Assignment 3 Chemistry 365 W2013

Due Friday March 22, 2013

1. Vibrational and Rotational Energy Levels for CO (g)
O
vib
= 3103 K O
rot
= 2.77 K o=1

Vibrational Energy Levels CO (g)
n
Vib
0 2 4 6 8 10
f
k
,

V
i
b
0.0
0.2
0.4
0.6
0.8
1.0
1.2
300 K
3000 K

a) Calculate the fraction of CO (g) molecules in J =5 rotational energy level at 300 K and
3000K



Starting with the molecular partition function for the vibrational degree of freedom,
Derive the vibrational contribution to the heat capacity
which is given below :








b) At which temperature (300 or 3000K) would you expect a significant contribution from
the vibrational mode of CO to its thermodynamics properties? Provide a molecular level
justification for your answer by making reference to Figure A above.







Rotational Energy Levels CO (g)
J
Rot
0 20 40 60 80 100
f
J
,

R
o
t
0.00
0.02
0.04
0.06
0.08
0.10
300 K
3000 K
A B
e - 1
e

T
Nk C
2
T
T
2
Vib
Vib V,
V
V
(

|
.
|

\
|
O
=
O

2. Rotational Heat Capacity of Water

a) Calculate the contribution of the rotational modes to the molar rotational heat
capacity of H
2
O (g) at 600K

Data for H
2
O (g) O
vib
5360K, 5160K, 2290K O
rot
40.1K, 20.9K, 13.4K o=2


3. Equipartition Limit

a) Estimate the internal energyE in the high temperature (equipartition) limit for CO.
b) Estimate the heat capacity C
V
in the high temperature (equipartition) limit for NH
3
.
Do not use partition functions in your calculations.

4. Chemical Potential of an ideal nonlinear polyatomic gas

Using Q, derive a general formula for the chemical potential () of a system containing N
arbitrary polyatomic nonlinear molecules. Take into account the translational, vibrational,
rotational (assume asymmetric top), and electronic contributions.


5. Calculation of an electronic partition function for gaseous vanadium

Due to the presence of unpaired electrons in V, the electronic exited state are accessible relative
to kT (depends on temperature of course).

The lowest nine energy level for V (g) are:

Level (n) Energy (cm
-1
) Degeneracy
0 0 4
1 137.38 6
2 323.46 8
3 552.96 10
4 2112.28 2
5 2153.21 4
6 2220.11 6
7 2311.36 8
8 2424.78 10


Calculate the electronic partition function for V (g) at 298 K including as many terms in the sum
as are significant (use Excel or equivalent computer program).
Plot the fractional occupancy of the electronic energy levels as a function of level for 298 K.