Electrostatic Focusing in Micellar and Microelectrode Kinetic Processes

Abstract

AbstractIn this paper we present a detailed characterization of the electrostatic environment of a charged organizate in order to determine the importance of field effects in influencing micellar and microelectrode kinetic processes. The electrostatic potential and associated ion distributions in the vicinity of a charged organizate are determined using a potential approach and, in particular, one based on a (previously reported) generalization of Poisson‐Boltzmann theory. The role of organizate size and geometry, and the importance of dielectric saturation, ionic strength and different assumptions on the behavior of the surface potential (boundary conditions) in influencing the potentials and ion distributions are studied. These calculations and the trends observed cast light on the general problem of micellar/micro‐electrode catalysis and, as well, lead to a number of specific results: we are able to place a lower bound on the effective size of a „microelectrode”︁ particle, colloidal dispersions of which have been used in the recent hydrogen evolution studies of Grätzel and coworkers, and Henglein.