Browsing by Author "Porter, D. A."

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    Energy Partition in the Photolysis of HI and of H2S
    (Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1972, 68 (12), 1972) Oldershaw, G. A.; Porter, D. A.; Smith, A.
    Yields of nitrogen from reaction (1) were used to determine the initial kinetic energy of hydrogen atoms produced by photolysis of HI and H2S in the presence of N2O. H* + N2O->N2 + OH. (1) The results show that the proportion of excited (52P±) iodine atoms formed by photolysis of HI at 279 nm is 0.11 ±0.14, and that 90±10 % of the residual energy following photolysis of H2S at 248 nm appears in translation of H and SH.
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    Probability of Reaction of H with N2O as a Function of Energy
    (Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1974, 70 (07), 1974) Oldershaw, G. A.; Porter, D. A.
    The net probabilities of reactions (1) and (2) have been determined as a function of the initial kinetic energy of H* by analysis of the products of photolysis, at various wavelengths, of Hl mixed with N2O. H* + N2O->N2 + OH H* + N2O->NO + NH (1) (2) Reaction (1) is predominant at all energies studied. The results have been used to calculate a crude excitation function for reaction (1), which has a maximum cross section of about 6x 10“ 3 nm2. By using the excitation function to calculate rate coefficients, which are in good agreement with experimental values, the hot atom results arc shown to be consistent with measurements of the rate of (1) in thermal systems at high temperatures.
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    Reaction of Hot Hydrogen Atoms with COS
    (Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1972, 68 (2), 1972) Oldershaw, G. A.; Porter, D. A.
    Hydrogen atoms of energy 104 kJ mol-1 and 68 kJ mol'1 produced by photolysis of Hl react with COS to give CO and SH (1). The net probability of reaction (1) for atoms of initial energy H*4-COS ->CO 4- SH (1) 104 kJ mol-1 is 0.62. Added CO2, He, Ar, Kr and Xe reduce the probability of (1) by removing energy in moderating collisions. Relative values of the energy-loss parameter a for collisions between H* and the rare gases agree qualitatively with those calculated assuming rigid sphere collisions. The maximum cross-section for reaction (1) is shown to be much smaller than the collision cross-section.