Mass Action Expressions for Bidentate Adsorption in Surface Complexation Modeling: Theory and Practice

Abstract

The inclusion of multidentate adsorption reactions has improved the ability of surface complexation models (SCM) to predict adsorption to mineral surfaces, but variation in the mass action expression for these reactions has caused persistent ambiguity and occasional mishandling. The principal differences are the exponent (α) for the activity of available surface sites and the inclusion of surface site activity on a molar concentration versus fraction basis. Exemplified by bidentate surface complexation, setting α at two within the molar-based framework will cause critical errors in developing a self-consistent model. Despite the publication of several theoretical discussions regarding appropriate approaches, mishandling and confusion has persisted in the model applications involving multidentate surface complexes. This review synthesizes the theory of modeling multidentate surface complexes in a style designed to enable improvements in SCM practice. The implications of selecting an approach for multidentate SCM are illustrated with a previously published data set on U(VI) adsorption to goethite. To improve the translation of theory into improved practice, the review concludes with suggestions for handling multidentate reactions and publishing results that can avoid ambiguity or confusion. Although most discussion is exemplified by the generic bidentate case, the general issues discussed are relevant to higher denticity adsorption.