Physics

Paper No. : Statistical Mechanics

Module : An Overview of Thermodynamics-I

Development Team
Prof. Vinay Gupta, Department of Physics and Astrophysics,
Principal Investigator
University of Delhi, Delhi

Prof. P.K. Ahluwalia,Physics Department,Himachal Pradesh

Paper Coordinator
University,Shimla-171005

Shimla 171 005

Content Writer Prof. P.K. Ahluwalia,Physics Department,Himachal Pradesh
University,Shimla-171005

Prof. P. N. Kotru, Department of Physics, university of Jammu

Content Reviewer

Statistical Mechanics
Physics
An Overview of Thermodynamics-I
Description of Module
Subject Name Physics
Paper Name Statistical Mechanics
Module Name/Title An Overview of Thermodynamics-I

Module Id

Statistical Mechanics
Physics
An Overview of Thermodynamics-I
Contents of this Unit
1.Introduction
1.1 Pre-requisites
1.2 Broad Learning Goals of This e-Course on Statistical Mechanics
2. What is Statistical Mechanics?
2.1 Microscopic Route to Thermodynamics
2.2 Complexity of the Task
2.3 Way Out: Statistical Approach
2.4 Dilemma of This Approach
2.5 Entropy: A Bridge between Thermodynamics and Statistical Mechanics
3. Why Study Statistical Mechanics?
3.1 Reach of the Statistical Mechanics in Physics
3.2 Statistical Mechanics Methodology beyond Physics
4. Summary

Learning Outcomes

After studying this module, you shall be able to

 know the broad learning goals of this course on Statistical Mechanics for PG students
 know the overall place of studying Statistical Mechanics in the study o f physics
 get an overview of representative models of statistical mechanics and their application in
various areas of physics
 know the importance of learning statistical methodology beyond physics in the new and
emerging areas in biology, geology, ecology, economicsand financial markets

Statistical Mechanics
Physics
An Overview of Thermodynamics-I
1. INTRODUCTION

Thermodynamics embodies a systematic empirical knowledge about thermal behavior of the

macroscopic systems in terms of the state of the system. Therefore, it is a phenomenological theory
with well- established terminology. The aim of this module and module VI is to have a recapitulation of
the various concepts, which are needed in statistical mechanics wherever a link with the state of the
system is to be made experimentally. These states most often shall be in a state of equilibrium as
described in module III.

2.Thermodynamical Terms Introduction

State Variables: State of the thermodynamic system which is a macroscopic system is described in
terms of a minimum number of variables known as state variables/ parameters which can be measured
and for each of these we have an intuitive feeling. These are volume , pressure , temperature ,
magnetic field etc. These are also known as thermodynamic variables or macroscopic variables.

Equation of State: The functional relationship between these minimum numbers of state variables is
called equation of state.

For example to describe the state of a gaseous system we require three thermodynamic variables,
, the equation of state of such system can be expressed as . Ideal gas equation for
an ideal gas, and van der Waal’s equation of state for a real gas, are
two most well-known examples of an equation of state.

Table 1 below gives some examples of thermodynamic systems, the state variables normally used to
describe their state and the corresponding equation of state. Some of these equations of state are
familiar and some are not familiar. However, we must remember there are numerous equations of state
available to describe the variety of thermodynamic systems, involving solids liquids and gases.

Table 1 System, System Variables and Equation of State

S. No. System State variables Equation of State
1 A mono phase
gas

2. Paramagnetic
substance
3. A system of P, n (number
particles density), T

Statistical Mechanics
Physics
An Overview of Thermodynamics-I
 S. No. System State variables Equation of State
interacting
through two
particle potential
4 A non-
relativistic Bose Here are Fermi
gas
integrals and is fugacity
5. A Non
Relativistic Here are Fermi
Fermi gas
integrals and is fugacity
6 Equation of
Where
State of a solid
(Murghnan and are respectively the bulk
Equation of modulus and derivative of bulk
State) modulus with respect to pressure
7 Equation of state
This is also called
of a photon gas
Stefan Boltzmann law
8. Equation of state
of a stretched Where are respectively Tension,
rubber band length and temperature, is the
length of rubber band when .
Introduction
3. Thermodynamic Transformation Types

Thermodynamic Transformation Types : It is nothing but change of state by change in external conditions of
the system. These changes can be classified as quasi static, reversible and irreversible.

In an irreversible process, change occurs so fast that during the process, thermodynamic variables can
not be defined. This actual means that during this process system is not in equilibrium because of number of
unexpected reasons, such as friction, turbulence or such situations, or the observation time being much smaller
than the time intervals involved at the molecular/atomic level. A non-equilibrium process is always irreversible.

A quasi static process is the process, when it occurs so slowly that at each step it is in equilibrium described by
thermodynamic variables.

If the process on removal of external conditions comes back to its original state via the same path or
intermediate states, it is said to be reversible. Here it needs to be emphasized that if time intervals involved in
going from non-equilibrium state to equilibrium state in each step of the reversible process is much smaller than
the characteristic observation time scale of the system, it can be treated at equilibrium in each of the steps of the
process.
5

Statistical Mechanics
Physics
An Overview of Thermodynamics-I
4. Inte rnal Energy(U), Heat (Q) and Work (W)

When a system is in a state of equilibrium, which happens when it is isolated, energy of the system is a
conserved quantity, i.e. Total energy is a well-defined quantity. If a system is in thermal equilibrium with its
surroundings say a heat reservoir, its energy may fluctuate, but its average energy denoted by is again
well defined. In certain systems this total energy may contain a part which may be termed as mechanical energy,
for example part of the energy possessed by the system in a gravitational field or kinetic energy of the system as
a result of its overall motion and these energies can be used easily, need to be separated from the thermodynamic
equilibrium, The rest of the energy possessed by the system is then called internal energy If there is no
mechanical energy of the say center of mass of the system in thermal equilibrium, the total energy of the system
is the internal energy.

The question which then arises is can we change the internal energy of the system? Answer is yes, by
performing work ( on the system or by supplying heat ( to it. Interestingly, energy which you supply to the
system by placing it on a hot plate and can not be considered as work is heat. Work can be performed on the
system by mechanical (say for example by compressing a gas) means or electromagnetic means.

Heat and work can be given to the system and extracted from it by variety of methods. This may lead to change
in its potential energy. This is what first law of thermodynamics tells us. If we supply a system amount of
heat and perform amount of work, the change in internal energy . It needs to noted that
and are not state variables, you cannot describe these when a system is in thermal equilibrium. For a system
in equilibrium it is meaningless to say that there is this much amount of heat and there is this much amount of
work. Heat and work come into picture when we go from one state of equilibrium to another.

In differential form, first law of thermodynamics can be written as

, we may replace by if there is no mechanical energy of the centre of mass of the system.
Note here is an exact or perfect differential where as and are inexact differential.

Table 2 below gives processes in an ideal gas, under various conditions, equation of state, work done and heat
capacity in each case.

Table 2 Thermodynamic Processes & conditions

S. No. Process Conditi on Equation of State Work Done ( ) Heat
Capacity
1. Isobaric =Constant Or

2. Isothermal =Constant

3. Isochoric =Constant

4. Adiabatic Or

Statistical Mechanics
Physics
An Overview of Thermodynamics-I
5. Notion of Thermo-dynamical or Macroscopic Generalized Co-ordinates and Gene ralised
Forcestroduction

These are the new set of co-ordinates which do not require detailed knowledge of various configurations of the
system described in terms of position co-ordinates and the momentum co-ordinates of individual particles of the
system. However, they are new set of co-ordinates describing in a collective way the motion of all these particles
of the system e.g. entropy not requiring solution of the equations of motion of each of the particles and we can
always associate a generalized force with it for example such that or . We can
recognize many such generalized co-ordinates and generalized forces which form conjugate pairs.

6. Basic Postulates of Equilibrium Thermodynamics: Phenomlogical Way of Looking at

Macroscopic Systems

The fundamental problem which needs to be formulated for a given macroscopic system in equilibrium
thermodynamics is how to determine the final equilibrium state of a macroscopic system and describe it. This
problem is addressed through a set of basic postulates of Thermodynamics, which cannot be proved from some
known laws but must be taken as fundamental axioms whose validity lies in their applications predictions
matching with experimental results pointing towards its phenomenological methodology. Incidentally,
thermodynamic or macroscopic state of a system can be fully described in terms of a very small number of
thermodynamic variables with introduction of additional number of thermodynamical variables to take care of
complexities as and when these arise.

These postulates are:

First Postulate: The equilibrium states of a macroscopic system can be fully described in terms of a set of
extensive variables including its internal energy . The other extensive parameters being volume and number
of particles in the system or more, as per the typical thermodynamic system.

Second Postulate: There exists an extensive parameter/variable called entropy , which is a function of theses
extensive parameters i.e. which is defined for all equilibrium states of the system. This function
contains all the information of the system and is a fundamental equation of the system. It has following
properties:

(a) S is continuous and differentiable and is a monotonically increasing function of internal energy,
provided all other extensive variables are kept constant. This implies that (which actually
means that temperature
(b) The entropy of a composite system (a system made up of macroscopic subsystems is an additive
quantity implying thereby that it is an extensive parameter it self. i.e.
. It also means that entropy is a homogeneous function of first
degree in all its variables i.e. .

Third Postulate: If a macroscopic state is not in a state of equilibrium, its entropy will be less than the entropy
of the equilibrium state with same values of extensive variables on which it depends. However, left to itself for
7

Statistical Mechanics
Physics
An Overview of Thermodynamics-I
the fixed values of extensive variables, a non-equilibrium state shall gain entropy to reach the equilibrium state
implying that entropy will be maximum for the equilibrium state. This postulate also states that entropy of a
system is zero in the state where, i.e. T=0. This is also called Nernst’s Theorem.

7. Fundamental Thermodynamic Relations and Intensive Variables:

To see this connection we must appreciate the first and second postulates together, which define a fundamental
relation where we limit ourselves to only three extensive variables (the simplest possible system).
But this relationship is not unique in the sense that we solve this to write or or
each being a homogeneous function of first order. However, we shall confine to only the first
two relations known as entropy representation and energy representation respectively and see how intensive
variables can be defined from these relations.

First let us look at the energy representation and write down it in differential form i.e.

(1)

Where subscripts represent the variables which are to be kept constant while taking the partial derivatives.

In terms of conservation of energy this change in internal energy must be equal to heat, mechanical work
performed for compression, and chemical energy resulting from raising the number of particles:

(2)

Leading to following definitions of intensive variables

Temperature

(3)

Pressure

(4)

Chemical potential

Statistical Mechanics
Physics
An Overview of Thermodynamics-I
 (5)

The functions , and are the equations of state in this

representation. These equations express an intensive variable in terms of extensive variables. For example, from
an ideal gas equation , we get , law of equipartition for an ideal gas leads to

another equation of state

On the other hand in the entropy representation, we have

(6)

(7)

Giving intensive variables as

(8)

(9)

(10)

Statistical Mechanics
Physics
An Overview of Thermodynamics-I
 and are homogeneous functions of degree zero such that
, and .

The above result can be extending further by identifying other pairs of conjugate variables as stated earlier,
whose product gives us energy e.g. velocity and momentum , angular velocity and angular momentum ,
electrifield and Polarisation , magnetic field and magnetization leading to

(11)

For multi component system, containing more than one type of particles the above equation becomes

(12)

8. Euler Relation and Gibbs Duhem Relation:

From the fact that internal energy is an extensive quantity we can derive two useful relations.

Extensivity implies that . Taking the derivative of both sides with respect to , we
get

(13)

Put

(14)

Which is Euler relation

(15)

10

Statistical Mechanics
Physics
An Overview of Thermodynamics-I
Differential form of this relation gives

(16)

This is true only if i.e

(17)

This relation is known as Gibbs-Duhem relation.

9. Summary
In this module we have learnt

 That state of a system is described in terms of thermodynamic variables also called macroscopic
variables.
 That equation of state is a functional relation ship between minimum number of state parameters needed
for describing the state of the system.
 That there are variety of thermodynamic processes which may occur in a themodynamic system and can
be classified as quasistatic, reversible and irreversible processes.
 That first law of Thermodynamics islaw of conservation of energy which relates internal energy, a
perfect differential, with heat and work which are inexact differentials of heat and work done under
various conditions.
 About processes undergone by an ideal gas under different conditions leading to different equations of
state, work done and heat capacity of the system.
 Basic postulates of equilibrium thermodynamics provide us a phenomenological way of looking at
macroscopic systems such that second postulate defines entropy and third postulate leads to Nernst’s
theorem
 Understand the entropic representation, energy representation, number representation and volume
representation of thermodynmamic relations.
 How to get intensive variables in terms of extensive variables starting from entropic representation and
energy representation
 The derivation of Euler relation and Gibbs-Duhem relation using extensive property of internal energy.

Bibliography

11

Statistical Mechanics
Physics
An Overview of Thermodynamics-I
1. Pal P.B., “An Introductory Course of Statistical Mechanics”, New Delhi: Narosa P ublishing House P vt. Ltd.,
2008.
2. Mat veev A.N., “ Statistical Physics,” Moscow: Mir Publishers, 1985.
3. Rao Y.V.C., “ Postitutional and Statistical Thermodynamics,” New Delhi: Allied Publishers, 1994.
4. Fermi E., “ Notes on Thermodynamics and Statistics,” Chicago, The University of Chic ago P ress, Phonix
edition, 1966.
5. Panat P.V., “Thermodynamics and Statistical Mechanics,” New Delhi: Narosa Publishing House P vt. Ltd.,
2008
6. Greiner W., Neise L., Stocker H., “ Thermodynamics and Statistical Mechanics,” New York, Springer Verlag, 1995.

Appendix
A1 Exact and Inexact Differentials

A differential is said to be exact if the function exists i.e. .

Also independent of the path followed.

If df is exact it is a state variable or function of the system, best examples are which are respectively
internal energy, entropy, Helmholtz free energy, Gibbs free energy.

To extend it to a case of more than one variables, is a perfect differential if

independent of the path

If a differential is not perfect then we represent it by , implying it is merely an infinitesimal quantity and

Or in case of more than one variables

There are some other interesting results corresponding to perfect or exact differentials.

12

Statistical Mechanics
Physics
An Overview of Thermodynamics-I
Let us take a perfect differential such that

Where and are continuous functions with their partial derivatives also continuous,
then if is exact then and must satisfy

And hence

and implying that

13

Statistical Mechanics
Physics
An Overview of Thermodynamics-I