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Ideal Behavior of Water Solutions of Strong Electrolytes and Non-electrolytes at High Concentrations

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Abstract

Contrary to widely held beliefs, many concentrated aqueous solutions of strong electrolytes and nonelectrolytes are shown to behave ideally by calculating the activity of water (a w) from vapor pressure data. The mole fraction of water (x w) is equal to the water activity a w(Raoult’s Law) when the mole fraction of water is calculated by accounting for water strongly bound to the solute, which is then not available to act as solvent. In this case x w=(55.51−mH T)/(55.51−mH T+im), where m is the molality of the solute particles, i is the stoichiometric number of solute particles produced per mole of dissolved solute, and H T is the thermodynamic hydration number H T. Published reservations about previous work of this type are addressed. The values of H T vary little over wide ranges of concentration and correlate with the Hofmeister series, the B coefficient of the Jones-Dole viscosity equation, and other properties of water. Activity coefficients of the bulk or “free” water remain at unity even at high concentrations.

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  1. Department of Chemistry and Biochemistry, Long Island University, University Plaza, Brooklyn, NY, 11201, USA

    Andreas A. Zavitsas

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Zavitsas, A.A. Ideal Behavior of Water Solutions of Strong Electrolytes and Non-electrolytes at High Concentrations. J Solution Chem 39, 301–317 (2010). https://doi.org/10.1007/s10953-010-9503-3

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