A Model for Metal Adsorption on Montmorillonite.

A consistent thermodynamic model is developed for metal sorption on expanding 2:1 layer clays such as montmorillonite. The particle of clay, including lamellae and interlayers, is represented as a porous solid bearing a permanent negative charge (resulting from isomorphic substitution) with an infinite plane interface (i.e., edges) with the solution. Cation exchange occurs inside the clay particle as the result of the negative potential of the clay. Surface complexation reactions take place at the interface whose surface charge and potential are pH dependent. The potential in the bulk of the clay and near the interface, as well as the surface potential-surface charge density relation, are calculated taking into account the effect of the permanent negative charge. The results are discussed and compared with the classic Gouy-Chapman theory. A subroutine (Clayeql) with the new potential-charge relationships is implemented in the thermodynamic equilibrium program Mineql +3.0 and is used to fit an extensive published experimental data set on adsorption of transition metals on montmorillonite. The model is shown not only to fit satisfactorily all the data, but also to explain specific features of adsorption on clays compared to oxides. In particular, the increase in the surface concentration of protons with decreasing ionic strength is successfully reproduced and the weaker dependence of metal sorption on pH compared to oxides is correctly fitted. Copyright 1999 Academic Press.