Jonah Shoemaker

Nanomaterials in Energy Production/Storage

Homework 6

Problem 1:

a)

b) Molecular dissociation is more likely when the molecular antibonding states are filled. The rank of
these electronic configurations from most filled molecular antibonding states to least is d -> b -> a = c.
a’s and c’s molecular antibonding states are both completely empty, so molecular dissociation is equally
unlikely for both.

c) Out of the two dissociative configurations d and b, d has both chemisorption bonding orbitals
completely filled and completely empty chemisorption antibonding orbitals. Since the strength of the
adsorption is associated with filled chemisorption bonding orbitals, d will have a higher adsorption
strength than b, which has a partially filled chemisorption anti-bonding orbital.

d) Out of the two nondissociative configurations c and a, if I had to pick one, I would guess that a has a
higher adsorption strength, since the chemisorption anti-bonding orbital is at a higher energy level than
that of c and is therefore less likely to be filled by electrons gaining enough energy from thermal
fluctuations to jump up.
Problem 2:

In order to find the ratio of the reaction rates for the [111] and [112] surfaces of Ni, we have to use the
figure on slide 17 of the tenth set of lecture slides to find the activation energies of the two Ni surfaces.
This figure gives estimates of 1.05 eV and 0.9 eV for the [111] and [112] surfaces, respectively. Using
these, we get a reaction rate ratio of exp(-1.05 eV/(R*700°C))/exp(-0.90 eV/(R*700°C)). Using the
Boltzmann constant in units of eV/K, we get a reaction rate ratio of 0.17.

Problem 3:

First we have to calculate the d-band energies of the bimetallic surfaces. For 50% Pd, 50% Ni, the d-band
energy is -1.71 eV. For 50% Fe, 50% Ni, the d-band energy is -1.26 eV. Using these d-band energies, we
can then use the figure on slide 15 of the tenth set of lecture notes to get the heats of adsorption. For
the Pd mixture, the heat of adsorption is about -2.7 eV, and for the Fe mixture, it is about -2.25 eV. I’m
not entirely certain of what this question is asking for, but based on what we are given, the most
obvious choice is to calculate the ratio of the fractional coverages of these two mixtures. We can do this
using the expression for the fractional coverage given in slide 10 of the ninth lecture notes and the heat
of adsorptions we have obtained. If we assume that both surfaces have the same number of sites and
the same characteristic residence time τ0, and assume a temperature of 700° C, the ratio of the
fractional coverage of the Pd mixture to that of the Fe mixture is exp(-2.7 eV / kT)/exp(-2.25 eV/kT),
Using the Boltzmann constant in units of eV/K, we get a fractional coverage ratio of 0.005 between the
two different materials.

Problem 4:

Based on the graph, the heats of adsorption for the different strained samples are ΔH1 = -5.32 eV, ΔH2 =
-5.21 eV, and ΔH3 = -5.38 eV. Using the BEP relationship, we know that k 2/k1 = 10 = exp(-(m*ΔH2-c))/
exp(-(m*ΔH1-c)). Solving for the slope gives m = -3.5e23. Plugging this back in for k 3/k1 = exp(-(m*ΔH3-
c))/ exp(-(m*ΔH1-c)) gives the relative rate k3/k1 = 0.28.