Smoluchowski equation and the Monte Carlo simulations are used to study the conditions leading to the reversal of the electrophoretic mobility. Zeta (zeta) potential is identified with the diffuse potential at the shear plane which, we argue, must be placed at least one ionic diameter away from the colloidal surface. For sufficiently strongly charged colloids, zeta potential changes sign as a function of the multivalent electrolyte concentration, resulting in a reversal of the electrophoretic mobility. This behavior occurs even for very small ions of 4 A diameter as long as the surface charge density of the colloidal particles is sufficiently large and the concentration of 1:1 electrolyte is sufficiently low. (c) 2006 American Institute of Physics.
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