Worked out examples on partition functions

Narayanan Kurur
November 19, 2012

1 Translational partition function

For a temperature of 273 K and a volume of 2.24 102 m3 determine the translational partition
function for Argon gas. THe translational partition function is


2mkT 3/2
ztr =
V
h2
m = 40 g mol1 = 6.64 1026 kg per atom
kT = 3.77 1021 J
ztr = 4.79 1030 states per atom

2 Vibrational partition function

The vibrational frequency of oxygen is 1580 cm1 . Determine the vibrational partition function
for oxygen gas. THe vibrational partition function is


h
exp 2kT


zvib =
h
1 exp kT
The vibrational frequency in Hz is 4.737 1013 , so that
vib =

h
= 2274 K
k

At room temperature (300 K) vib /T = 7.58, which indicates that the vibrational energy is
almost 8 times higher than the thermal energy. This would imply that the vibrational partition
function will predominantly have contribution from the ground state. Inserting these quantities
into the vibrational partition function expression gives a value of 1.0005.

3 Rotational partition function

The length of the bond in oxygen molecule is 1.2074
A. Determine the rotational partition
function for oxygen at 300 K. THe rotational partition function for a diatomic is
zrot =

8 2 IkT
T
=
,
2
h
rot

where I is the moment of inertia R2 , is a symmetry factor which accounts for equivalent
orientations of the molecule and is 1 for a heteronuclear diatomic and 2 for a homonuclear
molecule. For a polyatomic molecule, zrot becomes
 2
3/2
8 IkT
Ia Ib Ic
zrot =
.
2
h

Note that for a polyatomic the rotational partition function is a product of three terms corresponding to rotation about three perpendicular axes. Returning to the problem at hand, the
moment of inertia of oxygen molecule is


kg
10 m)2
0.016
2
mol (1.207410
mR
2

= 1.937 1046 kg m2 ,
I = R =
=
molecules
23
2
2 6.023 10
mol
from which we determine the rotational temperature to be
rot =

h2
= 2.08 K
8 2 Ik

At room temperature, T /rot 150, which indicates that the thermal energy is almost 150
times higher than the rotational energy and we expect the rotational partition function to have
extensive contribution from the excited states. As expeted, we find that the rotational partition
to be zrot = T /(rot ) = 72.

4 Entropy of a monoatomic ideal gas

The entropy may be obtained from its relation to the Helmholtz energy


A
,
S=
T V,N
which in turn is related to the partition function as
A = kT ln Z.
If the energy is known, as is the case here, it is easier to obtaine the entropy from the classical
thermodynamical definition of the Helmholtz energy
A = U T S.
For a monoatomic ideal gas there is only a translational contribuion to the entropy and the
average energy is given by the equipartition principle
S = (U A)/T = (3/2N kT Atr )/T
with
zN
Atr = tr = N kT ln
N!

"

2mkT
h2

3/2

#
V
e .
N

In writing out the last equality we have used the Stirlings approximation for

N ! = N N eN 2N
The entropy of a monoatomic ideal gas is hence
"
#

2mkT 3/2 V 5/2
S = N k ln
e
h2
N

4.1 Absolute entropy of argon

The expression for the entropy may be used to obtain the absolute entropy of monoatomic gases,
say argon at 300 K and 1 atm. The translational partition function of argon at 300 K is


2mkT 3/2
ztr =
V = 2.47 1032 V
h2
so that



S
32 V 5/2
.
= k ln 2.47 10
e
N
N

Using the equation of state to replace V /N by kT /p = 4.10 1026 we get that the absolute
entropy of argon is
S/N = 158.4 J K1 mol1

5 Chemical equilibrium of the water-gas reaction

The water-gas reaction is C O2 + H2 *
) H2 O + C O for which the experimentally determined
equilibrium constants are 2.0, 2.8, and 3.5, at 1295, 1565, and 1823 K respectively. Determine
the equilibrium constant at 1565 from the partition function.
The basic equation for the statistical thermodynamic calculation of the equilibrium constant
is:


qH 2 O qC O
E0
Kc =
exp
qC O2 qH2
RT
where E0 is the difference in energy between the ground rotational/vibrational states of the
reactants and products, and the qs are the unit-volume partition function and may be written
in terms of the partition functions for the different modes of motion
q = qtrans qrot qvib
It follows that the expression for Kc may be split into factors


E0
Kc = Kc(trans) Kc(rot) Kc(vib) exp
RT
where Kc(trans) is
Kc(trans) =

qH2 O (trans) qC O (trans)

qC O2 (trans) qH2 (trans)

The equilibrium constant is dimensionless, and thus all fundamental constants in Kc(trans) cancel.
But they do not in Kc(rot) because of the difference in the number of rotational degrees of freedom
on the right, five, and the left, four.
Because the numbers of the molecules on the two sides of the equation are the same Kc(trans)
may be written as


MH2 O MC O 3/2
Kc(trans) =
MC O2 MH2
The rotational factor in Kc is

Kc(rot)

 2 3/2
 2 
p
(Ia Ib Ic )H2 O 8h2kT
IC O 8h2kT
C O2 H2




=

2
2
H2 O C O
IC O2 8h2kT IH2 8h2kT
! 
p
1/2
(Ia Ib Ic )H2 O IC O
8 2 kT
=

2
IC O IH2
h2

2 a change is necessay in the factor containing

If all moments of inertia are expressed in amu A
the fundamental constants
!
p
1/2
2 (Ia Ib Ic )H2 O IC O
8 2 kT 1020
Kc(rot) =
IC O IH2
h2 LA
The second factor

8 2 kT 1020
h2 LA


= 114.8

The vibrational factor in Kc is

Kc(vib) =

qvib(H2 O , 3 modes) qvib(C O , 1 mode)

qvib(C O2 , 4 modes) qvib(H2 , 1 mode)

The molecular and other parameters are given in the table below

Property
Heat of formation at 0 K (kJ mol1 )
Bond length

(1010

m)

C O2

H2

H2 O

CO

393.165

0.000

238.935

113.813

1.160

0.741

0.960

1.128

Bond angle (degrees)

180

Moment of inertia (amu

A2 )

43.0

0.277

1.27

2350

4160

3652

Vibration frequencies

(cm1 )

104.5

1320

3756

668

1595

8.73
2168

668
1

Ia Ib Ic for H2 O is 1.128

The vibrational partition functions, the energies of the states being measured from their respective ground state, are listed below.

(cm1 )

qvib

2350

1.13

1320

1.43

668

2.18

668

2.18

H2

4160

1.02

H2 O

3652

1.04

3756

1.04

1595

1.30

2168

1.16

Molecule
C O2

CO
The heat of the reaction at 0 K is

E0 = 113.813 238.935 + 393.165 + 0.000 = +40.417 kj mol1

We finally obtain for Kc :


Kc =

18.02 28.01
44.01 2.016

= 2.98

3/2

2 1.27 8.73
114.8 0.208 exp(3.115)
43.0 0.277