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Thermodynamics
Christopher J. Cramer
Video 4.6
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
# 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
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
= 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