PHY461: Statistical physics and thermodynamics

Lecture 04

THE PARTITION FUNCTION

From the M-B distribution (equation 4.0):

ns = gs eα+βs = gs A eβs

From equation 2.9,

X X
N= ns = A gs eβs = AZ, (4.8)
s s

where

X
Z= gs eβs (4.9)
s

Z is the partition function (P.F) of a particles in a system. It gives a sum over all accessible
states of the particle. It depends on β and s which varies from level to level. The partition
ZN
function of the system is Z N for distinguishable particles and N! for indistinguishable particles.
It tells us how the particles are arranged or partitioned among the various energy levels of the
system, hence the name partition function. The P.F is different for different systems and should
be evaluated for each system.
From equations 4.0 and 4.8 we get:

N
ns = gs eβs (5.0)
Z

This gives the number of particles in level s in terms of the partition function. Let us now
express some thermodynamic quantities of an ideal gas in terms of the partition function:
(a) Entropy
From equation 4.2 we have:

S = k lnW

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From equation 2.3 we have:

gsns
 
W = N! Π
s ns !

Hence,

X
lnW = N lnN − N + (ns lngs − ns lnns + ns )
s

such that:

X gs
lnW = N lnN + ns ln
s
ns

For the most probable arrangement, we have the distribution function:

ns = gs eα+βs

That is,

ns
= e−α−βs
gs

Substituting into lnW we get:

X
lnW = N lnN + ns ln e−α−βs
s
X
= N lnN + ns (−α − βs )
s (5.0a)
X X
= N lnN − α ns − β ns s
s s

= N lnN − α N − β E,

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where E is the total energy of the system. Substituting for α = lnA and β = − kT , we get:

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 E
lnW = N lnN − N lnA +
kT (5.0b)
E
= N lnZ +
kT

Substituting into equation 4.0 gives:

 
E
S = k N lnZ +
kT

That is,

E
S = N k lnZ + (5.1)
T

equation 5.1 gives entropy as a function of the partition function. By replacing N k by the
universal constant R, it can also be written as:

E
S = R lnZ + (5.2)
T

(b) Helmholtz free energy F

From thermodynamics, the Helmholtz free energy is given by:

F = E − TS

Substituting for S from equation 5.1 we have:

E
F = E − T (N k lnZ + )
T (5.3)
= −N kT lnZ

Equation 5.3 gives F in terms of the partition function.

(c) Total energy E
From the total energy of a system (equation 3.1):

X
E= ns s
3s
Also from equation 4.0:

ns = gs eα+βs

Hence,

X
E = eα gs s eβs
s
X
=A gs s eβs (5.4)
s
NX s
= gs s e− kT
Z s

But,

∂ s s
  
s
gs e− kT = gs e− kT
∂T kT 2

Hence,

s ∂ s
s gs e− kT = kT 2 gs e− kT
∂T

Therefore, equation 5.4 becomes:

N X 2 ∂ s
E= kT gs e− kT
Z s ∂T
N kT 2 X ∂ s
= gs e− kT
Z s
∂T
(5.5)
N kT 2 ∂Z
=
Z ∂T
N kT 2 ∂lnZ
 
=
Z ∂T V

(d) Pressure P
From the expression for free energy F , we have:

F = E − TS
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 Therefore,

dF = dE − T dS − SdT
(5.5a)
= −P dV − SdT

That is,

 
∂F
P =−
∂V T

 
∂F
S=− (5.6)
∂T V

But, F = −N kT ln Z
Therefore,

 
∂ln Z
P = N kT (5.7)
∂V T

(e) Specific heat CV

 
∂E
CV =
∂T

 
∂ln Z
E = N kT 2 (5.8)
∂T

Hence,

2
 
∂ln Z 2 ∂ ln Z
E = N k 2T +T (5.9)
∂T ∂T

THE CLASSICAL PERFECT GAS

By classical perfect gas we mean a system consisting of distinguishable, non-interacting gas
molecules. Hence we can apply M-B statistics to this system.
First we compute its partition function, from equation 4.9 we have:

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 X X s
Z= gs eβs = gs e− kT
s s

Replacing the summation by integration, we can write:

Z ∞ 
Z= e− kT g()d
0

Substituting for the density of states g()d from equation 2.8, we have:

Z ∞ Z ∞

− kT 2π 3 1 2π 3 1 
Z= e V (2m) 2 s2 d = V (2m) 2 s2 e− kT d
0 h3 h3 0

Using the identity:

Z ∞ √
−ax2 1 π
e x dx =
2
3
0 2a 2
Hence,

V 3
Z= 3
(2πmkT ) 2 (6.0)
h

Note that the partition function given by equation 6.0 is for translational motion of one
particle. in a system at temperature T , confined in volume V . This is because we are dealing
with a perfect gas with no interaction between its molecules. For ideal gases, we need to include
contributions due to other modes of energy as well, in the P.F. We can use the above expression
for Z to get all the thermodynamic functions of a perfect gas as follows:
(a) Total energy E
Substituting the value of Z from equation 6.0 into equation 5.8, we have:

 
2 ∂ln Z
E = N kT
∂T
 
∂ V 3
= N kT 2 ln 3 (2πmkT ) 2
∂T h
  (6.0a)
2 ∂ V 3 3
= N kT ln 3 + ln(2πmk) 2 + lnT 2
∂T h
 
∂ 3
= N kT 2 lnT
∂T 2
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 That is,

3
E = N kT (6.1)
2

What do you notice about this result?

(b) Equation of state
Substituting the value of Z from equation 6.0 into equation 5.7, we have:

 
∂ln Z
P = N kT
∂V
 
∂ V 3
= N kT ln 3 (2πmkT ) 2
∂V h
(6.1a)
∂ h 3
i
= N kT lnV − lnh3 + ln(2πmkT ) 2
∂V 

1
= N kT
V

That is,

P V = N kT (6.2)

This is the ideal gas equation for a perfect gas. Similarly, other thermodynamic functions can
be obtained from Z. Thus we see that once Z has been evaluated, all thermodynamic properties
of a system can be obtained using the results obtained in the previous section.

V 3
Z= 3
(2πmkT ) 2
h

In the following section we shall consider the sequences of the assumed distinguishability of
the classical particles on the entropy of the system.

THE GIBB’S PARADOX

We start by looking at an expression for entropy given by equation 5.1 and substitute for Z and
E from equations 6.0 and 6.1. Thus we get:

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 V 3 3
S = N k ln (2πmkT ) 2 + N k (6.3)
h3 2

Now consider a situation in which two equal volumes of the same gas are mixed together.
The two volumes are at the same temperature, and pressure, and have the same number of
molecules. Each has entropy S. On mixing the two volumes we get a single system with the
number of particles 2N and the volume 2V , while temperature and pressure are kept constant.
Therefore the total entropy of the mixture,

   
2V 3 3
ST = 2N k ln 3
(2πmkT ) +
2 2N k
h 2
   
V 3 3 (6.4)
= 2 N kln 3 (2πmkT ) 2 + N k + 2N kln2
h 2
= 2S + 2N kln2

Equation 6.4 shows that the removal of the partition has caused an increase in the entropy by
a factor of 2N kln2. However, entropy is an extensive property, and hence the total entropy of
the mixture should be 2S. This contradiction is known as Gibb’s paradox. The probelm arose
due to our assumption that the particles in our classical perfect gas are distinguishable. Hence
any two volumes of the gas should be considered to be made of dissimilar molecules. If they
are indsitinguishable, interchanging the two molecules cannot be identified, and so removal of
the partition will create two possible positions in place of every single position available before
removal. Since there are N molecules in each volume, there will be 2N times the number of
arrangements before the partition was removed. Thus equilibrium weight will now be W.2N .
The total weight of the mixture will be:

WT = (W.2N )2

Hence the total entropy

ST = k lnWT = k ln(W.2N )2 = k(2lnW + 2N ln2) = 2klnW + 2N kln2

That is,

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 ST = 2S + 2N kln2

This is the same result we got previosuly. Thus it is clear that if the molecules were
treated as indistinguishable, the entropy of the mixture would be 2S, and that there is error
in the assumption of distinguishability of the particles in the derivation of the thermodynamic
quantities using classical statistical mechanics.
Let us now see what happens to the above case if we regarded the molecules as
indistinguishable. To do that, we treat the system as one of indistinguishable particles, find
its weight and entropy, and finally obtain the entropy of the mixture. The weight of our new
system will be,

gsns
 
W =Π
s ns !

By removing the N ! term from the weight of a classical system.

Therefore:

X
lnW = (ns lngs − ns lnns + ns )
s

X gs

lnW = ns ln + ns
s
ns

We know that

gs s
= e kT −α
ns

Therefore,

Xh   i Xn  E
s s s
X X
lnW = ns − α + ns = − ns α + ns = − Nα + N
s
kT s
kT s s
kT

Thus entropy

 
E E
S = k lnW = k − Nα + N = − kN α + kN
kT T

From equation 4.8, A = N/Z hence, α = lnA = ln(N/Z)

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 Therefore,

E Z
S= + N k ln + N k (6.5)
T N

Substituting for Z and E from equations 6.0 and 6.1

" 3
#
3 (2πmkT ) 2 V
S = N k + N k ln + Nk
2 N h3
" 3
# (6.6)
(2πmkT ) 2 V 5
= N k ln +
N h3 2

This is the Sackur-Tetrode formula for entropy of a gas of indistinguishable, classical particles.
Let us now use this new expression to treat the problem of the mixing of two gases. The
total entropy (replacing V by 2V and N by 2N ), we have:

" 3
#
(2πmkT ) 2 2V 5
ST = 2N k ln +
2N h3 2
" 3
#
(2πmkT ) 2 V 5 (6.6a)
= 2N k ln +
N h3 2

= 2S

as expected. Thus we have resolved the paradox. Comparing the two expressions for entropy,
that is (6.3 and 6.6), we see that by removing the N ! term from W , the extensive variable V in
equation 6.3 has been replaced by the intensive term V /N in equation 6.6. We should also note
that if the two volumes contain molecules of different gases removal of the partition will double
the quantity V /N , because for each type of molecule, the total volume becomes 2V . Hence the
total entropy will still contain the extra term 2N kln2.
One can now derive the thermodynamic quatities and the gas law for the sem-classical gas
as we did for the perfect classical gas using the new expression for entropy.

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