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Non-equilibrium steady states of electrolyte interfaces

  • The non-equilibrium steady states of a semi-infinite quasi-one-dimensional univalent binary electrolyte solution, characterised by non-vanishing electric currents, are investigated by means of Poisson-Nernst-Planck (PNP) theory. Exact analytical expressions of the electric field, the charge density and the number density are derived, which depend on the electric current density as a parameter. From a non-equilibrium version of the Grahame equation, which relates the total space charge per cross-sectional area and the corresponding contribution of the electric potential drop, the current-dependent differential capacitance of the diffuse layer is derived. In the limit of vanishing electric current these results reduce to those within Gouy-Chapman theory. It is shown that improperly chosen boundary conditions lead to non-equilibrium steady state solutions of the PNP equations with negative ion number densities. A necessary and sufficient criterion on surface conductivity constitutive relations is formulated which allows one to detect such unphysical solutions.

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Metadaten
Author:Markus Bier
Persistent identifier:https://doi.org/10.1088/1367-2630/ad19a9
Parent Title (English):New Journal of Physics
Document Type:Article
Language:English
Year of publication:2024
Publishing Institution:Technische Hochschule Würzburg-Schweinfurt
Release Date:2024/03/07
Tag:Poisson-Nernst-Planck theory, non-equilibrium steady state, electrolyte interface, Gouy-Chapman model
Volume:26
Issue:1
First Page:013008
Institutes and faculty:Fakultäten / Fakultät für angewandte Natur- und Geisteswissenschaften
Open access colour:Gold
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