STATISTICAL PHYSICS: COMPUTATIONAL ASSIGNMENT I

D UE DATE
This assignment is due Thursday, June 8, 23:59.

H ANDING IN THE ASSIGNMENTS

Submission of the notebooks (1 per problem) is done on Brightspace (one submission per group!)
Your last submission counts. MAKE SURE THAT, E.G., ONE DAY BEFORE THE DEADLINE, YOUR
GROUP HAS ALREADY A NEAR-FINAL VERSION HANDED IN!!!
Wrap all notebook files into a single zip file. This file should be named using the net ID and
student NUMBER of the people in your group, as follows:
statfys_x_ID_NUMBER_ID_NUMBER.zip
where the x stands for the number of the session. A similar notation is to be used for groups con-
sisting of 1 or 3 students.

1. S YNGAS PRODUCTION
Syngas is a mixture of CO and H2 gases and is used mainly as intermediate product in the pro-
duction of ammonia and synthetic natural gas. One production route is by the steam reforming
reaction of natural gas (all products are gaseous):
C H4 + H2O ↔ CO + 3H2 . (1)
The Gibbs free energies of the various products involved (at 298 K, at atmospheric pressure) are
listed in the table.
(1) (6 points) Calculate the total change of Gibbs free energy for this reaction. Give the con-
dition that the reactants and products obey when in equilibrium, assuming the gases are
ideal.
Your notebook states the change of Gibbs free energy and the equilibrium condition.
Equilibrium conditions do not state anything on the rate of a chemical reaction. Assume
the forward and backward reaction rates (i.e. the number of reactions per unit time) at
some given condition are given as
p C H4 p H2 O
µ ¶µ ¶
R f or w ar d = k f (2)
p0 p0
pCO p H2 3
µ ¶µ ¶
R backw ar d = k b (3)
p0 p0

X G 0 (kJ/mol)
C H4 -50.5
H2O -228.6
CO -137.2
H2 0
1
2 STATISTICAL PHYSICS: COMPUTATIONAL ASSIGNMENT I

where p A denotes the partial pressure of substance A. k f = 10 and k b = 1 (never mind the
units).
(2) (3 points) Explain why the above expressions for the rates make sense?
Your notebook contains an explanation.
(3) (9 points) The reaction runs at constant pressure and temperature (both unknown but
fixed). We start with 1 mole of each of the 4 reactants, i.e. the partial pressure is 1/4 p 0
for each. The partial pressure can be calculated from the number of moles of A, N A , versus
the total number of moles present. For example pCO /p 0 = NCO /(NC H4 +N H2 O +NCO +N H2 ).
From the given intial condition, integrate the equations to steady state using the Euler tech-
nique from the previous assignment. Plot the number of moles of each reactant as function
of time. Choose the final time such that the situation is in equilibrium (trial and error will
suffice). To refresh your memory: The Euler technique for the equation d x/d t = f(x) is
xn+1 = xn + ∆t f(xn ). In the present case, the unknown vector x contains 4 elements.
Your notebook contains a plot of the evolution of the number of moles of each of the reactants
and products.

2. H2 VIBRATIONAL ENERGY LEVELS

The vibrational energy levels of an H2 molecule are approximately given by

E j = (1.03 j − 0.03 j 2 ), j = 0, 1, 2 . . . ,
This approximation is accurate up to j = 15. After this point, the molecule dissociates and no
discrete levels exist.
(4) (8 points) Give an expression for the vibrational partition function, Zn , where n in the max-
imum energy level accounted for (so n may range from 0 to 15). Set α = k B T = 1 and make
a plot of Zn vs n. (You can use the (np.)cumsum function and thereby avoid for-loops).
Repeat the calculation for α = 3. Plot Zn as a function of n for α = 1 and 3 in the same
graph. What do you deduce from the figure?
Your report should include the plot of Zn versus n with a legend indicating which points
(or curve) correspond to which value of α. Give the important conclusions from this figure.

(5) (10 points) Give an expression for the average energy, E . Numerically determine, and plot
its value versus α for α ranging from 0.1 to 3. In the same figure plot the average energy for
the ideal harmonic oscillator, where E j = j . Draw conclusions. For the harmonic oscillator
also restrict the values of j to the same range.
Your report should include the requested plot. Give the important conclusion from the
figure.

(6) (4 points) Prove that the heat capacity can be written as

∂E
C = kB (4)
∂α
Your report should include the derivation.
Hint: Use the chain rule to rewrite the derivative wrt β in terms of the derivative wrt α.

(7) (8 points) Numerically determine and plot the normalized heat capacity, C /k B , as function
of α for the given vibrational energy states as well as for the harmonic oscillator for α ∈
 STATISTICAL PHYSICS: COMPUTATIONAL ASSIGNMENT I 3

[0.1, 3]. To do so, evaluate the above derivative using finite differences as

∂E E (αi +1 ) − E (αi −1 )
|αi ≈ . (5)
∂α αi +1 − αi −1
Your report should include the figure containing the heat capacity, C /k B , as function of α.

3. R OTATIONAL ENERGY STATES OF A DIATOMIC MOLECULE

The rotational partition function is calculated as a sum over all rotational states that are acces-
sible to a diatomic molecule with two different atoms, such as CO. For angular momentum states
bounded by some integer number n, it is calculated as follows:
n
(2 j + 1)e −β² j ( j +1) ,
X
Zn =
j =0

where β = 1/(k B T ) and ² is some number involving the moment of inertia of the molecule. For
theoretical background, consult p 115 of the lecture notes, or 234-235 of Schroeder’s book.
(8) (8 points) Calculate Zn for n from 0 to 25 for α = k B T /² = 5 and make a plot of Zn vs n. (You
can use the (np.)cumsum function and thereby avoid for-loops).
Repeat the calculation for α = 50. Plot Zn as a function of n for α = 5 and 50 in the same
graph.
From this graph, estimate how large n should be to justify that the series for Zn has
converged for α = 5. We call that value n max .
Same question for α = 50. Do you need more or fewer terms in that case compared with
α = 5?
Your report should include the plot of Zn versus n with a legend indicating which points (or
curve) correspond to which value of α. Give the value for n max . Comment on the differences
between the two α values (5 and 50).

(9) (10 points) Now take n max = 5 and plot Znmax versus α for α ranging from 0.1 to 5 in steps
of 0.1 (please use blue dots in the plot). In the same plot, draw the line y = α (in red). This
is an approximation for the partition function at high temperature (α À 1, see eq. 6.31 in
Schroeder or the final part of section 5.4 of the lecture notes). Explain the results.
Your report should include the plot of Znmax vs. α (blue dots for Znmax , red line for the high-
temperature approximation). Also provide an explanation of the results.

(10) (5 points) Use the definiton of the average rotational energy E r ot (see eqn 32) to rewrite it
in terms of the temperature and the derivative of the partition function w.r.t. α.

1 ∂Z (k B T )2 ∂Z αk B T ∂Z
E r ot = − = = (6)
Z ∂β ²Z ∂α Z ∂α
Your report should include the derivation.
Hint: Use the chain rule to rewrite the derivative wrt β in terms of the derivative wrt α.

(11) (10 points) Let us consider the CO molecule (data for ² is given in the book). Our goal is to
determine the qualitative behaviour of the heat capacity, C . To this end first determine the
4 STATISTICAL PHYSICS: COMPUTATIONAL ASSIGNMENT I

average energy as function of α and store this in an array for further use. In order to do so,
approximate the derivative of Z wrt α at αi as
∂Z Z (αi +1 ) − Z (αi −1 )
|α ≈ . (7)
∂α i αi +1 − αi −1
Plot the average energy (in units of k B ) as function of T , together with the value from the
high temperature limit in a single graph. What do you conclude?
Your report includes the figure containing the normalized rotational energy for the exact and
approximate high temperature limit and an explanation of the results.

Submit this assignment following the instructions on the first page.