Cornell University, Physics Department

PHYS-3341 Statistical Physics

Fall 2014
Prof. Itai Cohen

Solutions to Problem Set 8

David C. Tsang, Woosong Choi

8.1

Chemical Equilibrium
Reif 8.12: At a fixed temperature T = 1200K the gases
CO2 + H2
CO + H2 O
are in chemical equilibrium in a vessel of volume V . If the volume of this vessel is increased, its temperature being maintained constant, does the relative
concentration of CO2 increase, decrease, or remain the same?

At constant V, T in equilibrium, F is minimized. This imples that

X
0
*0
*
dF = 0 = S
dT
p
dV
+
i dNi = CO2 dNCO2 + H2 + dNH2 + CO dNCO + H2 O dNH2 0
i

From the chemical equation we know that dNCO2 = dNH2 = dNCO = dNH2 O and thus
CO2 + H2 CO H2 O = 0
But we also know (from Reif 8.10.24) that
= kT ln

0 (T )V
N

where 0 is the single species partition function with the volume dependance removed. Hence
we have
0
0
0
0
CO
(T )V
H
(T )V
H
(T )V
CO
(T )V
2
2
ln
+ ln
ln
ln 2 O
NCO2
NH2
NCO
NH2 O
NCO2

0
0
CO
(T )H
(T )NCO NH2 O
2
2
=
.
0
0
CO
(T )H
(T )NH2
2O

(1)

This is independant of volume. Thus the number of the different species do not change, and
the relative concentrations remain the same.
2

8.2

Partial Pressure
Reif 8.14: Consider the following chemical reaction between ideal gases:
m
X

bi Bi = 0

i=1

Let the temperature be T , the total pressure be p. Denote the partial pressure
of the ith species by pi . Show that the law of mass action can be put into the
form
(2)
pb11 pb22 pbmm = Kp (T )
where the constant Kp (T ) depends only on T .
The law of mass action can be written
bm
bm
N1b1 N2b2 Nm
= KN (T, V ) = 1b1 2b2 m

Weve already seen that we can rewrite i (T, V ) = V i0 (T ), thus we have



N1
V1

The ideal gas law gives us

b1 

N1
V1

N2
V2

b2

p
kT

hence

Nm
Vm

bm

= 0 11 0 22 0 mm

pb11 pb22 pbmm = Kp (T )

where Kp (T ) =

Qm

0
bi
i=1 (kT i (T )) .

8.3

Paramagnet

(a) This problem is similar to a random walk but instead of steps to the right and left we
have spins that are up and down. Let s =# of particles with si = 12 .
Then


N
s+

(s+ ) =

NN
N!
s+ s
=
s+ !s !
s+ s

N
2s+ s

using Stirlings approximations.

Since s+ + s = N and E = B H(s s+ ) we have s = N2 a where a 2EB H . If

we drop the square root term of th term of the stirling approximation we get
(E) = N

N
+a
2

( N2 +a) 

N
a
2

( N2 a)

for integer values of N/2 + a. Defining E to coarse grain such that B H  E 

N B H this gives us
(E) = N

N
+a
2

( N2 +a) 

N
a
2

( N2 a)

E
2B H

(b)
 
 
 

N
N
N
N
+ a ln
+a
a ln
a
N ln N
2
2
2
2





ln
a
N
N
=
1 + ln
+ a 1 ln
a
E
E
2
2


N B H E
1
ln
2B H
N B H + E
 
1
2B H
N B H E
ln
k
N B H + E


ln =
=
=
T =
(c) Let b

B H
,
kT

we then have

e2b =

N B H E
N B H + E

E=

N B H(1 e2b )
= N B H tanh b
1 + e2b

We also have
S = k ln



 

N
N
N
N
k N ln N
tanh b ln
tanh b
2
2
2
2

 

N
N
N
N

+ tanh b ln
+ tanh b
2
2
2
2
3

Which reduces to

S = k N ln N
since 1 tanh b =

2eb
eb +eb

N eb
ln
eb + eb

N eb
eb + eb



N eb
b
ln
e + eb

N eb
eb + eb

2eb
.
eb +eb

and 1 + tanh b =



 b
 b
eb
eb
e + eb
e + eb
S = kN b
ln
ln
e + eb
eb
eb + eb
eb


eb ln eb + eb ln eb
b
b
= kN ln(e + e )
eb eb


beb beb
= kN ln(2 cosh b) b
e + eb


 


B H
B H
B H
S = kN ln 2 cosh

tanh
kT
kT
kT
This gives us a Helmholtz free energy
 


B H
B H
B H
B H
F = E T S = N B H tanh
N kT ln 2 cosh
tanh

kT
kT
kT
kT


B H
F = N kT ln 2 cosh
kT

(d) The canonical partition function is given by

Z=

N
Y

B H

+e

B H

i=1


N
B H
= 2 cosh
kT

(e) From the partition function we can calculate

B H
ln Z
= N B H tanh
,

kT


B H
S = k(ln Z + E) = N k ln(2 cosh B H) B H tanh
,
kT


B H
F = kT ln Z = N kT ln 2 cosh
,
kT
E=

as above.

8.4

Quantum Harmonic Oscillator

(a) We have
1

Zn (T ) = eEn = e kT ( 2 +n)
~

(b)
(, T ) =

Zn en = e 2kT

e kT (~)

n
~/2kT

e
e/2kT
=
1 e(~)/kT
2 sinh[(~ )/2kT ]

(c) For the energy we have





ln

E =
ln 2 ln(sinh((~ )/2))
=

,V

2
~
=
coth[(~ )/2kT ]
2
For the entropy we have
i

h
[kT ln ] =
kT ln(2 sinh[(~ )/2kT ]
T 
 T 2


~
~
~
= k ln 2 sinh
coth

2kT
2kT
2kT

S =

(d) Using the normal canonical parition function given in the problem we see,
ln Z

~
E =
=
ln[sinh(~/2)] =
coth(~/2)

2
and
S = k ln Z E = k ln(2 sinh(~/2))

~
coth(~/2kT )
2kT

Thus we see we must have = 0 for the oscillation quanta.

2

8.5

Equilibrium Fluctuations

(a) The grand canonical parition function is

 
X

(Er N )

= N
=
e

V,T
r

= kT
N

ln


V,T

We also have


2
2

= 2

X
(N 2 + 1)e(Er N ) = 2 (1 + N 2

V,T

Noting that
 2



 2


2
ln
1 2
1
1 2
N
=

2 V,T
2 V,T 2 V,T
2 V,T (kT )2
Solving for N 2 we see



 
 2
(kT )2 2
ln
2
2
2
= kT N
2
N =
1 (kT )
+N
+N
2
2

V,T

V,T
V,T
which gives us
 
N
var N = kT
V,T
(b) The isothermal compressibility can be expressed as
T =

1 V
1 v
=
V P
v P

where v = V /N is the volume per particle.

From the maxwell relation for F , we have




P

=
N T,V
V T,N


 
v P
1

=
N v T
N v T
since dN = Nv dv.
This gives us



=

P
v
6

 
T

1
=
T

1
v

Taking another derivative with respect to we see







 2 
1
1
V
1
N
1 V v
1 v
P
=
=
=
= 2
= 3
2
2
T,N
v
Nv
T,N
V v P T,V
V v v P T
v P


2P
2


=
T,N

1
T
v2

Noting that P V = kT ln and using the second last equation in part (a) we see

var N = kT V

2P
2

2 T
kT V T
kT N
=
v2
V


=
T,N

8.6

Grand Canonical Ensemble

(a) The grand canonical ensemble for an ideal gas where V , T , and N can vary is given as
=

eN ZN

N =0

where

3N/2

1 N 2m
V
Zn =
N!
h2

is the canonical partition function.

This gives

X
1
=
N!
N =0

V e

2m
h2

3/2 !

Recognizing this as a Taylor series for an exponential we see

"
= exp V e

2m
h2

3/2 #
(3)

(b) We have
pV

= kT ln = kT V e
/kT

p = kT e

2m
h2

3/2

2m
h2

3/2

Solving for the chemical potential , we see

"

p
= kT ln
kT

h2
2m

3/2 #
.
2