Analysis of steric hindrance effects on adsorption kinetics and equilibria

Most existing adsorption models do not properly consider steric hindrance effects of preadsorbed solutes. As a consequence, the models often fail to represent the adsorption kinetics and equilibria accurately. In this work, we extend the random sequential adsorption concept for irreversible adsorption to analyze reversible adsorption on a continuous surface and a random site surface. Based on simulation results of these processes, general kinetic equations for one‐component adsorption are developed. The equations are used to correlate chromatography frontal curves of lysozyme and isotherm data of ethane adsorption on activated carbon and ethylene adsorption on a molecular sieve. The significance of the equations, as compared with the Langmuir equation, lies not only in their ability to correlate the experimental data more accurately, but in the physical significance of the adsorption parameters such as the maximum adsorption capacity obtained from the correlation. Our study shows that steric hindrance effects alone result in nonlinear Scatchard and Hill plots with negative cooperativity.