Organic electrolyte solutions: Modeling of deviations from ideality within the binding mean spherical approximation

Abstract

Deviations from ideality in organic electrolyte solutions are described within the Binding Mean Spherical Approximation (BiMSA) theory, in which ions are regarded as charged hard spheres and unlike ions may associate to form an ion pair. Association is modeled within the Wertheim theory (as done in SAFT-type models). The model includes a mass action law with a thermodynamic association constant. The literature about the thermodynamic properties of this type of solution is reviewed. Besides, it is attempted to gain some insight into the solvation of ions by computing their Stokes hydrodynamic diameters from conductivity experiments, and by employing an original analysis introduced by Fawcett. The BiMSA model is used to represent the osmotic coefficient of 1-1 electrolytes in pure methanol, ethanol, 2-propanol, acetone and acetonitrile. The optimized cation sizes in the solvents are compared with their hydrodynamic diameters. The regressed association constants are compared with literature values derived from conductivity and vapor pressure experiments.