Laboratory study reveals chain propagation kinetics in 1,1-dichloroethylene photochlorination, indicating shared radical termination pathways across chloroalkenes.
The photochlorination of 1,1-dichloroethylene (vinylidene chloride) has been studied in a static system between 25 and 48°C using either continuous or intermittent illumination. The reaction follows a chain mechanism, similar to that established for other chloroalkenes, in which chain termination is by bimolecular association of trichloroethyl radicals at olefin pressures greater than 2 mm. The rate constants for recombination of C2H2Cl radicals (k4) and for reaction with chlorine molecules (k3) are given by log10k4(l. mole–1 sec–1)=(10.02±0.06)–(1.2±0.7 kcal mole–1)/RT, log10k3(l. mole–1 sec–1)=(8.84±0.4)–(4.1±0.7 kcal mole–1)/RT. The Arrhenius parameters for reactions in the photochlorination of all the chloroalkenes (C2H4Cl4–n, 0⩽n⩽4) are summarized and discussed.
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Ayscough et al. (1966) studied this question.
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