.gamma.-Radiolysis of cyclohexane-perfluorocyclohexane solutions

Abstract

An investigation has been made of the products from the Co-60 gamma radiolysis of liquid phase mixtures of cyclohexane and perfluorocylcohexane. All experiments were done at 64 +- 1/sup 0/C, at which temperature the two compounds are completely miscible. In general, the products obtained over most of the concentration range are the main products characteristic of the radiolysis of pure cyclohexane, namely hydrogen, cyclohexene, and dicyclohexyl. The yields of hydrogen and cyclohexene are decreased in such a way as to suggest fairly efficient scavenging, but the dicyclohexyl yield is actually enhanced compared to pure cyclohexane. The only major organic product deriving from perfluorocyclohexane is c-C/sub 6/F/sub 11/H. A small yield of mixed dimer, possible formed in a spur reaction, is also found. These results apparently require that cyclohexyl radicals do not react with perfluorocyclohexane, but that perfluorocyclohexyl radicals efficiently abstract hydrogen from cyclohexane. The data strongly suggest that perfluorocyclohexane undergoes electron capture followed by dissociation, either directly or in a subsequent step, and also that hydrogen atoms are able to abstract fluorine from perfluorocyclohexane. 14 refs., 12 figs.