Sulfite induced autoxidation of Ni(ii) and Co(ii) tetraglycine complexes. Spectrophotometric and rotating ring-disc voltammetric studies

Abstract

The oxidation of Ni(II) and Co(II) tetraglycine complexes in borate buffer aqueous solution, by dissolved oxygen, is strongly accelerated by sulfite. The formation of Ni(III) and Co(III) complexes with maximum absorbances at 327 and 265 nm, respectively, was followed by spectrophotometric measurements. Ni(III) formation was also characterized by voltammetry at low temperatures, whose anodic and cathodic components were observed in the recorded voltammograms. Spectra and rotating ring-disc voltammograms, recorded at various rotation speed values, showed that the Ni(III) species decomposes. The electrochemical process related to the couple Co(II)/Co(III), in a medium containing tetraglycine, was not reversible. In both Ni(II) and Co(II) complexes the metal ion oxidation in the presence of oxygen and sulfite involves the reduction of some initial Ni(III) or Co(III) by sulfite to produce the SO₃˙⁻ radical, which rapidly reacts with dissolved oxygen to produce SO₅˙⁻, which then oxidizes Ni(II) or Co(II).