CHARGE TRANSFER IN THE RADIOLYSIS OF DILUTE SOLUTIONS OF HYDROCARBONS IN KRYPTON MATRICES AT 77 °K

Abstract

The radiolysis of dilute solutions (0.3 to 10 electron %) of saturated hydrocarbons in krypton matrices at 77 °K results in the production of much more hydrogen than that obtained in the absence of krypton. This enhanced hydrogen yield is independent of hydrocarbon concentration over the range studied. The cyclohexane–krypton system wds studied in detail: The energy transferred from the krypton to the cyclohexane results in a large first-order yield of hydrogen with a corresponding large yield of cyclohexene. Cyclohexane-d12 are irradiated at the same concentration in a krypton matrix has the same product yields. However, when mixtures of cyclohexane and cyclohexane-d12 are irradiated in a krypton matrix the hydrogen evolved has a high H2 content which must be the result of an isotope effect in the energy transfer process. This isotope effect and the enhancement of product yields is consistent with a charge transfer mechanism.