Computation of Electrical Conductivity of Multicomponent Aqueous Systems in Wide Concentration and Temperature Ranges

A comprehensive model for calculating the electrical conductivity of multicomponent aqueous systems has been developed. In the infinite-dilution limit, the temperature dependence of ionic conductivities is calculated on the basis of the concept of structure-breaking and structure-making ions. At finite concentrations, the concentration dependence of conductivity is calculated from the dielectric continuum-based mean-spherical-approximation (MSA) theory for the unrestricted primitive model. The MSA theory has been extended to concentrated solutions by using effective ionic radii. A mixing rule has been developed to predict the conductivity of multicomponent systems from those of constituent binary cation−anion subsystems. The effects of complexation are taken into account through a comprehensive speciation model coupled with a technique for predicting the limiting conductivities of complex species from those of simple ions. The model reproduces the conductivity of aqueous systems ranging from dilute to concentrated solutions (up to 30 mol/kg) at temperatures up to 573 K with an accuracy that is sufficient for modeling industrially important systems. In particular, the conductivity of multicomponent systems can be accurately predicted using data for single-solute systems.