PHYSICS STATISTICAL

THERMODYNAMICS
1. BASIC TERMS AND CONCEPTS
• A thermodynamic system  an assembly of submicroscopic
entities (atoms, molecules, photons, electrons, oscillators) in a
very large number of ever changing quantum states.
• Each entity has a probability of being in a particular state
• A probability function describes the likelihood that each entity
will be in a particular state
• Assembly (system)  a large collection of identical particles
• Basic postulate  all possible microstates of an isolated
assembly are equally probable
• A microstate is specified by the number of particles in each
“energy” state
• A macrostate is specified by the number of particles in each of
the energy levels of the system
2. PURPOSE OR OBJECTIVE OF STATISTICAL
THERMODYNAMICS
•1.  Predict the properties of an assembly (system)
2. Because of large numbers → analysis must be
done statistically
3. Numbers
4. Molecules interact via collisions (ignore Van
Derwaal's forces)
5. Statistical thermodynamics provides a means
of averaging
AN ASSEMBLY TENDS TOWARDS :
• The most probable state
• Highest disorder
• Highest entropy
• Thermal equilibrium
3. UNDERSTANDING THROUGH A COIN TOSS
EXPERIMENT
 4 coins are tossed : there are 16 different outcomes
Macrostate Thermodynamic Mathematic
Macrostate Macrostate Microstates Thermodynamic Mathematic
Macrostate Specification Microstates Probability Probability
Specification Probability Probability
Coin 1 Coin 2 Coin 3 Coin 4
1 4 0 H H H H 1
Coin 1 Coin 2 Coin 3 Coin 4
H H H T
H H T H
2 3 1 4
1 4 0 H
H T
H H
H H
H 1
T H H H
H H T
H T
H T
H H
T T
H
2 3 1 4
H T T
H H
3 2 2 6
T H H T
H
T H T H
H
T H
T T
H T
H
H T H T
H
H T
T T
T T
H
3 2 2 T H T T 6
4 1 3 T H H T 4
T
T T
H H
T T
H
T
T T
T T
H H
H
5 0 4 T T T T 1
H T T T
T H T T
4 1 3 4
T T H T
T T T H

5 0 4 T T T T 1

  joule/mol.K
4. UNDERSTANDING THROUGH A COIN TOSS EXPERIMENT

• 
4 coins are tossed : there are 16 different outcomes
• N = number of coins tossed
• = number of heads
• = number of tails = N-
• = number of entities in state

• Heads and tails represent 2 energy states /levels

• The macrostate of a system or configuration is specified by the number of particles
(entities) in each of the energy levels of the system
• Number of microstates for each macrostate = (, )
• Total numer of microstates =
• 2 energy levels =1,2 4 particles N=4
• 5 macrostates
1
2
3
4
5
5. THE AVERAGE OCCUPATION NUMBER
•  coins are tossed : there are 16 different outcomes
4
(the average number of heads in all the
macrostates)
, where
(#of heads)
= number of macrostates (1-5)
Average number of heads =
 6. HOW TO CALCULATE THE NUMBER OF
MICROSTATES
•  coins are tossed : there are 16 different outcomes
4
Number eof microstates for (#of microstates in
the )

2 3 2

1 1 1 1
 7. STIRLING’S APPROXIMATION
•   = ? = 100.99.88. …. . 2.1 = ? n! = ? When n is large
100!