A generalization of the linear adsorption model to include electrosorption

Abstract

The adsorption phenomenon on surfaces is investigated both with and without the presence of an external electric field. A simple interpretation of the adsorption coefficient and desorption time, as they appear in Langmuir’s isotherm model, is presented. A model for electrosorption is proposed, which explicitly takes into account the applied external voltage and the reaction field resulting from the adsorbed charges. Both saturation, stemming from the finite density of adsorption sites, and non-saturation regimes are considered. The case of a system in contact with a reservoir of particles is also analyzed for its experimental importance. The model’s validity is assessed by analyzing experimental data published by several research groups. A comparative study of the proposed model is conducted in relation to the commonly used pseudo-first and pseudo-second order models. Unlike the latter models, the proposed model allows for the assessment of the impact of the external voltage on the model parameters. The model takes into account ion generation resulting from electrolysis phenomena.