The Particle Surface as a Carrier of Functional Groups

Abstracting from the complexity of the real systems, there is one common property of all natural particles. Their surfaces contain functional groups which can interact with H+, OH and metal ions and - if Lewis acid sites, e.g., =AI and =Fe, are available on the surface - with ligands. Many inorganic solids (oxidesQand silicates) contain hydroxo groups carbonates and sulfides expose -C-oh,-c oh, MeOH and -SH groups, respectively. While the interaction of alkaline and earth-alkaline ions 

Model Studies. In model studies of adsorption, one deals with simple, well-defined systems, where usually a single well-characterized solid phase is used and the composition of the ionic medium is known, so that reactions competing with the adsorption may be predicted. It is not a trivial problem to compare the results from such model studies with those from field studies, or to use model results for the interpretation of field data. In field studies, a complex mixture of solid phases and dissolved components, whose composition is only poorly known, has to be considered competitive reactions of major ions and trace metal ions for adsorption may take place, and the speciation of the trace metal ions is often poorly understood. In order to relate field studies to model studies, distribution coefficients of elements between the dissolved and solid phases are useful. These distribution coefficients are of the following form  

The distribution coefficients are independent of the concentration of suspended solids in water, which can vary over a wide range they thus give a better picture than the fraction of metal ions in solution. Such distribution coefficients can be predicted on the basis of the equilibrium constants defining the complexation of metals by surfaces and their complexation by solutes (Table 11.1). 

Distribution coefficients based on adsorption equilibria are independent of the total concentrations of metal ions and suspended solids, as long as the metal concentrations are small compared with the concentration of surface groups. Examples of the Kd obtained from calculations for model surfaces are presented in Fig. 11.1. A strong pH dependence of these Kd values is observed. The pH range of natural lake and river waters (7 - 8.5) is in a favorable range for the adsorption of metal ions on hydrous oxides. 

Increasing concentrations of a soluble ligand cause a decrease in Kq for the simple case in which the complexation in solution and at the surface are competing with each other (see Example 11.1 and Fig. 11.4). 

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