PHYS4006: Thermal and Statistical Physics Lecture Notes

Part-1 (Unit - IV)

Method of Ensembles: Partition Functions

Dr. Neelabh Srivastava

(Assistant Professor)
Department of Physics
Programme: M.Sc. Physics Mahatma Gandhi Central University
Semester: 2nd Motihari-845401, Bihar
E-mail: [email protected]
In earlier lectures, we have discussed the concept of
Ensembles viz. Microcanonical, Canonical and Grand-
canonical.

Herein, we will use that concept in deriving the

thermodynamical functions of a thermodynamic system.

Before we proceed, let us recall the concept of partition

function .

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 The Maxwell-Boltzmann distribution function is given by,

ni  gi e e  i (i  1, 2, 3,..... k )

This equation gives the number of gas molecules in the ith cell and
known as Maxwell-Boltzmann law of energy distribution.

simply,  
N   ni   gi e  e   i  e   gi e   i  A. Z
i i i

where, A  e  and Z   gi e   i
i
This Boltzmann distribution applies
to systems which have
distinguishable particles and N, V
ni N   i
Occupation index, fi   e and U are fixed. The Maxwell-
gi Z Boltzmann Distribution is
applicable only to dilute gases.
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 N Ng i e   i
A   ni 
Z  i
g e   i

g i e   i
Pr obability , P i   
ni
N  g i e   i
i

Z   gi e   i

i
   / kT
The quantity Z represents the sum of the Boltzmann factor Z e i e i
over all the accessible states and is called the partition function (derived from German term
Zustandssummae). The quantity Z indicates how the gas molecules of an assembly are
distributed or partitioned among the various energy levels.
The energy term in the expression for partition function does not
mean only the translational component but also may contain the
components corresponding to other degrees of freedom too e.g.
rotational, vibrational and electronic too. 4
• This partition function can be used for calculating the
various thermodynamical properties of ensembles having
independent systems (obeying classical laws) irrespective
of whether the ensembles have distinguishable or
indistinguishable independent systems.

• Consider an assembly of classical gas where the

distribution of energy states is considered to be
continuous. So, the number of energy levels in the
momentum range p and (p+dp) is given by -

4Vp 2
g ( p)dp  3
dp
h
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Number of energy levels between energy range ε and
(ε+dε) is given by –

g ( )d 
2V 2m 3/ 2
 1/ 2
d
3
h
Since, the distribution of energy states is continuous,
therefore

Z   gi e  i kT
  g ( ) d e  kT

i 0

2V 2m 3/ 2



 kT
Z 3
1/ 2
e d
h 0

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After solving, we get

Z
2V 2m 3/ 2

kT 
3/ 2
3
h 2
V
Z 3
h
2mkT  3/ 2

This gives the translational partition function for a

gas molecule.

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 Partition Function and its relation
Thermodynamic Quantities
1. with Entropy (S):
Consider an assembly of ideal gas molecules obeying
M-B distribution law and according to Boltzmann’s
entropy relation –
S  k ln W  k ln  .........(i)
The maximum thermodynamic probability is given by -

g ini
W  N! .........(ii )
i ni !
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Taking logarithms and apply Stirling’s approximation,
we get
ln W  N ln N   ni ln gi  ni ln ni  ........(iii )
i

According to M-B distribution law

ni  gi e e  i  gi Ae   i
Now, from eqn. (iii)
ln W  N ln N   ni ln gi   ni ln gi   ni ln A   ni  i
i i i i
Putting,
n
i
i N and n 
i
i i E

N
ln W  N ln N  N ln A  E  N ln  E
A
ln W  N ln Z  E
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  S  k ln W  k N ln Z  E   Nk ln Z 
kE
kT
E
S  Nk ln Z  ............(iv )
T
3
but for an ideal gas, E  NkT ............(v)
2

from (iv) and (v),

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S  Nk ln Z  Nk ............(vi)
2

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2. with Helmholtz Free Energy (F):
 E
 F  E  TS  E  T  Nk ln Z  
 T
F   NkT ln Z ............(vii)

3. with Total Energy (E):

Average energy of a system of N particles is given by,

E  ni i  i i
g A e   i

E  i
 i
N  nii
 i i
g A
i
e   i

 ii
g  e   i

E i
..........(viii ) 11
Z
Since, partition function
Z   g i e   i   g i e  i / kT
i i
For isothermal-isochoric transformation,

 Z   1 g  e 
  kT   i / kT

 T 
2 i i
i
V

 Z  kT 2  Z 
kT 2
 
 g  e   i / kT
 ZE  E   
 T  T
i i

V
i Z
  V
Total energy,
NkT 2  Z   
Z  T   T log Z 
E  NE  E  NkT 2
.........(ix )
 
V V
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4. with Enthalpy (H):
Enthalpy is given by,
H = E+PV = E+RT (for an ideal gas, PV=RT)

  
H  NkT 2

 T log Z 
 RT .........( x)
V

5. with Gibb’s Potential (G):

 
 G  H  TS  NkT 2

 T log Z 
 RT  TS
V

putting the value of S from eqn. (iv) in above, we get

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   
G  NkT 2

 T log Z 


E
 RT  T  Nk ln Z  
T
V

  
G  NkT 2
 T log Z  
 RT  NkT ln Z  E
V

putting the value of E from eqn. (ix), we get

    
 T log Z   T log Z 
G  NkT 2
 RT  NkT ln Z  NkT 2

V V

G  RT  NkT ln Z ..........( xi )

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6. with Pressure (P) of the gas:

 F    
 V log Z 
 P     NkT ..........( xii )
 V V V

7. with Specific heat at constant volume, (CV):

 E       
 C   T 
 NkT

2
log Z 


 T   T
V

V    V

  2 
2 
CV  Nk 2T (log Z ) T (log Z ) ..........( xiii )
 T T 2
 V

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 References: Further Readings

1. Statistical Mechanics by R.K. Pathria

2. Statistical Mechanics by K. Huang

3. Statistical Mechanics by B.K. Agrawal and M. Eisner

4. Statistical Mechanics by Satya Prakash

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For any questions/doubts/suggestions and submission of
assignment
write at E-mail: [email protected]
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