Journal Articles (before-1995)

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    Heats of Solution of Electrolytes in Ethanol and Derived Enthalpies of Transfer from Water
    (Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1978, 74 (02), 1978) Abraham, Michael H.; Ah-Sing, Eric; Namor, Angela F. Danil De; Hill, Tony; Nasehzadeh, Asadollah; Schulz, Ronald A.
    Heats of solution of 12 1:1 electrolytes in ethanol have been determined calorimetrically, and have been extrapolated to zero electrolyte concentration to give iXH° values for these electrolytes. Together with literature data for 9 other 1:1 electrolytes, these measurements yield a set of single ion enthalpies of transfer from water to ethanol for 11 univalent cations and 6 univalent anions. Using the assumption that A/7t‘?(Ph4As+) = A//°(Ph4B~), it is shown that small univalent cations are enthalpically more stable in ethanol than in water, but that the larger tctra-alkylammonium ions are less stable in ethanol. With the same assumption, it is also shown that all the univalent cations and anions studied are of almost the same enthalpy (within about ±0.5 kcal mol-1) in the three alcohols methanol, ethanol and 1-propanol.
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    Carbonylation of Methanol and Ethanol on a Rhodium-Zeolite Catalyst
    (Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1978, 74 (09-12), 1978) Christensen, Bjarne; Scurrell, Michael S.
    The carbonylation of methanol and ethanol on a rhodium-X zeolite has been studied. Particular emphasis has been placed on the effect of the concentration of the required alkyl iodide “promoter” on the selectivity of the reaction. A maximum in selectivity for carbonylation is observed for both alcohols as the alkyl iodide content of the reactant stream is increased. The side products are dimethyl ether and ethylene with methanol and ethanol respectively. Some comparative experiments with either rhodium-on-carbon or the unmodified NaX support show that at least for ethanol the zeolite support offers a sufficiently high activity to account for the rate of formation of side product under carbonylation conditions. For methanol carbonylation the necessity to employ near-stoichiometric quantities of methyl iodide and the effects which the absence of “promoter” has on catalyst behaviour are discussed. Comparison between the action of rhodium catalysts in homogeneous and heterogenised forms leads to the conclusion that close similarities in behaviour exist, probably due to the operation of a common mechanism.