Adsorption of chalcophile metals onto thiol-based resins: Modeling adsorption capacity and behavior using surface complexation modeling

Abstract

Adsorption of chalcophile metals from aqueous solution by thiol resins represents an efficient means of reusing these metals and remediating waste streams, and a predictive modeling approach is needed in order to design and optimize adsorption applications. In this study, potentiometric titration measurements, metal adsorption experiments and surface complexation modeling (SCM) approaches were used to characterize three thiol-based resins (BT40, SP70, and SP300), and to model their proton, Cd, Zn, and Pb adsorption capacities and behaviors. We find that the extent of Cd adsorption onto the three resins correlates strongly to the measured concentration of proton-active thiol sites on each resin, and that the BT40 resin has a significantly higher concentration of proton-active thiol sites than the other two resins tested. Using the BT40 as a model resin, we demonstrate that the measured stability constant (K) of the Cd-thiol surface complex on the resin successfully accounts for the effects of both the metal:resin ratio and pH over a wide range of experimental conditions. We also find that a linear free-energy relationship (LFER) exists between the K values of metal-thiol surface complexes on the BT40 resin and the K values of metal-thiol aqueous complexes for Cd, Zn and Pb. This LFER can be used to estimate the K values of other metal-thiol resin surface complexes that have not been measured experimentally, therefore enabling prediction of the adsorption behavior of a wide range of metals onto thiol-based resins under a wide range of system conditions. This study demonstrates that a SCM approach, coupled with potentiometric titration measurements and metal adsorption experiments, represents a powerful tool for the design and optimization of strategies for separating and recovering chalcophile metals from aqueous media.