Thermodynamic Properties of Electrolyte Solutions, Derived from Fluctuation Correlations: A Methodological Review

This article presents a review of an approach for studying solution thermodynamics, which is based the on hydrodynamic fluctuation correlations analysis method suggested by Landau and Lifshitz. We show that the method is very general, and its applicability goes beyond hydrodynamics. It starts with examining the entropy production and fluctuating transport fluxes, which are related to concentration fluctuations and molecular interactions. The approach can be successfully applied to compute a wide range of thermodynamic properties such as the osmotic pressure (i.e., equation of state) and provides information about the interactions between the dissolved species. Using dilute electrolyte solutions as a case study, we reproduce results from the Debye and Huckel theory while starting from a very different physical perspective.