Journal Articles (before-1995)

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    Partial molar volumes of organic compounds in water. Part 1.—Ethers, ketones, esters and alcohols
    (Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1977, 73 (05), 1977) Edward, John T.; Farrell, Patrick G.; Shahidi, Fereidoon
    The partial molar volumes of a number of ethers, ketones, esters and alcohols in water at 25.0°C have been determined and related to their van der Waals volumes by one of two equations, depending on whether the molecules are spherical or cylindrical in shape. Allowance has been made for the void volume associated with each molecule and the results imply that calculated volumes must be reduced by a constant amount for each carbonyl or hydroxyl group present, owing to hydrogen bonding to water. No such reduction in the calculated volume is required for the oxygen atom of an ether. It is shown for diols that the amount of void volume per additional —CH2— group remains constant for straight-chain compounds (i.e., cylinders), whereas for spherical molecules the amount of void volume decreases with increase in the number of carbon atoms, as predicted.
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    Salting-in of Alcohols by Symmetrical Tetra-alkylammonium Bromides
    (Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1974, 70 (11), 1974) Aveyard, Robert; Heselden, Roy
    The changes in free energy, enthalpy and entropy associated with the transfer of several alkanols at high dilution from water to aqueous solutions of some symmetrical tetra-alkylammonium bromides (R4NBr) have been determined at 20°C. The enthalpies were determined calorimetrically for several salt concentrations. The treatment of salt effects based on the scaled particle theory has been applied to the salting-in of butanol by solutions of R4NBr. For this purpose it was necessary to obtain the cation diameter indirectly by fitting experimental salting-in data for alkanes to the theory. It is concluded that the theory is as successful for butanol as it is for the alkanes. The thermodynamic parameters of transfer are consistent with the assumption that the salting-in of alkanols (and alkanes) by R4N+ ions is caused by the formation of short-lived cation-solute “pairs” and the resultant disruption of water structure surrounding both the cation and non-electrolyte.