Electrical Double Layers: Effects of Asymmetry in Electrolyte Valence on Steric Effects, Dielectric Decrement, and Ion-Ion Correlations

Langmuir : the ACS Journal of Surfaces and Colloids
Ankur Gupta, H A Stone

Abstract

We study the effects of asymmetry in electrolyte valence (i.e., non z: z electrolytes) on mean field theory of the electrical double layer. Specifically, we study the effect of valence asymmetry on finite ion-size effects, the dielectric decrement, and ion-ion correlations. For a model configuration of an electrolyte near a charged surface in equilibrium, we present comprehensive analytical and numerical results for the potential distribution, electrode charge density, capacitance, and dimensionless salt uptake. We emphasize that the asymmetry in electrolyte valence significantly influences the diffuse-charge relations, and prior results reported in the literature are readily extended to non z: z electrolytes. We develop scaling relations and invoke physical arguments to examine the importance of asymmetry in electrolyte valence on the aforementioned effects. We conclude by providing implications of our findings on diffuse-charge dynamics and other electrokinetic phenomena.

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Citations

Mar 25, 2019·The European Physical Journal. E, Soft Matter·G S GanchenkoE A Demekhin
Aug 29, 2020·Physical Review Letters·Ankur GuptaHoward A Stone
Aug 7, 2020·Soft Matter·Ankur GuptaHoward A Stone
Jan 16, 2021·Electrophoresis·Sirsendu Sekhar BarmanPrashanta Dutta
Nov 17, 2020·Physical Review Letters·Ankur GuptaHoward A Stone
Mar 5, 2021·The Journal of Physical Chemistry. B·James D SterlingYun L Luo
Oct 19, 2019·Langmuir : the ACS Journal of Surfaces and Colloids·Aditya Vikram KhandelwalShalini Gupta
Feb 1, 2020·Langmuir : the ACS Journal of Surfaces and Colloids·Jessica L WilsonHoward A Stone
Dec 11, 2021·Physical Chemistry Chemical Physics : PCCP·Andresa MessiasEudes E Fileti

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