Calculations

1. The translational contribution

The translational partition function, qT, of a molecule of mass m in a container of volume V is
34

h := 6.626 10

joule sec

mA :=

0.001kg mol

joule K

mB :=

Na

23

k := 1.381 10

mass := mA + mB

0.0355kg mol
Na

V :=

1mol 8.314joule K

10

c := 2.998 10 cm s

( T) := h

2 mass k T
1

q T( T) := V

T( T) :=

2 mass k T
h
2

d q ( T)

q T( T) dT T
k T

mol

101325Pa

V = 24.452 L

T := 10 K , 20 K .. 1000 K

23

Na := 6.022 10 mol
298 K

 d ( T)
T
dT

C VT( T) := Na

15

10
CVT( T)
5

0
0

200

400

600

800

1 10

T
2

m kg

C VT( 300 ) = 12.475

mol K s

2. The rotational contribution

The rotational partition function, qR, of a nonsymmetrical linear rotor with the general formula AB
is
12

rAB := 127 10

J := 0 , 1 .. 30

I :=

mA mB

r
mA + mB AB
h

B :=

8 I
B1 :=

B
c

3 1

B1 = 1.075 10

q R( T) :=

[ h B J ( J + 1 ) ]

k T
( 2 J + 1 ) e

8
6

( 2 J+ 1) e

[ h B J ( J+ 1) ]
4
k T

2
0

10

20
J

R( T) :=

k T

q R ( T)

d q ( T)
R
dT

30

 d ( T)
R
dT

C VR( T) := Na

15

10
CVR( T)
5

0
0

200

400

600

800

110

3. The vibrational contribution

The vibrational partition function of a diatomic molecule in the harmonic approximation is:
8

c := 2.998 10 m s

kf := 512.6 N m

mA mB
meff :=
mA + mB

kf
:=

2 c meff

0.5

q V( T) :=

1e

5 1

h c
k T

= 2.991 10

1.015

1.01
qV( T)
1.005

1
0

200

400

600
T

V( T) :=

k T

q V( T)

d q ( T)
V
dT

800

1 10

 d ( T)
V
dT

C VV( T) := Na

15

10
CVV ( T)
5

0
0

200

400

600
T

800

1 10

4. The electronic contribution

Electronic energy separations from the ground state are usually very large, so for most cases
qE = gE, where gE is the degeneracy of the electronic ground state. However, some atoms and
molecules have low-lying electronically excited states.
g1 := 1
g2 := 0
E2 := 100000cm

q E( T) := g1 + g2 e

E( T) :=

Very large!!!

h c E2
k T

d q ( T)

q E( T) dT E
k T

d ( T)
E
dT

C VE( T) := Na

15

10
CVE( T)
5

0
0

200

400

600

800

1 10

C V( T) := CVT( T) + CVR( T) + C VV( T) + CVE( T)

50
40
30
CV ( T)
20
10
0
0

200

400

600
T

800

110

q total( T) := q E( T) q T( T) q V( T) q R( T)
total( T) := T( T) + E( T) + R ( T) + V( T)

23

N := 6.02 10

F( T) := k T N ln q total( T) N ln( N) + N

Stotal( T) :=

total( T) F( T)
T

200

150
2

Stotal( 300K) = 166.003

S total( T) 100

m kg
K s

50

0
0

200

400

600
T

800

1 10

he general formula AB