Rami Kraft Statistical Physics, FK8008

Hand-in 3: Grand Free Energy, Grand Partition Function and the Ideal Gas
We consider the following thermodynamic potential, namely the Grand free energy

  F   N  U  TS   N (1)

, where F is the Helmholtz free energy.

Question 1

The thermodynamic identity is given by

dU  TdS  PdV   dN (2)

Then differentiating (1) gives

d   dU  TdS  SdT   dN  Nd  (3)

Inserting (2) into (3) yields

d    PdV  SdT  Nd  (4)

When volume V and chemical potential  are fixed we get

  
   S (5)
 T V , 

When temperature T and chemical potential  are fixed we obtain

  
   P (6)
 V T , 

When temperature T and volume V are fixed we obtain

  
   N (7)
  T ,V

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Rami Kraft Statistical Physics, FK8008

Question 2

Another thermodynamic potential is the Gibbs free energy G

G  U  TS  PV (8)

Moreover G is an extensive quantity which implies that it grows in proportion to the number of
particles 1

G  N (9)

Inserting (9) into (1)

  U  TS   N  U  TS  G (10)

Inserting (8) into (10)

  U  TS   N  U  TS  U  TS  PV   U  TS  U  TS  PV   PV (11)

Question 3

We want to prove the following formula

  kT log Z g (12)

  
We know from (1) that   U  TS   N and from (7) that    N .
  T ,V

We solve (1) for N and we get

  U  TS
N  (13)


Inserting (13) into (7) gives

     U  TS
   (14)
  T ,V 

Equation (14) is a first order differential equation for the unknown function  (  ) while T and V
are fixed.

Now we define the following function

  kT log Z g (15)

1
An Introduction to Thermal Physics, Daniel V. Schroeder, p164.

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Rami Kraft Statistical Physics, FK8008

, where Z g  e
s
[ E ( s )   N ( s )] 
and   1/ kT .

Next we differentiate  with respect to 

  N ( s) e[ E ( s )   N ( s )]

  
  kT log Z g   kT log Z g  kT s s

    e[ E ( s ) N ( s )]

s
(16)

 kT   N ( s )  kT  N   N
s

We conclude that  obeys exactly the same differential equation as  .

In order to complete the proof, we need to show that    at one particular value of the chemical
potential  e.g.   0 .

At   0

  U  TS   N  U  TS  F (17)

We know that the Helmholtz free energy F is given by

F   kT log Z (18)

, where Z is the partition function or the sum of all Boltzmann factors

Z   e E ( s )  (19)
s

We apply the same initial condition   0 to (15)

  kT log Z g  kT log  e[ E ( s ) N ( s )]   kT log  e E ( s )   kT log Z  F (20)
s s

By inserting (17) into (20) we obtain

F  (21)

Now our definition in (15) stated that   kT log Z g and we have now shown two things, first that

 obeys exactly the same differential equation as  , second that    at   0 . Therefore we can
write that   kT log Z g which was asked to be proven.

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Rami Kraft Statistical Physics, FK8008

Question 4

V
For an ideal gas the single-particle partition function is Z1  Z int and the partition function for a
vQ
system of N indistinguishable, non-interacting particles is

N
1 N 1 V 
Z Z1   Z int  (22)
N! N !  vQ 

For an ideal gas using the grand partition function we get

N N
1 V  1 V  1
Zg   e  E N
 Z e N
   Z int  e  N     Z int  e      x  (23)
N
e

N N !  vQ
 
N N !  vQ
 N N!
N N  

V
, where x  Zint  e  .
vQ

xN
We know that e x  
N N!
, therefore the grand partition function becomes

V
Zint e 
Zg  e
vQ
(24)

Question 5

We begin by what we proved in question 3, namely   kT log Z g . We calculate the logarithm of
the grand partition function

V
Zint e 
V
log Z g  e  Zint  e 
vQ
(25)
vQ

Therefore

V
  kT  Zint  e  (26)
vQ

3
3
 h   h2  2
, where the quantum volume vQ      .
 2 mkT   2 mkT 

Equation (26) becomes

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Rami Kraft Statistical Physics, FK8008

3 3
 2 mkT  2  2 m  2
5
V
  kT  Zint  e   kT     V  Z int e    kT 

  2   V  Z int e 
2
(27)
 h   h 
2
vQ

We can now calculate the pressure P using (6)

 3
 3
      2 mkT  2    2 mkT  2 
P     kT     V  Zint e   kT     Z int e (28)
 V T ,  V   h
2
  h
2

 

In addition we calculate the number of particles from (7)

 3
 3
      2 mkT  2    2 mkT  2
N     kT     V  Zint e    V  Z int e  (29)
  T ,V N   h
2
   h 2

 

Now we put equation (28) and (29) together and we get

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 2 mkT  2 
PV  kT     Z int e  V  kT  N  NkT (30)
 h 
2

, which is the usual equation of state.