Effects of olefins on the radiolysis of liquid cyclohexane. Part 2

Abstract

Solutions of cyclohexene in cyclohexane have been irradiated with ⁶⁰Co gamma rays. G values for C₁₂ products were measured. Effects of a number of additives on product yields were investigated. Transfer of reactivity from solvent to solute occurs, giving rise to relatively large yields of C₁₂H₁₈. This proceeds by positive charge transfer. Dimeric products are formed by a free radical mechanism. Addition of cyclohexyl radicals to cyclohexene does occur, but a similar reaction of cyclohexenyl radicals is not important. Specific activities were compared of C₁₂ products formed by radiolysis and Hg-sensitized photolysis of solutions of ¹⁴C cyclohexene in cyclohexane. Scavenging of homogeneously distributed cyclohexyl radicals by cyclohexene is complete at [C₆H₁₀] 3 × 10^–2M. However, at this concentration and also at [C₆H₁₀]= 11 × 10^–2 M the major fraction of dicyclohexyl in the radiolysis is formed in reactions between cyclohexyl radicals. This indicates an inhomogeneous distribution of these radicals in the solution.