Pseudo-Second-Order Kinetic Equation for Describing the Effect of Sorbent and Sorbate Concentrations.

Abstract

The sorbent concentration (Cs) effect and sorbate initial concentration (C0) effect are common phenomena observed in the study of adsorption kinetics at solid-liquid interfaces. That is, adsorption rate constants simulated with classical kinetic equations, such as the pseudo-second-order (PSO) model, for a given system vary with Cs and C0. The classical kinetic equations cannot predict or describe the "Cs-effect" and "C0-effect" (called "C-effects" here). In the current work, the dynamic partition coefficient of sorbate between solid and liquid phases (Kt) was used to describe the adsorption kinetic processes. Based on the surface component activity (SCA) model, which assumes the activity coefficients of the surface components (fs) are not equal to unity but rather a function of Cs and the adsorption capacity (or C0) and referring to the classical PSO model, a new kinetic equation was established, called the "SCA-PSO kinetic model", and its two parameters, the intrinsic equilibrium partition coefficient (Ke0) and the intrinsic rate constant (k20), are independent of Cs and C0. In addition, the new model relates Kt and the rate constant (k2) to Cs and C0 via fs, and can thus describe the C-effects. The fs can be estimated from the change of equilibrium partition coefficient (Ke) with Cs and C0. The new model predicts that with the increase of Cs and C0, Ke decreases while k2 increases. Its rationality was confirmed by the literature-reported adsorption kinetic data of heavy metals on inorganic and biomass sorbents with the C-effects.