
vapour(Vv) thus Vl can be neglected in comparison to Vv. Hence equation (vii)
may be written as (omitting the subscript in Tb)
𝑑𝑃 ∆𝐻𝑉
= ………(viii)
𝑑𝑇 𝑇𝑉𝑣

Further assuming that the vapour behave like an ideal gas, we will have

PVv = RT
𝑅𝑇
Or Vv = ……..……(ix)
𝑃

Substituting this value in equation (viii), we get

dP ∆Hv
= P
dT RT2

1 dP ∆Hv
Or =
P dT RT2

dlnP ∆Hv
Or = ………..(x)
dT RT2

This is equation is called differential form of Clausius- Clapeyron equation.

The equation (x) can also be written in another form called integrated form of
Clausius- Clapeyron equation as explained below. Equation (x) may be rewritten
as
∆Hv
dlnP = dT …….(xi)
RT2

If the temperature changes from T1 to T2 when the vapour pressure changes from
P1 to P2 then integrating equation (xi) between the appropriate limits, we get
𝑃
2 2 𝑇 ∆𝐻
∫𝑃 𝑑𝑙𝑛𝑃 = ∫𝑇 𝑅𝑇 𝑣2 𝑑𝑇
1 1

𝑃2 ∆𝐻𝑣 𝑇2 1
Or 𝑙𝑛 = ∫𝑇 𝑑𝑇
𝑃1 𝑅 1 𝑇2

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 ∆𝐻𝑣 1 1
= [ − ]
𝑅 𝑇1 𝑇2

Changing from natural logarithm to the logarithm to base 10, we get

𝑃2 ∆𝐻𝑣 𝑇2 −𝑇1
2.303 log = [ ]
𝑃1 𝑅 𝑇1 𝑇2

𝑃2 ∆𝐻𝑣 𝑇2 −𝑇1
Or log = [ ]
𝑃1 2.303𝑅 𝑇1 𝑇2

This is called the integrated form of Clausius- Clapeyron equation

Applications

i. If the vapour pressure of a liquid is known at one particular temperature, the

value at any other temperature can be calculated, if the latent heat of
vaporisation of the liquid is known.
ii. If the vapour pressures of a liquid at two different temperatures are known, the
latent heat of vaporisation of the liquid can be calculated from the equation.
iii. If the boiling point of a liquid is known at some particular pressure, the boiling
point at any other pressure can be obtained, provided the latent heat of
vaporisation of the liquid is known.

Van’t Hoff’s reaction isotherm

Consider the following reaction

aA + bB +…. ⇌ lL + mM +….

Taking place under any conditions of temperature, pressure and composition. The free
energy change of the reaction is given by the expression.

∆G = (G) products – (G) reactants …………(i)

= (lµL + mµM + ….) – (aµA +bµB+….)

Where µA, µB. µL, µM etc., represent chemical potentials of the species concerned.

Let us suppose that various reactants and products are in gaseous state. Chemical
potentials of a gaseous substance in any state is given by the equation.

µi(p) = µ0i(p) + RT lnPi ………….......(ii)

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Where µ0i(p) is the chemical potential of a gaseous component i, in the standard state
and µi(p)is the chemical potential of the gaseous component i in any state of partial
pressure Pi . Substituting the values of chemical potentials of various species at their
partial pressure from equation (ii) in (i)

∆G = {𝑙 (𝜇𝐿0(𝑝) + 𝑅𝑇 𝑙𝑛𝑃𝐿 ) + 𝑚 (𝜇𝑀

0
(𝑝)
+ 𝑅𝑇 𝑙𝑛𝑃𝑀 ) + … … … }

− {𝑎 (𝜇𝐴0 (𝑝) + 𝑅𝑇 𝑙𝑛𝑃𝐴 ) + 𝑏 (𝜇𝐵0 (𝑝) + 𝑅𝑇 𝑙𝑛𝑃𝐵 ) + … … … } ………(iii)

Rearranging, we have
(𝑃 )𝑙 (𝑃 )𝑚 ….
∆G= {(𝑙𝜇𝐿0(𝑝) + 𝑚𝜇𝑀
0
(𝑝)
+ ⋯ ) − (𝑎𝜇𝐴0 (𝑝) + 𝑏𝜇𝐵0 (𝑝) + ⋯ )} + 𝑅𝑇 𝑙𝑛 (𝑃𝐿 )𝑎 (𝑃𝑀 )𝑏
𝐴 𝐵 …..

……(iv)

The first expression on the right hand side is the free energy change of the reaction
when the products and the reactants are all in their respective standard states. This
expression may be substituted by ∆G0.

Hence,

∆G = ∆G0 + RTlnQP …….(v)

Where Qp stands for the reaction quotient of partial pressures of the products and the
reactants.
(𝑃𝐿 )𝑙 (𝑃𝑀 )𝑚 ….
i.e. (𝑃𝐴 )𝑎 (𝑃𝐵 )𝑏 …..
= QP

Equation(v) is known as van’t Hoff’s reaction isotherm. This gives the free energy
change of a reaction at any given temperature, pressure and composition of the
reacting system.

Qp is different from KP. Here the values PL, PM, PA, PB….. etc., are not the partial
pressures at equilibrium, but for any state. If the partial pressure values correspond to
equilibrium state, then QP will become equal to KP

We know that,

∆G0 = − RTln Kp
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Substituting for ∆G0 in equation (v), we have

∆G = − RTln Kp + RTln Qp ……(vi)

Equations (v) and (vi) are two forms of van’t Hoff’s reaction isotherm.

Applications

i. It is used to show the direction in which a reaction tends to proceed.

ii. It is difficult to determine ∆G0 experimentally. It involves the measurements of
standard enthalpy change and entropy change. But equilibrium constant can be
easily determined. Using van’t Hoff’s reaction isotherm we can calculate ∆G 0
from the known value of KP.

Nernst heat theorem

This theorem gives variation of enthalpy change (∆H) and free energy change (∆G) of a
system with decrease of temperature.

According to Gibb’s –Helmholtz equation,

𝜕(∆𝐺)
∆G = ∆H + T [ ]
𝜕𝑇 𝑃

From this equation, it is evident that at the absolute zero i.e., when T=0 , ∆G = ∆H. Nernst
𝜕(∆𝐺)
observed that as the temperature is lowered towards absolute zero, the value of
𝜕𝑇
decreases and then approaches zero asymptotically. Mathematically, it is expressed as
𝑑(∆𝐺) 𝑑(∆𝐻)
lim = lim = 0 …………..(i)
𝑇→0 𝑑𝑇 𝑇→0 𝑑𝑇

This means that ∆G and ∆H are not only at absolute zero but the values approach each other
asymptotically near this temperature. This is known as Nernst heat theorem.

Graphically, the result may be represented as shown in figure.

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In figure ∆G has been shown as greater than ∆H at temperature away from absolute zero.
𝜕(∆𝐺)
However the reverse is also possible because can be both positive and negative.
𝜕𝑇

∂(∆G)
Further [ ] = −∆S ……………(ii)
∂T P

∂(∆H)
[ ] = ∆Cp ( Kirchoff’s equations) …………(iii)
∂T P

From equations (i), (ii) and (iii) we can say as T → 0

∆S = 0 and ∆Cp = 0

i.e., as the temperature is lowered to absolute zero, the enthalpy change of the reaction and
difference in the heat capacities of products and reactants also tends to be zero. Since gases
do not exist at the absolute zero, this means that the heat theorem is not applicable to gases.
Similarly it has been found to be inapplicable to liquids also. Nernst heat theorem is
applicable to solids only.

Third law of thermodynamics

It states that “The entropy of all perfectly crystalline solids may be taken as zero at the
absolute zero temperature”

Partial molar quantities

The thermodynamic properties such as free energy, enthalpy, entropy etc., are
extensive properties. Their values change with change in mass of the system. Consider
an open system containing n1, n2, n3…. moles of various components. Let the

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property ‘X’ be a function of temperature, pressure and number of moles of various
constituents.

i.e. X = f(T, P, n1,n2,n3……..ni) …………….(i)

where n1 + n2 + n3 +….ni = N

For a small change in temperature, pressure and the number of moles of constituents,
the change dX in property X will be given by the following equation.
∂X ∂X ∂X ∂X
dX= ( ) dT + ( ) dP + ( ) dn1 + ( ) dn2 + ⋯
∂T P,n1 n2… ∂P T,n1 n2 … ∂n1 T,P,n n ∂n
2 T,P,n1 n3…
2 3…

……..(ii)

At constant temperature and pressure of the system, dT=0 and dP=0

Equation (ii) then becomes

∂X ∂X
(dX) T,P = [ ] dn1 + [ ] dn2 +……….
∂n1 T,P,n n … ∂n2 T,P,n n …
2 3 1 3

…………(iii)

Each term on right hand side of equation (iii) is called partial molar property of that
particular component. It is represented by putting a bar over the concerned property
̅1, X
i.e. X ̅ 2 for the first and second component respectively.

𝜕𝑋
Thus [ ] =̅
X1
𝜕𝑛1 𝑇,𝑃,𝑛 𝑛
2 3…..

𝜕𝑋
[ ] =̅
X2
𝜕𝑛2 𝑇,𝑃,𝑛 𝑛
1 3…….

In general, for an ith constituent, we can write

∂X
[ ] =̅
X𝑖
∂ni T,P,n n
1 2…..

Partial molar volume

The partial molar volume of ith component of system is given by the relation

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 𝜕𝑉
̅i = [ ]
V
𝜕𝑛𝑖 𝑇,𝑃,𝑛
1 𝑛2……. 𝑛𝑖

Where ni indicates number of each component except ith are held constant.

The partial molar volume can be defined as the change in volume of system when one mole
of ith component is added to a large quantity of system at constant pressure and temperature
keeping number of moles of other components constant.

Partial molar free energy: Concept of chemical potential

The partial molar free energy is also called chemical potential and is represented by
symbol µ.

For an ith component, it is written as

𝜕𝐺
̅𝑖 = [
µ=G ] ..........(i)
𝜕𝑛𝑖 𝑇,𝑃,𝑛 𝑛
1 2…..

If dni is taken as 1 mole,

Then µ = (𝑑𝐺)𝑇,𝑃,𝑛1𝑛2 ………. (ii)

The chemical potential of a given substance is defined as the change in free energy of
the system which results on the addition of one mole of that particular substance at a
constant temperature and pressure, to such a large quantity of the system that there is
no appreciable change in the overall composition of the system.

Gibb’s –Duhem equation

Free energy is an extensive property. Besides temperature and pressure, it also

depends on the composition of the system. For a system having n 1,n2… moles of
components 1,2…. We can write

G = f(T,P, n1,n2……..) ……….(i)

Where n1 + n2 + n3 +…. = N

A small change in free energy with change in temperature, pressure and number of
moles of various components can be obtained by partial differentiation of equation (i)

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 ∂G ∂G ∂G ∂G
dG= ( ) dT + ( ) dP + ( ) dn1 + ( ) dn2 + ⋯
∂T P,n1 n2… ∂P T,n1 n2 … ∂n1 T,P,n n ∂n
2 T,P,n1 n3…
2 3…

……..(ii)

At constant temperature and pressure, dT = 0 and dP = 0

Equation (ii) becomes

∂G ∂G
(dG) T,P = [ ] dn1 + [ ] dn2 +……….
𝜕𝑛1 T,P,n n … 𝜕𝑛2 T,P,n n …
2 3 1 3

…………(iii)

We can write
𝜕𝐺
[ ] = µ1
𝜕𝑛1 𝑇,𝑃,𝑛 𝑛
2 3…..

𝜕𝐺
[ ] = µ2
𝜕𝑛2 𝑇,𝑃,𝑛 𝑛
1 3…..

Thus, (dG)T,P = µ1dn1 + µ2dn2+ …….. (iv)

For a system having definite composition, the equation(iv) on integration gives

GT,P,N = n1µ1 + n2µ2 + ….. ………(v)

The total differential of G in equation (v) gives

dG = µ1dn1 + n1dµ1 + µ2dn2 + n2dµ2 + ……

= (µ1dn1+ µ2dn2+……..) + (n1dµ1+n2dµ2+….) ..…….(vi)

From equation (iv) and (vi) we have

n1dµ1 + n2dµ2 + ……….. = 0

or ∑ 𝑛𝑖 𝑑𝜇𝑖 = 0

This relationship is called as Gibb’s -Duhem equation.

*****

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