Volume 62, 1966

Activated chloroethyl radicals in the chlorination of 1,2-dichloroethylenes

Abstract

The addition of a chlorine atom to dichloroethylene (DCE) gives an activated trichloroethyl radical ACl*, which may decompose to produce a mixture of cis- and trans-DCE or be deactivated to give a normal trichloroethyl radical which subsequently reacts with chlorine to form tetrachloroethane. Between 35 and 133°C, ACl* decomposes to give 78% cis-DCE, and 22% trans-DCE. Deactivation occurs with comparable efficiency with Cl2, DCE, C3H8 and CO2. Assuming that every collision with Cl2 is efficient the rate constant for unimolecular decomposition of ACl* is ka= 2.5 × 109 sec–1. By competing the chlorination of DCE with that of propane the absolute rate constants for addition of Cl to cis- and trans-DCE were obtained: k2c= 8 × 1010 exp [–190/1.99T] mole–1 l. sec–1, and k2t= 3 × 1010 exp [+170/1.99T] mole–1 l. sec–1. It is deduced that internal rotation in both ACl* and the transition state complex ACl[graphic ommitted] must be effectively unhindered.

Article information

Article type
Paper

Trans. Faraday Soc., 1966,62, 1190-1205

Activated chloroethyl radicals in the chlorination of 1,2-dichloroethylenes

J. H. Knox and J. Riddick, Trans. Faraday Soc., 1966, 62, 1190 DOI: 10.1039/TF9666201190

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