Abstract
The thermodynamic properties of ionic solutions are described within the mean spherical approximation (MSA). The original MSA and binding MSA (BiMSA) have been supplemented so as to include solvation effects. The model is shown to be capable of representing ionic solution thermodynamics in a wide range of concentration, generally up to saturation, in the case of strong and associating electrolytes. It constitutes an interesting alternative to the Pitzer model.
Highlights
The modeling of the thermodynamic properties of ionic solutions is of interest in many areas, such as solution chemistry, chemical engineering, atmospheric chemistry and geochemistry
We give an outline of the main results obtained in our group by using the mean spherical approximation (MSA), derived from statistical mechanics
The MSA model constitutes an interesting alternative to the Pitzer model
Summary
The modeling of the thermodynamic properties of ionic solutions is of interest in many areas, such as solution chemistry, chemical engineering, atmospheric chemistry and geochemistry. Besides the celebrated Debye-Hückel (DH) theory, the Pitzer model has been widely used in these areas because of its relative simplicity and flexibility, and for its accuracy up to the typical concentration of 6 mol/kg for a 1-1 electrolyte. This semi-empirical model, consisting of a modification of the DH theory by adding a virial type series correction, involves parameters that do not have a direct physical meaning. We will restrict ourselves to the so-called “primitive” model (Blum, 1980) in which the solvent is regarded as a dielectric continuum (in contrast with the “non-primitive” model in which the solvent is modeled as a hard sphere with embedded point dipole)
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