skip to main content

Title: Electric double layer for a size-asymmetric electrolyte around a spherical colloid

We have studied the structure of a size-asymmetric electrolyte on charged colloids by a density functional perturbation theory. The hard-sphere contribution has been approximated as the direct pair correlation function with the coupling parameter, whereas the electronic contribution has been approximated as the mean-spherical approximation in the bulk phase. The calculated results for the ionic density distributions and mean electrostatic potentials are in very good agreement with the computer simulations over a wide range of colloid sizes and electrolyte concentrations. The present theory provides better structural results than the hypernetted-chain equation based on the mean spherical approximation. We have confirmed that the overcharging appears when the counterions are larger than the coions. The overcharging disappears everywhere when the electrostatic repulsion becomes strong enough, while the charge reversal is observed when the coions are larger than the counterions, and the reversal effect appears for a size-asymmetric electrolyte at high surface charge densities. The charge reversal occurs even for the point of zero charge, mainly due to the depletion force between two ions. The present theory is able to provide interesting insights about the charge reversal and overcharging phenomena occurring at the interface.
Authors:
;  [1]
  1. Department of Physics, Andong National University, Andong 760-749 (Korea, Republic of)
Publication Date:
OSTI Identifier:
22253097
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 140; Journal Issue: 15; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; APPROXIMATIONS; CHARGE DENSITY; COLLOIDS; COMPUTERIZED SIMULATION; DENSITY; DENSITY FUNCTIONAL METHOD; ELECTROLYTES; PERTURBATION THEORY