Transport phenomena in electrolyte solutions: Non-equilibrium thermodynamics and statistical mechanics

TL;DR

This paper develops a comprehensive theoretical framework for transport phenomena in electrolyte solutions, integrating thermodynamics, electromagnetism, and statistical mechanics, and validates it with molecular simulations and experimental data.

Contribution

It introduces Green-Kubo relations for transport coefficients in electrolyte solutions and connects them with classical models and experimental measurements.

Findings

Derived Green-Kubo relations for transport coefficients.

Computed ion transport coefficients using molecular dynamics.

Validated theoretical predictions with experimental data.

Abstract

The theory of transport phenomena in multicomponent electrolyte solutions is presented here through the integration of continuum mechanics, electromagnetism, and non-equilibrium thermodynamics. The governing equations of irreversible thermodynamics, including balance laws, Maxwell's equations, internal entropy production, and linear laws relating the thermodynamic forces and fluxes, are derived. Green-Kubo relations for the transport coefficients connecting electrochemical potential gradients and diffusive fluxes are obtained in terms of the flux-flux time correlations. The relationship between the derived transport coefficients and those of the Stefan-Maxwell and infinitely dilute frameworks are presented, and the connection between the transport matrix and experimentally measurable quantities is described. To exemplify application of the derived Green-Kubo relations in molecular simulations, the matrix of transport coefficients for lithium and chloride ions in dimethyl sulfoxide is computed using classical molecular dynamics and compared with experimental measurements.