Secondary reactions in the γ-radiolysis of hydrocarbons with electron scavengers

Abstract

Secondary reactions in the liquid phase radiolysis of cyclohexane in the presence of N2O and SF6 have been examined by determining the yields of liquid products. When we added up to 0.3 M N2O, the hydrogen yield was reduced from its initial yield of 5.5 G units to 2.5 G units. The nitrogen yields were about twice the decrease in hydrogen yields. Bicyclohexyl and cyclohexene yields increased from their initial values to 2.27 and 3.50 G units respectively. When we added up to 0.12 M SF6, all the yields were decreased to about one half of their initial value.These results may be interpreted in terms of Dyne's general mechanism for the radiolysis of hydrocarbons if two cyclohexyl radicals are produced for every electron scavenged by N2O, but if none are produced for electrons scavenged by SF6. It is suggested that the total electron yield in pure cyclohexane is about 4.1 G units, of which only 3.0 G units produce hydrogen. The other 2.5 G units of hydrogen from the radiolysis of pure cyclohexane are presumed to arise from direct excitation.