paper

From solvent free to dilute electrolytes: Essential components for a continuum theory

arXiv:1707.06940 · doi:10.1021/acs.jpclett.7b03048

Abstract

The increasing number of experimental observations on highly concentrated electrolytes and ionic liquids show qualitative features that are distinct from dilute or moderately concentrated electrolytes, such as self-assembly, multiple-time relaxation, and under-screening, which all impact the emergence of fluid/solid interfaces, and transport in these systems. Since these phenomena are not captured by existing mean field models of electrolytes, there is a paramount need for a continuum framework for highly concentrated electrolytes and ionic liquids. In this work, we present a self-consistent spatiotemporal framework for a ternary composition that comprises ions and solvent employing free energy that consists of short and long range interactions, together with a dissipation mechanism via Onsagers' relations. We show that the model can describe multiple bulk and interfacial morphologies at steady-state. Thus, the dynamic processes in the emergence of distinct morphologies become equally as important as the interactions that are specified in the equilibrium-free energy. The model equations not only provide insights to transport mechanisms beyond the Stokes-Einstein-Smoluchowski relations but also enables to qualitative recovery in the full range (three distinct regions) of non-monotonic electrical screening length that has been recently observed in experiments using organic solvent to dilute ionic liquids.

20 pages, 2 figures

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