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Heats of dilution of trialkyl phosphates in iso-octane and carbon tetrachloride: Interpretation in terms of self-association

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Abstract

The heats of solution and dilution of triethyl phosphate (TEP), tripropyl phosphate (TPP), and tributyl phosphate (TBP) in iso-octane have been measured at 25°C. The enthalpy of dilution was found to decrease with hydrocarbon chain length. The resulting apparent molal heat content, φL, values are interpreted in terms of the degree and nature of the associated species present assuming that the heat of dilution is essentially due to the breakdown of the various associated species. The results are consistent with a monomer-to-dimer model. Equilibrium constants and enthalpy change values are calculated for the dimerization reaction. The heat of dilution of TBP in carbon tetrachloride was exothermic rather than endothermic, indicating significant solute-solvent interaction.

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Authors and Affiliations

  1. Pharmaceutical Chemistry Department, McCollum Laboratories, The University of Kansas, 66045, Lawrence, Kansas

    J. Howard Rytting & Siegfried Lindenbaum

Authors
  1. J. Howard Rytting
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  2. Anne Goldkamp
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  3. Siegfried Lindenbaum
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Rytting, J.H., Goldkamp, A. & Lindenbaum, S. Heats of dilution of trialkyl phosphates in iso-octane and carbon tetrachloride: Interpretation in terms of self-association. J Solution Chem 4, 1005–1010 (1975). https://doi.org/10.1007/BF01074742

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  • DOI: https://doi.org/10.1007/BF01074742

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