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

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.

arXiv commentfixed typos, added references, addressed comments

References in corpus (4)

• Electroneutrality Breakdown and Specific Ion Effects in Nanoconfined Aqueous Electrolytes Observed by NMR
• The irreversible thermodynamics of curved lipid membranes
• Time reversal symmetry breaking in two-dimensional non-equilibrium viscous fluids
• Colloidal electrophoresis: Scaling analysis, Green-Kubo relation, and numerical results

Cited by in corpus (7)

• The Role of Energy Scales for the Structure of Ionic Liquids at Electrified Interfaces -- A Theory-Based Approach
• Electrophoresis of ions and electrolyte conductivity: from bulk to nanochannels
• The $(2+\delta )$-dimensional theory of the electromechanics of lipid membranes: I. Electrostatics
• STable AutoCorrelation Integral Estimator (STACIE): Robust and accurate transport properties from molecular dynamics simulations
• Combining Molecular Dynamics and Experimental Methods for the Parametrization of Binary Carbonate-Based Electrolytes
• The irreversible thermodynamics of curved lipid membranes II: Permeability and osmosis
• Modelling and Simulation of an Alkaline Ni/Zn Cell