The Mercury Sensitized Reactions of Methane, Deuteromethanes and the Hydrogen Isotopes

Abstract

The interaction of methane and deuterium and of methane and methane‐d 4 under the influence of excited mercury have been studied. The influence of temperature, reactant concentration, light intensity and mercury concentration on the yield of deuteromethanes has been measured. Below 200° the results indicate that the production of deuteromethanes is governed by the photosensitized formation of free methyl radicals. At higher temperatures chain reactions become important and high quantum efficiencies of interaction are observed. A simultaneous process of condensation of methane to yield higher saturated hydrocarbons has been shown to occur and its kinetics and quantum efficiency studied. The condensation occurs in presence of hydrogen and its isotope. A sequence of reactions has been postulated and approximate energies of activation suggested which permit a description of the observed phenomena over the whole range of temperatures, light intensity and concentrations studied.