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Heterogeneous catalysis
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Reaction rate
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Langmuir–Hinshelwood Mechanism
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Of the numerous boundary conditions that are possible, we will consider only
two in more detail here:
1) When both starting materials are only weakly adsorbed, then both KA and KB
<< 1 and the rate equation becomes reff = k’ pA pB and k’ = kKAKB. The reaction
is first order in both reactants and second order overall.
2) When A is weakly and B strongly adsorbed, KA <<1 << KB and the rate
equation reduces to
The reaction order is one with respect to A and minus one with respect to B.
Effect of pressure
Let us consider the reaction rate as a function of the partial pressure of component
A, that is, at constant partial pressure pB:
1) At low partial pressure pA, the product KA pA in the denominator of Equation is
negligible compared to (1 + KB pB) and it follows that
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Examples of LH mechamism
1) Oxidation of CO on Pt catalysts
2 CO + O2 Þ CO2
2) Methanol synthesis on ZnO catalysts
CO + 2 H2 Þ CH3OH
3) Hydrogenation of ethylene on Cu catalysts
C2H4 + H2 Þ C2H6
4) Reduction of N2O with H2 on Pt or Au catalysts
N2O + H2 Þ N2 + H2O
5) Oxidation of ethylene to acetaldehyde on Pd catalysts
CH2=CH2 + O2 Þ CH3CHO
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Eley–Rideal Mechanism
In this mechanism only one of the gaseous reaction partners (e. g.,
A) is chemisorbed.
Component A then reacts in this activated state with starting
material B from the gas phase to give the chemisorbed product C. In
the final step the product is desorbed from the catalyst surface.
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Reduction of CO2
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Oxidation of ammonia
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Comparison of a
heterogeneously
catalyzed reaction with
the uncatalyzed
equivalent.
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Molecular chemisorption
Dissociative chemisorption
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Heterolytic chemisorption
CO adsorption
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Diatomic chemisorption
One of the first predictions made on the basis of steric effects was
that the ease of chemisorption of diatomic molecules should
strongly depend on the lattice dimensions of the metallic catalysts.
The reasoning was that for large interatomic distances, diatomic
molecules would have to dissociate to be completely chemisorbed,
while for closely packed lattices, repulsion effects would hinder
chemisorption.
This is exemplified by the cyclohexane dehydrogenation. It was
shown that only elements with interatomic distances between 0.248
and 0.277 nm catalyze the dehydrogenation of cyclohexane.
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BCC
HCP
Hexagonal close packing
FCC
Face-centered cubic
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Steric effects
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