____________________________________________________________________________________________________

Subject Physics

Paper No and Title P10 Statistical Mechanics

Module No and Title Module VI Statistical Foundation of Thermodynamics

Module Tag Phy_P10_M7.doc

Content Writer Prof. P.K. Ahluwalia

Physics Department
Himachal Pradesh University
Shimla 171 009

TABLE OF CONTENTS
1. Learning Outcomes

2. Introduction

3. Thermodynamic Limit

4. Macroscopic State and Microscopic State

5. Principle of Equal Apriori Probabilities

6. Linking Thermodynamics with Statistics

 Thermal Contact Between Two Systems: Notion of Statistical Mechanics

Temperature
 Mechanical Contact Between Two Systems: Notion of Statistical Mechanics
Pressure
 Chemical Contact Between Two Systems: Notion of Statistical Mechanics
Chemical Potential

7. Recipe for Deriving Thermodynamics from Statistical Route

9. Summary
Appendix
A1 Particle in a one dimensional box
A2 Particle in a cubical box
A3 Quantum degeneracy of a level

Physics PAPER No. 10: Statistical Mechanics

MODULE No7. : Statistical Foundation of Thermodynamics
____________________________________________________________________________________________________

1. Learning Outcomes
After studying this module, you shall be able to

 Understand the meaning of thermodynamic limit and importance of particle density.

 Differentiate between macrostate and microstate of a system.
 Understand the notion of equal likely possibility of each of the microstates of a given
macrostate, principle of equal apriori probability, as the corner stone of statistical
mechanics.
 Count number of possible microstates for a given macrostate leading to idea of
thermodynamic probability.
 Establish the meaning of statistical mechanical temperature, pressure and chemical
potential and show its equivalence with thermodynamic temperature, pressure and
chemical potential.
 Define statistically the Boltzmann formula for entropy.
 have a recipe for deriving thermodynamics from statistical route.

Physics PAPER No. 10: Statistical Mechanics

MODULE No7. : Statistical Foundation of Thermodynamics
____________________________________________________________________________________________________

Introduction

2. Introduction

In this module from the inherent statistical nature of macroscopic systems, we underline
the statistical formulation of thermodynamics. We will see how this approach provided
microscopic basis to thermodynamics by successful application of this approach linking
entropy with the probability of microstates overcoming the lack of information about the
system made up of a large number of particles of the order of avogadro’s number. We
shall see that the statistical-mechanic meaning of temperature, pressure and chemical
potential is the same as thermodynamic meaning of temperature, pressure and chemical
potential. Las of all we shall later try to get a prescription to derive thermodynamic
functions related to the system under study. System of study shall always be treated as a
system in equilibrium.

3. Thermodynamic Limit

Realizing the fact that macroscopic systems are made up of typically 𝟔. 𝟎𝟐𝟑 × 𝟏𝟎𝟐𝟑
points to the enormity of the systems involved. Thermodynamic limit is a way to express
this enormity and a natural way to express this by carrying out the limit number of
particles 𝑵 → ∞ and volume 𝑽 → ∞, such that the particle density 𝒏 remains fixed.
Taking this limit amounts to saying that extensive properties of the system varies
proportional to the size of the system i.e. 𝑵 or 𝑽 where as intensive properties remain
independent of the size of the system. The process can be start with a finite system with a
fixed density and keep on adding more and more such identical finite systems to it such
that number density remains the same causing increase only in extensive parameters
without change in the intensive parameters. Not going to thermodynamic limit in the
mathematical sense can lead to serious problems with the strict compliance of the
extensive nature of extensive parameters such as entropy.

4. Macroscopic State and Microscopic State

There are two ways to characterize a macroscopic system in equilibrium under consideration.
These two ways are respectively macroscopic state and microscopic state of the system. A given
macroscopic state corresponds to a large number of different microstates.

A macroscopic state also called a macrostate is described in terms of macroscopic variables such
as total energy 𝑬, volume 𝑽 and number of particles 𝑵. In describing a macrostate we are not at
all bothered by the description of the properties of individual particles constituting the system
such as their momentum, spin etc.

A microscopic state also called microstate is specified by describing the state of each particle in a
given macrostate. Counting the number of microstates in a given macrostate is the most basic task
to indulge in statistical mechanics

Physics PAPER No. 10: Statistical Mechanics

MODULE No7. : Statistical Foundation of Thermodynamics
____________________________________________________________________________________________________

To further appreciate the difference, let us take a system m ade up of N number of non-interacting
particles with total energy 𝑬. This energy is the sum of the energies 𝝐𝒊 of individual particles,
such that

𝑬 = ∑ 𝒏𝒊 𝝐𝒊 (1)
𝒊

Where 𝒏𝒊 is the number of particles each with energy 𝝐𝒊 . Obviously.

𝑵 = ∑ 𝒏𝒊 (2)
𝒊

It may be recalled (see appendices A1 and A2) that 𝝐𝒊 are the single particle energies which
have two distinct properties:

(i) These are quantized, leading to quantization of total energy 𝑬

(ii) Their value depends on the volume to which they are confined. However, it is worth
noting that as volume increases the difference between the adjacent energy levels
decrease rapidly and E goes from being a discreet variable to a continuous variable.

So macrostate of a system under consideration is defined by specification of 𝑵, 𝑽 and 𝑬.

This macrostate can be realized at the microscopic level in many different possible ways
known as microstates. In simple words, it implies that total energy 𝑬 can be distributed
among 𝑵 particles constituting the system in large numer of different ways.

Quantum mechanically this amounts to specifying all possible independent solutions

𝝍(𝒓𝟏 , 𝒓𝟐 , 𝒓𝟑 , … … … . 𝒓𝑵 ) of the N particle Schrodinger equation of the system under
consideration with energy eigen value 𝑬.

One of the aims of statistical mechanical formulation is count the number of all the possible
microstates. In this course this number shall be denoted by 𝛀, which is a function of
macroscopic variables of the system, which in the present case are 𝑵, 𝑽 and 𝑬. Therefore,
𝟏
this count is a number denoted by the function 𝛀(𝑵, 𝑽, 𝑬). The value 𝛀, gives the pro bability
of ocuurance of any one of the states, which is as per the principle of equal apriori probability
𝟏
the same for each microstate. This 𝛀, is also known as thermodynamic probability. 𝑷𝒓 .

The equilibrium state of the system then is the state for which function 𝛀(𝑵, 𝑽, 𝑬) maximizes
for each of its arguments. It is interesting to note that though a system corresponding to a
given macrostate remains in a state of equilibrium, its microscopic states may keep on
changing continuously.

Principle of Equal Apriori Probabilities

This principle is the back bone of the statistical mechanics for systems at equilibrium. It states
that all allowed microstates compatible with a given macrostate, (i.e. subject to constraints

Physics PAPER No. 10: Statistical Mechanics

MODULE No7. : Statistical Foundation of Thermodynamics
____________________________________________________________________________________________________

imposed by equations (1) and (2) or any other constaint on macroscopic variables involved) are
equally likely.

Allowing possibility of all microstates of a given macrostate has resulted in derivation of ideal
gas laws and derivation of Maxwell Boltzmann velocity distribution law which were later
confirmed experimentally. Justification of this principle, therefore, lies in the results derived from
it and observed experimentally. This principle is treated as one of the postulates of statistical
mechanics.

6. Linking Thermodynamics with Statistics

We now proceed to establish a link between thermodynamics with statistics based on the the
state that the equilibrium state of the system then is the state for which function 𝛀(𝑵, 𝑽, 𝑬)
maximizes for each of its arguments leading to three conditions of equilibrium for each of the
microscopic variable 𝑬, 𝑽 and 𝑵.

For this we consider two physical systems: system 1 and system 2 which are separately in
equilibrium, described by the macroscopic variables 𝑵𝟏 , 𝑽𝟏 , 𝑬𝟏 and 𝑵𝟐 . 𝑽𝟐 , 𝑬𝟐 . System 1 has
𝛀𝟏 (𝑵𝟏 , 𝑽𝟏 , 𝑬𝟏 ) number of microstates and system 2 has 𝛀𝟐 (𝑵𝟐 , 𝑽𝟐 , 𝟐) as shown in figure

System 1 System 2
𝑁1 , 𝑉1 , 𝐸1 𝑁2 , 𝑉2 , 𝐸2

Figure 1 Two systems ready for making contact in three ways (a) when the partition is
conductiong (b) when the partition is made conducting as well as movable and (c) when
the partition also allows for exchange of particles.

Case I: Thermal Contact Between Two Systems: Notion of Temperature in

Statistical Mechanics: Let us consider first the case in which 𝑵𝟏 , 𝑽𝟏 and 𝑵𝟐 𝑽𝟐 are kept
constant but energy can be exchanged by making the intervening partition conducting.
However, in this case the total energy 𝑬 = 𝑬𝟏 + 𝑬𝟐 remains conserved i.e.

𝑬 = 𝑬𝟏 + 𝑬𝟐 = 𝑪𝒐𝒏𝒔𝒕𝒂𝒏𝒕 (3)

At any instant system 1 is equally likely to be in any one of the microstates

𝛀𝟏 (𝑵𝟏 , 𝑽𝟏 , 𝑬𝟏 ) and system 2 is equally likely to be in any one of the microstates
𝛀𝟐 (𝑵𝟐 , 𝑽𝟐 , 𝑬𝟐 ). Then the combined system is equally likely to be any one of the microstates
𝛀(𝑵, 𝑽, 𝑬), such that

𝛀(𝑵, 𝑽, 𝑬) = 𝛀𝟏 (𝑵𝟏 , 𝑽𝟏 , 𝑬𝟏 ) 𝛀(𝑵𝟐 , 𝑽𝟐 , 𝑬𝟐 ) (4)

= 𝛀(𝑵𝟏 , 𝑽𝟏 , 𝑬𝟏 )𝛀(𝑵𝟐 , 𝑽𝟐 , 𝑬 − 𝑬𝟏 )

Physics PAPER No. 10: Statistical Mechanics

MODULE No7. : Statistical Foundation of Thermodynamics
____________________________________________________________________________________________________

Since 𝑵𝟏 , 𝑽𝟏 and 𝑵𝟐 , 𝑽𝟐 are constant, we can write (4) as

𝛀(𝑬) = 𝛀( 𝑬𝟏 )𝛀(𝑬 − 𝑬𝟏 ) (5)

𝛀 number of microstates of the combined system here vary with 𝑬𝟏 till equilibrium is
established, and this happens until 𝛀 maximizes. The combined system then attains a
macrostate which has the most number of microstates. The important point to note is that
this macrostate of the system is that state in which the system spends the largest portion
of its time and presents itself as an equilibrium state.

Mathematical this condition when applied to (5) means

𝝏𝛀(𝑬,𝑬𝟏 ) (6)
= 𝟎, when 𝑬𝟏 = ̅𝑬̅̅𝟏̅, the equilibrium value of 𝑬𝟏 and 𝑬𝟐 = ̅𝑬̅̅̅𝟐
𝝏𝑬𝟏

We, therefore, obtain

𝝏𝛀𝟏 (𝑬𝟏 ) 𝝏𝛀𝟐 (𝑬𝟐 ) 𝝏(𝑬𝟐 )

( ) ̅̅̅𝟐̅) + 𝛀𝟏 (𝑬
𝛀𝟐 (𝑬 ̅̅̅𝟏̅) ( ) =𝟎
𝝏𝑬𝟏 𝑬 ̅̅̅̅ 𝝏(𝑬𝟐 ) 𝑬 ̅̅̅̅ 𝝏𝑬𝟏
𝟏 =𝑬 𝟏 𝟐 =𝑬𝟐

Note 𝑬𝟐 = 𝑬 − 𝑬𝟏

𝝏𝛀𝟏 (𝑬𝟏 ) 𝝏𝛀 (𝑬 )
( ) ̅̅̅𝟐̅) − ( 𝟐 𝟐 )
𝛀𝟐 (𝑬 ̅̅̅𝟏̅) = 𝟎
𝛀𝟏 (𝑬
𝝏𝑬𝟏 ̅̅̅̅
𝑬=𝑬
𝝏(𝑬𝟐 ) 𝑬 ̅̅̅̅
𝟏 𝟐 =𝑬 𝟐

𝟏 𝝏𝛀𝟏 (𝑬𝟏 ) 𝟏 𝝏𝛀𝟐 (𝑬𝟐 )

( ) = ( )
̅̅̅̅
𝛀𝟏 (𝑬𝟏 ) 𝝏𝑬𝟏 ̅̅̅̅
̅̅̅̅
𝛀𝟐 (𝑬𝟐 ) 𝝏(𝑬𝟐 ) 𝑬 ̅̅̅̅
𝑬=𝑬 𝟏 𝟐 =𝑬 𝟐

𝝏 𝐥𝐧 𝛀𝟐 (𝑬𝟏 ) 𝝏 𝐥𝐧 𝛀𝟐 (𝑬𝟐 ) (7)

( ) =( )
𝝏𝑬𝟏 𝑬 ̅̅̅̅ 𝝏𝑬𝟐 ̅̅̅̅
𝟏 =𝑬 𝟏 𝑬 𝟐 =𝑬 𝟐

This (7) is the condition for equilibrium of the system 1 and system 2. Where

𝝏 𝐥𝐧 𝛀(𝑵,𝑬,𝑽) (8)
We define 𝜷 = ( 𝝏𝑬
)
̅ ,𝑽,𝑵
𝑬=𝑬

So equation (7) implies

𝜷𝟏 = 𝜷𝟐 (9)

Physics PAPER No. 10: Statistical Mechanics

MODULE No7. : Statistical Foundation of Thermodynamics
____________________________________________________________________________________________________

What have we achieved? We found that

 When two systems are brought in contact and allowed to exchange energy
through conducting partition, the exchange of energy continues till equilibrium
values 𝑬𝟏 = ̅𝑬̅̅𝟏̅ and 𝑬𝟐 = ̅𝑬̅̅𝟐̅ of the two systems is not attained. Once this happens
systems come to thermal equilibrium
 This stage of thermal equilibrium is indicated when the respective values of the
parameter 𝜷, 𝜷𝟏 and 𝜷𝟐 become equal, pointing towards zeroth law of thermodynamics
which defines temperature as that parameter. It is, therefore, natural to look for this
connection between 𝜷 and temperature 𝑻.
 If we recall that the temperature is defined by the derivative of the entropy with respect to
energy 𝑬:

𝝏𝑺 𝟏 (10)
( ) =
𝝏𝑬 𝑵,𝑽 𝑻

On comparing equations (8) and (10) we find that

𝚫𝑺 𝟏 (11)
= = 𝐂𝐨𝐧𝐬𝐭𝐚𝐧𝐭
𝚫(𝐥𝐧 𝛀) 𝜷𝑻

Equation (11) was first established by Ludwig Boltzmann. He also underlined the
connection between the two approaches i.e. thermodynamic approach, equation
(10) and statistical approach equation (8) and further concluded that the constant
in equation (11) should be a universal constant, which was later named as
Boltzmann constant by Planck as

𝑺 = 𝒌𝑩 𝐥𝐧 𝛀 (12)

Also,

𝟏 𝟏 (13)
= 𝒌𝑩 𝒐𝒓 𝜷 =
𝜷𝑻 𝒌𝑩𝑻

 According to formula (12), one can get ent ropy of a system by knowing the total number
of microstates of a macrostate for a given system.
 If 𝛀 = 𝟏, this corresponds to a unique completely ordered state, with entropy 𝑺 = 𝟎. As
𝛀 increases, the number of microstates increase and more is the number of microstates
more is the entropy. Therefore, in a given system disorder is manifested through the
count of the microstates of a given macrostate of the system, larger this number larger is
the disorder and less the degree of predictability.
 Furthermore, maximization of the number of possible microstates or probability amounts
to maximizing the entropy for equilibrium.

Physics PAPER No. 10: Statistical Mechanics

MODULE No7. : Statistical Foundation of Thermodynamics
____________________________________________________________________________________________________

Case II: Mechanical Contact Between Two Systems: Notion of Pressure in

Statistical Mechanics :

If we extend the considerations of the case I and further relax the constraint on the
partition separating system 1 from system 2 by making it movable as well as conducting
figure 1(b), then the volumes of the two systems also become variables, though the total
volume𝑽 = 𝑽𝟏 + 𝑽𝟐 , remains constant and besides equation (7) corresponding to thermal
equilibrium

𝝏 𝐥𝐧 𝛀𝟐 (𝑬𝟏 ) 𝝏 𝐥𝐧 𝛀𝟐 (𝑬𝟐 )
( ) =( )
𝝏𝑬𝟏 𝑵 ̅̅̅̅ 𝝏𝑬𝟐 ̅̅̅̅
𝟏 ,𝑽𝟏 ,𝑬𝟏 =𝑬𝟏 𝑵 𝟐 ,𝑽𝟐 ,𝑬𝟐 =𝑬𝟐

We have another equation which can be obtained in an analogous way as in case I giving
another condition for the system to be in mechanical equilibrium as well

𝝏 𝐥𝐧 𝛀𝟐 (𝑽𝟏 ) 𝝏 𝐥𝐧 𝛀𝟐 (𝑽𝟐 ) (14)

( ) =( )
𝝏𝑽𝟏 𝑵 ̅̅̅̅ 𝝏𝑽𝟐 ̅̅̅̅
𝟏 ,𝑬𝟏 ,𝑽𝟏 =𝑽 𝟏 𝑵 𝟐 ,𝑬𝟐 ,𝑽𝟐 =𝑽 𝟐

And we can define another parameter 𝜼,

𝝏 𝐥𝐧 𝛀(𝑵, 𝑬, 𝑽) (15)
𝜼=( )
𝝏𝑽 ̅ ,𝑬,𝑵
𝑽=𝑽

On comparing with, again recalling thermodynamic formula

𝝏𝑺 𝑷 (16)
( ) =
𝝏𝑽 𝑵,𝑬 𝑻

Equation (14) implies that

𝚫𝑺 𝑷 (17)
= = 𝐂𝐨𝐧𝐬𝐭𝐚𝐧𝐭
𝚫(𝐥𝐧 𝛀) 𝜼𝑻

Therefore, we can conclude

 The equilibrium condition during thermal and mechanical contacts, such that
𝑷 𝑷
= 𝒌𝑩 or 𝜼 = 𝑲 𝑻becomes
𝜼𝑻 𝑩

𝑷𝟏 𝑷𝟐 (18)
=
𝑻𝟏 𝑻𝟐

i.e. 𝑻𝟏 = 𝑻𝟐 and 𝑷𝟏 = 𝑷𝟐 .

Physics PAPER No. 10: Statistical Mechanics

MODULE No7. : Statistical Foundation of Thermodynamics
____________________________________________________________________________________________________

Case III: Chermical Contact Between Two Systems: Notion of Chemical Potential in
Statistical Mechanics :

Next if we consider besides thermal contact, partition such that it not only allows thermal
contact but also allows exchange of particles between system 1 and system 2, but keep
the volume fixed. Then only total Number of particles 𝑵 = 𝑵𝟏 + 𝑵𝟐 and total Energy
𝑬 = 𝑬𝟏 + 𝑬𝟐 remain fixed but 𝑽𝟏 , 𝑽𝟐 , 𝑬𝟏 and 𝑬𝟐 of the two systems can change. So
besides equation (7)

𝝏 𝐥𝐧 𝛀𝟏 (𝑬𝟏 ) 𝝏 𝐥𝐧 𝛀𝟐 (𝑬𝟐 )
( ) =( )
𝝏𝑬𝟏 𝑵 ̅̅̅̅ 𝝏𝑬𝟐 ̅̅̅̅
𝟏 ,𝑽𝟏 ,𝑬𝟏 =𝑬 𝟏 𝑵 𝟐 ,𝑽𝟐 ,𝑬𝟐 =𝑬 𝟐

We have another equation which can be obtained in an analogous way as in case I giving
another condition for the system to be in chemical equilibrium as well

𝝏 𝐥𝐧 𝛀𝟏 (𝑵𝟏 ) 𝝏 𝐥𝐧 𝛀𝟐 (𝑵𝟐 ) (19)

( ) =( )
𝝏𝑵𝟏 𝑵 ̅̅̅̅ 𝝏𝑵𝟐 ̅ 𝟐 ,𝑬𝟐 ,𝑽𝟐
𝟏 =𝑵 𝟏 ,𝑬𝟏 ,𝑽𝟏 𝑵 𝟐 =𝑵

And we can define another parameter 𝝁,

𝝏 𝐥𝐧 𝛀(𝑵, 𝑬, 𝑽) (20)
𝝁=( )
𝝏𝑵 ̅ ,𝑬,𝑽
𝑵=𝑵

On comparing with, again recalling thermodynamic formula

𝝏𝑺 𝝁 (21)
(𝝏𝑵) = −𝑻
𝑵,𝑬,𝑽

We get
𝚫𝑺 𝝁
= − = 𝐂𝐨𝐧𝐬𝐭𝐚𝐧𝐭
𝚫(𝐥𝐧 𝛀) 𝑻

Therefore,

𝝁
 The equilibrium condition during Chemical contact, such that − 𝑻 = 𝒌𝑩 or 𝝁 =
−𝒌𝑩 𝑻 becomes

𝝁𝟏 𝝁𝟐 (22)
=
𝑻𝟏 𝑻𝟐

i.e. 𝑻𝟏 = 𝑻𝟐 and 𝝁𝟏 = 𝝁𝟐 .

Physics PAPER No. 10: Statistical Mechanics

MODULE No7. : Statistical Foundation of Thermodynamics
____________________________________________________________________________________________________

If we combine the three case discussed above such that if we allow exchange of energy, change of
volume and exchange of particles simultaneously, the conditions of equilibrium are

𝑻𝟏 = 𝑻𝟐 , 𝑷𝟏 = 𝑷𝟐 and 𝝁𝟏 = 𝝁𝟐 (23)

7. Recipe for Deriving Thermodynamics from Statistical Route

Now we are ready to derive thermodynamics from statistical considerations. Recipe is as given
below:

 For the macrostate (𝑵, 𝑽, 𝑬) of a given system count the number of all possible
microstates accessible to the macrostate denoted by 𝛀(𝑵, 𝑽, 𝑬)
 The entropy of the system can be calculated by equation the equation (12)
𝑺 = 𝒌𝑩 𝐥𝐧 𝛀
 The intensive parameters, 𝑻, 𝑷 and 𝝁 can then be calculated by the following
thermodynamic relations (See Module 6)

𝟏 𝝏𝑺 (24)
=( )
𝑻 𝝏𝑬 𝑵,𝑽

𝑷 𝝏𝑺 (25)
=( )
𝑻 𝝏𝑽 𝑵,𝑬

𝝁 𝝏𝑺 (26)
= −( )
𝑻 𝝏𝑵 𝑽,𝑬

Or alternatively

𝝏𝑺 (27)
(𝝏𝑽) 𝝏𝑬
𝑵,𝑬
𝑷= 𝝏𝑺
= −( )
( ) 𝝏𝑽 𝑵,𝑺
𝝏𝑬 𝑵,𝑽

And

Physics PAPER No. 10: Statistical Mechanics

MODULE No7. : Statistical Foundation of Thermodynamics
____________________________________________________________________________________________________

𝝏𝑺 (28)
(𝝏𝑵) 𝝏𝑬
𝑽,𝑬
𝝁=− 𝝏𝑺
=( )
(𝝏𝑬) 𝝏𝑵 𝑽,𝑺
𝑵,𝑽

As explained in module 6, with 𝑼 ≡ 𝑬, rest of the thermo dynamics follows from

Helmholtz free energy 𝑭 = 𝑬 − 𝑻𝒔 (29)

Gibbs free energy 𝑮 = 𝑬 − 𝑻𝑺 + 𝑷𝑽 (30)

Enthalpy 𝑯 = 𝑬 + 𝑷𝑽 = 𝑮 + 𝑻𝑺 (31)

Furthermore , specific heat at constant volume, 𝑪𝑽 and Specific heat at constant pressure, 𝑪𝑷 are
given by

𝝏𝑬 (32)
𝑪𝑽 = ( )
𝝏𝑻 𝑵,𝑽

𝝏𝑯 (33)
𝑪𝑷 = ( )
𝝏𝑻 𝑵,𝑷

In nut shell,once one knows the entropy 𝑺(𝑵, 𝑬, 𝑽) of the system, equilibrium behavior of the
system can be known by using thermodynamics.

9. Summary
In this module we have learnt

 About statistical formulation of thermodynamics of a system in equilibrium by knowing

the accessible microstates of a macrostate of the given system.
 That as per principle of equal apriori probability, each of the accessible microstates is
equally likely to happen.
𝑵
 That thermodynamic limit means 𝑵 → ∞ and 𝑽 → ∞ keeping the number density 𝑽
constant.
 That entropy of a given macrostate of a system is related to the number of allowed
microstates 𝛀(𝑵, 𝑬, 𝑽) by the famous Boltzmann formula

𝑺 = 𝒌𝑩 𝐥𝐧 𝛀
 That equilibrium state of the system is that state for which 𝛀(𝑵, 𝑬, 𝑽) maximizes, which
further means maximization of entropy 𝑺.
 That the equilibrium conditions for two systems under different types of contacts are

Physics PAPER No. 10: Statistical Mechanics

MODULE No7. : Statistical Foundation of Thermodynamics
____________________________________________________________________________________________________

𝑻𝟏 = 𝑻𝟐 under thermal contact (34)

𝑷𝟏 𝑷 (35)
𝑻𝟏
= 𝑻𝟐 under mechanical and thermal contact
𝟐
If there is thermal equilibrium this amounts to
𝑷𝟏 = 𝑷𝟐

𝝁𝟏 𝝁
𝑻𝟏
= 𝑻𝟐 under chemical contact (36)
𝟐
If there is thermal equilibrium this amounts to
𝝁𝟏 = 𝝁𝟐

 That the knowledge of number of accessible microstates provides complete knowledge of

the equilibrium thermodynamics of the system via Boltzmann formula.

Bibliography

1. Pathria R.K. and Beale P. D., Statistical Mechanics, 3rd ed. (Elsevier, 2011).
2. Landau L.D., Lifshitz E.M., “ Statistical Physics Part 1,” 3rd Edition, Oxford:
Pergamon Press., 1982
3. Pal P.B., “An Introductory Course of Statistical Mechanics”, New Delhi: Narosa
Publishing House Pvt. Ltd., 2008.
4. Panat P.V., “Thermodynamics and Statistical Mechanics,” New Delhi: Narosa
Publishing House Pvt. Ltd., 2008
5. Ma S.K., “ Statistical Mechanics,” Singapore: World Scientific Publishing Co. Pte.
Ltd., 1985.
6. Greiner W., Neise L., Stocker H., “ Thermodynamics and Statistical Mechanics,”
New York, Springer Verlag, 1995.

Appendices
Following appendices provide a recapitulation of how quantization of energy levels arises
and how the value of single particle energy in a confined system is volume dependent.
We shall try to elaborate on the concept of degeneracy which is auseful idea in counting
the microstates of a physical system
A1 Particle in a one dimensional box:

Physics PAPER No. 10: Statistical Mechanics

MODULE No7. : Statistical Foundation of Thermodynamics
____________________________________________________________________________________________________

We are interested in quantum mechanical description of a particle confined to move on a

straight line bounded by two walls at each end at a distance 𝑳. The particles make elastic
collisions at the two walls. There is no force acting on the particle.

0 L
Figure 2 Particle moving on a line along x-axis

The motion of this particle is described by one dimensional schrodinger equation, whose
solution 𝝍, assumes the form of a stationary wave, with the boundary condition that

𝟎 𝒂𝒕 𝒙 = 𝟎 (37)
𝝍={
𝟎 𝒂𝒕 𝒙 = 𝑳

The Schrodinger wave equation for this system is given by

𝝏𝟐 𝝍 𝟐𝒎𝝐 (38)
𝟐
=− 𝟐 𝝍
𝝏𝒙 ℏ

Or
𝝏𝟐 𝝍
= −𝒌𝟐 𝝍
𝝏𝒙𝟐

Where 𝒉 is planks constant, m and 𝝐 respectively are the mass and energy of the particle.
The solution of this wave equation then is
𝝍 = 𝑨 𝐬𝐢𝐧 𝒌𝒙 + 𝑩 𝐜𝐨𝐬 𝒙 (39)

Physics PAPER No. 10: Statistical Mechanics

MODULE No7. : Statistical Foundation of Thermodynamics
____________________________________________________________________________________________________

𝒏𝝅
Putting in boundary conditions we obtain 𝑩 = 𝟎 and 𝒌 = , where 𝒏 = 𝟏, 𝟐, 𝟑 … … …
𝑳
Knowing 𝒌 yields momentum from 𝒑 = ℏ𝒌 i.e.
𝒏𝒉 (40)
𝒑 = 𝟐𝑳

Which shows that 𝒑 is quantized. Also, therefore, energy is also quantized as

𝒏𝟐 𝒉𝟐 (41)
𝝐=
𝟖𝒎𝑳𝟐
Here n stands for quantum state of the particle. It is worth noting that 𝑳 becomes large ≫
𝝀, n is very large and the separation between energy levels is very small.
The value of the amplitude A can be obtained from the normalization condition
𝑳
∫ 𝝍∗ 𝝍 𝒅𝒙 = 𝟏
𝟎

𝟐
Which gives 𝑨 = √𝑳 .

A2 Particle in a cubical box and quantum degeneracy of a level

Particle moving ia cubical box is a generalization of the one dimensional motion in three
dimensions as shown in figure below.

L
x
Figure 3 Particle in a cubical box

Schrodinger wave equation in this case is given by

𝝏𝟐 𝝍 𝝏𝟐 𝝍 𝝏𝟐 𝝍 (42)
+ + = −𝒌𝟐 𝝍
𝝏𝒙𝟐 𝝏𝒙𝟐 𝝏𝒙𝟐

Physics PAPER No. 10: Statistical Mechanics

MODULE No7. : Statistical Foundation of Thermodynamics
____________________________________________________________________________________________________

With the boundary conditions

𝟎 𝒂𝒕 𝒙 = 𝟎, 𝒚 = 𝟎, 𝒛 = 𝟎
𝝍={
𝟎 𝒂𝒕 𝒙 = 𝑳, 𝒚 = 𝑳, 𝒛 = 𝑳
The solution of the schrodinger wave equation now is a stationary wave in three
dimensions as given below
𝝍 = 𝑨 𝐬𝐢𝐧 𝒌𝒙 𝒙 𝐬𝐢𝐧 𝒌𝒚 𝒚 𝐬𝐢𝐧 𝒌𝒛 𝒛 (43)
𝒏 𝝅 𝒏 𝝅 𝒏 𝝅
with 𝒌𝒙 = 𝑳𝒙 , 𝒌𝒚 = 𝒚𝑳 , 𝒌𝒛 = 𝑳𝒛

⃗ ; 𝒏𝒙 , 𝒏𝒚 and
Where 𝒌𝒙 , 𝒌𝒚 and 𝒌𝒛 can be taken as the components of the wave vector 𝒌
𝟑
𝟐 𝟐
𝒏𝒛 are three quantum numbers taking integer values 𝟏, 𝟐, 𝟑 … … … … and 𝑨 = (𝑳) .
𝒏 𝒉
𝒙 𝒏𝒚 𝒉 𝒏𝒛 𝒉
Therefore, 𝒑𝒙 = 𝟐𝑳 , 𝒑𝒚 = 𝟐𝑳 𝒑𝒛 = and hence momentum p is quantised and the
𝟐𝑳
energy of the energy levels is
𝒑𝟐 𝒉𝟐 𝒉𝟐 (44)
𝝐= = (𝒏𝟐𝒙 + 𝒏𝟐𝒚 + 𝒏𝟐𝒛 ) = 𝒏 𝟐
𝟐𝒎 𝟖𝒎𝑳𝟐 𝟐
𝟖𝒎𝑽𝟑

Here note that 𝑽 is the volume of the cube. 𝝐 explicitily depends on 𝒏 and 𝑽.
A careful look at equation (44) shows that, a quanum state of the particle in a cube is
designated by a set of three quantum numbers and 𝒏𝒙 , 𝒏𝒚 and 𝒏𝒛 . For the lowest level this
set is (𝒏𝒙 = 𝟏, 𝒏𝒚 = 𝟏, 𝒏𝒛 = 𝟏) with 𝝐𝟏 = 𝝐𝟏,𝟏,𝟏 = 𝟑𝝐.This level is said to have
degeneracy 𝒈𝟏 = 𝟏.
However, for the next level any one of the quantum numbers can be 2 leading to three
possibilities (2,1,1), (1,2,1) and (1,1,2) having the same energy 𝝐𝟐 = 𝝐𝟐,𝟏,𝟏 = 𝝐𝟏,𝟐,𝟏 =
𝝐𝟏,𝟏,𝟐 = 𝟔𝝐. So this level is said to have degeneracy 𝒈𝟐 = 𝟑 and so on.
There are many other examples where gegeneracy manifests itself in physical systems
𝟏
quantum mechanically. If a particle has spin 𝟐, it introduces a double degeneracy because
of two orientations of the spin.

Physics PAPER No. 10: Statistical Mechanics

MODULE No7. : Statistical Foundation of Thermodynamics