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Statistical Mechanics - Homework Assignment 3

Alejandro Gomez Espinosa

March 4, 2013
Pathria 3.41 A system of N spins at a negative temperature (E > 0) is brought into contact with an
ideal-gas thermometer consisting of N molecules. What will the nature of their state of mutual
equilibrium be? Will their commom temperature be negative or positive, and in what manner will it
be aected by the ratio N

/N?
If the system of N spins has negative temperature its energy must be bounded. Then, if it is brought
into contact with a sistem of N molecules, the equilibrium will be reach when both temperatures are
the same. But since the thermometer does not have bounded energy, the temperature in equilibrium
should be greater than zero.
Then, by conservation of energy we can write:
N tanh
_

kT
_
+
3
2
N

kT

= E
T
(1)
where we can see that the ratio N

/N will not be aected by this result.

Pathria 4.8 Determine the grand partition function of a gaseous system of magnetic atoms (with J =
1
2
and g = 2) that can have, in addition to the kinetic energy, a magnetic potential energy equal to

B
H or
B
H, depending on their orientation with respect to an applied magnetic eld H. Derive
an expression for the magnetization of the system, and calculate how much heat will be given o
by the system when the magnetic eld is reduced from H to zero ar constant volume and constant
temperature.
In this case, the Hamiltonian of the system is given by:
H
i
=
p
2
i
2m
i

B
H (2)
Then, using the partition function for one particle and taking only the positive magnetic potential
energy:
Q
+
1
=
_
e
E
d
3
p d
3
q
h
3
=
_
e

p
2
2m
+
B
H

d
3
p d
3
q
h
3
=
e

B
H
h
3
_
e

p
2
2m
d
3
p d
3
q
=
V e

B
H
h
3
_

p
2
2m
d
3
p
=
V e

B
H
h
3
__
2m

_
3
=
_
2m
h
2
_
3/2
V e

B
H

gomez@physics.rutgers.edu
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The total partition function for one particle must be:
Q
1
= Q
+
1
+Q

1
=
_
2m
h
2
_
3/2
V e

B
H
+
_
2m
h
2
_
3/2
V e

B
H
=
_
2m
h
2
_
3/2
V
_
e

B
H
+e

B
H
_
=
_
2m
h
2
_
3/2
2V cosh(
B
H)
Therefore, the partition function for the system of N particles:
Q
N
=
Q
N
1
N!
=
1
N!
_
2m
h
2
_
3N/2
(2V )
N
cosh
N
(
B
H)
Thus, the grand partition function, given by (4.3.15) is:
Q =

N=0
z
N
Q
N
=

N=0
z
N
N!
_
_
2m
h
2
_
3/2
2V cosh(
B
H)
_
N
=

N=0
1
N!
_
2V z
_
2m
h
2
_
3/2
cosh(
B
H)
_
N
= exp
_
2V z
_
2m
h
2
_
3/2
cosh(
B
H)
_
For the magnetization:
M =
_
F
H
_
T
=

H
kT ln Q
N
= kT

H
_
_
ln
1
N!
_
_
2m
h
2
_
3/2
2V cosh(
B
H)
_
N
_
_
= NkT

H
_
ln
_
_
2m
h
2
_
3/2
2V cosh(
B
H)
_

1
N
ln N!
_
= NkT

H
_
ln
_
2V
2m
h
2
_
3/2
+ ln cosh(
B
H)
_
= NkT

H
(ln cosh(
B
H))
= NkT
B
sinh(
B
H)
cosh(
B
H)
= N
B
tanh(
B
H)
2
Finally, the heat in the system at constant volume and temperature is given by Q = TS. Therefore,
let us begin by calculating the entropy of the system:
S =
_
F
T
_
V,N
= k

T
_
_
T ln
1
N!
_
_
2m
h
2
_
3/2
2V cosh(
B
H)
_
N
_
_
= k

T
_
_
T ln
1
N!
_
_
2mkT
h
2
_
3/2
2V cosh
_

B
H
kT
_
_
N
_
_
= k

T
_
TN ln
_
_
2mkT
h
2
_
3/2
2V cosh
_

B
H
kT
_
_
T ln N!
_
= k

T
_
3
2
TN ln
_
2mkT
h
2
_
+T ln cosh
_

B
H
kT
_
T ln
2V
N!
_
= k
_
_
3
2
N ln
_
2mkT
h
2
_
+
3N
2
+ ln cosh
_

B
H
kT
_
+

B
H sinh
_

B
H
kT
_
kT cosh
_

B
H
kT
_ ln
2V
N!
_
_
=
3
2
Nk ln
_
2mkT
h
2
_
+
3
2
Nk +k ln
N!
2V
cosh
_

B
H
kT
_
+

B
H
T
tanh
_

B
H
kT
_
(3)
Then, for the nal state, H = 0:
S
f
=
3
2
Nk ln
_
2mkT
h
2
_
+
3Nk
2
(4)
The dierence in entropy (S) is given by the subtraction of (3) and (4), and nally the heat
relation is nd as:
Q = T(S
f
S
i
)
= T
_
k ln
N!
2V
cosh
_

B
H
kT
_
+

B
H
T
tanh
_

B
H
kT
__
= ln
N!
2V
cosh (
B
H)
B
H tanh (
B
H)
Pathria 4.10 A surface with N
0
0
) gas molecules adsorbed on it. Show
that the chemical potential of the adsorbed molecules is given by
= kT ln
N
(N
0
N)a(T)
(5)
where a(T) is the partition function of a single adsorbed molecule. Solve the problem by constructing
the grand partition function as well as the partition function of the system. (Neglect the intermolec-
ular interaction among the adsorbed molecules.)
Since a(T) is the partition function of a single molecule, then the total partition function must be:
Q
N
=
Q
N
1
N!
=
a
N
(T)
N!
(6)
3
and the grand partition function:
Q =
N

N=0
z
N
a
N
(T)
N!
(7)
To calculate the chemical potential,
=
F
N
(8)
let us compute rst the free energy:
F = kT ln
a
N
(T)
N!
= kT
_
ln a
N
(T) ln N!
_
= kT (N ln a(T) ln N!)
Plugging this result into (8):
=

N
(kT (N ln a(T) ln N!))
= kT
_
ln a(T) ln
N!
N
0
N
_
= kT
_
ln a(T) + ln
N!
N
0
N
_
= kT ln
N
(N
0
N)a(T)
Pathria 5.6 Determine the values of the degeneracy discriminant (n
3
) for hydrogen, helium, and oxygen
at NTP. Make an estimate of the respective temperature ranges where the magnitude of this quantity
becomes comparable to unity and hence quantum eects become important.
The thermal wavelenght is:
n
3
=
nh
3
(2mkT)
3/2
=
N
V
h
3
(2mkT)
3/2
=
P
kT
h
3
(2mkT)
3/2
=
h
3
P
(2m)
3/2
(kT)
5/2
(9)
Then,
For H: n
3
=
(6.63 10
34
Js)
3
(101325Pa)
(2(1.67 10
27
kg))
3/2
)(1.38 10
23
m
2
kgs
2
K
1
)293K)
5/2
= 2.64 10
5
For He: n
3
=
(6.63 10
34
Js)
3
(101325Pa)
(2(6.64 10
27
kg))
3/2
)(1.38 10
23
m
2
kgs
2
K
1
)293K)
5/2
= 3.33 10
6
For O: n
3
=
(6.63 10
34
Js)
3
(101325Pa)
(2(2.56 10
26
kg))
3/2
)(1.38 10
23
m
2
kgs
2
K
1
)293K)
5/2
= 4.40 10
7
In this cases, the temperature must be in the range of approximate 10
3
K to this quantity becomes
comparable to unity. Since this quantity is very small compare to the physical world, this eects
will become important when some particles reaches a temperature close to this value.
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