Chapter 12

Statistical
Thermodynamics
12.1 Introduction
• The object: to present a particle theory which can
interpret the equilibrium thermal properties of
macroscopic systems.

• Quantum mechanical concepts of quantum states,

energy levels and intermolecular forces are useful
here.

• The basic postulate of statistical thermodynamics

is that all possible microstates of an isolated
assembly are equally probable.
A few new concepts
1) Assembly: denote a number N of identical entities,
such as molecules, atoms, electrons.
2) Macrostate: is specified by the number of particles in
each of the energy levels of the system.
3) Microstate: is specified by the number of particles in
each energy state.
4) Degeneracy: an energy level contains more than one
energy state.
5) Thermodynamic probability: the number of microstates
leading to a given macrostate. It is donated by Wk
where k represents the kth macrostate.
A true probability Pk can be calculated
n as

Pk = Wk/Ω with Ω = Wk
k 1
 12.2 Coin-tossing Experiment
Example: assuming that there are four students to
be assigned into two classrooms, how many
possibilities to split them?
# students in Room 1 # students in Room 2
case 1 4 0
case 2 3 1
case 3 2 2
case 4 1 3
case 5 0 4

Using A1, A2, A3 and A4 to represent the identity of

these four students, there will be many different
combinations for each case (i.e. macrostate).
  # students in Room 1 Total

Case 1 A1, A2, A3 and A4 1 

Case 2 A1, A2 and A3

  A1, A2 and A4

  A2, A3, A4

  A1, A3 and A4 4

Case 3 A1 + A2; A1 + A3

  A1 + A4; A2 + A3

  A2 + A4; A3 + A4 6

Case 4 A1

  A2

  A3

  A4 4

Case 5 0 1
In this example, the macrostate corresponds to
the case (i.e. the # students can be found in
each room), whereas the number of possible
arrangements for each case is viewed as the
corresponding thermodynamic probability.
More specifically,
for the macrostate 2 (i.e. case 2), the
thermodynamic probability is 4.
The thermodynamics probability for
macrostate 3 equals 6.
Making a plot with Wk ~ k

Wk maximum occurs at Case 3.

If the total number of students increased, the
peak in the above figure will become very
sharp. The center of the peak will remain at
where N is the total number of students.

The number of combinations for having N1

students in a room can be calculated from

WN1 =
 The average occupation
numbers
• In the above case, it means the average
number of students in room 1 or room 2.

• Let j = 1 or 2 , where N1 is the number of

students in room 1 and N2 is the number of
students in room 2; Let Njk be the number of
students in room j for the kth case

 N W jk k
Nj k

Wk
k
The value of thermodynamic probability WN1 will become
extremely large as the values of N and N1 are increased.

To facilitate the calculation, Stirling’s approximation

becomes useful:
ln (n!) = n ln(n) – n

When n is more than 50, the error in using Striling’s

approximation becomes very small.

Extend the above example into the situation where there

are multiple rooms (n rooms)
Now, the macrostate will be defined by the # of
students in each room, say: N1, N2 …Nn

Note that
N1 + N2 + N3 + … + Nn-1 + Nn = N
The number of microstates for the above macrostate
can be calculated from

W= x x ... x

=
N!
N1! N 2 ! N 3! N n !
 12.3 Assembly of distinguishable
particles
• An isolated system consists of N
distinguishable particles.
• The macrostate of the system is defined by (N,
V, U).
• Particles interact sufficiently, despite very
weakly, so that the system is in thermal
equilibrium.
• Two restrictive conditions apply here
n
(conservation of particles)
 N N
j 1
j

n
(conservation of energy)
 j j
N E
j 1
 U

where Nj is the number of particles on the energy

level j with the energy Ej.

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
j 0
j 3
(here the index j starts from 0)
3

N E
j 0
j j  3E

# particles on # Particles on # particles on # particles on

Level 0 Level 1 E Level 2E Level 3E
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.
• The second law of thermodynamics is a consequence
of the theory of probability: the world changes the
way it does because it seeks a state of probability.
12.4 Thermodynamic Probability
and Entropy
Boltzman made the connection between the classical
concept of entropy and the thermodynamic probability
S = f (w)
f (w) is a single-valued, monotonically increasing function
(because S increases monotonically)
For a system which consists of two subsystems A and B

Stotal = SA + SB (S is extensive)
Or…
f (Wtotal) = f (WA) + f (WB)
The configuration of the total system can be
calculated as Wtotal = WA x WB
thus: f (WA x WB) = f (WA) + f (WB)

The only function for which the above

relationship is true Is the logarithm.
Therefore:
S = k · lnW
where k is the Boltzman constant with the
units of entropy.