Concentrated binary aqueous solutions of lanthanide (Nd(3+) and Dy(3+)) salts (ClO(4)(-), Cl(-), and NO(3)(-)) have been studied by means of classical molecular dynamics (MD) simulations with explicit polarization and UV-visible spectroscopy. Pair interaction potentials, used for the MD simulations, have been developed in order to reproduce experimental hydration properties. Nd(3+) and Dy(3+) have been chosen because of their position in the lanthanide series: Nd(3+) being a light lanthanide and Dy(3+) a heavy one. They are respectively coordinated to nine and eight water molecules, in pure water, involving changes in their salt hydration structures. Both MD simulations and UV-visible experiments highlight the stronger affinity of nitrate anions toward Ln(3+) compared to perchlorates and chlorides. Dissociation/association processes of Nd(3+)-Cl(-) and Nd(3+)-NO(3)(-) ion pairs in aqueous solution have been analyzed using potential of mean force profile calculations. Furthermore, from MD simulations, it appears that the affinity of anions (perchlorate, chloride, and nitrate) is stronger for Nd(3+) than Dy(3+).

This work is aimed at a description of the thermodynamic properties of highly concentrated aqueous solutions of nitric acid salts at 25 °C within the binding mean spherical approximation (BIMSA) theory. The predictive capability of this model was examined. First, Raman spectroscopy was used to study the proportion of associated nitric acid as a function of concentration. The corresponding apparent association constant values were compared with literature values. Besides, the BIMSA model, taking into account complex formation, was used to represent literature experimental osmotic coefficient variation with concentration. This theoretical description led to an assessment of the degree of association. The so calculated amount of associated nitric acid coincides accurately with our Raman experimental results up to a high concentration of acid.

Osmotic coefficients of aqueous solutions of lanthanide salts are described using the binding mean spherical approximation (BIMSA) model based on the Wertheim formalism for association. The lanthanide(III) cation and the co-ion are allowed to form a 1-1 ion pair. Hydration is taken into account by introducing concentration-dependent cation size and solution permittivity. An expression for the osmotic coefficient, derived within the BIMSA, is used to fit data for a wide variety of lanthanide pure salt aqueous solutions at 25 degrees C. A total of 38 lanthanide salts have been treated, including perchlorates, nitrates, and chlorides. For most solutions, good fits could be obtained up to high ionic strengths. The relevance of the fitted parameters has been discussed, and a comparison with literature values has been made (especially the association constants) when available.