Discreteness-of-Charge Adsorption Micropotentials. I. Infinite Imaging

Abstract

Articles you may be interested inEffects of image charges, interfacial charge discreteness, and surface roughness on the zeta potential of spherical electric double layers A selfconsistent study of ion adsorption and discrete charge effects in the electrical double layerThe Ershler infinite imaging model for adsorption of ions from electrolytes is discussed ill detail. An incorrect derivation of the basic equations for the micropotential is critically examined and a correct derivation provided. ~he potential arising from discret~ adions and their images is determin~d exactly based upon a method which heretofore has only been applIed to crystal field problems. Finally the accurate results obtained using a digital computer are compared with the approximate results of othe~ treatments.

An Indirect Laser-Induced Temperature Jump Determination of the Surface pKa of 11-Mercaptoundecanoic Acid Monolayers Self-Assembled on Gold

“…One possible origin for a putative stabilization of the carboxylate anion at the monolayer interface is the image charge interactions which arise from the fact that the charges on these anions are discrete − and are, therefore, not smeared out over the entire monolayer/solution interface as well as from the fact that these charge are bound to a very high dielectric medium (the gold electrode) by a very low dielectric constant medium (the monolayer up to the PAD). However, calculations based upon the three phase (i.e., solution/film/electrode) model for the image charge interactions of an ion present on the solution side of an interface with a film-coated electrode which has been proposed by Liu and Newton demonstrate that the stabilization (i.e., negative change in the free energy for the hydrogen ion dissociation reaction (Δ G r )) effected by these image charge interactions is not strong enough to overcome the positive change in Δ G r caused by transferring the carboxylate anions from a high dielectric constant medium (an aqueous electrolyte solution) to a relatively low dielectric constant medium (the MUA monolayer/electrolyte solution interface) .…”

Thermal Stability of an Adsorbed Array of Charges in the Einstein Approximation

“…In a number of treatments of the electrolyte double layer (9-13), it has again been assumed that a t least above some miniinun~ surface coverage, the ions adsorbed on the electrode (usually a mercury drop) arrange themselves in a fixed hexagonal array. In this situation, there is the possibility of imaging of adions in the diffuse double layer as well as in the electrode (10)(11)(12)(13). Such imaging leads to an infinite array of image charges perpendicular to the adsorbent surface and has been termed infinite imaging (13).…”

“…Clearly, the treatments of Buff and Stillinger and those which assume an array model ab initio are complementary, but one should knoxv where the crossover occurs, and this question, while not considered by Buff and Stillinger, is approxiinately answered by this paper. As we shall see, even for infinite imaging (13), where adsorbed concentrations must be somexvhat Can. J. Chem.…”

“…In this situation, there is the possibility of imaging of adions in the diffuse double layer as well as in the electrode (10)(11)(12)(13). Such imaging leads to an infinite array of image charges perpendicular to the adsorbent surface and has been termed infinite imaging (13). When the imaging in the diffuse layer is assumed to be incomplete, the situation is termed partial imaging, whose limit is the present single-imaging situation (8) when imaging in the diffuse layer (if it exists) is absent or negligible.…”

Competitive membrane adsorption of Na+, K+, and Ca2+ in smooth muscle cells

“…We have used theories that have been satisfactorily applied in both biological [12,21] and model membrane [3,18,29,381 systems. Double layer theory, though ignoring discreteness of charge effects [5,14,34], is a reasonable starting point for understanding surface charge effects. Not only does smeared charge theory allow for screening effects, it also permits one to mathematically couple bulk screening to adsorption theory in a self-consistent, relatively simple way.…”