1 THE TRANSLATIONAL PARTITION FUNCTION 1

Partition Functions and Ideal Gases Examples

These are the examples to be used along with the powerpoint lecture slides. The problems
are numbered to match the tags in the the lower left hand corner of the powerpoint slides.
The numbers of the examples are # the in the PFIG EX# tags on the slides.

1 The translational partition function

We will work out the translational partition function. Start with the general expression for
the atomic/molecular partition function,
X
q= e "
states

For translations we will use the particle in a box states,

h2 n2
"n = along each degree of freedom (x, y, z)
8ma2
And the total energy is just the sum along all three degrees of freedom,

"trans = "nx + "ny + "nz

Inserting the particle in a box energies, and realizing that the exponential of a sum is the
product of exponentials,
1
X
qtrans = exp "nx + "ny + "nz
nx ,ny ,nz =1
1
X
= exp ( "nx ) exp "ny exp ( "nz )
nx ,ny ,nz =1
1
X 1
X 1
X
= exp ( "nx ) exp "ny exp ( "nz )
nx =1 ny =1 nz =1

Note that all three of the n quantum numbers have the same range of 1 to 1,
"1 # 3
X h2 n2
qtrans = exp
n=1
8ma2

Since the energy levels for translation are so closely spaced (remember that we estimated the
translational spacing to be roughly 10 12 kJ/mol compared with the energy of kB T at room
2 TAKE THE DERIVATIVE OF THE NATURAL LOGARITHM 2

temp which is 2.4kJ/mol) that we can consider the levels to be continuous. For a continuous
distribution the sum becomes an integral and we have,
Z 1 3
h2 n2
qtrans = dn exp
0 8ma2
Note that we changed the lower limit from 1 to 0, however for such a small step size this will
have almost no eect on the value of the integral.
We can use the definite integral (look it up in a table for example),
Z 1 1/2
2 h2
dn e n = with =
0 4 8ma2
and the result is the translational partition function,
3/2
2mkB T
qtrans (V, T ) = V
h2

2 Take the derivative of the natural logarithm

One of the most common operations we will perform on the partition function will be to
take the derivative of the natural log with respect to one of the variables. As an example
consider,
@
ln [qtrans (V, T )] =?
@V
Remember the properties of logs,

ln ABC = ln A + ln B + ln C and ln Ax = x ln A

We have
" 3/2 #
@ 2mkB T 3 @ 2mkB T d 1 1
ln V = ln + ln V = 0 + =
@V h2 2 @V h 2 dV V V
| {z }
no V dependence

3 Contribution to qelec by the first excited state

Here we consider the contribution of the first excited electronic state to the molecular elec-
tronic partition function. We can write the partition function as the sum over states,
"e2
qelec = ge1 + ge2 e +
4 FRACTION OF ATOMS IN THE FIRST EXCITED STATE 3

were we have referenced the ground electronic state to zero, "e1 = 0. So the contribution from
the ground state is eectively unity (or the value of the degeneracy) and we can compare
that to the contribution from the first excited state.
Consider a typical value for the energy of the first excited state (relative to the ground
state) of "e2 40000 cm 1 .
First we must make the units of "e2 and kB agree. Note that kB has units of energytemperature 1 ,
so you should be able to convert kB to cm 1 K 1 (check to see that you can do this!),

1 1
kB = 0.695 cm K

Now calculate the argument of the exponential,

"e2 40000 cm 1 1 5 104 K

"e2 = 1
kB T 0.695 cm 1 K T T
This means even at T = 1000 K the argument of the exponential is still 50,

"e2 50 22
At 1000 K: e =e 2 10

Even if the excited state is only 7000 cm 1 above the ground state, "e2 7000 cm 1 , the
argument of the exponential would be 10 and,

"e2 10 5
At 1000 K: e =e 4.5 10

This shows that at typical temperatures the contribution of the first excited state is 10 5
that of the ground state, and we can ignore it.
*However realize that there could be exceptions if we had a system with a very small energy
gap to the first excited state and/or a very high temperature. (On the next lecture slide we
will note that halogen atoms are a good example of a small energy gap to the first excited
state and may require keeping the second term.)

4 Fraction of atoms in the first excited state

Here we will compare the fraction of atoms in the first electronic excited state for Helium
and Fluorine. The fraction in the first excited state is,

ge2 e "e2 ge2 e "e2

f2 = =
qelec ge1 + ge2 e "e2 + ge3 e "e3 +
5 VIBRATIONAL CONTRIBUTIONS TO THE HEAT CAPACITY 4

First consider Helium. Using the values in MS Table 4.1,

(159850 cm 1)
3e
f2 = (159850 cm 1) (166272 cm 1)
1 + 3e + 1e +
3 334
At 300 K: = 4.796 10 cm ! f2 10
4 33
At 3000 K: = 4.796 10 cm ! f2 10
Note that these are typical values for nobel gases. No need to worry about the first
excited state when calculating the electronic partition function for a nobel gas.

Now consider Fluorine. Using the values in MS Table 4.1,

(404 cm 1)
2e
f2 = (404 cm 1) (102406 cm 1)
4 + 2e + 6e +
3
At 300 K: = 4.796 10 cm ! f2 0.0672
3
At 1000 K: = 1.439 10 cm ! f2 0.219
4
At 2000 K: = 7.194 10 cm ! f2 0.272
Here we see that since halogens have a low lying first excited state, we must consider
the first excited state when calculating the partition function. Note that the second
excited state is up by about 100000 cm 1 and can be neglected.

5 Vibrational contributions to the heat capacity

Consider the contribution to the heat capacity for N2 and Br2 . Our general expression for
the vibrational contribution to the molar heat capacity of a single harmonic oscillator is,
2
vib e vib /T
CV,vib = R 2
T (1 e vib /T )
First consider 14 N2 , with = 2330 cm 1 .
Calculate the vibrational temperature,
h (energy)
vib = = 1
kB (energy) K
1
Using kB in cm K 1,
2330 cm 1
vib = = 1 = 3353 K
kB 0.695 cm 1 K
6 THE ROTATIONAL PARTITION FUNCTION 5

Calculate CV,vib at 500 K,

vib 3353 K
= = 6.706
T 500 K
e 6.706
CV,vib = 8.314 J K 1 mol 1 (6.706)2 0.459 J K 1
mol 1
(1 e 6.706 )2

Compare to 79 Br2 , with = 323 cm 1 .

Calculate the vibrational temperature,

323 cm 1
vib = = 1 465 K
kB 0.695 cm 1 K
Calculate CV,vib at 500 K.
vib 465 K
= = 0.93
T 500 K
e 0.93
CV,vib = 8.314 J K 1 mol 1 (0.93)2 7.74 J K 1
mol 1
(1 e 0.93 )2

Notice the relationship between the vibrational temperature (frequency), the tempera-
ture, and the relative contribution to the heat capacity. When the temperature is near
or above the vibrational temperature, the contribution to the heat capacity approaches
the classical limit of R.
At 500 K:
Br2 (vib = 465 K) ! CV,vib 0.93R
N2 (vib = 3353 K) ! CV,vib 0.06R

6 The rotational partition function

Work out the integral for the rotational partition function. After assuming the the energy
levels can be approximated as continuous, the sum becomes an integral,
Z 1
qrot (T ) = (2J + 1) e rot J(J+1)/T dJ
0

Make a substitution,
x = J(J + 1) dx = (2J + 1)dJ
Z 1
rot x/T
qrot (T ) = e dx
0
7 DIATOMIC ENERGY AND HEAT CAPACITY FROM Q 6

Work the integral, 1

T rot x/T
= e
rot 0

T rot 1/T T rot 0/T
= e e
rot rot
T
=0+
rot
T
qrot (T ) =
rot

7 Diatomic energy and heat capacity from q

(This follows example 4-5 Gold or 18-5 Red in MS.) For a diatomic, use our expression for
q(V, T ) to calculate U and CV . We have derived,
3/2
2M kB T T e vib /2T
q(V, T ) = V ge1 eDe /kB T
h2 rot 1 e vib /T

So we start with the general expression,

[q(V, T )]N
Q(N, V, T ) =
N!
and we will use,
2 @ ln Q 2 @ ln q
U = kB T = N kB T
@T N,V @T V

Now using our expression for q(V, T ),

3 vib vib /T De
ln q = ln T + ln T ln 1 e + + (terms not containing T )
2 2T kB T
Now take the derivative with respect to T ,
vib
@ ln q 3 1 vib T2
e vib /T De
= + + +
@T V 2T T 2T 2 1 e vib /T kB T 2

2 @ ln q N =NA and NA kB =R 2 @ ln q
U = N kB T ! U(per mole) = RT
@T V @T V
vib /T
3 vib vib e
U = RT + RT + R +R vib /T
NA De
2 2 1 e
8 WORK OUT THE POLYATOMIC PARTITION FUNCTION 7

Note that you get 12 RT for each translational degree of freedom and 12 RT for each rotational
degree of freedom, followed by the zero point vibrational contribution, the vibrational con-
tribution, and the electronic contribution which is T independent because we only consider
the ground state. And the heat capacity is just the derivative with respect to temperature,
2
@ U 3 vib e vib /T
CV = = R+R+R 2
@T N,V 2 T (1 e vib /T )

Note that here we get 12 R for each translation and rotation, and this is T independent because
we assumed that the levels were continuous. Note that the vibrations are quantized, so they
have a complex contribution, and since we assumed only one electronic state there is no
electronic contribution to CV .

8 Work out the polyatomic partition function

This is clarification of eq 4.45 and 4.46 in the Gold or 18.45 and 18.46 in the Red McQuarrie
and Simon.
For polyatomic vibrations we consider normal coordinates or normal modes (remember?).
These modes act as independent harmonic oscillators, therefore the total vibrational energy
of a polyatomic molecule is (eq 4.45 Gold or 18.45 Red),
X
1
"vib = hj vj +
j=1
2

where

= the number of vibrational degrees of freedom.

vj = the vibrational quantum number for the jth vibrational mode. This can range
from 0 to 1

j = the vibrational frequency for the jth mode.

So if we consider water there are 3 vibrational modes,

1 1 1
"vib = h1 v1 + + h2 v2 + + h3 v3 +
2 2 2
Now use the expression for the total vibrational energy to get the vibrational partition
function, X
qvib = e "vib
states
9 HEAT CAPACITY AND CONTINUOUS ENERGY LEVELS 8

Insert the energy expression and sum over all possible states (all possible quantum numbers),
1
X
e ([h1 (v1 + 2 )]+[h2 (v2 + 2 )]+[h3 (v3 + 2 )])
1 1 1
qvib =
v1 ,v2 ,v3 =0

and the sum of exponential arguments is the product of exponential (since the energy is the
sum, the partition function will be the product),
1
X 1
X 1
X
h1 (v1 + 12 ) h2 (v2 + 12 ) h3 (v3 + 12 )
qvib = e e e
v1 =0 v2 =0 v3 =0

Each of the sums is just an individual vibrational partition function,

vib,1 /2T vib,2 /2T vib,3 /2T
e e e
qvib = vib,1 /T vib,2 /T vib,3 /T
1 e 1 e 1 e

Introduce the product symbol and we have equation 4.46 Gold or 18.46 Red,

Y vib,j /2T
e
qvib = vib,j /T
j=1
1 e

**Can you get equation 4.47 Gold or 18.47 Red?

9 Heat capacity and continuous energy levels

Why do continuous energy levels lead to CV being temperature independent? Consider a
demo to show how temperature and energy in dierent modes is related, and how quantized
energy levels will change how the addition of thermal energy is related to the temperature.
This demos can also show how more degrees of freedom will provide more places to put the
energy and will increase the heat capacity.
[Work out this demo with Joe Franek] This is the Green juice demo.