Homework 3

João Felipe Chaves e Silva

September 2021
Ideal Gas in the Canonical
Ensemble

Consider an ideal gas of N particles in the canonical ensemble, i.e., it can

3N
X p2i 1
H(p) = , ΛN =
i=1
2m N !h3N

(1) Show that the partition function is:

3N Z Z 
−p2i /2mkb T −p2i /2mkb T
Y
N
QN = ΛN dpi dqi e = ΛN V dpi e
i=1

= ΛN V (2πmkb T )3N/2
N

after performing an Gaussian integral.

"  3/2 #
V 2πmkb T
A = −kb T lnQN = −N kb T ln
N h2
∂ 3
U =− lnQN = N kb T
∂β 2
 
∂A N kb T
P =− =
∂V T,N V

You may need the Stirling formula lnN ! ≈ N lnN − N + 12 ln(2πN )

Solution
(1) First, let’s write the partition function:

1
 P3N p2
i
QN = e−βH → QN = e−β i=1 2m

Considering that our momentum distribution is a continuous, we can inte-

3N Z
P3N p2
i
Y p2
i
QN = e−β i=1 2m = ΛN dpi dqi e−β 2m
i=1

Integrating the phase space volume:

Z 3N
p2
i
N −β 2m
QN = ΛN V dpi e

The remaining integral is gaussian, so we get:

Z 3N
p2
N i
−β 2m 3N/2
QN = ΛN V dpi e = ΛN V N [2πmkb T ]

(2) Calculating Helmholtz free energy:

 
h
3N/2
i 1 3N/2
A = −kb T lnQN = −kb T ln ΛN V N [2πmkb T ] = −kb T ln V N
[2πmk b T ]
N !h3N
" #
3/2
h
1/2
i V (2πmkb T )
= −kb T N lnV − N lnh + N ln (2πmkb T ) − N lnN + N = −kb T N ln + N ln +N
N h3
" # " 3/2 #
3/2 
V (2πmkb T ) V 2πmkb T
= −N kb T ln − N kb T = −N kb T ln − N kb T
N h3 N h2

Calculating U :

" # !3/2
  
 3/2 2 
 3/2

∂ ∂ V 2πm N h V 2πm  3
U = − lnQN = N ln +N =N β 3/2   =
∂β ∂β N βh2 V 
2πm N  h2 2β 5/2

3N 3
= = N kb T
2β 2
Calculating P :

!3/2
 3/2
  
h2
   
∂A N 1 β 1 2πm N kb T
P =− = N  =
∂V T,N β V 2πm h2 β
N V
 

2
Ideal Gas in the Grand
Canonical Ensemble

Now consider the same ideal gas described by Eq. (1), but in the grand canonical
ensemble, i.e., the system can exchange energy and particles with the reservoir.
The fugacity z = eβµ is defined from the chemical potential µ.
(1) Use Eq. (2) to show that the grand partition function is

∞ h i
zV
(2πmkb T )3/2
X
Q(z, V, T ) = z N QN = e h3

N =0

(2) Show that the average particle number is

∂
hN i = z lnQ
∂z
and hence Q = ehN i
(3) Show that the particle number fluctuation is

∂hN i PV KT
hN 2 i − hN i2 = z = hN i = lnQ = = kb T hN i
∂z kb T v
where v = V /hN i, and hence the isothermal compressibility is just inverse
of the pressure

1
KT =
P
(4) We may write the average particle number as

∞ ∞
1 X X z N QN
hN i = N z N QN = PN N, PN = ,
Q Q
N =0 N =0

3
 where PN is the probability for the system to have particle number N . Use
Eq. (2), Q = ehN i , and the Stirling formula to show that as N is close to the
average number N = hN i + δN , the probability distribution takes a gaussian
form:

hN iN 1 2
PN = ehN i ≈p e−(N −hN i) /hN i
N! 2πhN i

In other words, the distribution is highly peaked at the average value hN i

" #
V (2πmkb T )3/2
µ = −kb T ln
hN ih3

Solution
First, let’s consider the probability of finding the system in a specific state i,
with an energy EI and particle count of Ni :

Pi = cΩR (E0 − Ei , N0 − Ni )

Now, taking the expansion:

   
∂lnΩR ∂lnΩR
lnPi = C + (−Ei ) + (−Ni ) + ...
∂E E0 ,N0 ∂V E0 ,N0

We can identify these quantities as:

   
∂lnΩR ∂lnΩR
=β , = −µβ
∂E E0 ,N0 ∂N E0 ,N0

So:

1 −β(Ei −µN )
lnPi = C − Ei β + µNi β → Pi = e
Q
Where Q is:

X X X
Q= e−β(Ei −µN ) = z N e−βEi = z N QN
i i i

4
 As we wanted to prove!
(2) First, let’s consider

X
hN i = Q−1 Ni z Ni e−βEi
i

If we derive z in the partition function:

∂ ∂ X N −βEi X
Q= z e = Ni z Ni −1 e−βEi
∂z ∂z i i i

Now let’s try derivating the lnQ in z:

∂ ∂
lnQ = Q−1 Q
∂z ∂z
Comparing that to hN i we’re only missing on the power of z, so fixing that,
we get:

∂
hN i = z lnQ
∂z
(3) Firstly:

∂
hN i = z lnQ
∂z
Doing it again:

  −2  
Ni
P
∂ ∂ ∂ i Ni z QN X 2 Ni −1 X X
z z lnQ = z = z Ni z QN −  z Ni QN   Ni z Ni −1 QN  =
P 
∂z ∂z ∂z N
i z QN
i
i i i
  −2     
−2
X X X X X
= Ni2 z Ni QN −  z Ni QN   Ni z Ni QN  =  Ni2 z Ni QN − (Q)  Ni z Ni QN  =
   
i i i i i

= hN 2 i − hN i2

So: