Abstract
Transient flash desorption spectra arising from coadsorbed CO and O on polycrystalline Rh wire are analyzed in terms of a bimolecular reaction between CO(a) and O(a) to produce CO 2(g) by a Langmuir-Hinshelwood path. An activation energy which decreases with increasing oxygen coverage is found to adequately describe the data but cannot be unambiguously distinguished from other models in which the activation energy increases with CO coverage or in which the orders in oxygen and carbon monoxide coverage depart from unity. Phenomenological descriptions in terms of separate domains of carbon monoxide and oxygen are discussed. Comparison of the rates of CO 2 production in the presence and absence of gas phase CO indicates that the entire rate can be adequately described by a Langmuir-Hinshelwood path in which the activation energy decreases with oxygen coverage.
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