Thermodynamics and Statistical

Mechanics

Partition Function

Thermo & Stat Mech - Sprin 1

Free Expansion of a Gas

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 Free Expansion

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Isothermal Expansion

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 Isothermal Expansion
Reversible route between same states.
f đQ = đW + dU
dQ
S   Since T is constant, dU = 0.
i
T Then, đQ = đW.
nRT
dW  PdV  dV
V
dQ dW nRT dV dV
dS     nR
T T T V V
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 Entropy Change
2V
dV  2V 
S  nR   nR ln   nR ln 2
V
V V 
The entropy of the gas increased.
For the isothermal expansion, the entropy of the
Reservoir decreased by the same amount.
So for the system plus reservoir, S = 0

For the free expansion, there was no reservoir.

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 Statistical Approach

 wf 
S  S f  Si  k ln w f  k ln wi  k ln 
 wi 
N!
wi  1
N !0!
N! N!
wf  
( N / 2)!( N / 2)!  ( N / 2)! 2

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 Statistical Approach
 wf   N! 
S  k ln   k ln 
w   ( N / 2)! 
2
 i   
S  k[ln N !2 ln( N / 2)!]
S  k[ N ln N  N  2{( N / 2) ln( N / 2)  N / 2}]
 N 
S  k[ N ln N  N ln( N / 2)]  Nk ln 
 N/ 2 
S  Nk ln 2  nR ln 2
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 Partition Function
  j
g je
Nj  N n


  j
g je
j 1
n


  j
g je Z Partition Function
j 1
  j
g je
Nj  N
Z

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Boltzmann Distribution
  j
g je
Nj  N n

 g je
  j

j 1
n

  j g je
  j
n

 j N j  U  N j 1
n

 g je
j 1   j

j 1

Z

U   ln Z
 
N Z 
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 Maxwell-Boltzmann Distribution

Correct classical limit of quantum

statistics is Maxwell-Boltzmann
distribution, not Boltzmann.

What is the difference?

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 Maxwell-Boltzmann Probability

n ( N j  g j  1)! n g j!
wBE   wFD  
j 1 N j !( g j  1)! j 1 N j !( g j  N j )!
Nj Nj
n g n g
wB  N ! wMB  
j j

j 1 N j! j 1 N j!

wB and wMB yield the same distribution.

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Relation to Thermodynamics
U   N j j
j

dU    j dN j   N j d j
j j

d j
 j   j ( X ), so d j  dX
dX
 d j 
dU    j dN j    N j  dX
j j  dX 
 d j 
Call   N j   Y
j  dX 
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 Relation to Thermodynamics

 d j   d j 
dU    j dN j    N j  dX and j  N j dX   Y
j j  dX   
dU    j dN j  YdX This is like
j

dU  TdS  YdX (or dU  TdS  PdV )

If dX  0
(dU ) X    j dN j  TdS and j N j d j  YdX
j

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 Chemical Potential

dU = TdS – PdV + dN

In this equation,  is the chemical energy

per molecule, and dN is the change in the
number of molecules.

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 Chemical Potential

dU  TdS  PdV  dN

F  U  TS
dF  TdS  PdV  dN  TdS  SdT
dF   SdT  PdV  dN
 F 
  
 N T ,V
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 Entropy
Nj
n gj
S  k ln wMB where wMB  
j 1 N j!
 
S  k  N j ln g j   ln N j !
 j j 
 
S  k  N j ln g j   N j ln N j   N j 
 j j j 
  Nj 
S  k  N   N j ln 
 g 
j  j 
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 Entropy
  Nj 
S  k  N   N j ln 
 g 
j  j 
j
Nj N 
 e kT
gj Z
 j 
S  k  N   N j ln N   N j ln Z   N j 
 j j j kT 
U
S   Nk (ln Z  ln N  1)
T
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 Helmholtz Function

U
S   Nk (ln Z  ln N  1)
T
U
F  U  TS  U  T  NkT (ln Z  ln N  1)
T
F   NkT (ln Z  ln N  1)

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 Chemical Potential
F   NkT (ln Z  ln N  1)
 F 
  
 N T ,V
 1
  kT (ln Z  ln N  1)  NkT   
 N
N
  kT (ln N  ln Z )  kT ln 
Z
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 Chemical Potential

N  N
  kT ln  so  ln 
Z kT Z

N
Then e kT

Z

So,  
kT

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Boltzmann Distribution
  j
N j  e  g j e
n n

N g e
   j
j N e j
j 1 j 1

 N
e  n

g e
  j
j
j 1
  j
g je
Nj  N n

 g je
  j

j 1

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 Distributions

Nj 1
    j
 fj Boltzmann
gj e
Nj 1
    j
 fj Bose - Einstein
gj e 1
Nj 1
    j
 fj Fermi - Dirac
gj e 1
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 Distributions
Nj 1
  j 
 fj Boltzmann
gj
e kT

Nj 1
  j 
 fj Bose - Einstein
gj
e kT
1
Nj 1
  j 
 fj Fermi - Dirac
gj
e kT
1
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 Ideal Gas

3/ 2
 2 mkT 
Z  V  2

 h 
F   NkT (ln Z  ln N  1)
 3  2 mkT  
F   NkT ln V  ln 2
  ln N  1
 2  h  

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 Ideal Gas

 3  2 mkT  
F   NkT ln V  ln 2
  ln N  1
 2  h  
 F  1
P     NkT
 V T , N V
PV  NkT  nRT

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 Ideal Gas
3/ 2 3/ 2
 2 mkT   2 m 
Z  V    V  2 
h  
2
 h 
3/ 2
 2 m  3
ln Z  ln V  2   ln 
 h  2
U  ln Z 3 1 3
   kT
N  2 2
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 Entropy
U
S   Nk (ln Z  ln N  1)
T
3/ 2
 2 mkT 
ln Z  ln V  2

 h 
3NkT  V  2 mkT 
3/ 2

S  Nk  ln    1
2T  N  h 2  
 
5 V  2 mkT 
3/ 2

S  Nk   ln   
2 N  h 2  
 
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 Math Tricks

For a system with levels that have a constant

spacing (e.g. harmonic oscillator) the partition
function can be evaluated easily. In that case,
n = n, so,
 
  
Z  e   n
 e   n
 e   n

n 0 n 0 n0

1 1
x  n
  
for e βε
 1.
n 0 1  x 1  e
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 Heat Capacity of Solids

Each atom has 6 degrees of freedom, so based

on equipartition, each atom should have an
average energy of 3kT. The energy per mole
would be 3RT. The heat capacity at constant
volume would be the derivative of this with
respect to T, or 3R. That works at high enough
temperatures, but approaches zero at low
temperature.

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 Heat Capacity

Einstein found a solution by treating the solid

as a collection of harmonic oscillators all of the
same frequency. The number of oscillators was
equal to three times the number of atoms, and
the frequency was chosen to fit experimental
data for each solid. Your class assignment is to
treat the problem as Einstein did.

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 Heat Capacity
Heat Capacity

30
25
20
Cv (J/K)

15
10
5
0
-5 0 100 200 300 400

T (K)

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