Theoretical and experimental work is described which leads to a novel hypothesis for explaining the selectivity in heterogeneous vapor phase hydrocarbon oxidation catalysis. Two essential postulates of the hypothesis are:1. The oxygen atoms must be distributed on the surface of a selective oxidation catalyst in an arrangement which provides for limitation of the number of active oxygen atoms in various isolated groups.2. The metal-oxygen bond energy of the active oxygen atoms, a t the conditions of reaction, must be in a range where rapid removal (hydrocarbon oxidation) and addition (regeneration by oxygen) is assured.Monte Carlo methods are used to illustrate the distribution of isolated sites on catalytic surfaces under the dynamic conditions of hydrocarbon oxidation reactions. Differences in catalyst and process requirements between oxidation processes operating in an overall oxidizing or reducing atmosphere are discussed.
detected by Craig, Diller, and Rowe (12) may be derived from it. Experimentally determined stoichiometric ratios are summarized in Table 1, for comparison with Eq. 7.No attempt is made at present to specify the structure of the crosslinks formed, which may depend on temperature. The instability of olefinic disulfides at curing temperatures is well known (13, 14).
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