The photochlorination of chloroform in continuous flow systems

Data on the vapor phase photochlorination of chloroform in flow reactors are interpreted on the basis of reaction mechanisms presented in the literature. In order to estimate the rates of light absorption it is also necessary to interpret the rate data obtained for the uranyl sulfateoxalic acid reaction. The chlorination results are represented quite well by a mechanism in which the most important termination step is a termolecular reaction between trichloromethyl radicals and chlorine. Deviations from this model are observed as the flow of reactants becomes turbulent and as the light intensity increases. The observed decrease in reaction rate under such conditions is attributed to the increased significance of a second termination step, the unimolecular deactivation of chlorine radicals at the reactor wall.