Statistical Molecular

Thermodynamics
Christopher J. Cramer

Video 4.6

Ideal Diatomic Gas: Q

 Energy of an Ideal Diatomic Gas

In addition to translational and electronic degrees of freedom,
a diatomic also can rotate and vibrate. These motions can be
treated within the rigid rotator and harmonic oscillator
approximations, respectively (exactly solvable QM problems)

The Energy:
diatomic = trans + rot + vib + elec (sum)

total energy
electronic
translational rotational vibrational energy
energy energy energy
(( m1
((
m1 m2
m2
harmonic
rigid rotor oscillator
 One Wrinkle
Due to quantum mechanical boundary conditions
associated with the indistinguishability of
particles, we need to add a symmetry number to
the rotational partition function,

T =1 heteronuclear diatomic
qrot = ,
rot = 2 homonuclear diatomic

symmetry number

So, last lecture our derivation was valid only for

heteronuclear diatomic rotation, = 1.
The Full Diatomic Partition Function

q (V , T ) = qtrans qrot qvib qelec

# 2 ( m + m ) k T & 3 / 2 T e vib / 2T
1 2 B D e / kBT
q(V,T) = %% 2
(
( V vib /T g1e
$ h ' rot 1 e
The Full Diatomic Ideal Gas U and CV

q (V , T ) N
Q( N ,V , T ) =
N!
# 2 ( m + m ) k T & 3 / 2 T e / 2T
vib
1 2 B D / kBT
with q(V,T) = %
% 2
(
( V /T g1e e

$ h ' rot 1 e vib

From Q

translations zero-point
vib energy electronic
vib energy above
rotations zero point

3 vib vib
Energy U = RT + RT + R + R vib /T N A De
2 2 e 1
5 # vib & 2 e vib /T
Heat Capacity CV = R + R% (
2 $ T ' (1 e vib /T ) 2

 Self assessment insert here
Andys Week 4 question 9.
 Vibrational Heat Capacity: Example
14N has vib = 2330 cm1
# vib & 2 e vib /T 2
CV ,vib = R% (
$ T ' (1 e vib /T ) 2 79Br
2 has vib = 323 cm1

h Noting h is in wavenumbers here, we

Recalling vib = use kB = 0.695 cm1 K1 to determine:
kB
14N has vib = 3353 K
2

79Br has vib = 465 K

2
At 500 K:
# 3353 & 2
e 3353 / 500
CV ,vib ( 14 N 2 ) = (8.314 J K 1 mol1 )% (
$ 500 ' (1 e 3353 / 500 ) 2

= 0.459 J K 1 mol1
= 0.06 R
 Self assessment insert here
# vib & 2 e vib /T
Given CV ,vib = R% ( and a vibrational
$ T ' (1 e vib /T ) 2
temperature
for 79Br2 of 465 K, what is the vibrational heat capacity of
bromine gas at 500 K expressed as a multiple of R?

Answers can be 0.06, 0.42, 0.61, and 0.93 (final answer
correct)
 Vibrational Heat Capacity: Example
14N has vib = 2330 cm1
# vib & 2 e vib /T 2
CV ,vib = R% (
$ T ' (1 e vib /T ) 2 79Br
2 has vib = 323 cm1

14N has vib = 3353 K

At 500 K: 2

14N has CV,vib = 0.06 R 79Br has vib = 465 K

2 2

79Br has CV,vib = 0.93 R

2

As the temperature of a diatomic ideal gas goes from

below to above its vibrational temperature, the molar
heat capacity goes from ~(5/2)R to ~(7/2)R
(cf. Video 1.4 last slide!)
Next: Ideal Polyatomic Gases: Part 1

 Call Out Demo Here
Energy Partition