UNIVERSITY OF GHANA

DEPARTMENT OF PHYSICS

HOME WORK (3): STATISTICAL MECHANICS

NAME: APURI SIMON BAJONGDO

STUDENT ID: 10875216

QUESTION (1)

(a):
If N is the total number of identical systems, then the number of microstates is a
function of the occupation numbers nr and it is given by:
N! N! [1.1]
W {nr }    N! (nr!)1
n0!n1!n2!...  nr !
r

Using the expectation of the occupation numbers:

 nr w ( nr )

 nr 
( nr )
[1.2]
 w(n )
( nr )
r

We can evaluate the expectation of the occupation numbers as follows:

N !0 0 1 12 2 ....
n n n
 r nr 
W {nr }  !
 W nr   N !  

n0 n1!n2!... r  nr !  [1.3]

Taken into account the condition that;

n
r
r N [1.4]

By using the gamma function,

 r nr 
( N ,U )  W {nr }   N !  
 [1.5]
{nr } {nr } n  nr ! 

From equation [1.5],

n 1
  r n  r n
 N! nr  r  N! r  r [1.6]
r nr ! r nr !

  r n
r  N! nr  r [1.7]
r nr !
 1
 ln  1  nr  n N! n !  n W {n }
r
r  N ! nr  r   r r r
[1.8]
 N! n ! W {n }
allr 1
r  nr ! 1 r

Clearly,

r
 ln 

 n W {n }  n
r r
 [1.9]
W {n }
all r 1
r
r
r

Using equation [1.9],I can do the following;

   r n
r r  N! nr  r
2
[1.10]
r r nr !

1
N ! nr 
2

 n W {n }
2
1   nr !
r r   r r
[1.11]
W {nr } W {n }
allr 1
 r r r

Clearly,

 n W {n }  n
2
1  
r r  r r 2
 [1.12]
W {n }
allr 1
 r r
r
r

1            
 n   n
2 2
   nr  2    r  r () allr 1    r  r (ln )
   r  r    r  r 
r


   1 
  r    allr 1 (ln ) allr 1  [1.13]
 r    

1 1
() allr 1 Tends zero as N gets large, () allr 1  0 [1.14]
 

Hence :  n    
2
r
  1

r   
all r 1

 [1.15]

(b)

From the textbook, equation 3.2.37 is given by:

 (nr ) 
2
  r exp(  Er )   r exp(  Er )   
 r    r  U   r  all 1 [1.16]
N r  r r exp(  Er )  r r exp(  Er ) 
 r  r
 

From the textbook, equation 3.2.38 is also given by:

U   E 
  E exp( E )
r r r r
[1.17]
  exp( E )
r r r

1
Where   [1.18]
kT

From equation [1.17],

 r Er exp(   ) r  r r exp(  Er )

E


 
[1.19]
r  r exp(Er
2
r

Therefore:

 Er  U  nr 
all1 1  (Equation3.2.39) [1.20]
r  Er  2  U 2 N

Again recall equation [1.16],

 (nr ) 
2
  r exp(  Er )   r exp(  Er )   
 r    r  U   r  allr 1 [1.21]
N r  r r exp(  Er )  r r exp(  Er ) 
  
 r

nr    1 1 Er  U 2  (Equation3.2.40)

2
  1  2 
[1.22]
nr    nr  N  Er  U   
QUESTION (2)
For an ideal gas, the partition function for a system of particles can be written in
terms of the partition function for a single non interacting particle as:

[ ] [2.1]

Taking the natural log of both sides of equation [2.1],

[ ] [2.2]

The first term on the right hand side can be evaluated by Stirling’s approximation:

[2.3]

By substitution,

[ ] [2.4]

[ ]

Multiplying both sides by gives;

( ) * ( ) + [2.5]

The Helmholtz free energy is given by

( ) [2.6]

Equation [2.5] then becomes

* ( ) + [2.7]

Taking the derivative of A(N,V,T) with respect to T,

, * ( ) +- [2.8]

Employing the product rule;

* ( ) + ( ) [2.9]

Q 
As N   in the first term on the right hand side, ln 1  will dominate. For the second
N
term on the right: [2.10]

Equation[2.9] then reduces to:

 * ( )+ [2.11]

The entropy [2.12]

[* ( )+ ] [2.13]

Clearly,

[* ( )+ ( ) ] [2.14]

QUESTION (3)

The partition function for an ideal gas system in a canonical ensemble of N

particles with 3N degrees of freedom can be expressed as:
1
N!h3 N 
QN (V , T )  exp( E (qi , pi )d [3.1]

1
is a correction factor for over counting, d  dqi dpi denote the volume
3N 3N
Where
N!
d 1
element in phase space which correspond to 3N
distinct states and   [3.2]
N !h kT
N
For an extreme relativistic gas, E  pc  E (qi , pi )  E ( pi )   pi c [3.3]
i 1

1
3N 
QN (V , T )  dqi dpi exp( pi c)
3N 3N
[3.4]
N !h
The qi integrations are constrained to be inside the box which just shrinks to the volume of
the box for N particles. Therefore:
3N
 dqi V N [3.5]

The momenta pi integration involves the integral of the products:

dp1e cp1  dp2e cp2  dp3e cp3 ... Up to the 3Nth power of each integral [3.6]

3N
dp1e  cp1  dp2e  cp2  dp3e  cp3 ...3Nth, power   dp 3 N e  cp
n 1 [3.7]
These simplify equation to the following:
VN N

  dp
3 N  cp
QN (V , T )  e [3.8]
N !h 3 N n 1

QN (V , T ) 
VN
N !h 3 N
 e  cp
dp 
3 N
[3.9]

3
dp
 4p 2  d p  4p 2 dp
3
But [3.9]
dp

QN (V , T ) 
VN
N !h 3 N

4  e  cp p 2 dp 
N
[3.10]

dy dy y2
Let y  cp   c  dp  and y 2  ( c)2 p 2  p2  [3.11]
dp c ( c) 2
Substituting equations [3.11] into equation [3.10],
N
VN   2 
 4 e  y  y 2  dy  
QN (V , T ) 
N !h 3 N    
 c  c  
[3.12]

N N
VN  1 y 2  VN  1 
3 
QN (V , T )   4 dye y 
   4 .2! [3.13]
N !h 3 N  c  N !h 3 N  ( c)
3
 
N
 
  N
VN  1  VN   kT 3  1   kT  
3

QN (V , T ) 
N !h 3 N  8 3 

N !h 3 N
8     8V   
  c   N!   hc  
[3.14]
  1  
 .c  
  kT  
N
1   kT  
3

QN (V , T )  8V    [3.15]
N !   hc  

The thermodynamics of the system now follows straightforwardly from equation [3.15].
The Helmholtz free energy can be written as:
1  3 N
  kT   
A( N ,V , T )  kT ln QN (V , T )  kT ln  8V     [3.16]
 N!   ch   


 1  3 N  3 N
  kT       kT   
A( N ,V , T )  kT ln  ln 8V      kT ln(1)  ln( N!)  ln 8V     [3.17]
 N!   ch       hc   
   

  3 N
  kT   
A( N ,V , T )  kT ln(1)  ln( N!)  ln 8V     [3.18]
   hc   
 
A better approximation of N! Following from Stirling’s formula is the following:
N ! N N e  N  ln N! ln( N N e N )  ln N N  ln e N  N ln N  N [3.19]

Substituting these into [3.18],

  3 N
  kT   
A( N ,V , T )  kT ln(1)  ( N ln N  N )  ln 8V     [3.20]
   ch   


  3 N
  kT   
A( N ,V , T )  kT 0  ( N ln N  N )  ln 8V     [3.21]
   ch   


   kT   
3

A( N ,V , T )  kT  N ln N  N  N ln 8V     [3.22]

   ch   

   kT  
3
   8V  kT 3  
A( N ,V , T )   NkT 1  ln 8V     ln N    NkT 1  ln     [3.23]
   ch      N  ch   

  8V  kT 
3
 
A( N ,V , T )   NkT 1  ln     [3.24]
  N  ch   

Now,

  8V  kT 3  
A  U  ST  U  A  ST   NkT 1  ln       ST [3.25]
  N  ch   

From equation [3.25],

 A 
P    N ,T [3.26]
 V 

 A A  8V  kT 
3
  A  A  8V  kT 
3
 
P    NkT  (1)  ln      ( ST ) = NkT 0  ln      0 [3.27]
 V V  N  ch    V  V  N  ch   


 A  8V  A  kT  
3
  A  8V  
P  NkT  ln  ln    NkT  ln   0 [3.28]
 V  N  V  ch  
   V  N  

 A  8V   A A A 
P  NkT  ln   NkT  ln(8 )  ln(V )  ln( N )  [3.29]
 V  N   V V V 

 1  1 NkT
P  NkT  0   0  P  NkT    P [3.30]
 V  V  V
PV  NkT (Ideal gas equation) [3.31]
From A  kT ln QN , it is clear that;

  8V  kT 
3
    8V  1 
3
 
ln QN  N 1  ln      N 1  ln    
  N  ch      N  ch   
[3.32]

 ln QN     8V    1  
3

But, U    N  (1)  ln  ln  

     N    ch  
N ,V

[3.33]

 ln QN    1        
U    N  3 ln    N  ln(1)  3 ln(  )  ln( ch )  
    ch      
N ,V
 
[3.34]

 1  3N 1
U   N  0  3    3NkT (Since   ) [3.35]
   kT

U
CV   3Nk
T
V
[3.36]
H  U  PV  3NkT  NkT  4 NkT [3.37]

U CP 4 Nk 4
CP  (4 NkT )  4 Nk   
T
P
CV 3Nk 3 [3.38]

For the entropy, recall equation [3.24],

  8V  kT 
3
 
A( N ,V , T )   NkT 1  ln    
  N  ch   
[3.24]
Also,
A  U  ST And U  3NkT A  3NkT  ST [3.39]
From equation [3.39],
A A
 3Nk  S  S  3Nk  [3.40]
T T
But from [3.24],

A 
  8V  kT  
2
    8V    kT 
  NK 1  ln       ( NkT )  ln   3 ln 
T 
  ch  ch     T  N  T  ch 
[3.41]
A 
  8V  kT  
2
     k 
  NK 1  ln       ( NkT ) 0  3 ln(T )  3  
T 
  ch  ch     T T  ch 
[3.42]

A 
  8V  kT  
2
  1
  NK 1  ln       NkT 3 
T 
  ch  ch     T
[3.43]

A 
  8V  kT  
2

  NK 1  ln       3Nk
T 
  ch  ch    [3.44]
Hence,


  8V  kT  
2

S  3Nk   NK 1        3Nk

  N  ch    [3.45]


  8V  kT 
2


S  Nk 1    ch    6 Nk

  N 
 [3.46]


  8V  kT 
2


S  Nk 1       6 

  N  ch  
 [3.47]

The chemical potential can also be obtained from the derivative of equation [3.24]

  8V  kT 
3
 
A( N ,V , T )   NkT 1  ln     [3.24]
  N  ch   

 A    8V  kT   A   8V  
3 3
 kT 
   V ,T  kT 1  ln      (  NkT ) 1  ln     [3.48]
 N    N  ch   N   N  ch   

 A    8V  kT  
3
 A  A 8V A  kT 3  
   V ,T  kT 1  ln      ( NkT ) (1)   ln  ln   
 N    N  ch    N  N N N  ch   
[49

 A  
  8V  kT 
3

   1
   V ,T  kT 1  ln   ch    ( NkT ) 
 N  
  N 
 N
[3.50]

 A  
  8V  kT 
3


   V ,T  kT 1  ln   ch    kT )
 N  
  N 
 [3.51]

 A  
  8V  kT 
3


   V ,T  kT 1  ln      1
 N  
  N  ch  
 [3.52
(b):
Given the inversion formula

∫ [3.53]

But

[ ( ) ] [3.54]

Therefore;

∫ [ ( ) ] [3.55]

( ) ∫ [3.56]

Using the standard integral

∫ [3.57]

Now,

∫ [3.58]

Therefore the density of state of the thermodynamic system is

( )
[3.59]
QUESTION (4)
The partition function for an ideal gas system in a canonical ensemble of 3N
particles with 3N degrees of freedom can be expressed as:
1
(3N )!h3 N 
Q3 N (V , T )  exp(  E (qi , pi )d [4.1]

1
is a correction factor for over counting, d  dqi dpi denote the volume
3N 3N
Where
(3N )!
d 1
element in phase space which correspond to 3N
distinct states and   [4.2]
(3N )!h kT
N
For an extreme relativistic gas, E  pc  E (qi , pi )  E ( pi )   pi c [4.3]
i 1

1
3N 
Q3 N (V , T )  dqi dpi exp( pi c)
3N 3N
[4.4]
3 N !h
The qi integrations are constrained to be inside the box which just shrinks to the volume of
the box for 3N particles. For N particles therefore:
3N
 dqi  L3 N [4.5]

The momenta pi integration involves the integral of the products:

dp1e cp1  dp2e cp2  dp3e cp3 ... Up to the 3Nth power of each integral [4.6]
N
dp1e  cp1  dp2e  cp2  dp3e  cp3 ...3Nth, power   dp 3 N e  cp
n 1

These simplify equation to the following:

VN N

  dp
3 N  cp
QN ( L, T )  e [4.7]
N !h 3 N n 1

QN (V , T ) 
VN
N !h 3 N
 e  cp
dp 
3 N
[4.8]

But dp3  p 2dpd  d p  4p 2 dp

3
[4.9]

QN ( L, T ) 
VN
N !h 3

4  e  cp p 2 dp 
N
[4.10]

dy dy y2
Let y  cp   c  dp  and y 2  ( c)2 p 2  p2  [4.11]
dp c ( c) 2
Substituting equations [4.11] into equation [4.10],
 N
VN  y  y2 dy  

   c 2 c  
QN (V , T )  ( 4 ) N
e    [4.12]
N !h 3 N   
3N 3N
L3 N  1  L3 N  1 
Q3 N ( L, T ) 
(3N )!h3 N

 c 
 dye y y 2 


(3N )!h3 N

 ( c)
.2!

[4.13]

3N
 
  3N
1  3 1  1   kT  
Q3 N ( L, T )   2L   2 L   [4.14]
(3N )!h3 N  1 
 (3N )!   ch  
  .c  
  kT  
3N
1   kT  
Q3 N ( L, T )   2 L  
(3N )!   ch  
[4.15]
The thermodynamics of the system now follows straightforwardly from equation [4.15]. The
Helmholtz free energy can be written as:
1  
3N

  kT  
A( N , L, T )  kT ln QN ( L, T )  kT ln  2 L    [4.16]
 N!   ch   

 1   kT  
3N
    kT  
3N

   
A( N , L, T )  kT ln  ln 2 L      kT ln(1)  ln( N!)  ln 2 L    [4.17]


N!   ch   
 
   hc   


   kT  
3N

 
A( N , L, T )  kT ln(1)  ln( N!)  ln 2 L    [4.18]

   hc   

A better approximation of N! Following from Stirling’s formula is the following:
N ! N N e  N  ln N! ln( N N e N )  ln N N  ln e N  N ln N  N [4.19]

Sub

   kT  
3N

 
A( N , L, T )  kT ln(1)  ( N ln N  N )  ln 2 L    [4.20]
   ch   

   kT  
3N

 
A( N , L, T )  kT 0  ( N ln N  N )  ln 2 L    [4.21]
   ch   

   kT   
3N

A( N , L, T )  kT  N ln N  N  N ln 2 L    [4.22]
   ch   
    kT  
3N
   2 L  kT  
3N

   
A( N , L, T )   NkT 1  ln 2 L    ln N    NkT 1  ln      [4.23]
   ch    
  N  ch   


  2 L  kT  
3N

 
A( N , L, T )   NkT 1  ln      [4.24]

  N  ch   

From equation [4.24],
 A 
P    N ,T [4.25]
 L 

 A A  2 L  kT   
3
 A  A A 2  kT   
3

P    NkT  (1)  ln       0 = NkT 0  ln  ln L  ln    

 L L  N  ch     L  L L N  ch   

1 NkT
P  NkT 
L L
PL  NkT