Statistical Mechanics (PHYS512) - Homework 1

김영진
October 15, 2021

Problem 1. 6.1 Show that the formulas (6.27), (6.28), and (6.29) are equivalent to one
another.

Proof. From the formula (6.13),

log Γ(E) = k log ω(E) + log ∆. (1)

Since ∆ is a constant independent of N , we get (6.27) and (6.28) is same up to constant.

Also,

log[Γ(E)] = log [Σ(E + ∆) − Σ(E)]

  
Σ(E)
= log Σ(E + ∆) 1 −
Σ(E + ∆) (2)
 
Σ(E)
= log [Σ(E + ∆)] + log 1 − )
Σ(E + ∆)

Since log Γ(E, N ) ∼ O(N ), we have log ω(E) = log Γ − log ∆ ∼ O(N ). In thermodynamic
Σ(E)
limit, Σ(E+∆) → 0, and ∆  E implies log [Σ(E + ∆)] ∼ log [Σ(E)].
Therefore (6.27), (6.28) and (6.29) are equivalent.

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Problem 2. 6.3 Consider a system of N free particles in which the energy of each particle
can assume two and only two distinct values, 0 and E(E > 0). Denote by n0 and n1 the
occupation numbers of the energy level 0 and E, respectively. The total energy of the system
is U .

(a) Find the entropy of such a system.

(b) Find the most probable values of n0 and n1 , and find the mean square fluctuations of
these quantites.

(c) Find the temperature as a function of U , and show that it can be negative.

(d) What happens when a system of negative temperature is allowed to exchange heat
with a system of positive temperature?

Reference. N. F. Ramsey, Phys. Rev. 103, 20 (1956).

Solution. (a) The number of states is

N!
Ω= (3)
n0 !n1 !

Hence S = k ln Ω = k ln n0N!n!1 !

(b) Ω is maximized when n0 = n1 . The most probable values are n0 = N/2 and n1 = N/2.
Using the following equation,
N   N
1 X N 1 X N!
hn0 i = N n0 = N n0
2 n =0 n0 2 n =0 n0 ! (N − n0 )!
0 0
N
(4)
N X (N − 1)! N
= n0 =
2N
n0 =1
(n0 − 1)! (N − n0 )! 2
N  
1 X N
hn0 (n0 − 1)i = N n0 (n0 − 1)
2 n =0 n0
0
N
(5)
N (N − 1) X (N − 2)! N (N − 1)
= =
2N n =2
(n0 − 2)! (N − n0 )! 4
0

the fluctuations of n0 is as follows.

N
n0 − hn0 i2 = hn0 (n0 − 1)i + hn0 i − hn0 i2 = .

2
(6)
4
By symmetry, we also get
N
2 N
hn1 i = , n1 − hn1 i2 = . (7)
2 4

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 (c) Using Stirling’s formula,

N!
S = k ln Ω = k ln ≈ k (N log N − n1 log n1 − n0 log n0 )
n0 !n1 !
         (8)
U U U U
= k N log N − log − N− log N −
E E E E

we get the following.

     
1 ∂S 1 U 1 1 U 1
= = k − log − + log N − +
T ∂U V E E E E E E
(9)
k NE − U
= log .
E U
So,
E 1
T = · N E−U

(10)
k log U

Note that, we can get the same result using n1 /n0 = exp(−E/kT ) as follows[1].

E 1 E 1
T = · n0 = · N E−U

(11)
k log n1 k log U

(d) “Heat will flow from a negative temperature system to a positive temperature system.
This is because the negative temperature system has higher energy on account of
population inversion, i.e., it has more particles in higher energy states than in lower
energy states”[1].

References
[1] Yung-Kuo Lim. Problems and solutions on thermodynamics and statistical mechanics.
World Scientific, 1990.

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Problem 3. 6.4 Using the corrected entropy formula (6.62), work out the entropy of mixing
for the case of different gases and for the case of identical gases, thus showing explicitly that
there is no Gibbs paradox.

Solution. (1) different case

Assume that there are N1 particles in the box of volume V1 and N2 particles in V2 with
the same density ρ = NVii . Then the initial and final entropy is as follows.
    
V1 3/2 V2 3/2
Si /k = N1 log u + N2 log u
N1 N2
     (12)
3 5 4πm1 5 4πm2
+ N1 + log + N2 + log
2 3 3h2 3 3h2
= (N1 + N2 ) log ρu3/2

(13)
    
3 5 4πm1 5 4πm2
+ N1 + log + N2 + log
2 3 3h2 3 3h2
    
V1 + V2 3/2 V1 + V2 3/2
Sf /k = N1 log u + N2 log u
N1 N2
     (14)
3 5 4πm1 3 5 4πm2
+ N1 + log + N2 + log ,
2 3 3h2 2 3 3h2

So,
V1 + V2 V1 + V2
∆S = N1 k log + N2 k log >0 (15)
V1 V2

(2) identical case

Since the gases are identical, m = m1 = m2 ,

Si /k = N1 log ρu3/2 + N2 log ρu3/2

(16)
    
3 5 4πm 5 4πm
+ N1 + log + N2 + log
2 3 3h2 3 3h2
 
3/2

3 5 4πm
= (N1 + N2 ) log ρu + (N1 + N2 ) + log (17)
2 3 3h2
 
3/2

3 5 4πm
Sf /k = (N1 + N2 ) log ρu + (N1 + N2 ) + log (18)
2 3 3h2

so Si = Sf , and ∆S = 0