Improved thermodynamic calculations for concentrated mixed electrolyte systems including ion pairing (or the absence of it)

Abstract

Knowledge of the activity coefficients of solutes under temperature and pressure ranges of interest is generally required for calculations of the physicochemical properties of aqueous multicomponent electrolyte solutions such as seawater. Whilst these activity coefficients are well characterized for the predominant salts individually, fewer data are available for minor components under a sufficiently wide range of conditions and there are significant interactions between some of the chemical species involved which can substantially alter the required activity coefficients in mixtures. For these reasons, accurate thermodynamic predictions for seawater and other multi-electrolyte solutions in moderate or high concentration are more difficult than is often supposed. In particular, progress in this area has been slowed by uncertainty regarding the nature and extent of ion pairing in concentrated strong electrolyte solutions, a problem that has been debated for decades. Zdanovskii's rule, described originally almost a century ago but widely neglected, provides a fundamentally sound method for calculating the properties of mixed electrolyte solutions. Modelling developments are described, which accord with various types of experiment, from our laboratory and from the chemical literature. It has become clear that, when treated in an appropriate way based on solvent activity, linear mixing behaviour of strong electrolyte solutions can be considered the norm. This is an inevitable consequence, first recognized by Guggenheim, of the cancellation of ion pairing and other interactions as, conceptually, one ion replaces another. Stronger solute–solute interactions, described by equilibrium constants, can then easily be coupled in a thermodynamically consistent manner.