Temkin's theory of rates of catalytic reactions on non-uniform surfaces is extended to the MoO3-catalyzed oxidation of ethanol to acetaldehyde. Two types of sites are assumed to be present, an oxygen atom site that can be modeled with uniform properties and a metal atom site characterized by non-uniform properties both for ethanol chemisorption to an ethoxide intermediate and the conversion of this intermediate to acetaldehyde. The rate-limiting step is the cleavage of a C-H bond in the absorbed ethoxide intermediate. Non-uniform surface kinetics leads to a kinetic rate expression of the form $$v = kP_{C_2 H_5 OH}^{1 - m} P_{O_2 }^{(1 - m)/4} P_{H_2 O}^{ - (1 - m)/2} $$ . Such a rate expression, withm=0.14, is shown to provide a good fit to kinetic data for the selective oxidation of ethanol on a silica supported molybdenum oxide catalyst.
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