Journal Articles (before-1995)

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    Reaction of Hydrogen Atoms with Ethane
    (Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1974, 70 (08), 1974) Camilleri, Patrick; Marshall, Roger M.; Purnell, J. Howard
    The reaction between hydrogen atoms and ethane has been studied in a flow-discharge system over the wide temperature range 503–753 K at pressures between 8 and 16 Torr. The major products are methane and ethane, reformed by methyl recombination. Minor products are propane and ethylene with traces of n-butane. The detailed mechanism has been established and computer calculations have been used to derive the set of best-fit rate parameters which reproduce all the experimental results. The results of this work yield the result k1/cm3 mol–1 s–1= 1014.27 ± 0.13 exp (–40.9 ± 1.6 kJ mol–1/RT); H + C2H6→ H2+ C2H5. (1) A survey of all published data some of which have been revised by us to take account of wrongly assumed stoichiometry in the original work, shows that, over a range of 1000 K, the data can be represented by the Arrhenius expression, k1/cm3 mol–1 s–1= 1014.12 ± 0.09 exp (–39.2 ± 0.9 kJ mol–1RT). There is thus no reason to suppose curvature in this plot as has been suggested. Values of the rate constants for the reactions H + C2H5→ 2CH3(2), CH3+ H → CH4(5), and, H + C2H5→ H2+ C2H4(11), are found to be k2/cm3 mol–1 s–1= 1013.57, k5/cm3 mol–1 s–1= 1012.04 at 8 Torr, 1012.20 at 12 Torr and 1012.34 at 16 Torr and k11/cm3 mol–1 s–1= 1012.23. We have reassessed our earlier data on the reaction of hydrogen atoms with ethylene in the light of the recent “low” values for the rate constant of ethyl recombination. From this, we find values for k2 and k5 at 290 K which are, respectively, lower and higher than the corresponding values in the range 503–753 K. It is shown that the slight temperature dependence observed is consistent with the order of reactions (2) and (5).
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    Hydrogenolysis of Ethane on Evaporated Copper-Nickel Alloy Films
    (Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1972, 68 (4), 1972) Plunkett, T. J.; Clarke, J. K. A.
    The hydrogenolysis of ethane has been studied on a series of copper-nickel film catalysts at temperatures greater than 320°C, where the alloys are single-phased. A gradual fall in activity with nickel content is found with no break at median compositions and, while activity persists to ca. 4 % nickel content, copper films are inactive. This behaviour is not amenable to description by the simple (rigid) band approach to the electronic structure of alloys but emphasizes the retention of catalytic character of individual nickel atoms