Assignment 3: due before class time on —- 2021

1. Treat carbon monoxide as a perfect gas and apply equilibrium statistical thermodynamics to the study

of its properties, in the temperature range 100–1000 K at 1 bar. ν̄ = 2169.8cm−1 , B̃ = 1.931cm−1 , and

D0 = 11.09 eV; neglect anharmonicity and centrifugal distortion. Examine the probability distribution of

molecules over available rotational and vibrational states.

2. Obtain an expression for the ionization constant for the ionization of sodium atom. Use standard data

to obtain the value at 300K.

3. What does a surface of constant energy look like in the phase space of an oscillator of frequency ν?

Find the volume Γ0 (E) in the phase space with energy ≤ E. Then find the number of quantum states Ω0 (E)
Γ0 (E)
with energy ≤ E and show that when E is large we have h ∼ Ω0 (E) [Hint: 1. imagine a 2-D phase space

for a 1-D H.O. The volume then means area under a curve. 2. Recall the eigen-spectrum of a 1-D Q.M. H.O.]
2
4. Show that the energy fluctuation in a canonical distribution is given by (E − U ) = kB T 2 CV (This is

actually worked out in an early chapter in McQuarrie’s book), where symbols have usual meaning.
3 2
 4 ∂CV


Prove : (E − U ) = kB T ∂T V
+ 2T 3 CV
(E−U )2 2 (E−U )3 8
Also, show that for an ideal monatomic gas of N molecules, U2 = 3N and U3 = 9N 2 . Comment

on the significance of these results.

5. Calculate the equilibrium constant at (a) 298 K and (b) 800 K for the gas-phase exchange reaction

H2 O + DCl
HDO + HCl from the following data:

molecule ν/cm−1 e cm−1

A e cm−1
B e cm−1
C

H2 O 3656.7, 1594.8, 3755.8 27.88 14.51 9.29

HDO 2726.7, 1402.2, 3707.5 23.38 9.102 6.417

HCl 2991 10.59

DCl 2145 5.449