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The Heat Capacity of a Diatomic Gas

15.1 Introduction
• Statistical thermodynamics provides deep
insight into the classical description of a
MONATOMIC ideal gas.
• In classical thermodynamics, the principle of
equipartition of energy fails to give the
observed value of the specific heat capacity for
diatomic gases.
• The explanation of the above discrepancy was
considered to be the most important challenge
in statistical theory.
15.1 The quantized linear oscillator
• A linear oscillator is a particle constrained to move
along a straight line & acted on by a restoring force
d 2x
F= -Kx = ma = m 2
dt

If displaced from its equilibrium position and 1 K


released, the particle oscillates with simple v
2 m
harmonic motion of frequency , given by

Note that the frequency depends on K and m, and is


independent of the amplitude X.
• Consider an assembly of N one-dimensional
harmonic oscillators, in which the oscillators are
loosely coupled so that the energy exchange among
them is small.
• In classical mechanics, a particle can oscillate with
any amplitude and energy.

• From quantum mechanics, the single particle energy


levels are given by
EJ = (J + ½)h , J = 0, 1, 2, …..
• The energies are equally spaced and the ground state
has non-zero energy.
• The internal degrees of freedom include
vibrations, rotations, and electronic excitations.
• For internal degrees of freedom, Boltzmann Statistics
applies. The distinguishable property arises from the
fact that those diatomic molecules have different
translational energy.

• The states are nondegenerate, i.e. gj = 1


• The partition function of an oscillator
• Introducing the characteristic temperature θ = h/k

  2 3
 
 e 1  e  e  e  ......
2T T T T

 

• The solution for the above eq. is (in class derivation)


• The internal energy is:
U = NkT2
since

    
1 e T  1 1 
U  Nk      Nk    
 2 
1 e T   2
e T  1 
  
1
0
For T → 0 
eT 1

For

thus
15.3Vibrational Modes of Diatomic
Molecules
• The most important application of the above
result is to the molecules of a diatomic gas

• From classical thermodynamics

for a reversible process!


Since

Or

At high temperatures
At low temperature limit

On has

So

approaching zero faster


than the growth of (θ/T)2 as T → 0
Therefore Cv  0 as T  0

The total energy of a diatomic molecule is made


up of four contributions that can be separately
treated:
1. The kinetic energy associated with the
translational motion
2. The vibrational motion
3. Rotation motion (To be discussed later)

Example: 15.1 a) Calculate the fractional number


of oscillators in the three lowest quantum
states (j=0, 1, 2,) for T   4 and forT  
Sol:
J=0
• 15.2) a) For a system of localized
distinguishable oscillators, Boltzmann
statistics applies. Show that the entropy S is
given by  NJ 
S    N J ln  
J  N 

• Solution: according to Boltzmann statistics


NJ
gn
W  N!  J
J 1 N
J
So
S  k ln w 1
ln w  ln N!  N J ln g J   ln N J
g J  1  ln 1  0
ln w  ln N!  N J ln 1   ln N J !
ln w  ln N! ln N!
ln w   ln       J ln 1    J
ln w   ln     J ln  J
   J
ln w    J ln     J ln  J
ln w    J ln   ln  J 
  
ln w    J ln  
 J 
  
S     j ln  
 
 j
n
j 
S     j ln  
J 1   
15.4 Rotational modes of diatomic
molecules

The moment of inertia,


where μ is the reduced mass
r0 is the equilibrium value of the distance
between the nuclei.
From quantum mechanics, the allowed angular
momentum states are
where l = 0, 1, 2, 3… …

From classical mechanics, the rotational energy


equals with w is angular velocity.
The angular momentum
therefore, the energy
Define a characteristic temperature for rotation

θrot can be found from infrared spectroscopy


experiments, in which the energies required to
excite the molecules to higher rotational states
are measured.
Different from vibrational motion, the energy
levels of the above equation are degenerate.
for level
Now, one can get the partition function

For , virtually all the molecules are in


the few lowest rotational states.

As a result, the series of can be


truncated with negligible errors after the first
two or three terms!
For all diatomic gases, except hydrogen, the
rotational characteristics temperature is of the
order of 10 k (Kelvin degree).
At ordinary temperature,
Therefore, many closely spaced energy states are
excited. The sum of may be replaced by
an integral.
Define:
Note that the above result is too large for
homonuclear molecules such as H2, O2 and N2
by a factor of 2… why?
The slight modification has no effect on the
thermodynamics properties of the system such
as the internal energy and the heat capacity!
  ln Z 
Using U  NkT  2

 T V
(Note: )

 U 
CV , rot     Nk again
 T v
At low temperature

Keeping the first two terms


Using the relationship

2 ro t
2   ln Z    rot 
U  NkT    NkT  3  e
2 T
2 2 
 T V  T 

(for )

And 2 rot


 U    rot 
CV ,rot     6 Nk rote T
2 2 
 T V  T 
(for )
Characteristic Temperatures
Characteristic temperature Characteristic temperature
of vibration of diatomic of rotation of diatomic
molecules molecules
Substance θvib(K) Substance θrot(K)
H2 6140 H2 85.4
O2 2239 O2 2.1
N2 3352 N2 2.9
HCl 4150 HCl 15.2
CO 3080 CO 2.8
NO 2690 NO 2.4
Cl2 810 Cl2 0.36
15.5 Electronic Excitation
The electronic partition function is

where g0 and g1, are, respectively, the


degeneracies of the ground state and the first
excited state.
E1 is the energy separation of the two lowest states.
Introducing
For most gases, the higher electronic states are
not excited (θe ~ 120, 000k for hydrogen).
therefore,
  ln Z 
U  NkT 
2
 0
 T V
 U 
CV    0
 T V

At practical temperature, electronic excitation


makes no contribution to the external energy
or heat capacity!
15.6 The total heat capacity
For a diatomic molecule system

Since

Discussing the relationship of T and Cv (p. 288-289)


Heat capacity for diatomic molecules
• Example I (problem 15.7) Consider a diatomic
gas near room temperature. Show that the
entropy is
 7  2mk  2 T 5 2  
3

S  Nk   ln  2   ,
 2  h  2 rot  

• Solution: For diatomic molecules


S  Strans  S vib  S rot  S excit
At room temperature
S excit  0
1 1 

Nk    
  e  T 
S vib   2 e  1   Nk ln 
T

T  1  e  T 
 
 0 (does not contribute!)
• For translational motion, the molecules are
treated as non-distinguishable assemblies
3
U  NkT three degrees of freedom 
2
3
 2mkT  2
Z V 
 h 
2

Str   Nk ln Z  ln N  1
U
T
5  V   2mkT  2 
 3

Str  Nk  Nk ln    
 N  h  
2
2
  
• For rotational motion (they are distinguishable
in terms of kinetic energy)
T 1 
U  NkT Z  due to homonuclea r molecule 
2 rot 2 

S
U
 Nk ln Z for distinguis hable assembly 
T
T
 Nk  Nk ln
2 rot
    2mkT  3 2  
5  V     T
S system  Nk  Nk ln   Nk  Nk ln
2 N   h 2    2 rot

    
 
 V   2mk  T 2 
 3/ 2 5
7
S system  Nk  Nk ln   
2 N   h 2  2 rot 

  

• Example II (problem 15-8) For a kilomole of
nitrogen (N2) at standard temperature and
pressure, compute (a) the internal energy U;
(b) the Helmholtz function F; and (c) the
entropy S.

• Solution:
calculate the characteristic temperature first!
 vib  3352k and  r  2.9k for N 2

U  U trans  U vib  U rot


3 1 1 

U  NkT  Nk   vib      NkT

2  2 e T 1 
because  r T
5 1 1 
U NkT  Nk   vib   3352 

2  2 e 298  1 
 1 3352 
 Nk  2.5  298   3352  11.25 
 2 e 1 
 3352 
 Nk  2272  11.25 
 e 1 
 1.0kmol  8.314 103 J  kmol1  k 1  2272
 1.89 10 7 J
F   NkT ln Z  ln N  1 non  distinguis hable particles 
F   NkT ln Z Distinguis hable particles such as vib & rotation
Ft   NkT ln Z t  ln N  1
3
 2mkT  2
Zt  V  
 h 
2

3
 2  4.65 10 1.38110  26  23
Jk  298 
1 2
 22.4m 3   68

 6.626 2
 10 

 22.4 273.86 10  19
3
2

 22.427.3  10 
3 3
2 20 2

 3.195 1033
 3.195 1033 
Ft   NkT  ln  1
   NkT ln 5.15   
10 6
1  
 6.02 10
26

  NkT 16.4
Fvib   NkT ln Z vib
 3352
e 2298
e 5.62
Z vib  3352

1 e 298 1  e 11.24
 1 
ln Z vib  5.62  ln 1  11.24   5.62
 e 
T
Frot   NkT ln Z rot Z rot  for T  rot
2 rot
298
Z rot   102.72 ln Z rot  4.63
2 .9
Frot  4.63 NkT
F  Frot  Fvib  Ft
 4.63 NkT  5.62 NkT  16.4 NkT
 15.41NkT
 15.41 6.02 10 26  1.38  10  23  298  3.817  107 J