8.

08 Statistical Physics II

Micro-canonical and Canonical Ensembles

(Dated: February 7, 2011)

1. The average energy  in thermal

equilibrium is hEi. Prove that the mean square deviation of the

of a system
energy from hEi, (E − hEi)2 is given by (E − hEi)2 = kT 2 Cv , where Cv is the heat capacity of the entire
system at constant volume. Use this result to show that the energy of a macroscopic system may ordinarily be
considered constant when the system is in thermal equilibrium.
Solution

 D 2
E

2
(E − hEi)2 = E 2 − 2E hEi + hEi = E 2 − hEi
En e−En /kT
P
Suppose we have a system with discrete energy levels En hEi = P
e−En /kT
= − Z1 ∂Z
∂β
P −En /kT
where Z = e is the partition function and β1 = kT .

2  P En2 e−En /kT 2
E = P e−En /kT = Z1 ∂∂βZ2
 

2 2 ∂ 1 ∂Z ∂
E − hEi = ∂β Z ∂β = − ∂β hEi

We know that ∂
∂β
∂
= −kT 2 ∂T and ∂hEi
∂T = CV


Putting everything together (E − hEi)2 = kT 2 CV
 2 1/2  1/2
hE i−hEi2 kT 2 CV
Consider a macroscopic system hEi 2 = hEi 2

Consider the simple scaling argument hEi ∼ N kT , which also gives us CV ∼ N k. If we substitute these to the
right hand side of the previous equation, it becomes

2 1/2

 !
E 2 − hEi
2 ∼ N −1/2
hEi

For a macroscopic system where the number of particles is of the order of the Avogadro constant (6 · 1023 ), we
see that the fluctuations in energy are indeed very small.
2. Consider a three dimensional ideal relativistic gas of N particles. The gas is confined within a square wall of
size L. Assume that the temperature is T .
(a) Find the free energy F of the gas.
(b) Find the pressure of the gas.
Solution
(a) We start by calculating the partition function
N  N Z N
L3N
Z 3
d p1 d3 p2 d3 pN −βH L3N
Z 3
d p −βpc L3N L3N 4π 2 −βpc
Z= ... e = e = = p dpe
N! h3 h3 h3 N! h3 N! N! h3

" 3  #N
1 KT 8πL3
Z=
N! c h3

The free energy is F = −kT lnZ. Using Stirling’s approximation this gives us

" 3  #
KT 8πL3
F = kT N lnN − kT N − N kT ln
c h3
 2

∂F ∂F N kT
(b) The pressure is P = − ∂V = − ∂L3 = L3

3. A solid contains N mutually noninteracting nuclei of spin 1. Each nucleus can therefore be in any of three
quantum states labeled by the quantum number m, where m = −1, 0, +1. Because of electric interactions with
internal fields in the solid, a nucleus in the state m = 1 or in the state m = −1 has the same energy  > 0, while
its energy in the state m = 0 is zero. Derive an expression for the entropy of the N nuclei as a function of the
temperature T , and an expression for the heat capacity in the limit /kT  1.
Solution
P −E/kT
The partition function of the system is Z = e = (1 + 2e−/kT )N . This is true because the spins are
non-interacting, so the total partition function is just the product of the single spin partition functions.
The free energy is

F = −kT lnZ = −N kT ln(1 + 2e−/kT )

This gives the entropy

∂F 2N  e− /kT
S=− = N kln(1 + 2e−/kT ) +
∂T T (1 + 2e−/kT )

The energy of the system is

2N e−/kT 2N    
U= −/kT
≈ 1−
(1 + 2e ) 3 3kT

Finally, the heat capacity becomes

∂U 2N 2 2   2
C= = 2
= Nk
∂T 9kT 9 kT