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

Table of Contents

Chapter: Maxwell’s Thermodynamical Relations

 Introduction

o Thermodynamical variables

o Extensive and intensive variables

o Distinction between intensive and

extensive variables

o Maxwell’s thermodynamical relations

 Proof of the above relations

 Thermodynamical Potentials

 Value Addition

 Summary

 Exercise/Practice

 References/Bibliography

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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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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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 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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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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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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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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Value Addition

James Clerk Maxwell

From Wikipedia, the free encyclopedia

James Clerk Maxwell

James Clerk Maxwell (1831–1879)

Born 13 June 1831

Edinburgh, Scotland

Died 5 November 1879(aged 48)

Cambridge, England

Citizenship British

Nationality Scottish

Fields Physics and mathematics

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Institutions Marischal College, Aberdeen

King's College London
University of Cambridge

Alma mater University of Edinburgh

University of Cambridge

Academic advisors William Hopkins

Notable students George Chrystal

Known for Maxwell's equations

Maxwell distribution
Maxwell's demon
Maxwell's discs
Maxwell speed distribution
Maxwell's theorem
Maxwell material
Generalized Maxwell model
Displacement current
Maxwell's Wheel

Notable awards Smith's Prize (1854)

Adams Prize (1857)
Rumford Medal (1860)
Keith Prize (1869–71)

Signature

CONTRIBUTIONS OF THE MAN WHO DERIVED MAXWELL’S

THERMODYNAMICAL RELATIONS

James Clerk Maxwell FRS FRSE (13 June 1831 – 5 November 1879) was a
Scottish mathematical physicist. His most prominent achievement was to formulate
a set of equations that describe electricity, magnetism, and optics as manifestations
of the same phenomenon, namely theelectromagnetic field. Maxwell's contribution
was his extension and formulation of Michael Faraday's theory of electricity and
magnetic lines of force. Maxwell showed that a few relatively simple mathematical

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 Maxwell’s Thermodynamical Relations

equations could express the behaviour of electric and magnetic fields and their
interrelation.

Maxwell's achievements concerning electromagnetism have been called the "second

great unification in physics",after the first one realised by Isaac Newton.
In 1862, Maxwell calculated that the speed of propagation of an electromagnetic field
is approximately that of the speed of light.
With the publication of A Dynamical Theory of the Electromagnetic Field in 1865,
Maxwell demonstrated that electric and magnetic fields travel through space
as waves moving at the speed of light. Maxwell proposed that light is in fact
undulations in the same medium that is the cause of electric and magnetic
phenomena. The unification of light and electrical phenomena led to the prediction of
the existence of radio waves.

Maxwell helped develop the Maxwell–Boltzmann distribution, which is a statistical

means of describing aspects of the kinetic theory of gases. He is also known for
presenting the first durable colour photograph in 1861 and for his foundational work
on analysing the rigidity of rod-and-joint frameworks (trusses) like those in many
bridges. Maxwell also continued his work on the kinetic theory of gases. By treating
gases statistically in 1866 he formulated the Maxwell-Boltzmann kinetic theory of
gases. This theory showed that the temperatures and heat involved only movement
of molecules. Maxwell's approach did not reject the earlier studies on
thermodynamics but it used a better theory to explain the observations. Maxwell has
also derived the thermodynamical relations, which relate the un-measurable
properties with those properties that can be measured.

His discoveries helped usher in the era of modern physics, laying the foundation for
such fields as special relativity and quantum mechanics. Many physicists regard
Maxwell as the 19th-century scientist having the greatest influence on 20th-century
physics, and his contributions to the science are considered by many to be of the
same magnitude as those of Isaac Newton and Albert Einstein. In the millennium
poll—a survey of the 100 most prominent physicists—Maxwell was voted the third
greatest physicist of all time, behind only Newton and Einstein. On the centenary of
Maxwell's birthday, Einstein himself described Maxwell's work as the "most profound
and the most fruitful that physics has experienced since the time of Newton."
It is advised to follow this link to view added information of Maxwell’s relations.

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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

Fill in the Blanks

Q1. ___________________ is the Maxwell’s first thermodynamical relation.

Q2. ___________________ is the Maxwell’s second thermodynamical relation.

Q3. ___________________ is the Maxwell’s third thermodynamical relation.

Q4. ___________________ is the Maxwell’s fourth thermodynamical relation.

Q5. ___________________ is the Maxwell’s fifth thermodynamical relation.

Q6. ___________________ is the Maxwell’s sixth thermodynamical relation.

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Q7. ________ & _________ are the Maxwell’s relations apart from the four
basic thermodynamical relations.

Q8. Derive Maxwell’s Thermodynamical relations?

Q9. List the Maxwell’s fundamental relations.

Q10. Maxwell’s thermodynamic relation is:

 S   P 
(a)    
 T T  V T
 T   P 
(b)     
 V  S  S V
 T   V 
(c)    
 P  P  P  P
(d) none of these

Q11. Prove the thermodynamic relation

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

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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