RADIOLYSIS OF SOLUTIONS OF PERFLUOROCARBONS IN N-HEXANE

The radiolytic yields of hydrogen and hydrogen fluoride in dilute solutions of perfluorocarbons in n-hexane were determined, as well as the yields of cyclohexene and bicyclohexyl in solutions of perfluorocyclobutane in cyclohexane. The larger perfluoroalkane molecules, beginning with C4F10, were found to depress the hydrogen yield. The reduction in hydrogen yield was accompanied by formation of HF. The ability of perfluoroalkanes to reduce the hydrogen yield is correlated with data on resonant attachment of thermal electrons to some of these solutes in the gas phase. The decrease in hydrogen yield in the presence of unsaturated perfluorocarbon solutes is attributed to electron scavenging. Possible mechanisms for the formation of HF are discussed. The low yield of HF in the presence of unsaturated solutes is explained as being due to the ability of perfluoroolefin anions to extract protons from molecular solvent cations. The absence of any effect of perfluoroalkane solutes on the yield of olefins from the corresponding alkane solvent is interpreted as confirming the assumption that charge neutralization reactions between molecular cations and electrons do not lead to the formation of molecular hydrogen.