Maxwell’s Thermodynamical Relations

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

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 Maxwell’s Thermodynamical Relations

INTRODUCTION

Why Do We Use Maxwell’s Relations?

• Certain variables in thermodynamics are hard to measure experimentally

such as ‘entropy’.

• Some variables like Temperature and Pressure are easily measureable.

• Maxwell relations provides a way to exchange variables.

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.

Thermodynamics Variables

The thermodynamic state of a substance is specified by properties like pressure,

volume, temperature, internal energy and entropy. These properties change when
the system passes from one state to another. These variables are known as
thermodynamic variables. These are called macroscopic co-ordinates. They require a
few measurable properties of the system to define them and do not require the
knowledge of microscopic co-ordinates.

Extensive and Intensive Variables

An extensive variable of a system is a macroscopic co-ordinate, which describes a

system in equilibrium and has a value equal to the sum of its values in each part of
the system. It depends upon the mass or the size of the substance present in the
system.

Examples are

Mass, volume, internal energy, entropy, length, area, heat capacity, magnetization
etc.

An intensive variable of a substance is a microscopic co-ordinate which describes the

system in equilibrium and has the same value in any part of the system. It is
independent of mass or size of the system.

Examples are

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 Maxwell’s Thermodynamical Relations

Pressure, temperature, viscosity, refractive index, density, specific volume, surface

tension, electromotive force etc.

Distinction between extensive and intensive variables

In a homogeneous system in equilibrium, Suppose the system is divided into many

parts and the macroscopic, variable x of the system has the values x1, x2, x3, ….. in
each of these parts of the system respectively, then
x is said to be extensive variable, if x = x1 + x2 + x3 + …….., and
x is said to be intensive variable, if x =x1 = x2 =x3 = ………
An extensive variable may become an intensive variable by specifying unit amount of
substance. Like heat capacity is extensive variable but specific heat is an intensive
variable.

Maxwell’s Thermodynamical Relations

Measurable quantities

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 Maxwell’s Thermodynamical Relations

How does one measure the entropy or chemical potential from experiments? These
kinds of quantities are not usually directly accessible in the lab. What we can
measure, typically, are mechanical quantities like pressure, bulk quantities like
volume and density etc. thermal properties like temperature and heat flow (e.g., by
slow heat exchange experiments where we can measure temperature changes in a
coupled reference body). Of the thermodynamic variables that we have discussed
thus far, the following are considered measureable:

Measurable thermodynamic variables

temperature

pressure

volume or

number of particles or

mass (related by the molecular weight)

and enthalpy (latent heat) of phase change.

There are also several readily-measured material properties that depend on

derivatives of thermodynamic variables. These quantities measure the change in a
parameter in response to an infinitesimally small perturbation, they are termed as
response functions:

Measurable thermodynamic response functions

constant volume heat capacity
constant pressure heat capacity
isothermal compressibility
thermal expansivity / expansion coefficients.

Maxwell relations enable us to express experimentally-inaccessible quantities in

terms of the measurable ones just listed.

A thermodynamic relation is a rule which is obtained by thermodynamic reasoning

and applies to most of the systems. These relations are general and useful as they
simplify thermodynamic analysis of the system.
From the first and second law of thermodynamics, Maxwell was able to derive six
fundamental thermodynamical relations. The state of a system can be specified by
any pair of quantities, viz pressure (P), Volume (V), temperature (T), and entropy
(S). In solving any thermodynamical problem, the most suitable pair is chosen and
the quantities constituting the pair are taken as independent variables.
A thermodynamic relation is an exact rule which may be obtained by general
thermodynamic reasoning and applies to almost any system. These relations are
very general and extremely useful as they enormously simplify thermodynamic
analysis.

Proof:

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 Maxwell’s Thermodynamical Relations

From the first law of thermodynamics,

 Q = dU  W
 Q = dU  PdV
dU =  Q  PdV
From the second law of thermodynamics,
Q
dS =
T

 Q = TdS
Substituting the value of  Q , we get
 U = TdS  PdV ….(1)

Considering U, S and V to be functions of two independent variables x and y

in general, x and y can be any two variables out of P, V, T and S.
 U   U 
dU =   dx    dy
 x  y  y  x

 S   S 
dS =   dx    dy
 x  y  y  x

 V   V 
and dV =   dx    dy
 x  y  y  x

Substituting these values in equation (1) we get

 U   U   S   S  
  dx    dy = T    dx    dy 
 x  y  y  y  x  y  y  y 
 V   V  
 P   dx    dy 
 x  y  y  x 

  S   V  
= T    P   dy
  x  y  x  y 
  S   V  
 T    P    dy
  y  x  y  x 

Comparing the coefficients of dx and dy, we get

 U   S   V 
  = T    P  …(2)
 x  y  x  y  x  y

 U   S   V 
  = T    P  …(3)
 y  x  y  x  y  x

Differentiating equation (2) with respect to y and equation (3) with respect to x

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 Maxwell’s Thermodynamical Relations

 2U  T   S   2 S  P   V   2V
=     T       P
yx  y  x  x  y y.x  y  x  x  y V .x
 2V  T   S  2S
and =      T
x.y  x  y  y  x x.y
 P   V   2V
    P
 x  y  y  x x.y

The change in internal energy can be brought about by changing V and T, whether V
is changed by dV first and T by dT later or vice versa, the result is the same.
This is because dU is a perfect differential.

 which implies

 2U  2U
= and
y.x x.y

 T   S   2 S  P   V   2V
    T     P
 y  x  x  y y.x  y  x  x  y y.x

 T   S   2 S  P   V   2V
     T       P …(4)
 x  y  y  x x.y  x  y  y  x x.y

Since dS and dV are also perfect differentials so order of differentiation will not
matter, which implies

2S 2S
=
x.y y.x

V V
and =
x.y y.x

Equation (4), therefore reduces to

 T   S   P   V   T   S   P   V 
        =         …(5)
 y  x  x  y  y  x  x  y  x  y  y  x  x  y  y  x

Equation (5) is the general expression for Maxwell’s thermodynamical relations. In

place of the independent variables x and y, we can substitute any two of the four
variables S, T, P and V .So that there may be one mechanical variable (P and V) and
one thermal variables (S to T). There may be four sets of possible substitutions (S,
V) , (T, V), (S, P) and (T, P),which provide us the four Maxwell’s thermodynamical
relations.

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 Maxwell’s Thermodynamical Relations

First Relation

Putting x = S and y = V in equation (5), we get

S
= 1,
x
V
= 1
y

S
and = 0,
y

V
= 0
x

Substituting in equation (5), we have

 T   P 
  =  
 y  x  x  y

y  V (as y = V) and s  S (as x = S). Hence

 T   P 
  =   ….(6)
 V  S  S V

This is the Maxwell’s first thermodynamical relation.

The first relation tells us that for a thermodynamic system, increase in temperature
per unit increase in volume at constant entropy is equal to the decrease in pressure
per unit increase in entropy at constant volume.

Second Relation

We get the second relation by putting x = T and y =V in equation (5),

T
then = 1,
x

V
= 1
y

T
and = 0,
y

V
= 0
x

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 Maxwell’s Thermodynamical Relations

Substituting in equation (5), we have

 S   P 
  =   …(7)
 V T  T V

This is the Maxwell’s second thermodynamical relation.

This relation tells us that increase in entropy per unit increase in volume at constant
temperature is equal to increase in pressure per unit increase in temperature at
constant volume.

Third Relation

By putting x =S and y = P, in equation (5) we get

S
= 1,
x

P
= 1,
y

S
= 0
y

P
= 0
x

Substituting these in equation (5), we have

 T   V 
  =   …(8)
 P  S  S  P

This is the Maxwell’s third thermodynamical relation.

The third relation tells us that increase in temperature per unit increase in pressure
at constant entropy is equal to the increase in volume per unit increase in entropy at
constant pressure.

Fourth Relation

By putting x = T and y = P, then equation (5) becomes

T
= 1,
x

P
= 1,
y

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 Maxwell’s Thermodynamical Relations

T
= 0
y

P
and = 0
x

Substituting these values in equation (5), we get

 S   V 
  =   …(9)
 P T  T  P

This is the Maxwell’s fourth thermodynamical relation.

This relation tells us that increase in entropy per unit increase in pressure at
constant temperature is equal to the decrease in volume per unit increase in
temperature at constant pressure.

These are the four Maxwell’s fundamental thermodynamical relations.

Apart from these there are two more relations within the mechanical variables (P, V)
and thermal variable (T, S).

Fifth Relation

By substituting x =P and y =V

P
= 1,
x

V
= 1,
y

P
= 0
y

V
and = 0
x

Substituting these values in equation (5), we get

 T   S   T   S 
        = 1 …(10)
 P V  V  P  V  P  P V

This is the Maxwell’s 5th thermodynamical relation.

Sixth Relation

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 Maxwell’s Thermodynamical Relations

By putting x = T and y = S
T
= 1,
x

S
= 1,
y

T
= 0,
y

S
and = 0
x

Substituting in equation (5), we get

 P   V   P   V 
        = 1 …(11)
 T  S  S T  S T  T  S

This is the Maxwells 6th thermodynamical relation.

Out of the six thermodynamical relations, the one suited for a given problem is used
and the problem is solved. Let us see, some of the important applications of these
Maxwell’s thermodynamic relations.

Thermodynamic Potentials
We can also derive Maxwell’s Relations using Thermodynamical relations .

The state of a system can be completely described by any two of the five variables,
P, V, T, S, and U. Out of these, U the internal energy is determined by using the
remaining four, as shown below :

According to first law of thermodynamics,

 Q = dU  PdV

And from the second law of thermodynamics,

 Q = TdS

dU  PdV = TdS

dU = TdS  PdV

Thus U can be eliminated and we are left with four state variables, P, V, T and S.
This is the reason why only four variable of state are defined. Taking two of the four
state variables, P, V, T and S at a time, we get six possible pairs
(P, V), (P, T), (P, S), (V, T), (V, S) and (T, S).

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 Maxwell’s Thermodynamical Relations

The pair (P, V) is connected with an in exact differential quantity  W as  W  PdV

and pair (T, S) with  Q as  Q  TdS . Hence after eliminating these two pairs, we are
left with four pairs of thermodynamical variables
(P, T), (P, S), (V, T) and (V, S) and Corresponding to each pair we can write a
thermodynamical relation. These thermodynamical relations are known as Maxwell’s
thermodynamical relations.

There are four thermodynamic potentials:

(i) Internal energy, U

(ii) Helmholtz free energy, F = U – TS
(iii) Enthalpy H = U + PV
(iv) Gibbs function G = U + PV – TS

Each of the four Maxwell’s thermodynamical relations can be derived from one of
these thermodynamics potentials U, F, H and G. Only four thermodynamic potentials
are defined.
1. Internal energy U. The internal energy or the intrinsic energy is the total r of
the system
For an isochoric adiabatic process :

dU = 0
U = a constant

the internal energy of system remains constant in an isochoric adiabatic process.

2. Helmholtz Free Energy F. Helmholtz free energy is defined as

F = U – TS

For isothermal isochoric process :

dT = 0

dV = 0

dF = 0

F = a constant

i.e. the Helmholtz free energy remains constant during isothermal isochoric process.

3. Enthalpy H. This is known as the total heat and is given by

H = U + PV

For an isobaric adiabatic process :

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 Maxwell’s Thermodynamical Relations

dH = 0

H = a constant

i.e., enthalpy remains constant in a reversible isobaric adiabatic process.

4. Gibbs Function G or Gibbs Free Energy.

This is defined by the equation

G = U – TS + PV

(b) For an isobaric and isothermal process :

Hence, if the process is isothermal and isobaric then

dG = 0

G = a constant

Thus, Gibbs function (G) or Gibbs free energy remains constant in an isothermal-
isobaric process.

Significance of Thermodynamic Potential

Since the four function U, F, H and G play in thermodynamics the same role as
played by potential energy in mechanics, they are called thermodynamic potentials.
Maxwell’s thermodynamical relations can be derived from the thermodynamic
potentials.
Maxwell’s thermodynamical relations are

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

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

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

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

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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

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 Part -2

Discipline Course-I
Semester-II
Paper No: Thermal Physics : Physics-IIA
Lesson: Applications of Maxwell’s Thermodynamical
Relations Part -2
Lesson Developer: Dr. Vinita Tuli
College/ Department: ARSD College, University of Delhi

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 Applications of Maxwell’s Thermodynamical Relations Part -2

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.

8. Using Maxwell’s thermodynamical relations, To show that

 CV   2 S   2 P 
 V   T  V .T   T  T 2 
     V

From Maxwell’s relation we have

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

Differentiating equation (i) with respect to temperature we have

 2 S   2 P 
  =  2 …(ii)
 T .V   T V
We know that
 S 
CV = T   …(iii)
 T V

Differentiating equation (iii) with respect to volume we have

 CV   2S 
 V  = T   …(iv)
   T .V 

From equation (ii) and (iv) we have

 CV   2S 
 V  = T  
   T .V 

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 Applications of Maxwell’s Thermodynamical Relations Part -2

 2 P 
= T 2 
…(v)
 T V

9. Using Maxwell’s thermodynamical relations, To show that

 CP    S    2V 
2

 
    T  2
 P   PT   T  P

Sol. From Maxwell’s relations we have

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

Differentiating equation (i) with respect to temperature we get

 2S    2V 
  =   …(ii)
 T .P   T  P
We know that

 S 
CP = T   …(iii)
 T  P

Differentiating equation (iii) with respect to pressure we get

 CP   2S 
  = T   …(iv)
 P   T P 

From equations (ii) and (iv) we get

 CP   2S 
  = T  
 P   T P 
  2V 
= T 2 
…(v)
 T  P

9. To show that for a perfect gas

 U 
  = 0
 V T

Sol. From the Maxwell’s first equation we have

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

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 Applications of Maxwell’s Thermodynamical Relations Part -2

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

 Q   P 
  = T 
 V T  T V
From first law of thermodynamics

dQ = dU  PdV

Substituting in the above equation we have

 dU  PdV   P 
  = T 
 dV   T V

dU  P 
P = T 
dV  T V

 U   P 
  = T  P
 V T  T V
from perfect gas equation we have

PV = RT

Using the perfect gas equation we get

 P  R
  =
 T V V
We get
 U  R
  = T P
 V T V 
 U 
  = PP
 V T

= 0

 U 
   = 0
 V T

10.
To Prove the thermodynamical relation

 Q  = T  V  = TV 
   
 P T  T  p

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 Applications of Maxwell’s Thermodynamical Relations Part -2

show that heat is generated when a substance which expands on heating is

compressed and for substance which contracts cooling takes place

Sol. From Maxwell’s fourth thermodynamical relation we have

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

Multiplying both sides by T, we have

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

T .S = Q, substituting we get

 Q   V 
  = T   …(i)
 P T  T  P
this is the required relation.

1  V 
  represents the increase in volume per unit rise of temperature at constant
V  T  P
pressure. This is called the coefficient of volume expansion and is represented by .
1  V 
  = 
V  T  P

 V 
  = V …(ii)
 T  P
Substituting this in eqn. (i), we get

 Q 
   = TV  …(iii)
 P T

This is another form of the required relation.

From this equation it is clear that if  is positive .ie. if the substance expands on heating
 Q 
then   will be negative. It means heat must be withdrawn from the substance in order
 P T
to keep the temperature constant when the pressure is increased. We can say that increase
in pressure heats a body that expands on rise of temperature.
 Q 
if  is negative which means that the substance contracts on heating, then   will be
 P T
positive i.e. heat must be added to keep its temperature constant, when the pressure
increases i.e., cooling is produced when a substance, which contracts on heating, suddenly
compresses.

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 Applications of Maxwell’s Thermodynamical Relations Part -2

11. Joule-Thomson Cooling and Joule-Kelvin Coefficient

In Joule-Thomson porous plug experiment, if a gas at constant high pressure is forced

through a porous plug to a region of constant low pressure, then there is a change in
temperature of escaping gas. This is called the Joule-Thomson effect.

When the gas gets throttled, the gas gets wire drawn and it suffers expansion. Although
there is a difference of pressure on two sides of the porous plug but the enthalpy H of the
gas remains constant i.e.
H = U + PV = a constant
differentiating

dH = dU + PdV + VdP = 0

dQ = dU + PdV ( First law of thermodynamics)

from second law

dQ = TdS ( Second law of thermodynamics)

substituting in the first law

dQ = TdS + VdP = 0 …(i)

dS is a perfect differential and S being a function of P and T i.e. S = F (P, T), we have

 S   S 
dS =   dT    dP
 T  P  P T
Substituting in equation (i)

 S    S  
T  dT  T    V  dP = 0
 T  P   P T 
We know
 Q 
CP =  
 T  P
 S 
= T 
 T  P
Where CP is the specific heat at constant pressure.
We get

  S  
CP dT =  T    V  dP …(ii)
  P T 
From Maxwell’s fourth thermodynamical relation

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

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 Applications of Maxwell’s Thermodynamical Relations Part -2

  V  
CP dT = T    V  dP
  T  P 
Which implies

1   V  
dT = T    V  dP …(iii)
CP   T  P 
Joule-Thomson Coefficient () using Maxwell’s Relations

The Joule-Thomson coefficient is defined by

 T 
 =  
 p  h
From equation (iii) we get
1   V  
= T   V 
CP   T  P  …(iv)
 V 
From the definition of coefficient of volume expansion we have    V where  is the
 T  P
1  V 
isobaric coefficient of volume expansion, by definition     .
V  T  P
 From equation (iii), we have
V
dT = [ T  1]dP ….(v)
CP
Equation (iv) gives the change in temperature of the gas after it passes through the porous
plug
Here dP represents change in pressure of the gas in the porous plug experiment and it is
always a negative quantity because initial pressure of the gas is more than the final
pressure which is equal to the atmospheric pressure. All other quantities in equation (iv) are
+ve. Which implies
(i) There is a cooling effect because dT is negative if (T – 1) is +ve or  T> 1.

(ii) There is neither a cooling nor a heating effect if dT = 0 when (T – 1) = 0 or

T = 1

(iii) There is a heating effect if dT is positive if (T – 1) is negative or T < 1.

(a) For a perfect gas :

According to the perfect gas equation.

PV = RT (For a perfect gas)

At constant pressure we get

 V  R
   =
 T  P P

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 Applications of Maxwell’s Thermodynamical Relations Part -2

Multiplying by T we get
 V  RT
T  = =V
 T P P
Substituting in equation (iv) we get

  V  
T   V  = 0
  T  P 

Using equation (v), we have

For a perfect gas, dT = 0

In other words perfect gas shows no Joule-Thomson effect. The porous plug experiment
gives us a method to determine whether the given gas is perfect or not. It shows that for a
perfect gas the Joule-Thomson coefficient () is zero.

 T 
 =  
 P  H
1   V  
= T   V  = 0
CP   T  P 

13animation.swf

(a) For a Van der Waals gas

Van der Waals equation of a real gas is given by

 a 
 P  2  (V  b) = RT ...(vi)
 V 

a ab
PV  Pb   = RT …(vii)
V V2

both the Van der Waal’s constants a and b are very small quantities, therefore their product
ab
ab is very very small as compared to V2 and therefore can be neglected.
V2
Equation (vii) reduces to
a
 PV  Pb  = RT …(viii)
V
Differentiating both sides of equation (viii) with respect to T and keeping P constant, we
have,
 V  a  V 
P   2  = R
 T  P V  T  P

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 Applications of Maxwell’s Thermodynamical Relations Part -2

 V   a 
  P 2  = R
 T P  V 

 V  R
  = …(ix)
 T  P  a 
P 2 
 V 
From equation (vi) we have
RT a
P =  2
V b V
From equation (i) we get

 V  R
  =
 T  P  RT 2a 
  2
V b V 

Simplifying further

R(V  b)
=
 2a(V  b) 
 RT  V2 

As b is very small in comparison to V, we can write V-b = V

R (V  b)
= [b is very small, V-b =V]
2a
RT 
V
Multiplying by T
 V  RT (V  b)
 T  =
 T  P RT 
2a
V …(x)

Simplifying further

V b
=
2a
1
VRT

Taking the denominator to the numerator

1
 2a 
= (V  b) 1  
 VRT 
Expanding binomially and neglecting higher powers

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 Applications of Maxwell’s Thermodynamical Relations Part -2

 2a 
= (V  b) 1  
 VRT 

a 2a
Neglecting higher powers of as  1.
VRT VRT

Substituting in equation (x) we get

 V   2a 
 T  = (V  b) 1  VRT 
 T  P  

2a(V  b)
= V b
VRT
2a
= V b [ b is very small therefore V- b = V]
RT
simplifying
 V  2a
 T  V = b …(xi)
 T  P RT
Substituting equation (xi) in equation (iii)

According to Joule-Thomson effect, the change in temperature is given by

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

  V  
Substituting the value of T    V  from equation (xi), we have
  T  P 
1  2a 
dT =   b  dP
CP  RT 
dP  2a 
dT =   b …(xii)
CP  RT 
Equation (xii) gives the change in temperature of Van der Waals gas due to Joule-Thomson
effect. From this equation we can find the value of Joule Thomson Coefficient by substituting
in equation (iv)

Thus, we conclude that

2a 2a
If  b i.e. T is less than , then dT is positive. Since dP is –ve, dT will be –ve. Hence
RT Rb
there will be a cooling effect.

2a 2a
If  b i.e., T is greater than , then dT is negative, since dP is –ve, dT will be +ve.
RT Rb
Hence there will be heating effect.

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 Applications of Maxwell’s Thermodynamical Relations Part -2

2a 2a
If  b or T  , then dT = 0, there will be no change in temperature.
RT Rb

12. Temperature Change in Adiabatic Process

From the first thermodynamical relation we have

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

Multiplying and dividing the right hand side of equation (i) by T, we get

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

T .S = Q,
Substituting in equation (ii) we have

 P 
= T   …(iii)
 Q V

An increase in amount of heat ( Q) at constant volume results in an increase in pressure of

 P   T 
the gas.   is always positive. Hence the term   will always be negative. Which
 Q V  V  S
implies that the temperature will decrease with an increase in volume when entropy
remains constant (the process being adiabatic). Thus adiabatic expansion results in a fall of
temperature of the gas.

From the third thermodynamical relation we have

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

Multiplying and dividing equation (iv) by T we have

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

T .S = Q,

Substituting in equation (v) we get

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 V 
= T  …(vi)
 Q  P
Since, an increase in the quantity heat (Q) at constant pressure, always results in an
 V   T 
increase in the volume. The term   will be positive, hence the term   must also
 Q  P  P  S
be positive and the temperature must increase with increase in pressure of the gas at
constant entropy (when the process is adiabatic process). Thus, an adiabatic compression
must result in an increase in temperature of the gas.

13. The T. dS Equations

1. First T.dS Equations : The entropy S of a pure substance when taken as a function
of temperature and volume.
 S   S 
 dS =   dT    dV
 T V  V T …(i)

Multiplying both sides of the above equation by T we get

 S   S 
T .dS = T   dV  T   dV
 T V  V T …(ii)
Specific heat at constant volume is given by

 S 
CV = T  
 T V
And from Maxwell’s relations we know

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

Substituting these values in equation (ii) we get

 P 
TdS = CV dT  T   dV …(iii)
 T V
Equation (iii) is called the first T.dS equation.

2. Second T.dS Equation : The entropy S of a pure substance can also be taken
as a function of temperature and pressure. Therefore we can write

 S   S 
 dS =   dT    dP
 T  P  P T …(iv)
Multiplying both sides of equation (iv) by T

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 S   S 
T .dS = T   dT  T   dP
 T P  P T …(v)
specific heat at constant pressure is given by

 S 
CP = T  
 T  P
And from Maxwell’s relations we have

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

Substituting these values in equation (v) we have

 V 
T .dS = CP dT  T   dP …(vi)
 T  P
Equation (vi) is called the second T dS equation

14.
ENERGY EQUATIONS

To prove that

 U 
 V   0 for a perfect gas
T

 U  a
and    2 for a real gas
 V  T V

Sol. From first law of Thermodynamics

Q = du + w …(i)

From IInd Law

Q = TdS …(ii)

Substituting (ii) in (i)

TdS = du + PdV

or

du = TdS – PdV …(iii)

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dividing (iii) by dV

du ds
T P …(iv)
dv dv

for an isothermal change

 U   S 
 V   T  V   P …(v)
T T

using Maxwell's IInd relation

 S   P 
 V    T  in (V)
T V

we have

 U   P 
 V   T  T   P …(vi)
T V

for an ideal gas

PV = RT

which implies

 P  R
 T   V …(vii)
V

Substituting (vii) in (vi)

 U  R
 V   T V  P
T

=P–P

=0

for a real gas

Van der Waals equation –

Institute of Lifelong Learning University Of Delhi Page 15