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Phenomenological approach to cation-solvent interactions

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Structure and Bonding

Part of the book series: Structure and Bonding ((STRUCTURE,volume 12))

Abstract

The functional approach provides a unified pattern for the description of cation-EPD-solvent interactions in that it takes into account the respective covalent contributions in the solvate bonds. This approach is qualitative by its very nature, but a phenomenological property, namely the donicity of the electron-pair donor (the solvent molecule) can be used to obtain an astonishingly large number of semi-quantitative data. Though far from ideal, this approach is the best available at present to reconcile hitherto unrelated facts and goes some way to make up for the lack of means to calculate thermodynamic data for cation-solvent interactions, particularly for interactions with strong covalent contributions.

The applicability of donicities to cation-solvent interactions is most convincingly demonstrated by the polarographic reduction of various metal ions in solvents of different donicity. The observed variation of half-wave potentials with solvent donicity can be explained neither in terms of the Born equation nor by simple microscopic electrostatic models in view of the magnitude of the dipole moments of solvent molecules. The concept also provides the basis for an interpretation of complex formation reactions and the behaviour of electrolytes (ion pair equilibria) in a large number of EPD solvents.

The new concept restricts the term “ion pair” to “solvent-separated ion pairs” in its original sense, so-called “contact ion pairs” being regarded as unionized species with polarized covalent bonds.

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  1. Institut für Anorganische Chemie, Technische Hochschule, Wien, Austria

    U. Mayer & V. Gutmann

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  1. U. Mayer
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  2. V. Gutmann
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Mayer, U., Gutmann, V. (1972). Phenomenological approach to cation-solvent interactions. In: Structure and Bonding. Structure and Bonding, vol 12. Springer, Berlin, Heidelberg. https://doi.org/10.1007/BFb0117542

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  • DOI: https://doi.org/10.1007/BFb0117542

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  • Print ISBN: 978-3-540-05901-1

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