Hydrogen transfer reactions via organic radicals in gamma-irradiated chibaite

Abstract

Chibaite, a silica-framework structure with cage-like voids occupied by gaseous molecules, was found in marine sediments. Its formation age could be evaluated using electron spin resonance (ESR) if the radicals formed by natural radiation can be assumed to accumulate over time. To investigate whether hydrogen transfer reactions, where organic radicals withdraw hydrogen atoms from other molecules in adjacent cages, occur in chibaite and affect ESR dating, gamma-irradiated chibaite was measured by ESR. Methyl, ethyl, n-propyl, isopropyl, tert-butyl radicals and hydrogen atoms were created by gamma irradiation at 77 K. The amount of tert-butyl radicals increased around 240 K and the similar amount of the other organic radicals decreased simultaneously, implying that hydrogen transfer reactions occur between isobutane and the organic radicals in chibaite around 240 K and therefore would have no influence on ESR dating because the reactions are completed at the environmental temperature.