Polarography and Voltammetry in Non-Aqueous Solutions

Polarography and Voltammetry in Non-Aqueous Solutions Outer Sphere Electron Transfer Reactions... 

The characteristics of redox reactions in non-aqueous solutions were discussed in Chapter 4. Potentiometry is a powerful tool for studying redox reactions, although polarography and voltammetry are more popular. The indicator electrode is a platinum wire or other inert electrode. We can accurately determine the standard potential of a redox couple by measuring the electrode potential in the solution containing both the reduced and the oxidized forms of known concentrations. Poten-tiometric redox titrations are also useful to elucidate redox reaction mechanisms and to obtain standard redox potentials. In some solvents, the measurable potential range is much wider than in aqueous solutions and various redox reactions that are impossible in aqueous solutions are possible. 

Anodic stripping voltammetry has been used to determine total arsenic spedes . Pulse polarographic methods have been applied to aqueous and non-aqueous solutions of methyl- and dimethylarsenic adds at concentration levels down to 0.1 /rg/ml . These arsenicals are electroactive in aqueous buffers and in non-aqueous media in which the acidic supporting electrolyte, guanidinium porchlorate, is employed. A direct method of analysis, based on differential pulse polarography, is reported. Detection limits of roughly 0.1/xg/ml (for MMAA) and 0.3p[Pg.190]

To overcome some of the problems associated with aqueous media, non-aqueous systems with cadmium salt and elemental sulfur dissolved in solvents such as DMSO, DMF, and ethylene glycol have been used, following the method of Baranski and Fawcett [48-50], The study of CdS electrodeposition on Hg and Pt electrodes in DMSO solutions using cyclic voltammetry (at stationary electrodes) and pulse polarography (at dropping Hg electrodes) provided evidence that during deposition sulfur is chemisorbed at these electrodes and that formation of at least a monolayer of metal sulfide is probable. Formation of the initial layer of CdS involved reaction of Cd(II) ions with the chemisorbed sulfur or with a pre-existing layer of metal sulfide. 

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