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Volume 63, 1967
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Gas-phase chlorine-photosensitized oxidation and oxygen-inhibited photochlorination of tetrachloroethylene and pentachloroethane

Abstract

The oxygen-inhibited photochlorination and the chlorine-phostosensitized oxidation of tetra-chloroethylene and pentachloroethane have been studied in the gas phase at 353·5 and 373·4°K. The rate of chlorination of both compounds is given by –d{Cl2}/dt=k1I½a{Cl2}/(k21/k20+{O2})½ and that of oxidation by –d[C2Cl4] or d[C2HCl5]/dt– d[Cl2/dt]=Ia[O2]/(k+k′[O2]), k and k′ for C2HCl5 being about 35 % higher than for C2Cl4. The maximum quantum yield of oxidation is about 300. These results are explained by a mechanism involving the bimolecular radical chain propagating step 2C2Cl5O2→ 2C2Cl5O+O2. Rate constants have been estimated.

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Article type: Paper
DOI: 10.1039/TF9676301647
Trans. Faraday Soc., 1967,63, 1647-1655

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    Gas-phase chlorine-photosensitized oxidation and oxygen-inhibited photochlorination of tetrachloroethylene and pentachloroethane

    G. Huybrechts, J. Olbregts and K. Thomas, Trans. Faraday Soc., 1967, 63, 1647
    DOI: 10.1039/TF9676301647

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