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No description available.

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Metal cation adsorption is the predominant chemical mechanism governing the attenuation of toxic metal movement in soils. Clay minerals are the primary adsorbent surfaces in soils due to their ubiquitous nature and large reactive surface area. This study examined the relative affinity of the metals cadmium, nickel and zinc for the clay minerals kaolinite and montmorillonite. The influence which different mineral adsorbents and different complexing ligands in solution have on the adsorption of metal ions was assessed using the Hard-Soft Acid-Base Principle as a theoretical framework for predicting the maximum extent of adsorption and rate of adsorption. The HSAB principle is that hard bases prefer to complex hard acids and soft bases prefer to complex soft acids. The hypothesis that initiated these investigations was that the hard-soft character of mineral surfaces is due to their surface functional groups and can be measured using metal cation adsorption selectivity experiments where pH and complex ion formation are controlled. When complex ion formation in aqueous solution was minimized (i.e. in Ca(ClO₄)₂), adsorption decreased in the order of decreasing softness, CD > Zn > Ni for both clay minerals. Montmorillonite behaved as a slightly harder Lewis base than kaolinite, sorbing the harder Ni and Zn ions to a greater extent than Cd, although both minerals behaved as soft Lewis bases. In the presence of chloride and sulfate ligands, adsorption sequences changed and reflected results from typical soil solution studies. In some cases the adsorption sequences can be explained using the HSAB principle together with computer speciation data and this approach merits further consideration and research. Adsorption over time and calculated adsorption rate constants were generally consistent with equilibrium selectivity data. Adsorption rates decreased in the order Cd > Zn > Ni in Ca(ClO₄)₂ for both clay minerals. The adsorption curves reflect a two-step adsorption process involving a rapid exchange-type reaction followed by a much slower adsorption involving diffusion into the crystal or alteration of the surface through the formation of a new solid phase involving the adsorbed ions.

Methyl 3-mercaptopropionate was synthesized from 3-mercaptopropionic acid and purified by extraction into chloroform and column chromatography. The percent purity of the purchased material was determined by an iodine titration. Methyl 3-mercaptopropionate formed an insoluble complex with lead (II) when the pH was greater than 3. It also complexed with cobalt (II). The solubility of meso-dimercaptosuccinic acid was estimated by a spectrophotometric method using 5,5-dithiobis(2-nitrobenzoic acid) since the iodine titration did not give quantitative results. The acid dissociation constants were determined potentiometrically; two methods of calculation were used. Attempts to prepare crystals of the lead (II) complex of meso-dimercaptosuccinic acid in the following gels: agar, agarose, and gelatin, were unsuccessful.

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