Abstract
A model, originally developed for polarography of metal ions in mixtures of macromolecular and simple ligands, is extended to stripping voltammetric measurements carried out in such systems. Among other hypotheses, the model assumes excess of ligand and absence of both electrodic adsorption and kinetic effects (complexes are supposed to be totally labile or totally inert). The different hydrodynamic conditions in stripping voltammetry in respect to polarography make it necessary to modify some equations of the original model. The reliability of this semiempirical approach is tested by studying the ZnII + polymethacrylic acid + phthalate system, which is a typical system with labile complexation, The mean values of the formation constant and diffusion coefficient ratio obtained by this approach are quite similar to those determined from polarographic experiments. The introduction of a semiempirical hydrodynamic parameter p, analogous to that previously used in the model for a unique macromolecular complex, yields satisfactory results.
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