Statistical Mechanics Homework – I

Reading assignment
Chapters 1 & 2 of textbook.

Homework I‐1
Making use of the fact that the entropy S(N,V,E) of a thermodynamic system is an extensive
quantity, show that S  E ( S ) N ,V  N ( S ) E ,V  V ( S ) N , E
E N V

The result implies N  E  TS  PV

Homework I‐2
In a system of N identical free particle confined in space of volume V, please follow the
derivation to confirm the expression for entropy S , Eq. (21) of chapter.1 in textbook* by
evaluating the number of states
3
4mE
S  k B ln   Nk B ln[ (
V
h3 3N
) ]  3 Nk2 B
2

(1) Complete the deviation of heat capacity Cp and Cv , Eqs. (24) and (27) in textbook.
(2) Establish thermodynamically the formulae (see Homework I‐1)

S  V ( TP )  N  V ( P )T

Express the pressure P of an ideal classical gas in terms of the variables μ and T, and verify the
above formulae.
Homework I‐3
In a string of N monomers, in a sequence with each next monomer either pointing toward right
or left, the number of micro states with n+ monomers pointing toward right is
N!
(n ) 
n !( N  n )!
The entropy of one‐dimension polymer
1
N

S (n )  k B ln   k B ln[ N 2
1
N n  1
]
2 n n  2 ( N  n ) 2

The most probable approximation 1

N

S (n )  S (n * )  k B ln[ ]  k B N ln 2
N 2
1
N n*  1
2 n* n*  2 ( N  n* ) 2

where  ln  ( n )

|n  n*  0, that is , n *  N  n *, or n *  2  n (mean of binomial) N
n   

Since  (n ) 2  N4 (deviation of binomial distribution) the deviation becomes negligible

as N >> 1

If the bond length of nearest neighboring monomers is b, the end‐to‐end vector X of the
polymer is then X =2n+b‐Nb. The entropic tension Y can then be determined by consideration
the thermodynamic first law dE=TdS‐YdX+dN Y  T ( S ) N , E
X

Show that, when X << Nb , we can expand S in terms of X

Nb
to obtain Hook’s law
Y=kX
k T
with the spring constant k= B 2
Nb
Homework I‐4
Using the method of most probable approximation to consider the equilibrium state in an
isolated system of ideal‐gas mixture of atoms A, atoms B and molecules AB, with conserved total
energy. If the energy states of species A, B and AB are denoted by (EA)i, (EB)j and (EAB)l,
respectively, show that the most probable values for the number of particles, nA, nB and nAB, of
the three species, respectively, are
( E AB )l

( E A )i

( EB ) j

(nA ) i *  DAe kT
(nB ) j *  DB e kT (nAB ) l *  DAB e kT

with DAB=DADB. Using the result, derive the law of mass action
F F F
[ AB]  AB kTA B
 Ve  K (T )
[ A][ B]
for the concentrations (i.e. number densities) [A], [B] and [AB] of the species A, B and AB,
respectively, where FA, FB and FAB, are their one‐particle Helmholtz free energies and V is the
volume.
Euler’s theorem:
If f(x1,…,xn) is homogeneous of degree m, i.e. f(x1,…,xn)= mf(x1,…,xn)
then f(x1,…,xn) is homogeneous of degree m, i.e. f(x1,…,xn)= mf(x1,…,xn)

n
 ( m f ( x1 ,..., xn ))
 f ( x1 ,...,xn )
  f ( x(1,..., x n )  ( xi )
n
mf ( x1 ,..., xn )   f ( x1 ,..., xn )
xi
xi  
i 1
xi ) 
i 1
n
m m 1
f ( x1 ,..., xn )   f ( x(1,...,
xi )
xn )
xi
i 1

For Gibb’s free energy, as a degree-one (m=1) homogeneous function of particle numbers
G(T,P,N1,…,Nn)= G(T,P,N1,…,Nn)
n n
G (T , P, N1 ,..., N n )   G (T , P , N1 ,..., N n )
N i
N i   i N i
i 1 i 1
first law

dE  TdS  PdV  dN

dF  d ( E  TS )   SdT  PdV  dN
dH  d ( E  PV )  TdS  VdP  dN
dG  d ( E  TS  PV )   SdT  VdP  dN

Homogeneity for particle number

For Gibb’s free energy, as a degree-one homogeneous function of particle numbers

G  N  E  TS  PV fundamental equation of thermodynamics
dE  TdS  PdV  dN  TdS  PdV  Nd  d ( N )
We have  TdS  PdV  Nd  d ( E  TS  PV )
  Nd  dE  SdT  VdP
Nd   SdT  VdP

PV  G  E  TS  N  E  TS

d( PV )  d ( N )  d (TS )  dE  Nd  SdT  PdV

polymer in one‐dimension
In a string of N monomers, in a sequence with each next monomer either pointing toward right
or left, the number of micro states with n+ monomers pointing toward right is
N!
(n ) 
n !( N  n )!
and the probability of such a macro state is Stirling’s formula n! 2n ( ne ) n
N! 1
P (n )  ( )N
n !( N  n )! 2
The entropy of this one‐dimension polymer S  k B ln   k B ln[ n !(
N!
N  n )!
]

1
N 1
S (n )  k B ln   k B ln[ N 2 N
1
N n  1
]  k B ln[ N 2
]
n  2  2
2 n ( N  n ) 1
n  2 N n  1
2 n ( N  n ) 2

k B [( N  12 ) ln N  2( N2  12 ) ln N2 ]  k B [ N ln N  12 ln N  2( N2 ln N  12 ln N )  2( N2  12 ) ln 2]
The most probable approximation
 k B [ 12 ln N  N ln 2]
1
N

S (n )  S (n * )  k B ln[ ]  k B N ln 2
N 2
1
n*  2 N n*  1
2 n* ( N  n*  ) 2

where  ln  ( n )
|  0 , that is , n *  N  n * , or
n  n*
n *  2  n  (mean of binomial) N
n
Since  (n ) 2  N (deviation of binomial distribution) the deviation becomes negligible
4
as N >> 1

If the bond length of nearest neighboring monomers is b, the displacement X of the

polymer is then X = n+b‐(N‐n+b)=2n+b‐N. 1st law dE=TdS‐YdX+dN leads to Y  ( XS ) E , N
 Binomial distribution
N
N!
P (n , p) 
N!
p n (1  p ) N  n ( p  q)  N
 n !( N  n )! p n
q N  n
n !( N  n )! n  0  
N
n N !  N N! 
 n   n !( N  n )! p n
q N  n |
q 1 p p 
p n 0 n !( N  n )!
p n q N  n |
q 1 p p
p
( p  q ) N |q 1 p

 n  pN
n  0  

  N 
N 2
n N ! N!
 n   n N  n
|   p n q N  n |q 1 p  p pN ( p  q ) N 1 |q 1 p
2
p q q 1 p p p
n  0 n !( N  n )! p p n 0 n !( N  n )! p

 n  p (1  p ) N  p 2 N 2 pN ( p  q ) N 1 |q 1 p  [ pN ( p  q ) N 1  p 2 N ( N  1)( p  q) N  2 ] |q 1 p
2 p
p
 p(1  p ) N  p 2 N 2

 (n ) 2  p (1  p ) N
N! N  n N ( Ne ) N
P(n , p )  p (1  p )
n
 p n (1  p ) N  n
N >> n+, N-n+ >> 1 n !( N  n )! 2 n ( e )
n n N  n N  n
N  n ( e )
n
n

N (N )N
 p n (1  p ) N  n
n N  n 2 (n ) ( N  n )
n N  n

1
N2
(N )
 1
n  2 N  n  2
1 p n (1  p ) N  n
2 (n ) ( N  n )

1 Np n  12 N (1  p ) N  n  12
 ( ) ( )
N  n
1

(2Np (1  p )) 2 n

Stirling’s formula n! 2n ( ne ) n

Binomial distribution(cont’d)
 m   n  np  m   n  n (1  p )  m  n  ( m   m  )  n
 m 2
 n  n 2 ( 2 p  1 ) 2  4 n (1  p ) p  m 2  n  ( m   m  ) 2  n
 m   n  n 2 p 2  n (1  p ) p
2
 m   n  n 2 (1  p ) 2  n (1  p ) p
2

 m  m   n  n ( n  1 ) p (1  p )
deviation s of displacements
1
4
 (  m ) 2  n  (  m  ) 2  n  (  m  ) 2  n  n ( 1  p ) p

1
(1 p ) p 
 (m )  n /  m  n 
2 2
( 2 p 1 )
n 2

1
1 p 
 (m  )  n /  m   n 
2
p
n 2

1

 (m )  n /  m   n 
2 p
1 p
n 2