Radiolyses of mixtures of ammonia and hydrocarbons, 2

Abstract γ-radiolyses of gaseous mixtures of ammonia and olefins (ethylene, propylene and butadiene) have been investigated over the whole composition range of mixtures, and consideration was given on the primary processes of hydrogen formation. From the extrapolated values of G(H2) obtained in the γ-radiolyses of the mixture of ammonia and olefins, it was found that the non-scavengeable G(H2) of ammonia, ethylene, propylene and butadiene were 0.68–0.72, 1.26, 1.06, and 0.33, respectively. Gas-phase radiolyses of ammonia-perdeuterated olefin mixtures have also been investigated. From kinetic calculation on the data of isotopic mixtures of hydrogen, the following results were obtained; 1) both thermal and non-scavengeable hydrogen molecules are produced by the γ-radiolysis of ammonia, and the non-scavengeable hydrogen molecules are produced for the most part by a unimolecular process, 2) almost all the hydrogen molecules produced by the γ-radiolyses of olefins (ethylene, propylene, and butadiene) are non-scavengeable; a unimolecular process plays an important role in the case of ethylene, and in other cases a bimolecular process. G(H2) of the butadiene radiolysis is very small compared with that of other olefins and with the calculated value of butadiene, i.e., G(H2)<1. The discrepancies can be interpreted in terms of the addition reaction of the "hot" hydrogen radicals to butadiene to form t-2-butene.