Statistical Thermodynamics

Neelima Patil
 Intoduction
 When the system consist of large number of
particles, ordinary laws of mechanics to estimate
the properties of system could not be used due to
mathematical complications or due to insufficient
interpretations of observed phenomena.
 The problem of an atom with two electrons
presents great mathematical complications if
ordinary laws of mechanics are used so it is
impossible to solve the problem of a macroscopic
body consisting of about 1023 atoms with their
electrons. Such problems have been successfully
solved by the methods of statistical mechanics
 Intoduction
 Thermodynamics provides a framework of
relating the macroscopic properties of a system to
one another. It is concerned only with
macroscopic quantities and ignores the
microscopic variables that characterize individual
molecules (both strength and weakness).
 Statistical Mechanics is the bridge between the
microscopic and macroscopic worlds: it links the
laws of thermodynamics to the statistical behavior
of molecules.
 Intoduction
 Statistical mechanics is not concerned with actual motion of
individual particle of the system but investigates some average
or most probable all statistical properties of the system.
 The larger the number of particles in a physical system
considered, the more nearly correct the statistical predictions.
 Before the advent of quantum theory Maxwell, Boltzmann,
Gibbs applied statistical methods making use of classical
physics. These statistical methods are known as classical
statistics or Maxwell Boltzmann statistics.
 The classical statistics explain successfully many observed
physical phenomena like temperature, pressure, energy etc
but could not explain experimentally observed phenomena
like black body radiation, specific heat at low temperature etc.
 Intoduction
 For explaining such phenomena Bose, Einstein,
Fermi and Dirac made new approach by using
quantum concept. This new statistics known as
quantum statistics is divided into two categories:
(i) Bose-Einstein Statistics
(ii) Fermi Dirac statistics
The first of these holds good for photons while the
other for elementary material particles. The classical
statistics is only the limiting case of quantum
statistics.
 Macrostate and Microstate
Let us consider two particles (n=2) to be distributed in two identical
boxes
Particles are Indistinguishable Particles are Distinguishable

2 0 ab 0

1 1 a b b a

0 2 0 ab

Number of arrangements Number of arrangements

= 3= 2+1 i.e n+1 = 4= 22 = 2n
 Macrostate and Microstate
Let us consider 3 particles (n=3) to be distributed in two identical
boxes
Particles are Indistinguishable Particles are Distinguishable
3 0 abc 0

2 1 ab c ac b bc a

1 2 a bc b ac c ab

0 3 0 abc

Number of arrangements Number of arrangements

= 4= 3+1 i.e n+1 = 8= 23 = 2n
 Macrostate and Microstate

Number of arrangements Number of arrangements

= n+1 = 2n
Macrostate and Microstate

n-r

macrostate
 Macrostate and Microstate
Problem: Consider four particles a,b,c and d, explain the different ways (
macrostates and microstates) in which they can be distributed into 2 identical
compartments of a box.
Thermodynamic probability
Thermodynamic probability: The number of microstates
corresponding to a given macrostate is called thermodynamic
probability or thermodynamic frequency. Its value can be greater
than one.
It is donated by Wk where k represents the kth macrostate.

It depends upon two factors :

1) nature of particles i.e. whether particles are distinguishable or
indistinguishable
2) number of particles in the system.
 Probability
A true probability Pk can be calculated as

OR

This probability is minimum when r = 0 or r = n

=

This probability is maximum

(i) For n even: r = n/2 or n-r = n/2
x

(ii) For n odd: r = = OR r= =

x OR x
Example: Three distinguishable particles labeled A,
B, and C, are distributed among four energy levels, 0,
E, 2E, and 3E. The total energy is 3E. Calculate the
possible microstates and macrostates.

Solution: The number of particles and their total energy

must satisfy
3

N 3
j0
j

N E 3E
j0
j j
 # particles # Particles # particles # particles
on Level 0 on Level 1 on Level 2E on Level 3E
E
Case 1 2 0 0 1
Case 2 1 1 1 0
Case 3 0 3 0 0

So far, there are only THREE macrostates satisfying the conditions provided.

Configurations for case 1

Level 0 Level 1E Level 2E Level 3E

A, B C
A, C B

B, C A
Thermodynamic probability for case 1 is 3
 Configurations for case 2
Level 0 Level 1E Level 2E Level 3E
A B C
A C B
B A C
B C A
C A B
C B A

Configuration for case 3

Level 0 Level 1E Level 2E Level 3E

A, B and C

Therefore, W1 = 3, W2 = 6, and W3 = 1
 The most “disordered” macrostate is the state with the
highest probability.
 The macrostate with the highest thermodynamic
probability will be the observed equilibrium state of the
system.
 The statistical model suggests that systems tend to
change spontaneously from states with low
thermodynamic probability to states with high
thermodynamic probability.
 Constraints on a system
A set of conditions or restrictions that must be obeyed by a system
are known as constraints.
Consider an example of distribution of four particles in two
compartments, the system must obey the constraint that total
number of particles in the two compartments must be 4. In general
if there are N particles to be distributed in two compartments and
there are n1 particles in one compartment and n2 particles in the
another compartment such that
n1+n2=N
This relation is known as equation of constraint on the system a
typical set of constraints is

𝒊 𝒊

Where ni is the number of particles in the i th compartment, Ei is the energy of

each particle in i th compartment
 Accessible and inaccessible states
Accessible states: The states consistent with the given constraints of the system.
Example: Consider three particles to be distributed in two compartments.
Distribution is shown below:

Constraint: No compartment should remain empty

Accessible states: (2,1) and (1,2)
So only two macrostates and six microstates for distinguishable particles
two macrostates and two microstates for indistinguishable particles

Inaccessible states: The states which are not allowed under a constraint are called
inaccessible states. In above example (3,0) and (0,3) are inaccessible macrostates.
‘
 Basic postulates of Statistical Mechanics
For application of statistical mechanics to gases, certain fundamental postulates
are made. These are:
1. Any gas under consideration may be considered to be composed of large
number of molecules which are constantly in motion and behave like very
small elastic balls.
2. All accessible microstates corresponding to possible macrostates are equally
probable.
For example the distribution of four distinguishale particles a,b.c and d in two
cells i and j, then
Probability of microstates( abcd,0) = 1/24= 1/16
Probability of microstates( abc,d) = (1/23)(1/2) = 1/16
Probability of microstates( ab,cd) = (1/22)(1/22) = 1/16
Probability of microstates( a,bcd) = (1/2)(1/23) = 1/16
Probability of microstates( 0,abcd) = 1/24= 1/16
Thus we can conclude that probability of all accessible microstates of a system
is equal. The probability of occurrence of a given macrostate is proportional to
the number of microstates, corresponding to a given macrostate.
Thus the probability P(E) of a system possessing energy E is proportional to
thermodynamic probability W(E) i.e.
P(E) α W(E) or P(E) = C W(E)
 Basic postulates of Statistical Mechanics
4. The equilibrium state of a gas corresponds to the macrostate of
maximum probability
5. The total number of molecules is constant. This is in accordance
with principle of conservation of matter. If n1 is the number of
molecules in cell1, n2 in cell2, n3 in cell 3… etc. If n is the total
number of molecules then
n1 + n2 + n3 +…… + ni +…. + nk =
6. The total energy of a system is constant.
This is again in accordance with conservation of energy of a
system. If E1 is the energy of a particle in cell 1, E2 is the energy of a
particle in cell 2, etc. and E the total energy then
E1 n1 + E2 n2 + E3 n3 +…… + Eini +…. + Eknk = E
 Postulate of Equal a Priori Probability
Consider a system of 2 distinguishable molecules A and B. It is assumed that these
molecules can have any one of the three energy values E1,E2 and E3 such that both
of them cannot have the same energy E1or E2 or E3 . There are six different ways in
which this can occur. Thus the system has six accessible microstates.

E1 E2 E3
A B -
B A -
A - B
B - A
- A B
- B A

The system is equally likely to be in one of the accessible states And all the
accessible states are equally probable.
All the accessible microstates corresponding to possible macrostate
equally probable. This is the most fundamental and hence
important postulate of statistical mechanics.
Problems
Problems
Problems
Problems
Problems
Concept of Ensemble
 As a system is defined by the collection of a large
number of particles, so the “ensembles” can be defined
as a collection of a number macroscopically identical
but essentially independent systems.
 There are three equilibrium ensembles with a simple
form that can be defined for any isolated
system bounded inside a finite volume.
 These are the most often discussed ensembles in
statistical thermodynamics. In the macroscopic limit
(defined below) they all correspond to classical
thermodynamics.
Types of ensembles
There are three types of ensembles:

1. Micro-canonical Ensemble

2. Canonical Ensemble

3. Grand Canonical Ensemble

The ensembles are classified on the basis of interaction

between systems forming an ensemble. When physical
systems interact with each other, they can exchange energy or
matter or both energy and matter.
 Microcanonical Ensembles
It is the collection of a large no. of independent systems having
the same temperature T, same volume V and same no. of
particles N. The individual systems of a microcanonical
ensemble are separated by rigid, impermeable and well
insulated walls such that the values of E, V and N for a particular
system are not affected by the presence of other systems.
 Microcanonical Ensembles
 Systems which are isolated from the rest of world
(surrounding)
 An isolated system is always in equilibrium
 So, we can use a postulate of equal a priori probability,
 Which tells us that, the system is equaly likely to be in
any of its accessible states.

 Normalization condition
 Canonical Ensembles
It is the collection of a large no. of independent systems having the
same temperature T, same volume V and same no. of identical
particles N. The individual systems of a canonical ensemble are
separated by rigid, impermeable but conducting walls. As separating
walls are conducting hit can be exchanged between the systems till
they reach a common temperature T. Thus in a canonical ensemble
system can exchange energy but not matter i.e. particles.
 Canonical Ensembles
 Systems which exchange energy with the surrounding and is in
equilibrium
 When A (system) is having energy Es, rest of the system
has energy E0- Es.
 Therefore, the probability of finding A in the A

energy state Es is given as,

A’ (E0, Ω0)

Use tailor series expansion

 Canonical Ensembles
 The probability of finding a system in state s is given
by,

Partition Function, Z
Grand Canonical Ensemble
 A statistical ensemble where neither the energy nor
particle number are fixed.
 The ensemble is also termed as µVT ensemble as the
thermodynamic variables of the ensemble are chemical
potential (µ), Volume (V) and absolute temperature (T).
 The systems of a grand canonical ensemble are separated
by rigid permeable and conducting walls.
 As the inner separating walls are conducting and
permeable, the exchange of heat energy as well as that of
particles between the system takes place, in such a way that
all the systems achieve the same common
temperature T and chemical potential μ.
 Problems
1. A system with two energy levels is in thermal equilibrium with a heat reservoir at temperature
600K.
The energy gap between the levels is 0.1eV.
i) Find the probability that the system is in the higher energy level and
ii) The temperature at which P2 (E2) will equal to 0.25.

Solution:
i) Let E1=0, then E2=0.1eV

= 0.126

𝟐
 Classification of statistical distribution function
The assemblies consists of three kinds of identical particles
1. Identical but distinguishable particles without any spin. The
molecules of a gas are the particles of this kind. The Maxwell-
Boltzmann distribution holds for such particles.
2. Identical and indistinguishable particles of zero or integral spin.
Such particles are called bosons. Bose- Einstein distribution
function holds for them. Examples of bosons are αparticles
each having spin quantum number s=0, photons for which s=1,
deuterons for which s=1  mesons for which s=0 etc.
3. Identical and indistinguishable particles with odd half integral
spin(1/2,3/2,5/2…)etc. Such particles are called fermions and
obey Paulis exclusion principle. Fermi-Dirac distribution
function holds for them. Examples of fermions are electrons for
which s=1/2, positron for which s=1/2, protons for which s=1/2,
neutrons s= ½, µ-mesons s= ½ etc
Comparison of Maxwell- Boltzmann, Fermi- Dirac &
Bose – Einstien Statistics
Numericals
Numericals
Numericals
 Thermodynamics
 Laws of Thermodynamics
Laws of thermodynamics are merely reasonable hypothesis formulated as a result of
practical experience.
They have been applied to large number of phenomenon and have been proved to be
correct.
(I) Zeroth law of Thermodynamics
If two systems A and B are in thermal equilibrium with a third system C then A and
B must also be in thermal equilibrium with each other.
(II) First Law of Thermodynamics
 This is law of conservation of Energy
 A system containing large number of particles will always have in its equilibrium
state an internal energy U due to movements of particles constituting the system
and their interactions.
 If δQ amount of heat is supplied to the system, the change in the energy is
given by, --------(1)
Where, δW is the work done by the system. (by convention work done by the
system is taken +ve and work done on the system is taken as -ve).
Laws of Thermodynamics
 Suppose a gas is contained in a cylindrical vessel with a
piston of cross section A.
 The force acting on the piston due to the mean pressure
is
 The work done by displacing the piston through a distance
ds is =
 Hence eq (1) can be written as

This relation is the mathematical expression

for the first law of thermodynamics.
 Laws of Thermodynamics
 Second law
 The first law tells us about conversion of energy from one form to the other,
but it does not tell us how?
 eg. Can we transfer heat from colder system to hotter surrounding???
 The second law states, ‘No process is possible whose sole aim is the transfer of
heat from a colder to a hotter body’
 Mathematically, let,

devide both sides by T

In other words, The second law

states that the entropy of an
isolated system always increases,
i.e.

Entropy
--Third law
The entropy S has a limiting value S0 as the temperature tends to zero.
Statistical Interpretation of the basic thermodynamics variable
1) Mean Energy
Let, the canonical partition function is given as,
 ……..(1)

 Differentiate w. r. t. β , we get

 ………(2)
𝜷𝑬𝑹
 The probability Pr = 𝜷𝑬𝑹

 The mean energy of the system in rth state is given by

𝛃𝐄𝐫
𝐫 𝐫
𝛃𝐄𝐫 …….(3)
𝐫
Statistical Interpretation of the basic thermodynamics variable

Substituting (1) and (2) in eq (3)

𝝏𝒁
𝝏𝜷
= =
Statistical Interpretation of the basic thermodynamics variable
2) Work :
The work is done by the system is always at the cost of energy of the
system, i.e.
Suppose the system is acted upon by an external parameter x. A
change dx in this parameter, will cause a change dE in the energy of
the system in the state given by
…….(1)
The mean work done by the system as a result of such change is

Since the external parameter can change energy, one can think of this
as canonical ensemble.
……..(2)
Statistical Interpretation of the basic thermodynamics variable

 ……(3)
 Differentiating with respect to x we get
𝜷𝑬𝒓

= 𝒓

dx)
𝒓

dx) ………(4)
Statistical Interpretation of the basic thermodynamics variable
Using equations (3) and(4) in eqn (2)

= =

=
3) Pressure

V is the external
parameter
Replacing x by V,

Thus knowing the partition function and temperature, we can find the mean pressure of the system.
4) Entropy in terms of partition function and mean energy
4)Entropy in terms of partition function and mean energy
5)Helmoltz Free energy and Gibb’s Free energy:

Gibb’s free energy is defined as

G = F + PV