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All the models discussed in the present paper assume that dissociation of a reactant molecule is rate-limiting. If we instead impose stationary coverages, the assumption of a rate-limiting step is no longer necessary. We have implemented the stationary coverage microkinetic model for reactions, 1a, 1b, and 2. This model shows that under relevant reaction conditions the assumption of the rate-limiting step is well-justified and the qualitative behavior for the models discussed in the present paper stays unchanged in the relevant catalytic regime.
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32
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0141797998
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note
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Whereas the presented limit is correct for the model we discuss here, this limiting behavior is only correct when the dissociation of the reactant is the rate-limiting step. This is true close to the top of the volcano curve and to the right of it. A model that also takes the switching of the rate-limiting step into account shows a different limiting behavior for very low coverages of free stes. This happens further to the left of the top of the volcano, but this regime is, however, probably not experimentally accessible, as the metal surfaces there will have have a strong tendency to form nitrides, oxides, carbides, etc., depending on which reactants are used.
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