Reaction of hydrogen atoms with halogeno-methanes. Part 1.—Carbon tetrachloride

Abstract

Hydrogen atoms, generated in a Wood's tube, have been allowed to react with carbon tetrachloride vapour. The products of the reaction have been analyzed and found to be hydrogen chloride, chloroform, methylene dichloride and traces of methyl chloride. The effect of the relative concentrations of the reactants, of an inert gas and of added hydrogen chloride on the ratio of the principal products has been investigated. From these data it is possible to build up a complete picture of the reaction sequences. The initial step is chlorine abstraction by a hydrogen atom; the trichloromethyl radical so produced reacts with a further hydrogen atom to yield an excited chloroform molecule which either undergoes collisional deactivation or loses hydrogen chloride to yield dichlorocarbene.