A Summary of Statistical Thermodynamic Calculations

by
Sidney Young
Department of Chemistry
University of South Alabama
Mobile AL 36688-0002

and

Theresa Julia Zielinski

Department of Chemistry
Medical Technology and Physics
Monmouth University
West Long Branch, NJ 07764-1898

syoung@jaguar1.usouthal.edu
tzielins@monmouth.edu
Copyright Sidney H. Young and Theresa Julia Zielinksi, 1997. All rights reserved. You are welcome to use this
document in your own classes but commercial use is not allowed without the permission of the author.

Introduction: In this document the fundamental equations for calculating the thermodynamic
properties of molecules and equilibrium constants for reactions are presented. You will see how
the translation, rotational, vibrational and electronic states of molecules contribute to their
thermodynamic properties. After studying this document you will be able to use the Mathcad
equations as templates for determining the thermodynamic properties of molecules and
reactions of interest to you and for your own projects.
Goal: To provide students with the basic statistical thermodynamic equations for computing
thermodynamic properties of molecules and reactions.
Prerequisites:
1. Basic skills with Mathcad up to and including taking derivatives and using
evaluate from the Symbolic drop down menu.
2. Knowledge of the existence of quantum mechanical energy levels; prior study
of the classical ideas of translation, rotation, and vibrational modes that
contribute to heat capacity.
3. Be able to distinguish between linear and nonlinear molecules.
4. Knowledge of the relationship between the Gibbs free energy and the
equilibrium constant.
Performance Objectives:
1. Compute the translational, rotational, vibrational, and electronic partition functions.
2. Compute A, U, S, G, etc. thermodynamic functions from the translational, rotational,
vibrational, and electronic partition functions.
3. Compute the equilibrium constant for a reaction from the partition functions of
the reactants and products.
4. Explain the shape of heat capacity as a function of temperature curves.
5. Identify the contribution from rotation, vibration, translation, and electronic
degrees of freedom of the molecule or atom.
6. Explain the shape of heat capacity curves in terms of the degree of importance of the
rotation, vibration, translation, and electronic degrees of freedom in the atom or molecule.

Created: Spring 1997

Modified: August 1997

stat_thermo.mcd

Author; Sidney H. Young &Theresa Julia Zielinski

Page 1

Part I.
Thermodynamic properties of molecular nitrogen from statistical thermodynamics
The first substance that we will study in this statistical mechanics exploration is molecular
nitrogen. We will step through the process of determining the thermodynamic functions and
heat capacity as a function of temperature. We will liberally use units in this exercise.
First define some constants:
23
6.02. 10

23.

1.38. 10

6.626. 10

.028 .

mass

Avogadro's number
joule . K

34.

k = 1.38 10

joule. sec

23

34

h = 6.626 10

kg

kg m sec
2

kg m sec

26

mass = 4.651 10

kg

Boltzman constant

Planck's constant

Mass of Nitrogen

N
8
3.00. 10 . m. sec

c
R

8.314. joule. K

c = 3 10

m sec
2

R = 8.314 kg m sec

Speed of light
1

The gas constant

Now set the properties of the gas, i.e. the temperature and pressure
T

300. K

1 . atm

P = 1.013 10

R. T

kg m
3

sec

Compute the volume

V = 0.025 m

A. Calculating the Partition Functions

1. The translation partition function

qt

2 . . mass. k. T
2

1.5

.V

30

qt = 3.561 10

Created: Spring 1997

Modified: August 1997

stat_thermo.mcd

Author; Sidney H. Young &Theresa Julia Zielinski

Page 2

2. The rotation partition function

2.010. cm

B = 201 m

Rotational Wave Numbers

B. c. h

Thetar

k
Thetar = 2.895 K

T
.
2 Thetar

qr

Thetar is the rotational

temperature

The rotational partition function tells us the approximate

number of populated states.
On a separate worksheet calculate the rotational partition
function for a series of diatomic gases and determine how
the number of populated state varies as a function of
mass and bond length. Why is bond length important
here? Explain.

qr = 51.809

3. The vibration partition function.

2359.61 . cm

nu

nu is the vibrational frequency

of the nitrogen molecule.
5

nu = 2.36 10
Thetav

h. nu. c

Thetav is the vibrational temperature.

k
3

Thetav = 3.399 10

qv
1
qv = 1

Created: Spring 1997

Modified: August 1997

Thetav
T

qv is the vibrational partition function.

What is the significance of having a large vibrational
temperature? How does this correlate with the result
computed here to the left that shows that the
vibrational partition function qv=1.

stat_thermo.mcd

Author; Sidney H. Young &Theresa Julia Zielinski

Page 3

4. The electronic partition function

qe

Why is the electronic partition function equal to 1?

We explicitly include qe here to retain generality of the

method in this document.
q

qt. qr. qv. qe

The total partition function is the product of the

four contributing partition functions.

32

q = 1.845 10

Q is the canonical ensemble molar partition function. It is this

quantity that is connected to the thermodynamic property
known as the Helmholtz free energy. Q is so large that we can
only calculate lnQ.

lnQ

N . ln( q )

N . ln( N )

Using Sterling's approximation show that Q

leads to

n!
the equation on the left.

25

lnQ = 1.237 10

Created: Spring 1997

Modified: August 1997

Now that we have lnQ we can calculate the thermodynamic

properties of nitrogen gas at the temperature and pressure
specified near the top of this document.

stat_thermo.mcd

Author; Sidney H. Young &Theresa Julia Zielinski

Page 4

B. Calculating the Thermodynamic Properties

1. Helmholtz free energy
4

k. T. lnQ

A = 5.119 10

kg m sec

2. Internal Energy
Thetav

Notice how u is defined here

T
3. .
RT
2

R. T

R. Thetav
u

E = 6.236 10

kg m sec

3. Entropy
E

A
T

S = 191.429 kg m sec

Lit value: 191.6

4. The heat capacities, Cv and Cp

3.

Cv

2 u
R. u . e

Cv = 20.798 kg m sec
Cp

Cv

See below for the derivation of the of the

vibration heat capacity term.

2
2

Cp = 29.112 kg m sec

Lit value: 29.06

5. Enthalpy and Gibbs free energy.
H

R. T

H = 8.73 10
G

T. S

kg m sec
4

G = 4.87 10

kg m sec

6. The Helmholtz free energy again.

A

T. S

A = 5.119 10

kg m sec

Compare with above. This is a redundancy

confirmation to check that everything is working.
Created: Spring 1997
Modified: August 1997

stat_thermo.mcd

Author; Sidney H. Young &Theresa Julia Zielinski

Page 5

Part II. Mathematical Interlude:

Below we see the derivation of the vibrational contribution to the heat capacity. This
shows how the vibration term arises from the vibration partition function.

qv
1

Start with the definition of the vibration partition function and

use the ctrl = key sequence to write the equation.

Thetav
T

2 d
E R. T . ln( qv )
dT

Here we write the definition of E in terms of the vibrational

partition function.

2 d
E R. T . ln
dT

exp
E

Thetav
T

Thetav
T

R. Thetav.
1

exp

Thetav
T

You can obtain this equation by replacing qv by is

equivalent defined above using cut and paste. Then
symbolically evaluate the derivative as described
immediately below.

This is obtained by placing the selection box

around the derivative part of the equation just
above and choosing Evaluate followed by using
Evaluate Symbolically from the Symbolic menu.
Try these steps for practice.

by substitution, yields

. .
. u. T. exp( u ) R u T
u
exp( u ) )
e 1
R

E
(1

Created: Spring 1997

Modified: August 1997

Use cut and past to generate the

equation to the left.

stat_thermo.mcd

Author; Sidney H. Young &Theresa Julia Zielinski

Page 6

We can now extend the derivation to obtain the heat capacity equation.

Starting with

R. u. T

5. .
RT
2

Substituting for u yields

Thetav
T

5. .
RT
2

where

Thetav

R.
exp

Thetav

Next take the derivative with respect to T to obtain

Cv

5.

Thetav

R.

2
exp

2
2

Thetav

2
1 .T

. exp Thetav
T

Do this step to verify the

result.
Thetav u. T

by substitution, yields

Cv

5.
2

Created: Spring 1997

Modified: August 1997

R.

( exp( u )

1)

. exp( u)

stat_thermo.mcd

Author; Sidney H. Young &Theresa Julia Zielinski

Page 7

Part III. Obtaining the equilibrium constant for N2 <---> 2 N as a function of temperature
First obtain the partition function for each component of the equilibrium. In this case we need
the partition function for both N2 and N.

1.5

2 . . mass. k. T

qN2( T )

. V.

2 . Thetar
1

.014 .

massN

Thetav
T

.1

The partition function for N2

The mass of atomic nitrogen

kg

N
Now compute the atomic partition function for atomic N
1.5

2. . massN . k. T

qN( T )

.V . 4

6. e

27658.7. K
T

4. e

27671.7. K
T

6.e

41492.4. K
T

Immediately above is the partition function for atomic nitrogen. It includes

contributions from the first three excited states.
Note: This can be coupled to determination of the term symbols for the states of
nitrogen as a link between statistical thermodynamics and spectroscopy. Recompute
the partition function without the highest energy level term. Decide if this energy level
is essential in the final heat capacity calculation

lnQN2( T )
lnQN( T )

N . ln( qN2( T ) )
N . ln( qN( T ) )

N
N

Here we are computing the

natural log of molar partition
functions

Now we calculate the Helmholtz free energy for

each component of the equilibrium

k. T. lnQN( T )

GN2( T )

GN( T )

N . ln( N )

k. T. lnQN2( T )

AN2( T )
AN( T )

N . ln( N )

AN2( T )

AN( T )

Created: Spring 1997

Modified: August 1997

R.T

R. T

Here we calculate the Gibbs free energy. Using

what you know and your text explain why the
equation to calculate the Gibbs free energy is
different from that used for the molecular nitrogen
example.

stat_thermo.mcd

Author; Sidney H. Young &Theresa Julia Zielinski

Page 8

Now calculate delta G

( 2 . GN( T )

Delta_G( T )

GN2( T ) )

9.756. 1.6 . 10

19.

N . joule

The third term in the expression for the change in Gibbs free energy is
necessary because the bottoms of the potential energy functions of the
products and reactants do not match. One is displaced from the of the
other by the dissociation energy Do.

Keq( T )

Delta_G( T )
R. T

Keq( 300. K ) = 5.399 10

159

Keq( 1000. K ) = 3.266 10

Calculate the equilibrium constant and the value of the

equilibrium constant at several temperatures. How does K
vary with temperature? How does the equilibrium shift with
increasing temperature?

44

Keq( 8000. K ) = 0.349

At what temperature does this reaction become

spontaneous? What is K at the point where the reaction just
becomes spontaneous?

To answer this question you want to find the temperature

where the equilibrium constant equals 1. To do this we
can set up a solve block. Make an initial guess for this
temperature based on your observations on how the
equilibrium constant varies with temperature. Here we
have chosen T to be 8000 K. Next set up the solve block
using the Given statement. Set the condition for the
solution and then use the Find function. If you have a
good guess then the temperature will be found.

8000 . K

Given
Keq( T ) 1
Tout

Find( T )

Tout = 8.628 10

Here we have the temperature and the equilibrium

constant.

Keq( Tout ) = 1

Created: Spring 1997

Modified: August 1997

stat_thermo.mcd

Author; Sidney H. Young &Theresa Julia Zielinski

Page 9

Part IV. Heat Capacity of a Linear Polyatomic, CO2, at 15 C, 1 atm.

T
Cvt

293. K
3.

1997 . K
3380 . K

2
Thetav
Cvr

Thetavi

3
Cvv

Thetav

Thetav

e
2

Cvt

Cvr

2
i

Cvv = 7.715 kg m sec

.e

R.
i=0

Cvtot

960. K
960. K

How many modes of vibration are present in

CO 2? Are there degenerate modes? What are
the vibrational temperatures for these modes?

Here we compute the vibrational

contribution to the heat capacity. This
is an extension of the formula we
used for nitrogen gas above.

Cvv
2

Cvtot = 28.5 kg m sec

Here we compute the total heat capacity.

Lit: 28.09

Created: Spring 1997

Modified: August 1997

stat_thermo.mcd

Author; Sidney H. Young &Theresa Julia Zielinski

Page 10

Part V. Heat Capacity of a nonlinear Polyatomic, H2O, at 15 C, 1 atm.

3.

Cvt

Translation contribution to the heat capacity.

2
2

Cvt = 12.471 kg m sec

Cvr

3.

Rotational contribution to the heat capacity. Why is

the rotational contribution to the heat capacity for
water different from that for CO2?

2
2

Cvr = 12.471 kg m sec

5254 . K
2995 . K

Thetav

How are the number of modes of vibration

for H 2O different from the number of modes
for CO2 and why?

5404 . K

2
Cvv

Thetavi

Thetav

.e

R.

Thetav

i=0
e

Cvtot

Cvt

Cvr

Cvv

Cvv = 0.032 kg m sec

Here we are computing the vibrational

contribution to the heat capacity

Cvtot = 24.974 kg m sec

Here we compute the total heat capacity.

2

Lit: 25.28

Created: Spring 1997

Modified: August 1997

stat_thermo.mcd

Author; Sidney H. Young &Theresa Julia Zielinski

Page 11

Part VI. The strange case of NO: The effect of a low-lying electronic
energy level on the heat capacity of NO.
3.

Cvt

The translation contribution.

2
Cvr

The rotational contribution.

R
1
1904.20 . cm . c. h

Thetav

The vibrational temperature.

k
3

Thetav = 2.743 10

K
2

Cvv( T )

Thetav

R.
exp

Thetav

2
1 .T

. exp Thetav
T

This is the vibrational

contribution to the heat capacity.

T
Now we will consider the electronic partition function for the NO molecule. This molecule has
one unpaired electron in the highest occupied molecular orbital. The molecular term symbol is a
doublet. Also there is a low lying excited state molecular orbital. This level is sufficiently low so
that a significant population of molecules have the single electron in this energy level. This
energy level will be singly occupied and thus have a doublet molecular term symbol. Since both
of these levels are doublets they have a degeneracy of 2. Higher energy molecular orbitals are
not populated so they do not contribute to the partition function.

qe

qe( T ) 2

2. e

174.2. K
T

2.e

174.2. K
T

Here we write the Mathcad numerical definition of the

partition function for electronic partition function. The first
term on the right hand side of this equation is for the
ground state. Why is this term simply the integer 2?
Here we have the electronic partition function written
in the Mathcad symbolic form.
Place the blue selection cursor next to the T in the
equation and choose differentiate on variable from the
Symbolic menu.
Note: you can take the derivative of a symbolic but not of a
numerical definition.

This yields the following equation. Try it for yourself.

K
K
d
qe( T ) 348.4. . exp 174.2.
2
dT
T
T

Created: Spring 1997

Modified: August 1997

stat_thermo.mcd

Author; Sidney H. Young &Theresa Julia Zielinski

Page 12

Ue( T )

Create the equation on the left by cut and paste.

174.2
2 348.4. K .
R. T .
exp
2
T
T
2

2. e

What is the electronic heat capacity in

the limit of very high temperatures?

174.2. K
T

Select the equation above and choose Symbolic Simplify to get the following:

174.2

exp

Ue( T ) 174.2. R. K.

exp 174.2.

1.

K
T

differentiation yields (Verify the result shown here by using the appropriate Mathcad
procedure.)

exp 174.2.

K
d
Ue( T ) 30345.64. R. .
2
dT
T

exp 174.2.

T
1.

exp 174.2.

2
30345.64. R. K .

K
1.

K
exp 174.2.
T

. T2

simplifies to
exp 174.2.

K
T

d
2
Ue( T ) 30345.64. R. K .
dT
1.

exp 174.2.

. T2

T
Cut and paste to create the
numeric heat capacity equation
exp 174.2.
Cve( T )

K
T

2
30345.64. R. K .

1.

exp 174.2.

. T2

Created: Spring 1997

Modified: August 1997

stat_thermo.mcd

Author; Sidney H. Young &Theresa Julia Zielinski

Page 13

Now compute the total heat capacity and each of the contributing terms.
2

Cvt = 12.471 kg m sec

1
2

Cvr = 8.314 kg m sec

Cve( 100. K ) = 3.2 kg m sec

Cvv( 100. K ) = 7.657 10

kg m sec
2

Cv( T )

Cvt

Cvr

Cvv( T )
2

Cv( 40. K ) = 22.759 kg m sec

Cve( T )
2

Cvne( T )

Cvt

Cvr

Cvv( T )

Heat capacity without the electronic term.

Cvnv( T )

Cvt

Cvr

Cve( T )

Heat capacity without the vibrational term.

Created: Spring 1997

Modified: August 1997

stat_thermo.mcd

Author; Sidney H. Young &Theresa Julia Zielinski

Page 14

Now we systematically vary the temperature and examine the results graphically.

At very low temperatures the electronic contribution to

the heat capacity dominates and saturates as shown by
the peak in the graph. The heat capacity then declines to
a minimum until the vibration term kicks in.

20 , 40 .. 1000

30

Figure legend.
Cv( i . K )
20

Cvne is the heat capacity with

no electronic term

10

Cvnv is without the vibration term.

Cvne( i. K )
Cvnv( i. K )
Cve( i. K )

Cve is electronic term alone.

0

500

1000

Cv is the total heat capacity.

By inspection of the graph describe where the electronic contribution is most

important and how this contribution changes with temperature. Why is this
happening? When does the vibrational contribution become important? Why?

Mastery Exercise:
The energy levels for an electron constrained to move on a ring with a diameter of 0.4 nm

are given by E n

2 2
hbar . n

where n is the quantum number identifying the energy level, m is the mass
2
2 . m. d
of the electron and d is the diameter of the ring. Write the expression for the partition function for the
electron on the ring. At room temperature would the electronic partition function for this system
contribute significantly to the heat capacity. Explain by providing graphical or arithmetic evidence.

Acknowlegment: The authors acknowledges the National Science Foundation for support of the 1997
NSF-UFE Workshop on "Numerical Methods in the Undergraduate Chemistry Curriculum Using the
Mathcad Software" and the organizers (Jeff Madura, Andrzej Wierzbicki and Sidney Young, University of
South Alabama).

Created: Spring 1997

Modified: August 1997

stat_thermo.mcd

Author; Sidney H. Young &Theresa Julia Zielinski

Page 15