Effect of adsorption on solute dispersion: a microscopic stochastic approach.

We report on results obtained with a microscopic modeling approach to Taylor-Aris dispersion in a tube coupled with adsorption-desorption processes at its inner surface. The retention factor of an adsorbed solute is constructed by independent adjustment of the adsorption probability and mean adsorption sojourn time. The presented three-dimensional modeling approach can realize any microscopic model of the adsorption kinetics based on a distribution of adsorption sojourn times expressed in analytical or numerical form. We address the impact of retention factor, adsorption probability, and distribution function for adsorption sojourn times on solute dispersion depending on the average flow velocity. The approach is general and validated at all stages (no sorption; sorption with fast interfacial mass transfer; sorption with slow interfacial mass transfer) using available analytical results for transport in Poiseuille flow through simple geometries. Our results demonstrate that the distribution function for adsorption sojourn times is a key parameter affecting dispersion and show that models of advection-diffusion-sorption cannot describe mass transport without specifying microscopic details of the sorption process. In contrast to previous one-dimensional stochastic models, the presented simulation approach can be applied as well to study systems where diffusion is a rate-controlling process for adsorption.