Conductance of concentrated electrolytes: multivalency and the Wien effect

Abstract

The electric conductivity of ionic solutions is well understood at low ionic concentrations of up to a few millimolar but becomes difficult to unravel at higher concentrations that are still common in nature and technological applications. A model for the conductivity at high concentrations was recently put forth for monovalent electrolytes at low electric fields. The model relies on applying a stochastic density-functional theory and using a modified electrostatic pair-potential that suppresses unphysical, short-range electrostatic interactions. Here, we extend the theory to multivalent ions as well as to high electric fields where a deviation from Ohm's law known as the Wien effect occurs. Our results are in good agreement with experiments and recent simulations.

arXiv comment19 pages, 11 figures

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Cited by in corpus (6)

• Perspective: New directions in dynamical density functional theory
• Stochastic density functional theory for ions in a polar solvent
• Nonlinear conductivity of aqueous electrolytes: beyond the first Wien effect
• Frequency-Dependent Conductivity of Concentrated Electrolytes: A Stochastic Density Functional Theory
• Structural and Dynamical Crossovers in Dense Electrolytes
• Solving Lyapunov equations for electrically driven ternary electrolytes -- application to long-range van der Waals interactions