Chemistry 5302 Homework Problem Set 3 Solutions

McQuarrie, Chapter 7 and 12

1. Consider a perfect gas of molecules with permanent electric dipole moments µ in an

electric field E. Neglecting the polarizability of the molecules, the potential energy
is U = −µE cos θ, where θ is the angle between µ and E. Using classical mechanics,
derive an expression for the additional effect of E on the energy E and heat capacity
of the gas.
Solution:
We have that

H = K + U = K − µE cos θ
Z Z
Q = . . . e−βH dp1 . . . dq1 . . .
Z
Z = . . . e−βU dq1 . . . dqN configurational partition function

The additional effect of the electric field E on the energy is given by

Z 2π Z π
Z= eβµE cos θ sin θdθdφ let a = µE/kT
Z0 2π Z0 π
−d(a cos θ)
= ea cos θ · dθdφ
0 0 a
Z a  
−1 2π a x
Z
x
= 2π e dx = e dx where x = a cos θ
−a a a −a
2πkT  µE/kT
− e−µE/kT

= e
µE
 
4πkT µE
= sinh
µE kT

The change in the gas energy due to the electric field E is given by

1
 ∂ ln Z
E = kT
∂T    
2 ∂ 4πkT µE
= kT ln sinh
∂T µE kT
 
2 ∂ 4πkT ∂ µE
= kT ln + ln sinh
∂T µE ∂T kT
 
1 µE µE µE
= kT 2 − 2
coth = kT − µE coth
T kT kT kT

The heat capacity of the gas is

  
∂E ∂ µE
CV = = k − µE coth
∂T V ∂T kT
2 2
µE 1
=k− 2
kT 2 sinh (µE/kT )

2
2. It is possible to determine the value of Boltzmann’s constant by observing the distri-
bution of suspended Brownian particles in a gravitational field as a function of the
height z. Given the particles have a mass of 1.0 × 10−14 g, the temperature is 300K,
and the data in Table 1, calculate the value of Boltzmann’s constant.

z (cm) Number of particles

0.0000 100
0.0025 55
0.0050 31
0.0075 17
0.0100 9

Table 1: Distribution of Brownian particles

suspended in a gravitational field

Solution:

N e−βV (zi )
ni = P −βV (zi )
where V (zi ) = mgzi
ie
ni
= e−β(V (zi )−V (zj ))
nj
[0 − 10−17 kg][9.81m/s2 ][2.5 × 10−5 m]
 
100
= exp −
55 kb (300K)
−22
 
0.0817 × 10 J/K
1.82 = exp
kB
−22
0.0817 × 10 J/K
ln 1.82 =
kB
0.0817 × 10−22 J/K
kB =
0.598
kB ' 1.36 × 10−23 J/K
= 1.36 × 10−16 ergs/K

3
3. Prove that if the Hamiltonian is given by Eq (7-37), then each of the quadratic terms
will contribute kT /2 to the average molecular energy and k/2 to the molecular heat
capacity.
Prove that if
m
X m
X
H(p1 , p2 , . . . , qs ) = aj p2j + bj qj2 + H 0 (pm+1 , . . . , ps , qm+1 , . . . , qs )
j=1 j=1

then each quadratic term will constribute kT /2 to hEi and k/2 to CV .

Solution:
We have that

Z Z
Q= ... e−βH dp1 . . . , dqs
Z Z Pm
 Z Z Pm

−β aj p2j −β 2
j=1 bJ qj
= ... e j=1 dpj ... e dqj
| {z }| {z }
quadratic quadratic
Z Z 
−βH 0
× ... e dpm+1 . . . , dps , dqm+1 , . . . , dqs

Each of the quadratic momenta and coordinates contributes:

Z ∞
π
r
−βaj p2j
e dpj =
−∞ βaj
and so

   1/2 !
∂Q ∂ π
hEi = − =− ln
∂β N,V ∂β βaj
 
∂ 1 π
=− ln
∂β 2 βaj
1 kT
= =
2β 2
   
∂hEi ∂ kT k
CV = = =
∂T V ∂T 2 2

4
4. Extra Credit: McQuarrie, Problem 12-1: The usual form of a virial expansion is

pV B(T ) C(T )
=1+ + + ...
RT V V2
Some workers, however, prefer to express their data by expanding the compressibility
factor in a power series in the pressure

pV
= 1 + B 0 (T )p + C 0 (T )p2 + . . .
RT
Find the relations between the two sets of virial coefficients.
Solution:

RT B(T ) C(T )
p= (1 + + + . . .) (1)
V V V2

B(T ) C(T )
1+ + + . . . = 1 + B 0 (T )p + C 0 (T )p2 + . . . (2)
V V2
By putting Eqn. 1 into 2;

B(T ) C(T )
1+ + + . . . = 1 + B 0 (T )p + C 0 (T )p2 + . . .
V V2  
0 RT B(T ) C(T )
= 1 + B (T ) + RT + RT + . . .
V V2 V3
 2
0 RT B(T ) C(T )
+ C (T ) + RT + RT + . . . + . . .
V V2 V3

Then, collecting terms of V;

B(T ) B 0 (T )RT
=
V V
and

C(T ) B 0 (t)B(T )(RT ) C 0 (T )(RT )2

= +
V2 V2 V2
So,
C(T ) = B(T )2 + C 0 (T )(RT )2

5
5. Extra Credit: McQuarrie, Problem 12-9: Calculate the second virial coefficient for the
triangle potential

u(r) = ∞ if r < σ

= (r − λσ) if σ < r < λσ
σ(λ − 1)
=0 if r > λσ

Solution:

Z ∞
e−βu(r) − 1 r2 dr
 
B2 (T ) = − 2π
0
Z σ Z λσ h (r−λσ)
i
−∞ −β σ(λ−1)
− 1 r2 dr −2π − 1 r2 dr
 
= − 2π e e
Z0 ∞ σ

e0 − 1 r2 dr
 
− 2π
λσ

Then,

Z σ Z λσ (r−λσ)
Z λσ 
2 −β 2 2
B2 (T ) = −2π −r dr + e σ(λ−1) r dr − r dr
0 σ σ
"
σ Z λσ  #
3 λσ
−r3  (r−λσ) −r 
= −2π + e−β σ(λ−1) r2 dr +
3 0 
σ 3 σ
 3 Z λσ
(λσ)3 σ 3

−σ (r−λσ)
−β σ(λ−1) 2
= −2π − + + e r dr
3 3 3 σ

β
R
To solve the integral in the last equation, let’s define α = σ(λ−1) and use uv − v du
(integration by parts) where u = r2 , du = 2r dr, dv = e−α(r−λσ) dr and v = − α1 e−α(r−λσ)

Z λσ Z
−α(r−λσ) 2
e r dr = uv − v du
σ
λσ
r2 −α(r−λσ)  2 λσ −α(r−λσ)
Z
=− e  +α e r dr
α σ σ
−(λσ)2 σ 2 ασ(λ−1) 2 −1 eασ(λ−1)
 
1 ασ(λ−1)


= + e + + − 2 1−e
α α α α α α

So,

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 −(λσ)3 −(λσ)2
  2 
2 2 ασ(λ−1) σ 2 2
B2 (T ) = −2π + − 2 − 3 +e + 2+ 3
3 α α α α α α
3 2
  2 
(λσ) (λσ) 2 2 σ 2 2
= 2π + + 2 + 3 − eβ + 2+ 3
3 α α α α α α
β
Remember that α = σ(λ−1)
.