Thermodynamics

Y Y Shan

Chapter 7 The MaxwellBoltzmann statistics

In view of the examples in 4.3 of Chapter 6 where particles (such as dice or
tokens) are not real particles, energy was not assigned to individual particles.
However, in statistical thermodynamics, we deal with thermodynamic systems consisting
of millions of real particles with different energies. The total energy of a system is the
major factor we concern. Therefore, energies of individual particles (in different energy
states, i.e. quantum states) must be under consideration when counting microstates of
distributions for systems with certain total energies.
Consider a distribution of a system, denoted as {ai }, satisfying:
(i)

Total number of particles is N,

(ii)

Total energy of the system is U.

(iii)

Each particle can have energies (or energy levels) of:

(iv)

The degeneracy of energy levels are: g1 , g 2 ,L g i ,L accordingly (i.e., there are

1 , 2 , L i , L

g i states having same energy i ). The corresponding numbers of particles on

each energy level are: {ai } = {a1 , a 2 , a3 ,L ai , L}
Therefore a distribution {ai } describes :

1 , 2 , 3 ,L i , L

{a }
i

g1 , g 2 , g 3 , L g i , L
a1 , a2 , a3 , L ai , L

Total number of particles : N = ai

i

Total energy of the system : U = ai i

Eqn7-1

AP3290

92

Thermodynamics

Y Y Shan

7.1 Counting of Microstates

(a) Microstates by Maxwell-Boltzmann counting
In a system, if particles are distinguishable and different particles can have
same quantum states (occupy same quantum states), for such a distribution {ai }, the
total number of microstates can be counted and equals to:

g ia
= N !
ai !
i
i

MB

Eqn7-2

This is called Maxwell-Boltzmann counting, and such a system is called a Boltzmann

system.
(b) Microstates by BoseEinstein counting
In a system, if particles are indistinguishable and different particles can have
same quantum states (occupy same quantum states), for such a distribution {ai }, the
total number of microstate can be counted as:

BE =
i

( ai + g i 1)!
ai !( g i 1)!

This is called BoseEinstein counting, and such a system is called a Bose system.

AP3290

93

Thermodynamics

Y Y Shan

(c) Microstates by Fermi-Dirac counting

In a system, if particles are indistinguishable and different particles cannot have
same quantum states (can not occupy same quantum states, i.e., particles obey the Pauli
exclusion principle), for such a distribution {ai }, the total number of microstate can be
counted as:

FD =
i

gi!
ai !( g i ai )!

This is called Fermi-Dirac counting, and such a system is called a Fermi system.

Example: Check Eqn7-2. For a system having 3 distinguishable particles (3 pieces

of dice): N=3. Now play a three-dice-throwing game, suppose that showing the following
four sides (i.e. four individual states):
grade 1

= $10 ,

showing states

would have the same reward

(equivalent to energy level 1 with degeneracy of g1=4).

would have the same reward grade

energy level of 2 , with energy degeneracy g2=2).

formations (i.e. total microstates

MB

While

2 = +$20 (equivalent

to

Find the total number of possible

) for getting the reward of -$30, $0, +$10, +$60

(i.e. corresponding to the distributions of: {ai } = {3,0} , {ai } = {2,1} , {ai } = {1,2} ,

{ai } = {0,3}) and their probabilities, accordingly.

AP3290

94

Thermodynamics

Y Y Shan

(i) For the case of loosing -$30, i.e. showing any formations (microstates) from the
3,0}
{MB
= 4 4 = 64

distribution {ai } = {3,0} , the total number of microstates:

g ia
43 20
= N !
= 3!
= 64 )
ai !
3! 0!
i
i

(calculated by Eqn7-2: MB

(ii) For the case of winning $0, i.e. showing any formations (microstates) from the
{2,1}

distribution {a i } = {2,1} , the total microstates: MB = ( 4 4) ( 2) C3 = 96 .

1

g ia
4 2 21
= N !
= 3!
= 6 16 = 96 )
ai !
2! 1!
i
i

(calculated by Eqn7-2: MB

(iii) For the case of winning $10, i.e. showing any formations (microstates) from the
{1, 2}

distribution {ai } = {1,2}, the total microstates: MB = C3 (4) (2 2) C3 = 48 .

1

g ia
41 2 2
= N !
= 3!
= 6 4 2 = 48 )
ai !
1! 2!
i
i

(calculated by Eqn7-2: MB

(iv) For the case of winning $60, i.e. showing any formations (microstates) from the
{0 ,3}

distribution {ai } = {0,3}, the total microstates: MB = 2 2 2 = 8 .

g ia
40 23
= N !
= 3!
= 8)
ai !
0! 3!
i
i

(calculated by Eqn7-2: MB
So:

the

probability

of

$30-lost:

64/(64+96+48+8)=29.6%,

winning-nothing:

96/216=44.4%, $10-win:22.2%, and $60-win: 3.7%.

Conclusion: Dont gamble.

7.2 Maxwell-Boltzmann statistics

7.2.1 Maxwell-Boltzmann distribution
For a Boltzmann system of N particles {ai }, the total number of microstates is:

g ia
,
ai !
i

= N !
i

N = ai ,
i

U = ai i
i

Under what circumstance, will reach to its maximum?

According to the principle of equal a priori probabilities, if the number of
microstates of a distribution becomes maximum, this distribution is the most probable

AP3290

95

Thermodynamics
distribution.

Y Y Shan

It has the highest probability to be observed. This most probable

distribution is called the Maxwell-Boltzmann distribution.

Thus, our goal is to find out what {ai } will be ( ai = ?) to make the total number
of microstates become maximum.

Brief derivation of Maxwell-Boltzmann distribution:

From Eqn.7-2, and using Stirling's formula: ln x!= x(ln x 1), (for x >> 1) , we
can obtain:

ln = N ln N ai ln ai + ai ln g i
i

Eqn7-5

When gets to maximum, ln will also become maximum.

mathematical condition to get the maximum of ln is:

From Eqn.7-5, let

d ln
= 0.
dai

d ln
= 0 , by use of the Lagrange method,
dai

the solution ai (i.e. the number of particles occupying energy level

the details):

The

i ) is obtained (skip

ai = f ( i ) N

g i e i
f ( i ) =
Z

Eqn.7-6

is the probability of a particle occupying the energy level

distribution function. The function

Z = g i e

i , and is called the Boltzmann

is called the partition function. In

AP3290

96

Thermodynamics

Y Y Shan

terms of energy-level-occupation, i denotes the ith energy level. The factor

Boltzmann factor and can be proved to equal to

is called

1
, and k is called Boltzmann constant.
kT

For each energy level i , there are g i individual states (quantum states), in terms
of individual-state-occupation, The probability of an individual quantum state j to be
occupied is:

P( j ) =

f ( j )
gj

7.2.2 The partition function Z

In statistical physics, the partition function

Z = g i e

Eqn.7-7

is an important quantity that encodes the statistical properties of a system in

thermodynamic equilibrium. Most of the thermodynamic variables of the system, such as
the internal energy, free energy, entropy, and pressure, can be expressed in terms of the
partition function or its derivatives.

The partition function can be related to

thermodynamic properties because it has a very important statistical meaning.

Since

f ( i ) =
i

g i e i Z
= =1
Z
Z

The partition function thus plays the role of a normalizing constant, ensuring that the
probabilities add up to one. This is the reason for calling Z the "partition function": it
encodes how the probabilities are partitioned among the states to be occupied at different
energy levels ( i ), based on their individual energies. The letter Z stands for the German
word Zustandssumme, sum over states.

AP3290

97

Thermodynamics

Y Y Shan

7.3 Application of Boltzmann statistics--I

We have been emphasizing the importance of the partition function Z, which
encodes the statistical thermodynamic properties and is the key to calculating all
macroscopic thermodynamic properties of the system.
When we know

, we can calculate all macroscopic properties of the system -

the internal energy, free energy, entropy, and pressure.

(i) The statistical internal energy U

In order to demonstrate the usefulness of the partition function, let us calculate the
thermodynamic value of the internal energy.

Z
= g i i e

i
i
N
N Z
ln Z
U = ai i = Nf ( i ) i = g i i e =
= N
Z i
Z

i
i
Z = g i e ,
i

Therefore, the statistical expression of internal energy is:

U = N

ln Z

Eqn7-3a

This means that when the partition function Z is known, the internal energy U can be
calculated. Therefore, the specific heat CV can be calculated by:

U
CV =

T V
Example: Einsteins specific heat of solids

Since an atom in a solid, having three degrees of freedom, can vibrate

independently in three dimensions, it should really be considered to be equivalent to three
separate 1D quantum harmonic oscillators (QHO refer to AP3251). Therefore, Einstein's
model pretty much said that a solid of n atoms comprised 3n number of 1D quantum
harmonic oscillators, and assuming that all the 3n oscillators have the same oscillating
frequency of o. For each 1D QHO:

AP3290

98

Thermodynamics

1
2

i = (i + )h ,

Y Y Shan

i = 0,1,2,3...,+

, it is not degenerated, i.e., different states

have different energies, or energy levels).

The partition function for QMO (where the degenercy g i = 1 ) can be obtained as:

Z = g i e i = e

1
( i + ) h 0
2

=e

1
h 0
2

i =0

Here we applied the formula:

1
h 0
2

(e ) = 1 e

i =0

x
n =0

1
, (for x < 1) , and here
1 x

x = e h0 < 1 .

Now useEqn7-3-a, replacing N3n, the statistical internal energy U of a system having
the total number of quantum harmonic oscillators of N=3n is:

U = N

ln Z

= 3n

U =
(here

1
h0
)
2 h 0 ln(1 e

3nh
3n
h 0 + h 0 0
2
e
1

= 1 / kT , which will be proved later). Thus, the specific heat CV can be

calculated:
2

h 0
kT

e
h 0
U
CV =

= 3nk
2
T V
kT h0

e kT 1

AP3290

Eqn7-3b

99

Thermodynamics

Y Y Shan

(ii) To calculated the statistical pressure P

Since the statistical internal energy: U = ai i . Its differential form:

i

dU = dU ai + dU i = i dai + ai d i
i

Compare it with the 1st law of thermodynamics:

dU = dQ + dW = dQ PdV
Since the heat absorbing (or releasing) will excite the particle to different energy levels,
resulting in the change of particle numbers

dai at

energy level i .

Whereas the

quantized energies of the particles i depends on the volume (See AP3251: particle in a

potential box:

energy level

n n n

x y z

d i

2 h 2 n x2

n z2
=
+
+
2m L12 L22 L23 , V
n y2

= L1 L2 L 3 ), so that the change of

is related to the change of the volume. We get:

dQ = i dai ,
i

PdV = ai d i

Eq7-3c

AP3290

100

Thermodynamics

Y Y Shan

PdV = ai d i = Nf ( i )d i
i

i
i

g ie
N
1
d i = g i d (e )

Z
Z i
i
N 1
N 1
N
=
d ( g i e ) =
dZ = d ln Z
i
Z
Z

= N

The pressure can be expressed and calculated statistically by:

P=

N ln Z
V

(iii) Determination of Boltzmann factor

Eq7-3d

From the first law: dU = dQ PdV ,

dQ = dU + PdV , Using equations 7-3a, and 7-3d

ln Z N ln Z
1
dQ = d N
+
dV =
V

dQ =

ln Z
N
d N
N + d (ln Z )

ln Z
d N
+ N ln Z ,

Eq.7-3e

dQ = T dS
It can be concluded that the Boltzmann factor is reverse proportional to temperature

1
, which can be written as:
T

1
,
kT
where k is called the Boltzmann constant

Eq7-3f

From Eq.7-3e, entropy can be statistically expressed as:

ln Z
S = Nk ln Z

AP3290

Eq.7-3g

101

Thermodynamics

Y Y Shan

7.4 Application of Boltzmann statisticsII---mono-atomic ideal gases

(i) Semi-classical approximation

For classical gases (mono-atomic ideal gases), their molecules can be regarded
classical particles. The energy levels are becoming so condensed that they turn out to be
continuous energy band.

The changes in calculations using Boltzmann statistics will be:

1. The energy degeneracy:

g i replaced by

V
d3p
3
h

, the number states in the

volume element in momentum space, d 3 p , V is the volume of the system.

2. The Boltzmann distribution function:

f ( i ) =

g i e i
Z

f ( ) =

V e d 3 p
Z
h3

Eq.7-4a

3. The partition function will be changed to:

Z = g ie

V kT 3
Z = 3 e d p
h

Eq.7-4b

4. The number of particles on level i becomes the number of particles in the energy
range:

+ d
g i e
ai = Nf ( i ) =

Z
i

AP3290

V e d 3 p
a ( ) = N 3
h
Z

Eq.7-4c

102

Thermodynamics

Y Y Shan

2
2
2
1 2 1
p 2 px + p y + pz
2
2
2
where = mv = m(v x + v y + v z ), or =
=
2
2
2m
2m
3

, and d p is the volume element in momentum space.

d 3 p = dp x dp y dp z

in Cartesian coordinate system

d 3 p = p 2 sin dddp

in spherical coordinate system

(ii) The partition function of ideal gases (mono-atomic particles)

From Eq.7-4b, we obtain the partition function of ideal gas in Cartesian coordinates:

V
V
Z = 3 e kT d 3 p = 3
h
h
+

use

x2

p x2 + p y2 + p z2
2 mkT

dp x dp y dp z

dx =

Thus, the partition function of the ideal gas can be calculated:

V
Z = 3 e
h

px2 + p 2y + pz2
2 mkT

3
2

dpx dp y dpz = V

Eq.7-4-d

1
2m 2
where the constant = 2 , =
kT
h

AP3290

103

Thermodynamics

Y Y Shan

(iii) State equation of ideal gas in its statistical form , the determination of
Boltzmann constant k, and the calculation of the internal energy of ideal gas

Using Eq7-3-d, the gas pressure P can be statistically calculated by:

P=
P = NkT

N ln Z
V

[ln(V )] = NkT d (ln V ) = NkT

dV
V
V

PV = NkT

Eq.7-4-f

This is the statistical expression of the state equation of ideal gas.

Compare Eq.7-4f with the experimental state equation: PV = nRT ,

where n is mol number, i.e. Nk = nR . So the Boltzmann constant can be obtained:

nR
nR
R
8.314 JK 1mol 1
k=
=
=
=
= 1.381 10 23 JK 1
23
N nN 0 N 0 6.023 10 particles / mol
For n=1mol gas, N=N0 is the Avogadros number. R is the Gas constant.
(iv) The internal energy of ideal gas

The internal energy of ideal gas can be calculated statistically by Eqn7-3-a , Eq.7-4-d

V
Z = 3 e
h

U = N

p x2 + p 2y + p z2
2 mkT

dp x dp y dp z = 2V

ln Z

= N

3
3
3N

ln
+
ln(
V
)
=
=
N

kT

2
2
2

Example: Prove that, for mono-atomic ideal gas,

CP
= 1.667
CV

d
3 3
3
dU
CV =
=
N kT = Nk = nR
2 2
2
dT V dT
From classical thermodynamics (see chapter 2): C P CV = nR
Therefore C P = CV + nR =

AP3290

5
nR,
2

CP 5
= = 1.667
CV 3
104