Statistical Molecular Thermodynamics University of Minnesota

Homework Week 3
1. You are given the following partition function for a fictitious gas “Vikonium”. What
is the correct equation of state for Vikonium? In the equation A and B are constants,
the other variables have their usual meanings.
3N/2
A 2m2 β

2
Q(N, V, T ) = 2
(V − 2N B)N eβN /V
N ! 3πh
(a) P V = N kB T
 2 2

(b) P + AVN2 N


V −2N B
= N kB T
 2 2

(c) P − mV N2 (V − 2N B) = NA! kB T


 2 2

(d) P + AVN2 (V − 2N B) = kB T
 
N2
(e) P − V (V − 2N B) = N kB βT
 2

(f) P + NV2
V N = N BkB T
 

N2 N
(g) P − V 2 V1 = N kB T
 2

(h) 2B P − N 1


V2 V −2N
= 3N kB T
 2

(i) P + N
V2
(V − 2N B) = N kB T

2. In an Einstein crystal, one principal assumption is that each of the N atoms of the
crystal vibrate independently about their lattice positions. The crystal is thus pictured
in three dimensions as N independent three dimensional harmonic oscillators. Using
the partition function for a harmonic oscillator,

∞ ∞
−β(j+ 12 )hν
X X
−βhν/2
qho (T ) = e =e e−βjhν ,
j=0 j=0

determine the partition function for an Einstein crystal. It will be helpful to make use
of the geometric series,

∞
X 1
xj =
j=0
1−x

to derive this result.

  3
e−βhν/2
(a) Q = 1−e−βhν
 3N
e−βhν/2
(b) Q = 1−e−βhν

e−βhν/2
(c) Q = 1−e−βhν
 3N
1
(d) Q = 1−e−βhν
 3N
e−βhν/2
(e) Q = 1+e−βhν
 3
eβhν/2
(f) Q = 1+e−βhν

N
3. One of the requirements for the statistical result that Q(N, V, T ) = q(V,TN!
)
is that
the system have many more available states than particles. Usually, the number of
translational states alone are enough to satisfy this condition. Use the translational
partition function to determine which of the following conditions leads to an increased
number of accessible translational states:

(a) small molar volume

(b) low temperature
(c) small mass
(d) all of the above
(e) none of the above

4. The average energy for a monatomic van der Waals gas is

3 aNA2
hĒi = NA kB T −
2 V
Use the definition of the constant volume molar heat capacity discussed in lecture
video 3.4 to determine a formula for the constant volume molar heat capacity of a
monatomic van der Waals gas. Here, NA is Avogadro’s number and R is the universal
gas constant.

(a) C̄V = 23 NA kB
aNA2
(b) C̄V = 23 NA kB T − V
(c) C̄V = 23 NA kB − aNA2
aN 2
3
(d) C̄V = 2R
− VA
3
(e) C̄V = 2
R
3
(f) C̄V = 4
RT 2
 2T

3 aNA
(g) C̄V = N k T2
4 A B
− V

(h) the first and fifth answers above

(i) the second and seventh answers above
 (j) none of the above

5. In the lecture videos, a general formula for the average energy,

 
2 ∂ ln Q
hEi = kB T ,
∂T N,V

was derived.
Determine the average energy, hEi, for a monatomic ideal gas given the partition
function for this gas,
 3N/2
1 2πmkB T
Q(N, V, T ) = V N.
N! h2
N
(a) hEi = (3/4)N kB T 2 + V
(b) hEi = (3/2)N kB T
(c) hEi = (3/4)N kB T 2
N
(d) hEi = (3/2)N kB T + V
 
3N h2 N
(e) hEi = (3/4)N kB T + 2 2πmKB
+ V
3N
(f) hEi = 2T

6. We found that under certain conditions, the partition function for a collection of par-
ticles, Q(N, V, T ), could be written in terms of the partition function for individual
particles, q(V, T ), and the number of particles, N ,

q(V, T )N
Q(N, V, T ) = .
N!
This equation is correct for a gas described by the van der Waals equation of state.

(a) TRUE
(b) FALSE

7. For a system that has equally spaced non-degenerate energy levels, at a fixed tempera-
ture what will happen to the value of the partition function, Q(N, V, T ), if the spacing
between the energy levels INCREASES?

(a) Q will increase

(b) Q will decrease
(c) Q will remain the same
(d) either (a) or (b) depending on the temperature
(e) none of the above
 8. The following expresses the partition function of the system in terms of the partition
functions of the individual particles (such as atoms or molecules),

qN
Q= .
N!
For this to be true, it must be the case that there are many more particles than available
states.

(a) TRUE
(b) FALSE

9. Derive that the fraction of harmonic oscillators in the ground vibrational state is given
by
f0 = 1 − e−hν/kB T .

Then, given that ν̃ for N2 is 2330 cm−1 , calculate f0 for N2 (g) at 300 K and 1000 K.

(a) 1.0000 and 0.7457

(b) 0.9000 and 1.0000
(c) 1.0000 and 0.9650
(d) 1.0000 and 0.0000
(e) 0.9578 and 0.8762
(f) 0.9200 and 0.4578

10. Imagine you are given one mole of a homonuclear diatomic molecule, X2 , at a fixed
volume and temperature. If you increase the mass of the molecules, for example you
go from F2 to I2 , the partition function will,

(a) increase
(b) decrease
(c) not change