y-Radiolysis of Methane Adsorbed on '/-Alumina Part 2.1—Kinetics ot Reactions Occurring During Irradiation

Abstract

An earlier study showed that γ-alumina surfaces outgassed above 570 K contain sites involving exposed lattice ions at which methane is chemisorbed during γ-irradiation. When the species so formed are heated they decompose yielding C1—C3 alkanes and alkenes together with hydrogen. The present study investigates the kinetics of the reactions occurring during irradiation. These reactions are shown to be the activation of surface sites and the dissociative chemisorption of methane, in accord with the mechanism previously suggested. Overall product yields are chiefly determined by the rate at which excited charge carriers reach the surface, the highest rate observed being G(—CH4)= 2.0 but declining when fewer than ∼3 × 1015 m–2 chemisorption sites remain unoccupied. A kinetic scheme is proposed to account for the variation in yields with methane coverage, radiation dose and dose rate, and specific surface area of the γ-alumina. It is also shown that the individual products formed when the precursors decompose depend on the configuration of the methane chemisorption sites, and so on the origin of the γ-alumina and the outgassing temperature used.

Two subsidiary reactions are identified. The first of these resembles normal radiolysis but occurs at sites less accessible to methane. In the second, however, new surface species are formed when irradiation continues after either the methane or the chemisorption sites have been exhausted. These scavenge part of the adsorbed hydrocarbon material.