Chapter 6

Q5.

U


We know that CV =
V and since this is an ideal gas, we have pV = N
and U = 32 N = U
V = 0.

So the given equation becomes

1 N
d = CV d + dV
V
d dV
= d = CV +N
V
= d = CV d(log ) + N d(log V )

Integrating both sides gives,

= CV log + N log V + 1

Where 1 is a constant independent of and V . 

Q13.

(a) Gibbs Sum

(N s(N ) )
X  
G(, ) = exp

ASN
s(N ) )
   
X (N )
= G(, ) = exp exp

ASN
s(N ) )
X  
= G = N exp

ASN

Where exp( ) is the absolute cavity.

The partition function for this system is

s(N ) )
X  
ZN = exp

s,N

and so,
X
G= N ZN
N
.
(nQ V )N
But we are given that ZN = N! and so,

X (nQ V )N
G= N
N!
N
X (nQ V )N
= G =
N!
N
(nQ V )2 (nQ V )3
= G = 1 + nQ V + + + ...
2! 3!
This is the taylor series for exp(nQ V ) and therefore,

G = exp(nQ V )

as desired. 

(b) The absolute probability of the system is given by

exp( N 

s
)
P (N, s ) =
G
(nQ V )N
Substituting in exp( N 

s
)= N! , gives

(nQ V )N
P (N ) =
N !G

But from (a) we know that

G = exp(nQ V )

and so,

(nQ V )N
P (N ) =
N ! exp(nQ V )
(nQ V )N exp(nQ V )
= P (N ) =
N!
Note that < N >= V nQ and therefore,

(< N >)N exp( < N >)

P (N ) =
N!

as desired. 
 (c) Using the equation found in (b), we have,
X X (< N >)N exp( < N >)
P (N ) =
N!
N N
X (< N >)N
= exp( < N >)
N!
N

The sum on the RHS of the above equation is the taylor series for
exp(< N >) and therefore,
X
P (N ) = exp(0) = 1
N

as expected. 

Now, by using the equation found in (b) again, we have,

X X (< N >)N exp( < N >)
N P (N ) = N
N!
N N
X (< N >)N 1 (< N >) exp( < N >)
=
(N 1)!
N =1
X
= < N > P (N 1)
N =1
X
=< N > P (N 1)
N =1
=< N > [P (0) + P (1) + P (2) + ...]
X
=< N > P (N )
N
=< N > (1)

and,
X
N P (N ) =< N >
N

as expected.