Secondary kinetic isotope effects in hydrogen and deuterium abstraction by chlorine atoms from the chloromethyl group in gaseous ethyl chlorides: effects of isotopic substitution in the adjacent methyl group

Abstract

Ground state chlorine atoms have been generated photochemically to study the attack on hydrogen in the CH 2Cl group, or deuterium in the CD 2Cl group, as a function of deuterium substitution in the vicinal methyl group of a number of ethyl chloride molecules. The experiments were carried out in the gas phase, at temperatures 9–95°C, using methane as competitor ( k r). Rate constants for the following reactions are reported: ▪ The temperature dependences of the relative rate constants k i/ k r were found to obey the Arrhenius rate law: ▪