1 A.R Coaching Centre for Physics, Kallakurichi(Dt)- Cell: 8667737887.

A.R COACHING CENTRE

PG-TRB, POLYTECHNIC-TRB, SET COACHING FOR PHYSICS
Kallakurichi Dst, Contact-8667737887.

PG TRB - 2019
Unit IV - Statistical Mechanics

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Maxwell Boltzmann statistics:- (or) Classical statistics:

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Basics:

I The statistical methods are applied only to physical systems containing a very large number of

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particles.

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I Types of statistics:

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(1) Classical Statistics
(i) Maxwell-Boltzmann statistics (Ex: gas molecule).

(2) Quantum Statistics

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(i) Bose-Einstein statistics (Bosons −→ zero or integral spin, Ex: photon).
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(ii) Fermi-Dirac statistics (Fermions −→ half integral spin, Ex: Electron).
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Phase-Space:

To specify the state of gas from the molecular point of view we require the position and velocity (or
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more conveniently momentum) of each of its molecules, (i.e) we must specify six quantities x, y, z, px , py , pz
for each of the molecules.
The state of the point in the space will be described by a set of six co-ordinate x, y, z, px , py , pz . This
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six-dimensional space is called phase-space and element of volume in the space is termed as a cell.
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∴ Six dimensional phase space for a single particle is called molecular phase-space (or) µ− space and
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6N dimensional phase space is called τ −space (or) γ−space.

Note:-
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I The dimension of the volume element are (length × momentum)f = (joule second)f .
I The size of the cell (each) be hf .
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h −→ constant has the dimension of joule second .

Microstates:- (2n )
We must state to which cell each molecule of the system belongs temporarily.
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Example: In the 4 particles, the total number of microstates = 2n = 24 = 16 .

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Macrostates:- (n + 1)
The specication of the number of molecules (or) phase points in each cell of phase space.
Example: In the 4 particles, the total number of macrostates = (n + 1) = (4 + 1) = 5 .
I Many dierent microstates may correspond to the same macrostate.
I The microstates which are allowed under given restrictions are called accessible microstates.

Ensemble:-

A collection of large number of identical independent system is called an ensemble. In an ensemble

the systems play the same role as molecule in a gas.
2 A.R Coaching Centre for Physics, Kallakurichi(Dt)- Cell: 8667737887.

I Accessible states: are the states consistant with the given constraints of the system.

Thermodynamic probability:-

The number of microstates corresponding to that macrostate.

Example: The thermodynamical probability for the macrostate Ni = 3, Nj = 1 is 4. (i.e) Ω = 4.

cell i abc abd acd bcd

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cell j

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d c b a

N!

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I The thermodynamic probability Ω=
n1 ! n2 ! n3 !

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n!
I Number of meaning arrangements = =n Cr .

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r! (n − r)!
Example:

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A system of 4 distinguishable, for a macrostate (1,3), r = 1, (n − r) = 3 and n = 4 the number of
microstate.
n! 4!
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∴ Thermodynamic probability (Ω)(r,n−r) = = = 4.
r! (n − r)! 1! 3!
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Fundamental postulate of statistical mechanics:-

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1. All the cells in the phase space are of equal size.

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2. All the accessible microstate corresponding to possible macrostates are equally probable. (i.e) The
probability of all microstates of the system are equal.
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3. The equilibrium state of a gas corresponds to the macrostate of maximum probability.

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4. The total number of molecules is constant (N ) .

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5. The total number of the system is constant (E) .

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h = δpi δqi
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ENSEMBLE:-

An ensemble is dened as a collection of a large number of macroscopically identical but essentially

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independent system.

The condition of equilibrium between two systems in thermal contact - The β− parameter:-
Two systems which are capable of exchanging heat between one another, are said to be in thermal
contact.
According
 to statistical
 mechanics the two systems in thermal contact will be in equilibrium if their
∂
functions log Ω are equal.
∂E
 
∂ ∂ 0 0
log Ω(E) = log Ω (E )
∂E ∂E 0
3 A.R Coaching Centre for Physics, Kallakurichi(Dt)- Cell: 8667737887.

 
∂
I The function log Ω is generally represented by β ,
∂E
β −→ has the dimensions of reciprocal energy for thermally equilibrium we have,

1 1 ∂
= KT (or) β = = log Ω(E)
β KT ∂E

K −→ is a Boltzmann's constant (dimension −→ joule deg −1 ) (or) J K −1 .

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K= where, R −→ gas constant for 1 Kg mol, N −→ Avogadro number.
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Relation between entropy and probability:-

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I The probability of the system in equilibrium state is maximum. But from the thermodynamical
point of view the equilibrium state of a system is the state of maximum entropy.

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I S = K loge Ω S −→ Entropy, Ω −→ Probability.

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The above equation state that the entropy of a system is proportional to the logarithm of probability
of that system. (i.e) S ∝ loge Ω

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Boltzmann's canonical distribution law:-

I The number of molecules in each cell as a function of energy associated with each particle in that
cell.
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ni = A e−βεi ; ni = exp[−α − βεi ]
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ni = ;
eα+βεi
Partition function:-
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The quantity z is called the Boltzmann partition function or simply the partition function.
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N X X
z= = gi e−εi /KT (or) z= e−βεi
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i i
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z −→ the gas molecules of an assembly are distributed (or) partitioned among the various energy
levels. (Sum of state of the system)
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Kinetic theory of gases:-

1 2
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1. Pressure of gas P = ρc ; ρ = nm −→ density.

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2
2. P = Kinetic energy.
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3. Kinetic energy of temperature (one mole of an ideal monoatomic gas) E = KT ;
2
R 3
K= ; K = 1.38 × 10−23 joule/K ; E∝T ; E= RT
N 2
4. The mean square velocity of a molecules is directly proportional to the absolute temperature V 2 ∝ T
2 1
5. Boyle's law P V = N ; V ∝ (or) P V = constant .
3 P
V
6. Charle's law: V ∝ T at constant value of P −→ (or) = constant .
T
7. Gas equation: P V = RT .
4 A.R Coaching Centre for Physics, Kallakurichi(Dt)- Cell: 8667737887.

Classical Maxwell-Boltzmann Distribution law:-

The assemblies, in general, consist of three types of particles:

1. Identical but distinguishable particles:-

Molecules of a gas are the particles of the kind. The particles obey Maxwell-Boltzmann
distribution law.
2. Identical but indistingushable particle of Zero (or) Integral spin:-
Photons are the particles of this kind. The particle obey Bose-Einstein statistics and hence known
as Bose particle (Bosons).
3. Identical but indistinguishable particle of 1/2 integral spin:-
Electron, proton, neutron are the particle of this kind. They obey the pauli's exclusion principle and

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Fermi-Dirac ststistics. This particle are known as fermions.

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Evaluation of constatnt in the Maxwell-Boltzmann distribution law:

3N 3 3

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E= ; E= RT = nKT .
2β 2 2

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1
C=
(2πmKT )3/2 V

Maxwell - Boltzmann distribution law (statistics):-

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1. The total number of particles in the entire system is always constant.
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k  ni 
gi
2. The probability of a given distribution, P = N !
N

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.
n i
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i=1

3. The condition for most

 probable
 distribution (or) maximum probability,
ni
d(log p) = 0 (or) dni = 0 .
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log
gi
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gi ni 1
4. The M-B distribution law is, ni = gi e−α e−βEi (or) ni = (or) = α+βEi
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eα+βE i gi e
ni 1
(i.e)  .
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= 
gi exp Kεi −µ
BT
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5. The dierent ways of their distribution in for energy levels = gini .

6. Entropy of a perfect crystal is zero.
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7. The probability of nding one particle in the sth state is ns = e(µ−εs )/KT .
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8. At equilibrium, the chemical potential will be the same for all substances ns = N .
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9. For classical behaviour, eµ/KT << 1 .

Exercise: gi = 4, ni = 3 ∴ Number of ways gini = 43 = 64 .

5 A.R Coaching Centre for Physics, Kallakurichi(Dt)- Cell: 8667737887.

M-B energy distribution :

 
ni
I log = −α − βEi (or) ni = gi e(−α−βEi ) (or) ni = gi e−α e−βEi
gi
1
(or) ni = gi e−α e−Ei /KT ∴β=
KT
where, i = 1, 2, 3, ........ K
K −→ Boltzmann constant ; T −→ Absolute temperature.

I The quantity eX−Ei /KT

is known as the Boltzmann factor.
I The quantity is the sum over all states of the system and is called the partition

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−Ei /KT
gi e

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function of the system (Z) X .
Z= gi e−Ei /KT

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N
ni = gi e−Ei /KT

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Z
M-B energy distribution function:

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The general energy distribution function f (Ei ) is the average number of particles per quantum state
in the ith energy level Ei . It is given by,

f (Ei ) =
ni
gi
; f (Ei ) = e−α e−E/KT -8
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M-B Energy distribution function for an ideal gas:-

I An ideal gas consistingof free

 particle with no spin g(E) dE is
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2m
g(E) dE = 2πV E 1/2 dE
h2
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The M-B energy distribution law for the particles of ideal gas,
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 3/2
2N 1
E 1/2 e−E/KT dE
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n(E) dE = √
π KT
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 3/2
V 2πmKT
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α
I e = −→ is called the degeneracy parameter.
N h2
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Condition for application of M-B statistics:

I The M-B statistics is applicable to a system of particles for which the mean distance between the
particle is greater than the thermal
  De-Broglie wavelength of the particles.
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V
I The volume of per particle =
N
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 1/3
V
∴ The mean distance between the particle =
N
1/2
h2

I The de-Broglie wavelength associated is given by (λ), λ=
2πmKT
Thus, the condition for M-B statistical to become applicable is,
1/3 1/2 3/2
h2 h2
    
V V
≥ (or) ≥
N 2πmKT N 2πmKT
6 A.R Coaching Centre for Physics, Kallakurichi(Dt)- Cell: 8667737887.

  3/2
V 2πmKT
≥1 (or) eα ≥ 1
N h2
Three cases:

Case (i):

When the degeneracy parameter eα statistics this condition the gas is said to be non-degenerate
(i.e) eα ≥ 1.
Case (ii):

When eα > 1, but not too large, the gas is said to be weakly degenerate.
Case (iii):

When eα < 1, the gas is said to be strongly degenerate. The M-B statistics is valid for systems

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N
at high temperature, at low densities has a low value.

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V

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M-B law of distribution of momentum:

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 3/2
1 2 /2mKT
n(p) dp = 4πN p2 e−p dp
2πmKT

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Application of M-B distribution law:

1. Total internal energy and specic heat at constant volume of an ideal gas.

U=
3
KT ; Cv =
3
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E
2 2
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2. Maxwell - Boltzmann speed distribution:

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I M-B law of speed distribution

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 m 3/2 2 −mv2 /2KT

n(ν) dν = 4πN ν e dν
2πKT
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I gi = Number of cells in the zone under consideration.

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Volume of the zone in the phase space

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gi =
Volume of one cell
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RRR RRR
dxdydz dpx dpy dpz
gi =
h3
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4πV p2 dp
gi =
h3
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Maxwell's distribution law,

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2 /2KT
N (V ) dV = BV 2 e−mV dV

Three cases:

(i) If V = 0 ; N (V ) = 0. It means no molecule has a zero speed.

mV 2
(ii) For a small values of V , ∴ N (V ) ∝ V 2 .
2 /2KT
<< 1 and e−mV =1;
2KT
Thus, attains a maximum value for a value of V .
7 A.R Coaching Centre for Physics, Kallakurichi(Dt)- Cell: 8667737887.

(iii) For large values of V , N (V ) ∝ e−mV Thus value of N (V ) decreases exponentially with
2 /2KT

increasing of value V .
Maxwell's distribution law of velocities:

Maxwell's distribution law of velocities,

 m 1/2
 2
n(νx ) dνx = N e−mVx /2KT dVx
2πKT
 m 1/2 2
p(Vx ) dVx = N e−mVx /2KT dVx
2πKT
Limitation of M-B method:

1. It is applicable only to an isolated gas of identical molecules in equilibrium.

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(a) The mean potential energy due to mutual interaction between the molecule is very small

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compared to their mean kinetic energy (under this condition the gas is said to be ideal).
(b) The gas is dilute (i.e) the number of molecule per unit volume is small. So that the average

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separation between the molecules is large and hence individual molecules can be distinguished.
(Under this condition the gas is said to be non-degenerate ).

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2. The expression for M-B could does not give correct expression for the entropy S of an ideal gas
and thus leads to the Gibb's paradox.

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3. It cannot be applied to as system of indistinguishable particles.
4. From M-B distribution, we get the expression for the emission current density J = Ao T 1/2 e−φ/KT

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which is not correct, and correct is J = Ao T 2 e−φ/KT E
I Experimental verication of Maxwell's distribution of molecular speed experimentally arranged by
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I.F.Zartman and C.C.Ko (Bismuth).

(to be continue... )
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A.R COACHING CENTRE

IN

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H

Kallakurichi Dst, Contact-8667737887.

AC

Best Coaching Centre for Physics

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