Hard–Soft Interactions in Solvent Extraction with Basic Extractants: Comparing Zinc and Cadmium Halides

[Image: see text] Solvent extraction is often applied to separate and purify metals on an industrial scale. Nevertheless, solvent extraction processes are challenging to develop because of the complex chemistry involved. For basic extractants, much of the chemical behavior remains poorly understood due to the conditions far from thermodynamic ideality. To elucidate the extraction mechanism, we studied the speciation and extraction of zinc(II) and cadmium(II) from chloride, bromide, and iodide media by using a basic extractant consisting of a trioctylmethylammonium cation and, respectively, a chloride, bromide, or iodide anion. These systems were specifically selected to increase the understanding of the less-studied bromide and iodide media and to focus on the effect of hard–soft interactions on solvent extraction systems. It was observed that, in general, a metal is more efficiently extracted when its hydration in the aqueous phase is lower and its stabilization in the organic phase is higher. In the investigated systems, these conditions are obtained by forming metal complexes with a lower charge density by coordinating the right number of halide anions and by selecting a halide with a lower charge density. In the organic phase, the stability of the metal complex can be increased by forming strong metal–anion bonds and by decreasing the water content. These insights might be of interest in the development and optimization of separation schemes for metals.