Browsing by Author "Whan, D. A."

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    Hydrogenolysis of Saturated Hydrocarbons on Evaporated Platinum Films
    (Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1972, 68 (11), 1972) Dowie, R. S.; Whan, D. A.; Kemball, C.
    The reactions of ethane, propane, n-butane, isobutanc and neopentane have been examined in the presence of deuterium on platinum films. Details of the products of exchange, hydrogenolysis and, where possible, isomerization are reported. The kinetic behaviour of the hydrogenolysis reaction showed a trend in that reactions of ethane were acccleratory, those of propane maintained a constant rate and those of molecules with four or more carbon atoms decelerated with time. The retardation in rates was much more marked with branched chain than with linear hydrocarbons. The results are discussed in terms of the nature of the adsorbed species accumulating on the surface, species possessing some carbonium ion character being likely precursors to the material responsible for the observed poisoning. Little additional mechanistic information was obtained from an analysis of the deuterium contents of the various molecules as exchange was fast compared to hydrogenolysis or isomerization, leading to rapid isotopic equilibration. A fragmentation correction scheme taking into account the influence of molecular composition on bond rupture has also been developed for analysis of the mass spectral data.
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    Infrared Spectra and Catalytic Activity of Supported Molybdenum Hexacarbonyl
    (Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1972, 68 (12), 1972) Howe, R. F.; Davidson, D. E.; Whan, D. A.
    Infrared spectroscopy has been used to study the olefin disproportionation catalysts consisting of molybdenum hexacarbonyl supported on silica, alumina and magnesia. Activation of the catalysts is found to cause decomposition of the molybdenum hexacarbonyl. Decomposition occurs most readily on a silica support which is not able to stabilize intermediate sub-carbonyl species. The intermediate sub-carbonyl species observed on alumina and magnesia supports arc not active centres for olefin disproportionation ; the active species is formed by complete loss of all six carbonyl ligands. Indirect evidence suggests the active species is not molybdenum(O) but some higher oxidation state.