Abstract
The parameterization of the structuredness of a solvent as the difference between its molar heat of vaporization, Δvap H ° and the sum of its internal donor-acceptor interactions (in terms of DN and AN) and its vdW interactions (in terms of Δvap H ° of n-alkanes of the same molar volume) is criticized. As an alternative, the excess of the reduced Trouton constant, ΔvapS°/R over 12 and of Kirkwood's dipole correlation parameter g over 1.7 are suggested as criteria for the decision of whether a solvent is structured, both having to be met. Conversely, if either ΔvapS°/R is less than 11.6 or g is less than 1.3, then the solvent is to be considered unstructured. Exceptions are discussed.
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Marcus, Y. The structuredness of solvents. J Solution Chem 21, 1217–1230 (1992). https://doi.org/10.1007/BF00667218
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DOI: https://doi.org/10.1007/BF00667218