Abstract
The mean activity (γ±) and osmotic (Φ) coefficients for binary and ternary aqueous solutions of trivalent electrolytes (mainly made up of lanthanide salts) are described in the framework of the primitive model of ionic solutions, using the binding mean spherical approximation (BiMSA). This model, based on the Wertheim formalism, accounts for (chemical or electrostatic) association of ions. In this work, the multivalent cation and the anion are allowed to form 1:1 (pairs) and 1:2 (trimers) complexes. Expressions for γ± and Φ are given which satisfy the Gibbs−Duhem relation. The model involves concentration-dependent cation size and effective relative permittivity, variations that can be interpreted in terms of solvent effects. The theory is applied to aqueous solutions of binary and ternary mixtures at 25 °C with common anion.
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