Selective hydrogen atom abstraction by tritium and deuterium atoms in radiolysis of tritiated decane at 77 K. Mass effect on solid-state reaction

Abstract

The relative yields of five isotopic compounds of hydrogen produced in the radiolysis of partially tritiated deuteriodecane (n-C/sub 10/D/sub 22/(T))-protiated decane (n-C/sub 10/H/sub 22/) mixtures at 77 K were measured by conventional radiogas chromatography. The HT/DT ratio in hydrogen yields is much lower than the HD/D/sub 2/ ratio. Though D atoms react selectively with n-C/sub 10/H/sub 22/, T atoms do not react as selectively with n-C/sub 10/H/sub 22/ as D atoms do. The ratio ((p/sub C/sub 10/H/sub 22///p/sub C/sub 10/D/sub 22//)/sub T) of the reaction probability of the T atoms with n-C/sub 10/H/sub 22/ to that with n-C/sub 10/D/sub 22/ is 4.5-6.3, which is much lower than the ratio ((p/sub C/sub 10/H/sub 22///p/sub C/sub 10/D/sub 22//)/sub D/ = 30) for the D atoms. The ratio for the T atoms in the radiolysis is rather close to the ratio (2.3) for the recoil T atoms. The mass effect on the selective hydrogen atom abstraction reaction in the decane mixtures is discussed. 16 references, 3 figures, 1 table.