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Applications of Maxwell’s Thermodynamical Relations

Discipline Course-I
Semester-II
Paper No: Thermal Physics : Physics-IIA
Lesson: Applications of Maxwell’s Thermodynamical
Relations part1
Lesson Developer: Dr. Vinita Tuli
College/ Department: ARSD College, University of Delhi

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Applications of Maxwell’s Thermodynamical Relations

Table of Contents

Chapter: Maxwell’s Thermodynamical Relations


 Introduction

 Applications of Maxwell’s Relations

 Summary

 Exercise/Practice

 References/Bibliography

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Applications of Maxwell’s Thermodynamical Relations

Introduction
Out of several properties of a thermodynamic system some of these like internal energy and
entropy cannot be measured. So thermodynamic relations can relate these properties with
those that can be measured like pressure,temperature, compressibility etc. In
thermodynamic relations un-measurable properties can be written as partial derivatives
involving both intensive and extensive variables. A thermodynamical relations is a rule
which is obtained by a simple thermodynamic reasoning and applies to most of the systems.
The usefulness of the above relations lies in the fact that they relate quantities which seem
unrelated. They help us to link data obtained in various ways or replace a difficult
measurement by another one. They can also be used to obtain values of one variable from
the calculations of another variable. These relations are very general and immensely useful
as they simplify analysis of thermodynamic systems. The most convenient way to derive
these relations is to use partial differentiation.

Value Addition

How to Remember Maxwell’s Relation’s :

Note : The first four Maxwell’s thermodynamical relation need not be memorized. These
can be easily written by remembering the word SP or TV i e (sportive). In this, SP TV
represent entropy, pressure, temperature and volume. In deriving the first two relations,
S is written in the numerator on the left hand side of the equation and the rest of the
quantities P, T and V are written (i) in the clockwise order and (ii) in the anticlockwise
order. In the clockwise direction, the right hand side expression in with a + sign and for the
anticlockwise direction, it is –ve. These equations are
 S   P 
  =   …(i)
 V T  T V
 S   V 
  =   …(ii)
 P T  T  P
Similarly to write the other equation, S is written in the denominator of the right hand side
of the equation and the other quantities are written (i) in the anticlockwise direction and (ii)
in the clockwise direction. These equations are
 T   P 
  =   …(iii)
 V S  S V
 T   V 
  =   …(iv)
 P  S  S  P

Applications

1.
Specific Heat Equation

The specific heat at constant pressure is given by

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Applications of Maxwell’s Thermodynamical Relations

 Q 
CP =  
 T  P

 S 
= T  ( Q  T  S )
 T  P

the specific heat at constant volume is

 Q 
CV =  
 T V

 S 
= T 
 T V

if entropy S is taken as a function of T and V and since dS is a perfect differential,

 S   S 
dS =   dT    dV
 T V  V T

 S   S   T   S   V 
   =        
 T P  T V  T  P  V T  T  P

 S   S   S   V 
T  =T  T    
 T  P  T V  V T  T  P

 S   P 
  =   ( from Maxwell’s second relation)
 V T  T V

 S   S   P   V 
 T  T   = T   
 T  P  T V  T V  T  P

 P   V 
CP  CV = T     …(1)
 T V  T  P

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Applications of Maxwell’s Thermodynamical Relations

(a) For a perfect gas :

The equation of state for one mole of a perfect gas is

PV = RT

 P  R
   =
 T V V

 V  R
  =
 T  P P
equation (1) takes the form

 R  R 
CP  CV = T   
 V  P 

R 2T
=
PV

R 2T
=
RT

 CP  CV = R

(b) Van der Waals :

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Applications of Maxwell’s Thermodynamical Relations

The equation of state for a Van der Waals gas is

 a 
 P  2  (V  b) =RT
 V 

where a and b are constants.

From the Van der Waals equation, we get

 a  RT
P 2  =
 V  (V  b)

Differentiating the equation with respect to T at constant volume, we have

 P  R
  =
 T V (V  b)

and differentiating with respect to T at constant pressure we have

2a  V  RT  V  R
0 3   =  2   
V  T  P (V  b)  T  P (V  b)

 V   RT 2a  R
    3 =
 T  P  (V  b) V  (V  b)
2

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Applications of Maxwell’s Thermodynamical Relations

 R 
 (V  b) 
 V   
  =
 T  P  RT 2a 
 (v  b) 2  V 3 
 

 P   V 
Substituting the value of   and   in equation (1), we have
 T V  T  P

 R  R 
T  
CP  CV =
 V  b  V  b 
 RT 2a 
 (V  b) 2  V 3 
 

R
=
2a (V  b) 2
1 3 
V RT

Neglecting b in comparison to V as b is much smaller than V

R
CP  CV =
2a V 2
1 3 
V RT

R
=
2a
1
VRT

1
 2a 
= R 1  
 VRT 

Expanding binomially the above equation and neglecting higher powers of a as a is very
small in comparison to V, we have

 2a 
CP  CV = R 1  
 VRT 

2.
To Show that CP  CV  TE  2V
where T is the absolute temperature
E is the isothermal elasticity of the gas,
 is the coefficient of volume expansion and
V is the specific volume of the gas.

From Maxwell’s second thermodynamical relation

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Applications of Maxwell’s Thermodynamical Relations

 S   P 
  =  
 V T  T V

from the definition of CP and CV we have

 Q 
CP =  
 T  P

 S 
= T 
 T  P

 Q 
CV =  
 T V

 S 
= T 
 T V
Taking S  f (T ,V ), we have
 S   S 
dS =   dT    dV
 T V  V T
dividing the above equation by dT and then carrying out the process at constant pressure
we have

 S   S   T   S   V 
  =       
 T  P  T V  T   V T  T  P
But from the maxwell’s relation , we have

 S   P 
  =  
 V T  T V

 S   S   P   V 
 T  = T  T    
 T  P  T V  T V  T  P

 P   V 
 CP = CV  T     …(2)
 T V  T  P

taking the general equation of state for a gas as P  f (V , T )

 P   P 
 dP =   dT    dV
 T V  V T

Dividing the above equation by dT , we have

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Applications of Maxwell’s Thermodynamical Relations

dP  P   P   V 
=      
dT  T V  V T  T  P

At constant pressure

dP = 0

the above equation becomes

 P   P   V 
  =    
 T V  V T  T  P

Substituting the value in equation (2)

 P   V 
2

CP  CV = T     …(3)
 V T  T  P

 V   P 
2

CP  CV = T     …(4)
 T  P  V T

modulus of elasticity at constant temperature is given by

 P 
E = V  
 V T

and the coefficient of volume expansion is given by

1  V 
 =  
V  T  P

Substituting these values in equation (4) we have

C p  CV = TE 2V …(5)

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Applications of Maxwell’s Thermodynamical Relations

3. Clausius-Clapeyron’s Equation (First Latent Heat Equation)

dP L
The equation  was derived by Clapeyron using Carnot’s reversible cycle.
dT T (V2  V1 )
Therefore, it is also called Clapeyron’s eqauation.

Whenever there is a change of state, from a solid state to liquid state or from liquid state to
vapour state, the temperature remains constant as long as the change takes place. This
temperature (either melting point or boiling point) depends upon the pressure and is a
characteristic of each substance. The above relation tells us how melting or boiling points
vary with pressure. Later Clausius also obtained the same relation by using the Maxwell’s
thermodynamic relations.

Derivation :

From second thermodynamical relation, we have

 S   P 
  =  
 V T  T V
Multiplying both sides by T, we get

 S   P 
T  = T 
 V T  T V

We know that
T  S = Q
Substituting this in the above equation, we get

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Applications of Maxwell’s Thermodynamical Relations

 Q   P 
   = T  …(6)
 V T  T V
 Q 
  represents the quantity of heat absorbed or liberated per unit change in volume at
 V T
constant temperature. As there is a change in volume due to the heat absorbed at constant
temperature, the heat represents the latent heat used when a substance, changes from
solid to liquid (melting) or liquid to vapour (boiling) state when the temperature remains
constant, during the change of state.
If L is the quantity of heat required to change the sate of a unit mass of the substance,
V2 and V1 the corresponding specific volumes (Volume per unit mass) then
Q = L

V = V2  V1
Dividing the above equations we get

 Q  L
  =
 V T V2  V1

L  P 
Therefore we have =T  
V2  V1  T V

dP L
= …(7)
dT T (V2  V1 )

Where dT is the change in melting point or boiling point due to a change in pressure dP.

This is Clausius-Clapeyron equationt or first latent heat equation.

Effect of Pressure on Boiling Point of Liquid

When a liquid converts into vapour state, we know that there is always an increase in
 P 
volume. Implies that V2  V1 ; T and L are always positive quantities, therefore   is
 T V
+ve. This shows that boiling point of the liquid is raised by increasing the pressure. This is
known as

elevation of boiling point of the liquid.

Effect of Pressure on Melting Point of Solid

When a solid melts, there may be an increase in volume, as in case of wax (such substances

are called wax type substances) or there may be a decrease in volume, as in the case of

ice. (such type of substances are called ice type substances).

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Applications of Maxwell’s Thermodynamical Relations

In melting of wax type substances, volume of the substance always increases.

(V2  V1 ) = +ve
Which implies
dP
= +ve
dT

Hence the melting point of the substance is raised with the increase in pressure.

In case of ice

(V2  V1 ) = – ve

hence melting point of such substances is lowered with increase in pressure. This is known
as depression in melting point. Substances which expands on melting, have their melting
points raised with the increase of pressure and the substance which contract on melting
have their melting points lowered with the increase of pressure.

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4. To deduce the second latent heat equation of Clausius given as

dL L
C2  C1 = 
dT T

where C1 and C2 are the specific heat of a liquid and its vapour and
L is the latent heat of the vapour.

For a change of state from liquid to vapour we get


L
S2  S1 = …(8)
T

Where S1 and S2 are the entropies of the liquid and vapour states
Differentiating equation (8) with respect to T, we have

dS2 dS1 1 1 dL
 = L 2  
dT dT T T dT

Multiplying the above equation by T, we get

 dS   dS  L dL
T  2  T  1  =  
 dT   dT  T dT

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Applications of Maxwell’s Thermodynamical Relations

dL L
C2  C1 =  …(9)
dT T
This is known as Clausius second latent heat equation.

Problems based on second latent heat equation

i. Calculate the specific heat of saturated steam given that the specific heat of water at
100°C = 1.01 and latent heat of vaporization decreases with increase in temperature at
the rate of 0.64 cal/K. Latent heat of vaporization of steam is 540 cal.

Sol. Here C1 =1.01,

C2 = ?

T = 373 K

dL
= – 0.64 cal/K
dT

dL L
C2  C1 = 
dT T

dL L
C2 = C1  
dT T

540
= 1.01  (0.64) 
373

= – 1.077 cal/g

ii. If L = 800 – 0.705 T, show that the specific heat of steam is negative.

Sol. Given : L = 800 – 0.705 T

dL
 = – 0.705
dT

At normal boiling point of water i.e., at 100°C = 373 K, the value of L would be

L = 800 – 0.705 × 373 = 537

The specific heat of water in liquid state, C1 = 1

Using second latent heat equation


dL L
C2  C1 = 
dT T

537
= 1  (0.705) 
373
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Applications of Maxwell’s Thermodynamical Relations

= – 1.14467

Thus, the specific heat of saturated vapour pressure at 100°C in negative

5. To prove that for any substance, the ratio of the adiabatic and isothermal elasticities is
equal to the ratio of the two specific heats.

Isothermal elasticity of the gas is given by


 P 
ET = V  
 V T

Adiabatic elasticity of the gas is given by


 P 
ES = V  
 V  S

 P 
V  
ES  V  S
=
ET  P 
V  
 V T

 P 
 
 V  S
=
 P 
 
 V T

 P   T 
   
 T  S  V S
=
 P   S 
   
 S T  V T

Taking the first term of the numerator to the denominator and the first term of the

denominator to the numerator

 S   T 
   
ES  P T  V S
= …(i)
ET  T   S 
   
 P  S  V T
from the first four Maxwell’s equations we have

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 S   V 
  =  
 P T  T  P

 T   P 
  =  
 V  S  S V

 T   V 
  =  
 P  S  S  P

 S   P 
  =  
 V T  T V

Substituting these values in equation (i), we get

 V   P 
   
ES  T  P  S V
=
ET  V   P 
   
 S  P  T V

Taking the first term of the denominator to the numerator and the second term of the

numerator to the denominator

 S   V 
   
ES  V  P  T  P
=
ET  S   P 
   
 P V  T V

Multiplying and dividing the equation by T

 S 
T 
 T P
=
 S 
T 
 T V

 Q 
 
 T  P
=
 Q 
 
 T V

We know

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Applications of Maxwell’s Thermodynamical Relations

 Q 
  = CP
 T  P

 Q 
and   = CV
 T V

ES CP
= =  …(ii)
ET CV

6. Using Maxwell’s thermodynamical relations, to prove that the ratio of the adiabatic to
the isobaric coefficient of volume expansion is
1
(1   )

Sol. Adiabatic coefficient of volume expansion is given by

1  V 
S =   ...(i)
V  T  S

Isobaric coefficient of volume expansion is given by

1  V 
P =   …(ii)
V  T  P

Dividing the above two equations


1  V 
S  
V  T S
= …(iii)
P 1  V 
 
V  T P

 V 
 
 T S
=
 V 
 
 T P

Bringing the first term in the numerator to the denominator

1
=
 T   V 
   
 V  S  T  P

Using Maxwell’s relation

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Applications of Maxwell’s Thermodynamical Relations

 T   P 
  =  
 V S  S V

Substituting in the above equation


S 1
 = 
P    V 
P
   
 S V  T  P

Splitting the first term of the denominator

1
=
 P   T   V  
       
 T V  S V  T  P 

Taking the second term of the denominator to the numerator and multiplying by T

 S 
T 
 T V
=
 P   V 
T    
 T V  T  P

We know that

 P   V 
CP  CV = T    
 T V  T  P
and

 S 
CV = T  
 T V
Substituting these values in the above equation we get

S CV
=
P (CP  CV )

S 1
=
P C 
1  P 
 CV 

Dividing the numerator and denominator by

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Applications of Maxwell’s Thermodynamical Relations

CV

S 1
= …(iv)
P 1 

7. Using Maxwell’s thermodynamical relations prove that the ratio of the adiabatic to the
isobaric pressure coefficient of expansion is

(  1)

Sol. Adiabatic pressure coefficient of expansion is

1  P 
S =   ...(i)
P  T  S
Isochoric pressure coefficient of expansion is

1  P 
V =   …(ii)
P  T V

Dividing (i) by (ii) we get


1  P 
S  
P  T  S
 = …(iii)
V 1  P 
 
P  T V

 P 
 
 T  S
=
 P 
 
 T V

Taking the first term of the numerator to the denominator

1
=
 T   P 
   
 P  S  T V

Using Maxwell’s relation and substituting in the above equation

 T   V 
  =   …(iv)
 P  S  S  P

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Applications of Maxwell’s Thermodynamical Relations

S 1
= …(v)
V  V   P 
   
 S  P  T V

Splitting the first term of the denominator we get

1
=
 V   T   P 
     
 T  P  S  P  T V

Taking the second term of the denominator to the numerator


 S 
 
 T  P
=
 V   P 
   
 T  P  T V
And multiplying by T we get
 S 
T 
 T  P
=
 V   P 
T   
 T  P  T V

using

 P   V 
CP  CV = T    
 T V  T  P
And we get

S CP
=
V CP  CV

 CP 
 
S  CV 
=
V  CP 
  1
 CP 


= …(vi)
 1

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Applications of Maxwell’s Thermodynamical Relations

Summary

A thermodynamical relations is a rule which is obtained by a simple thermodynamic


reasoning and applies to most of the systems. The usefulness of the above relations lies in
the fact that they relate quantities which seem unrelated. They help us to link data obtained
in various ways or replace a difficult measurement by another one. They can also be used to
obtain values of one variable from the calculations of another variable. These relations are
very general and immensely useful as they simplify analysis of thermodynamic systems.
The most convenient way to derive these relations is to use partial differentiation. They can
also be derived from other methods.

Exercise
1. Derive Maxwell’s thermodynamical relations connecting the thermodynamic
quantities.

2. Show that
 P   V 
CP  CV = T    
 T V  T  P
where symbols have their usual meaning.

2. Use Maxwell’s relations to obtain CP  CV  R for an ideal gas where CP and CV are
specific heats at constant pressure and constant volume.

And show that


for a Van der Waal’s gas
 2a 
CP  CV = R 1  
 VRT 
Where symbols have their usual meaning.

3. prove the relation.


ES CP
=
ET CV

4. Derive the Clausius-Clapeyron equation given by

dP L
=
dT T (V2  V1 )
and explain the effect of pressure on

(a) boiling point of a liquid

(b) melting point of a solid.

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Applications of Maxwell’s Thermodynamical Relations

6. Prove the relations


 S   P 
  =  
 V T  T V

 S   P 
  =  
 P T  T  P

OBJECTIVE QUESTIONS

1. Four thermodynamic potential are given by:

(a) Pressure, volume, temperature and internal energy function.


(b) Pressure, volume, internal energy and Helmholtz function.
(c) Internal energy function, Helmholtz function, enthalpy and Gibbs function
(d) none of these

2. Specific heat of saturated vapour pressure is


(a) zero
(b) positive
(c) negative
(d) sometimes positive sometimes negative

ES
3. From Maxwell’s thermodynamic relations ?
ET
(a) 1
1
(b)

(c) 
(d) 2

4. The Clausius-CLapeyron equation is given by:


dP L
(a) 
dT T (V2  V1 )
dP L
(b) 
dT L(V2  V1 )
dP
(c)  TL(V2  V1 )
dT
(d) none of these

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Applications of Maxwell’s Thermodynamical Relations

5. The value of CP  CV for an ideal gas is given by


(a) TEV 2
(b) T 2 EV
(c) TE 2V
(d) TE 2 2V 2

6. Rice takes longest time to cook


(a) in submarine 100 m below the surface of the sea.
(b) at the sea level
(c) at Simla
(d) at Mount-Everest

7. Paraffin wax contracts on solidification. The melting point of wax will


(a) increase with pressure
(b) decrease with pressure
(c) no change with pressure
(d) decrease linearly with pressure

References:

1. Thermodynamics, kinetic theory and statistical thermodynamics by F.W. Sears


and G.L. Salinger.
2. Fundamentals of Statistical and Thermal Physics by F. Reif.
3. A Treatise on Heat by M.N. Saha and B.N. Srivastava.
4. Thermal physics by C. Kittel/H. Kroemer.
5. Heat and Thermodynamics by M.W. Zemansky and R.H. Dittman.
6. Thermal Physics by S.C. Garg, R.M. Bansal and C.K. Ghosh.

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