STATISTICAL THERMODYNAMICS OF IODINE SUBLIMATION

NAME

DATE

PRELIMINARY REPORT
To be completed and turned in at least 24 hours before you carry out the lab.
Assignment: Your goal in this lab will be to find the energy of sublimation of iodine by
measuring the vapor pressure of I2 at a series of different temperatures. The energy of
sublimation is defined as how much energy, E 00 , it takes to go from the vibrational ground state
of an iodine molecule in a crystal to the vibrational ground state of an iodine molecule in the gas
phase. You will also find the enthalpy and entropy of sublimation of iodine using partition
functions and the Clausius-Clapeyron equation.
References: This experiment and analysis is based on Experiment 48: Statistical
Thermodynamics of Iodine Sublimation in Shoemaker which you may find to be a useful
reference. A scanned copy of the Shoemaker pages is posted on Moodle under
Iodine_ShoemakerReference.
List of materials needed:
Brief outline of the procedure:
List data to be collected:
Any potential hazards (chemical, electrical, visual, etc.) associated with the lab:
Questions
1. For this experiment, you will determine the vapor pressure of I2 by using a uv-vis spectrometer
to measure the baseline corrected absorbance at 520 nm of I2 vapor. How will you translate the
absorbance measurements to pressure values? Pay attention to units.
2. What are the equations that define the translational partition function, rotational partition
function, and vibrational partition function?
3. What modes of motion (translational, vibrational, rotational) are important when describing
crystalline I2? Why?
4. How will you use the Clausius-Clapeyron equation to obtain the enthalpy of sublimation?

In this lab you will have the opportunity to apply statistical mechanical machinery to studying
the phase equilibrium between I2(s) crystals and I2(g). You will find that the experimental part of
the lab is straightforward, but the calculations are pretty complex. You will have to be organized
and careful if you hope to successfully complete this lab.
Your goal in this lab will be to find the energy of sublimation of iodine. In other words, how
much energy, E 00 , does it take to go from the vibrational ground state of an iodine molecule in a
crystal to the vibrational ground state of an iodine molecule in the gas phase? You will also find
the enthalpy and entropy of sublimation of iodine using partition functions and the ClausiusClapeyron equation.

Statistical Mechanical Background

In the temperature and pressure ranges you will use in this experiment, iodine exists in an
equilibrium between its gas and solid phases:
I2(s) I2(g)
If the two phases are in equilibrium then the chemical potentials for each of the two phases must
be equal:
mg = ms
We can use the partition functions for I2 in each phase and the machinery of statistical mechanics
to determine these chemical potentials. This will then let us continue on to work out the
energetics of the sublimation.
The chemical potential can be easily written as a derivative of the Helmholtz energy taken with
respect to the amount of material at constant temperature and volume.
A

n T ,V

We can write the Helmholtz energy as a function of the partition function as

A = -kB T ln Q
Combining these two equations yields:
A
lnQ
lnQ
= k B T
= RT

n T ,V
n T ,V
N T ,V

where n is the number of moles and N is the number of molecules.

(1)

Now we consider each of the two phases. First, lets look at the solid phase.
Solid Phase
Crystalline I2 can be reasonably approximated as a collection of independent harmonic
oscillators. Each of the oscillators will have its own molecular partition function, qi. Since we
have assumed the individual oscillators are independent the partition function for the solid is just
the product of the partition functions for the individual oscillators.
M

QS = qi
i=1

and
M

lnQS = lnqi
i=1

(2)

What should M, the number of oscillators be? Each atom can move in three dimensions and
there are two iodine atoms in each iodine molecule. Therefore the number of oscillators will be:
M = 3 x 2 x N = 6N.
We should subtract off six modes of motion for the three translational and three rotational
degrees of freedom of the crystal, but since the number of atoms is large, 6N 6 6N.
Because the oscillators in the crystal will vary in their vibrational frequencies it is best to define
a quantity qS which is the geometric mean of the qi for the crystal.
M
qS = qi
i=1

1 M
or lnqS = lnqi
M i=1

(3)

Since the only motion we have to consider in the crystal is vibrational motion, the partition
function qi will take the form of a vibrational partition function:

qi =

and

1

1 exp i
T

lnqi = 1 exp i
T

(4)

i is the vibrational temperature of each of the modes of vibration of the iodine crystal.

VIB =

h 0 hc 0
=
kB
kB

How should you think about the vibrations in the crystal? We will present a short summary here,
but you can consult books on solid state physics for a more complete discussion. One way is to
think of the iodine crystal as a giant molecule with 6N 6 normal modes. Lets start by thinking
about the vibrations in a single unit cell. Each unit cell in an iodine crystal has two molecules in
it for a total of four atoms. Four atoms in three dimensions give us twelve modes of motion. For
reasons which are a bit too technical to go into here, we can use the vibrational frequencies for
the two molecules in a unit cell as the frequencies we need to calculate the partition function for
the crystal.
If we had two individual I2 molecules there would be six translational modes, four rotational
modes, and two I I vibrations. In the unit cell, however, the I2 molecules are constrained from
translating and rotating the way they would in the gas phase. This results in six lattice modes,
four librational modes, and two internal bond-stretching vibrations. The lattice modes correspond
to motions in which the center of mass of each of the molecules moves. If both molecules move
in the same direction (either the x-, y-, or z-direction) the motion is called an acoustic vibration.
If the two molecules move out of phase (i.e. in opposite directions) then the mode is called an
optic vibration. There are three acoustic vibrations and three optic vibrations.
The four librations are oscillating or rocking motions. These correspond to the rotations in a free
molecule, but because the molecules are constrained from freely rotating because of the
adjoining unit cells, the molecules merely rock back and forth.
Finally, the two internal vibrations are coupled to each other rather than being identical
vibrations in each of the two molecules. One vibration is a symmetric stretch in which both
molecules vibrate in phase with each other. The other vibration is an antisymmetric stretch in
which one bond lengthens while the other shortens. The table below gives the phonon vibrational
frequencies for an I2 crystal.

Discrete phonon frequencies in I2 crystals

Mode number
1
2
3
4
5
6
7
8
9
10
11
12

Type of Mode
acoustic
acoustic
acoustic
optic
optic
libration
libration
optic
libration
libration
symmetric stretch
anti-symmetric stretch

Frequency (cm-1)
21.0
26.5
33.0
41.0
49.0
51.5
58.0
59.0
75.4
87.4
180.7
189.5

We can now calculate the partition function and chemical potential for the solid. Start with
equation (3), remembering that M = 6 N.

lnqS =

6N

1
lnqi
6N i=1

N
N
unit cells so we multiply by
and see that 12 is the number of degrees of freedom
2
2
per unit cell.

We have

lnqS =

1 N 12
1 12
lnq
=
j 12 lnq j
6N 2 j=1
j=1

and substitute in the expression from equation 4.

1 12
lnqS = ln1 exp i
T
12 j=1
If we do the sum in equation 3 explicitly for the case of iodine with M = 6N we see that

lnQS = 6N lnqS

We can then find the chemical potential for the solid as:

S = RT

lnQS
N

= 6RT lnqS
12

j
RT
=
ln1 exp

2 j=1
T
12
j
RT
=
ln1 exp

2 j=1
T

Gas Phase
When an iodine molecule is in the gas phase its energy can be approximated as a sum over four
different terms.

E tot = E trans + E rot + E vib + E elec

Since the energy terms are separable we can write the partition function as a product of the
partition functions associated with each of the motions of the molecule:
qg = qtransqrot qvib qelec

As discussed in your textbook, the translational partition function is given by:

3

2mk B T 2
qtrans =
V
h2
where m is the mass of a single molecule, kB is Boltzmanns constant, T is the temperature in
Kelvin, h is Plancks constant, and V is the volume of the container.
The rotational partition function is given by:

qrot =

kB T
hcB0

The constants are defined as before. In addition, B0 is the rotational constant. The rotational
constant for I2 is 0.037315 cm-1. Be aware that for consistent units you should put the speed of
light in cm s-1 units. s is the symmetry number for I2.
The vibrational partition function is based on the assumption that the vibrations in I2 can be
modeled as a quantum mechanical harmonic oscillator. The vibrational partition function is
derived by summing over the infinite series of vibrational levels in the harmonic oscillator. The
details are given in your text.
6

qvib

h 0
hc 0
= 1 exp
= 1 exp

k B T
k B T

0 is the vibrational frequency for I2 in units of s-1. 0 is the vibrational wavenumber in units of
cm-1. The vibrational wavenumber, 0 ,for I2 is 213.3 cm-1.
Notice that in evaluating the vibrational partition function we assumed that the zero of energy we
assumed that the vibrationless ground state of the I2(g) molecule is at zero energy. It turns out that
it is better to define the reference energy as the energy of an I2 molecule in a crystal when the
crystal is in its ground vibrational state. In order to accommodate this definition of the reference
state we need to add an amount of energy that we will call 0 to the energy of the gas phase
molecule. 0 is the amount of energy it takes to remove a molecule of I2 from the crystal at a
temperature of absolute zero. We will also need to define the amount of energy to remove a
mole of molecules from the crystal. This quantity will just be 0 multiplied by Avogadros
constant. E 00 = N 00 . Incorporating this change in reference state, the vibrational partition
function becomes:
qvib

hc 0
0
= 1 exp
exp

k B T
kB T

Lastly, the electronic ground state is non-degenerate and there are no low-lying excited
electronic states, so the electronic partition function equals one.

qelec = 1
Now for a one-component gas of indistinguishable molecules the partition function of the gas is
related to the molecular partition function by:

Qg =

qgN
N!

We can apply Stirlings approximation to eliminate the factorial term.

lnQg = N lnqg N ln N + N

Plugging this equation into equation (1) lets us find the chemical potential for the iodine in the
gas phase:

g = RT ln

qg
N

Plugging in the expression for the molecular partition function (qg = qtransqrot qvib qelec ) gives us the
following expression:
3
1

2 k T

hc
T
2

mk
T
0
B
g = E RT ln
1 exp
B

h 2 P rot
kB T

0
0

P in this equation is pressure. We have eliminated the volume from this expression by using the
Nk T
ideal gas law and letting V = B .
P
Equilibrium Between Solid and Gas
When the solid and gaseous iodine are in equilibrium with each other their chemical potentials
are equal. We can take the expressions for the chemical potential of the solid and the gas and set
them equal to each other. Following some rearrangement we find the following impressive
equation:
1
7 12

j 2
2
3
T
1
exp

2mk B 2 kB E 00
T
j=1

= ln
ln P ln

h 2 rot RT
hc 0

1 exp k T

(5)

Determining the pressure at one temperature allows you to solve this equation for E 00 . You can
do this calculation at each temperature to see how well the values agree with each other. If you
determine the pressure at several temperatures you can make a plot to determine E 00 . You can
check the quality of your plot by comparing the intercept from your plot to the constant term on
the right side of the equation.
You can also use your data and the Clausius-Clapeyron equation to obtain the enthalpy of
sublimation, H sub and entropy of sublimation, S sub . The Clausius-Clapeyron equation tells us
that:

ln P = constant

H sub
RT

The equations for the molar entropy of the solid is given by:

S S = S
T P

j
12

R
T
ln1 exp j
S S =
2 j=1 j
T

exp T 1

and for the gas phase:

S g = g
T P
vib

Sg = E 0 g + 7 R + R
vib
T
2

exp
T 1

where vib is defined the same way in the gas phase that it is in the solid phase, but with the
vibrational wavenumber of 213.3 cm-1. The expression for mg is given above.
The enthalpy of sublimation at some temperature, T, is given by:

H sub = TS sub = T (S g S S )
Experimental Procedure
You will measure the vapor pressure of iodine in 5 increments from 20 C to 70 C. You will
accomplish this by measuring the absorbance of I2 with a UV/vis spectrometer and then apply
Beers Law. Iodine has a strong electronic absorption from the ground electronic state to the
second excited state: X 1 +g B 3 0 + u . The absorption maximum for this transition is at 520 nm.
There is also an excitation to the lowest excited electronic state with a maximum at 700 nm, but
it is much weaker and we can neglect it. In addition to the iodine, the cell you are using also has
an atmosphere of air. The air collides with the iodine molecules and broadens and smoothes the
rotational lines in the spectrum. This makes it easier to get a value of the absorbance without
worrying about whether or not you are at the peak of a sharp rotational feature.
Make sure that you allow time for the temperature to stabilize. You should take three readings at
each temperature so you can get an idea of the reproducibility of your data.

Analysis of Experimental Results

There are two key things to remember when carrying out your calculations. Make sure your
spreadsheet is organized. Make sure you pay close attention to your units.
For each of your scans determine the difference between the absorbance at 520 nm and 700 nm.
There is weak absorbance at 700 nm so you are using that as a background to find a net
absorbance.
Beers Law tells us how to relate absorbance to pressure.

A = dc
We substitute in for the concentration term using the ideal gas law:
A=
P=

P
N
=
V RT

dP
RT
ART
d

d is the pathlength of your UV cell. e is the molar absorption coefficient at 520 nm. The table
l
below1 gives molar absorption coefficients in units of
.
mol cm
T (C)
(l/molcm)
20
691
30
682
40
672
50
663
60
654
70
646
Once you have determined the pressure at each temperature, you can use a plot of the ClausiusClapeyron equation to find H sub .
You can also calculate E 00 at each temperature using equation 5. How well do your values
agree with each other? You can also determine E 00 graphically using equation 5. How does
this value agree with the others? How close is the value of your y-intercept to the value you
would expect based on equation 5? Calculate the molar entropies for both the gas and the solid
at 320 K and find the molar heat of sublimation. How do your values compare to the literature
values2 for these quantities?

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Uncertainty Analysis
You can estimate the uncertainty in your E 00 measurements at the 6 different temperatures by
finding the standard deviation of these results. What assumption are you making when you make
this approximation? When determining E 00 graphically, make sure to include the uncertainty in
your slope (and also your intercept). Do your results agree with accepted values within your
uncertainty?
References
1. Shoemaker
2. D. A. Shirley and W. F. Giauque, J. Am. Chem. Soc. 31, 4778 (1959)

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