On the Transition-State theory approach to the Jones-Dole’s viscosity B-coefficient: A novel molecular-based interpretation, assessment of its implications, and experimental evidence

Abstract

We report a novel statistical mechanics interpretation of the frequently invoked Feakins’ transition-state theory approach to the Jones − Dole’s Bi- coefficient, and its temperature–pressure derivatives, in the context of their suitability as structure-making/breaking markers for the behavior of solutes in dilute electrolyte solutions. We provide additional rigorous molecular-based thermodynamic evidence to highlight the non-uniqueness of the Bi- and ∂Bi/∂TP- responses to the solute–solvent intermolecular asymmetries in these systems, and to illustrate the resulting outcomes according to a fundamental structure-making/breaking function involving the available experimental data for aqueous electrolyte solutions. Finally, we discuss the implications of our findings while providing a cautionary outlook on the pervasive use of the viscosity-based structural markers.