P115A Homework 6

Peter D. Alison
May 21, 2009

1 Problem 7.1
Consider a homogeneous mixture of inert monoatomic ideal gas at absolute
temperature T in a container of volume V . Let there be ν1 moles of gas 1,
ν2 moles of gas 2, . . . , and νk moles of gas k.

(a) By considering the classical partition function of this system, derive its
euqation of state, i.e., find an expression for its total mean pressure p̄.
According to Equation (7.1.6) the the partition function of a group of weakly
interacting distinguishable particles is the product of the component parti-
tion functions.
ln Z = ln Z1 + ln Z2 + · · · + ln Zk
Also the natural logarithm of the partition function of an ideal gas is
3 3 2πmi
ln Zi = Ni (ln V − ln β + ln 2 )
2 2 h0
Therefore,
k
X
ln Z = NA νi [ln V + · · ·]
i=1

The mean pressure is given by the expression

1 ∂ ln Z 1N
p̄ = =
β ∂V βV
k
1 NA X
p̄ = νi
β V i=1

1
Substituting β = 1/kB T and NA kB = R we obtain
k
X k
X
p̄V = kB T NA νi ⇒ p̄V = RT νi
i=1 i=1

(b) How is this total pressure p̄ of the gas related to the pressure p̄i which
the ith gas would produce if it alone occupied the entire volume at this tem-
perature.
The partition function of one of the component gases is
3 3 2πmi
ln Zi = NA νi (ln V − ln β + ln 2 )
2 2 h0
So the mean pressure of one the component gases is then
1 ∂ ln Zi 1 NA νi
p̄i = =
β ∂V β V
This implies that the total mean pressure in terms of the component mean
pressure is given by
k
X
p̄ = p̄i
i=1

2 Problem 7.2
An ideal monoatomic gas of N particles, each of mass m, is in thermal equi-
librium at absolute temperature T . The gas is contained in a cubical box
of side L, whose top and bottom sides are parallel to the earth’s surface.
The effect of earth’s uniform gravitational field on the particles should be
considered, the acceleration due to gravity being g

(a) What is the average kinetic energy of a particle?

Since the gas here is an ideal gas the average kinetic of a particle is simply
3
K̄i = kB T
2
so the overall average kinetic energy is
3
K̄ = N kB T
2
2
(b) What is the average potential energy of a particle?
To start we find the partition of the system. The energy E is defined as
K + U , where we’ll keep K as is and U = mgh.The partition function is then
Z L
e−βE = e−β(K+mgh) dh = ζ
X
0

because h is a continuous parameter.

e−βK
ζ= (1 − e−βmgL )
βmg

e−βK
Z = ζN = [ (1 − e−βmgL )]N
βmg
ln Z = N (−βK − ln βmg ln(1 − e−βmgL ))
The mean energy is given by the appropriate derivative of ln Z.
∂
Ē = − ln Z
∂β
1 mgL
Ē = K + +
β 1 − e−βmgL
Subtracting the kinetic energy K yields the average potential energy
− kmgL −1
Ū = kB T + mgL(1 − e )
BT

3 Problem 7.5
A rubber band at absolute temperature T is fastened at one end to a peg, and
supports from its other end a weight W . Assume as a simple microscopic
model of the rubber band that it consists of a linked polymer chain of N
segments joined end to end; each segment has length a and can be oriented
either parallel or parallel to the vertical direction. Find an expression for
the resultant mean length ¯l of the rubber band as a function of W . (Neglect
the kinetic energies or weights of the segments themselves, or any interaction
between the segments.)

3
The partition function of one segment ζ is

ζ = e−βU + eβU

The potential energy of one segment is given by

U = Wa

So
ζ = e−βW a + eβW a
Z = ζ N = (e−βW a + eβW a )N
We now a derivative of ln Z such that the dimensions of length come out of
the partition function.

¯l = ∂ ln Z = N a e
βW a
− e−βW a
∂(βW ) eβW a + e−βW a

¯l = N a tanh( W a )
kB T

4 Problem 7.7
Monoatomic molecules adsorbed on a surface are free to move on this surface
and can be treated as a classical ideal two-dimensional gas. At absolute tem-
perature T , what is the heat capacity per mole of molecules thus adsorbed
on a surface of fixed size?

The average kinetic energy is by

n
K̄ = RT
2
where n is the number of degrees of freedom.So

K̄ = RT

So the heat capacity per mole is simply R. QED

4
5 Problem 7.14
Consider an assembly of N0 weakly interacting magnetic atoms per unit vol-
ume at a temperature T and describe the situation classically. Then each
magnetic moment µ can make any arbitrary angle θ with respect to a given
direction (call it the z direction). In the absence of a magnetic field H in the
z direction, the probability that this angle lies between θ and θ + dθ is simply
proportional to the solid angle 2π sin θdθ enclosed in this range. In the pres-
ence of a magnetic field H the z direction, this probability must further be
proportional to the Boltmann factor e−βE , where E is the magnetic energy of
the moment µ making this angl θ with the z axis. Use this result to calculate
the classical expression for the mean magnetic moment M̄z of these N0 atoms.

The magnetic energy is

E = −µ • H = µH cos θ
Then the probability density is obtained
P (θ)dθ = CeβµH cos θ 2π sin θdθ
First we start by normalizing and finding the constant C.
Z π
CeβµH cos θ 2π sin θ dθ = 1
0

4Cπ sinh(βµH) βµHcsch(βµH)

=1⇒C=
βµH 4π
µz = µ cos θ
So the average magnetic moment is
Z π
µ¯z = µ cos θCeβµH cos θ 2π sin θ dθ
0

The average magnetic moment is then

1
µ¯z = µ coth(βµH) −
βH
So
1
M̄z = N0 (µ coth(βµH) − )
βH
µH kB T
M̄z = N0 (µ coth( )− )
kB T H

5
6 Sixth Problem
In class (see notes for lecture 10) we considered a system of N noninteracting
spins at temperature T in an external magnetic field H pointing along the z
axis. These spins have total angular momentum J = 1/2 and g = 2. What
is the entropy S of the system as a function of T and H?

The entropy is given by

S = kB (ln Z + β Ē)
The magnetic energy is the usual

E = −µ • H

= −gµB J • H
= −gµB Jz H
1
= −2µB (± )H = ±µB H
2
We now find the partition function

ζ = eβµH + e−βµH

Z = ζ N = (eβµH + e−βµH )
ln Z = N ln(eβµH + e−βµH )
The mean energy is given by

∂ ln Z N µH(eβµH − e−βµH ) µH
Ē = − = βµH −βµH
= −N µH tanh( )
∂β e +e kB T
µB H
S = kB N ((eµB /kB T + e−µB H/kB T ) − µB H tanh )
kB T
µB H µB H
S = kB N (2 cosh( ) − µH tanh( ))
kB T kB T