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The scaled-particle theory and solvent isotope effects on the thermodynamic properties of inert solutes in water and methanol

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Abstract

The scaled-particle theory has been applied to the calculation of the thermodynamic changes associated with the formation of a cavity in several isotopic varieties of liquid water and methanol. From these results, the thermodynamic functions for the transfer of a cavity (or a hard-sphere solute) have been computed for the following solvent pairs: H2O→D2O, H2O→H2 18O, H2 18O→D2 18O, D2O→D2 18O, CH3OH→CH3OD. For the last two of these solvents, density measurements required for the calculations were carried out as a function of temperature. The calculated deuterium solvent isotope effect on the heats and entropies of hard-sphere solutes in water is much greater than the18O isotope effect; the former also exhibits a more pronounced temperature dependence. The transfer functions computed for hard-sphere solutes are compared to experimental data on the transfer of various solutes from H2O to D2O and from CH3OH to CH3OD. In most of the cases examined, the cavity effect accounts for a large part of the transfer quantities measured for rare gases, hydrocarbons, and solutes containing a significant hydrocarbon substituent.

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Authors and Affiliations

  1. Service des Problèmes de l'Eau, D.I.P.P.N., Ministère de la Qualité de la Vie, 14 boul. du Général Leclerc, 92521, Neuilly, France

    Patrick R. Philip

  2. Department of Chemistry, Université de Sherbrooke, Sherbrooke, Quebec, Canada

    Carmel Jolicoeur

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  1. Patrick R. Philip
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  2. Carmel Jolicoeur
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Philip, P.R., Jolicoeur, C. The scaled-particle theory and solvent isotope effects on the thermodynamic properties of inert solutes in water and methanol. J Solution Chem 4, 105–125 (1975). https://doi.org/10.1007/BF00649153

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  • DOI: https://doi.org/10.1007/BF00649153

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