Browsing by Author "Cadman, P."

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    Abstraction of Chlorine Atoms from Alkyl Chlorides by the Trimethylsilyl Radical
    (Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1973, 69 (5), 1973) Cadman, P.; Tilsley, G. M.; Dickenson, A. F. Trotman
    The relative rates of chlorine atom abstraction from alkyl chlorides by the trimethylsilyl radical have been studied by a competitive technique between 400 and 580 K in the gas phase. These results have been put on an absolute basis by comparing the rate of abstraction of chlorine from ethyl chloride by trimethylsilyl radicals with their rate of combination to hexamethyldisilane. Using the known rate of combination of trimethylsilyl radicals, the following Arrhenius parameters for chlorine abstraction were obtained: [graphic omitted] The results of the chlorine abstractions by the trimethylsilyl radicals are compared with those for sodium atoms and for trichlorosilyl radicals.
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    Kinetics of Hydrogen Abstraction by Difluoroamino Radicals from n-Propyl Formate and the n-Propoxycarbonyl Radical Decomposition
    (Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1972, 68 (3), 1972) Cadman, P.; White, A. J.
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    Rate of Combination of Trimethylsilyl Radicals in the Gas Phase
    (Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1972, 68 (10), 1972) Cadman, P.; Tilsley, G. M.; Trotman-Dickenson, A. F.
    Trimcthylsilyl radicals have been generated by the mercury photosensitized decomposition of trimcthylsilane. The absolute rate of combination of these radicals has been measured by the classical rotating sector technique between 317 and 399 K, using the abstraction of chlorine from ethyl chloride to give chlorotrimcthylsilane as the pilot reaction. The activation energy for combination was found to be negligible and the rate coefficient to be given by: log (K/ml mol~l s-1) = 14.25±0.30 where the error is estimated from the experimental scatter.