Near Equilibration Times in the Diffusion-Controlled Adsorption

Langmuir. 2024 May 28;40(21):11078-11086. doi: 10.1021/acs.langmuir.4c00622. Epub 2024 May 13.

Abstract

A model of the Frumkin isotherm following adsorption on the surface of the rotating disk is developed with the purpose to calculate the time that is needed for the establishment of the near equilibrium state between the amount of adsorbate and the bulk concentration of surfactant. The "near" is quantified as 99% of the proper equilibrium surface coverage. The near equilibration time depends on the bulk concentration and on the coefficient of molecular attraction in the adsorbed layer. In the vicinity of the inflection point of the isotherm, this time exhibits sharp spike. It is caused by the diminished flux that increases surface coverage very slowly but continues for a long time. Eventually, both the flux and the surface coverage increase with time drastically under the influence of the exponential part of the Frumkin isotherm.