Gas-phase chlorine-photosensitized oxidation and oxygen-inhibited photochlorination of tetrachloroethylene and pentachloroethane
- 1 January 1967
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Transactions of the Faraday Society
- Vol. 63, 1647-1655
- https://doi.org/10.1039/tf9676301647
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=k1I½ a{Cl2}/(k2 1/k2 0+{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.Keywords
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