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Article
Effects of Electrostatic Correlations on Electrokinetic Phenomena
Physics Review E (2012)
  • Brian D. Storey
  • Martin Z. Bazant, Massachusetts Institute of Technology
Abstract

The classical theory of electrokinetic phenomena is based on the mean-field approximation that the electric field acting on an individual ion is self-consistently determined by the local mean charge density. This paper considers situations, such as concentrated electrolytes, multivalent electrolytes, or solvent-free ionic liquids, where the mean-field approximation breaks down. A fourth-order modified Poisson equation is developed that captures the essential features in a simple continuum framework. The model is derived as a gradient approximation for nonlocal electrostatics of interacting effective charges, where the permittivity becomes a differential operator, scaled by a correlation length. The theory is able to capture subtle aspects of molecular simulations and allows for simple calculations of electrokinetic flows in correlated ionic fluids. Charge-density oscillations tend to reduce electro-osmotic flow and streaming current, and overscreening of surface charge can lead to flow reversal. These effects also help to explain the suppression of induced-charge electrokinetic phenomena at high salt concentrations.

Publication Date
November, 2012
Publisher Statement

©2012 American Physical Society. This article was published in Physics Review E, vol. 86, iss. 5 and may be found here.

Citation Information
Brian D. Storey and Martin Z. Bazant. "Effects of Electrostatic Correlations on Electrokinetic Phenomena" Physics Review E Vol. 86 Iss. 5 (2012)
Available at: http://works.bepress.com/brian_storey/40/