Journal of the Chemical Society - Faraday Transactions p. 2151 - 2156 (1991)
Update date:2022-08-17
Topics:
Dyer, Peter E.
Matthews, Martin
Holbrock, Kenneth A.
Oldershaw, Geoffrey A.
The thermal decomposition of 1,2-dichloroethane to give vinyl chloride and hydrogen chloride has been reinvestigated at 703 K and the major features of this free-radical chain reaction found previously have been confirmed.A direct comparison of the pulsed KrF laser-induced process (248 nm) in the same static reactor at this temperature showed that a substantial increase in rate occurs even at low pulse-repetition rates (2 Hz).In an extended study of the laser-induced reaction at temperature where thermal reaction is negligible (476-577 K), quantum yields of vinyl chloride formation have been measured to be between 3000 and 13 000.Quantum yields decreased slighthly with increasing pressure and showed an inverse square-root dependence on initial chlorine atom concentration.The major by-products were identified as ethene, ethyne, 1,2,3,4-tetrachlorobutane and 1,1,2-trichloroethane.At 577 K and 150 Torr, the quantum yield of ethene production is close to unity, indicating that under these conditions reaction (2) is essentially complete. C2H4Cl2 + hν (248 nm) --> CH2ClCH2* + Cl (1) CH2ClCH2* --> C2H4 + Cl (2) Computer modelling of a complete reaction mechanism involving the propagation steps (3) and (4) Cl + C2H4Cl2 --> C2H3Cl2 + HCl (3) C2H3Cl2 --> C2H3Cl + Cl (4) was used to predict quantum yields of both vinyl chloride and the minor products.
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