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Group contributions to the partial molar volume of ionic organic solutes in aqueous solution

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Abstract

Partial molar volumes at infinite dilution\(\bar V^\circ \) in water at 25°C for more than 400 organic electrolytes (carboxylic acid and amine salts, sulfates, sulfonates, selected polyelectrolyes, aminoacids and derivatives) are described through a simple additivity scheme already adopted for non-electrolytes. Twenty-five charged groups are assigned a\(\bar V^\circ \) contribution and the partial molar volumes of more than 150 monofunctional organic ions are reproduced with a standard deviation of 0.8 cm3-mol−1. The different volumetric behavior of hydrophobic and hydrophilic centers, either charged or uncharged, is discussed. Deviations from additivity for mono-and polyfunctional ions are analyzed in terms of (i) extension of the hydration cosphere of different polar centres; (ii) intramolecular interactions and their dependence on the nature, number and mutual separation of interacting groups.

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  1. Dipartimento di Chimica e Chimica Industriale, Università di Pisa, via Risorgimento 35, 56126, Pisa, Italy

    Paolo Gianni

  2. Istituto di Chimica Quantistica ed Energetica Molecolare, CNR, via Risorgimento 35, 56126, Pisa, Italy

    Luciano Lepori

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Gianni, P., Lepori, L. Group contributions to the partial molar volume of ionic organic solutes in aqueous solution. J Solution Chem 25, 1–42 (1996). https://doi.org/10.1007/BF00972756

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