Fluctuation-enhanced electric conductivity in electrolyte solutions

DOI10.1073/PNAS.1714464114zbMATH Open1404.78032arXiv1706.06227OpenAlexW2962836248WikidataQ47662922 ScholiaQ47662922MaRDI QIDQ4646205FDOQ4646205

Alejandro L. Garcia, Jean-Philippe M. Péraud, Aleksandar Donev, J. B. Bell, Andrew J. Nonaka

Publication date: 11 January 2019

Published in: Proceedings of the National Academy of Sciences (Search for Journal in Brave)

Abstract: In this letter we analyze the effects of an externally applied electric field on thermal fluctuations for a fluid containing charged species. We show in particular that the fluctuating Poisson-Nernst-Planck equations for charged multispecies diffusion coupled with the fluctuating fluid momentum equation, result in enhanced charge transport. Although this transport is advective in nature, it can macroscopically be represented as electrodiffusion with renormalized electric conductivity. We calculate the renormalized electric conductivity by deriving and integrating the structure factor coefficients of the fluctuating quantities and show that the renormalized electric conductivity and diffusion coefficients are consistent although they originate from different noise terms. In addition, the fluctuating hydrodynamics approach recovers the electrophoretic and relaxation corrections obtained by Debye-Huckel-Onsager theory, and provides a quantitative theory that predicts a non-zero cross-diffusion Maxwell-Stefan coefficient that agrees well with experimental measurements. Finally, we show that strong applied electric fields result in anisotropically enhanced velocity fluctuations and reduced fluctuations of salt concentrations.

Full work available at URL: https://arxiv.org/abs/1706.06227

Mathematics Subject Classification ID

Magnetohydrodynamics and electrohydrodynamics (76W05) Electrochemistry (78A57)

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• Temporal response of the conductivity of electrolytes
• The conductivity of strong electrolytes from stochastic density functional theory
• Fluctuating hydrodynamics of dilute electrolyte solutions: systematic perturbation calculation of effective transport coefficients governing large-scale dynamics

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