Oxidation of cobalt(II) with air oxygen in aqueous ethylenediamine solutions

Oxidation of aqueous Co(NO₃)₂–ethylenediamine (En) solutions with air oxygen was investigated at 20 °C and pH 5.2–7.0, with and without mechanical stirring, by measuring the Co^II concentration, pH and redox potential on an Au electrode. In most cases, the oxidation rate was proportional to the concentration of CoEn ²⁺ _n (n = 2, 3) complexes, and the influence of the solution pH on the rate of reaction was accounted for by the pH dependence of the Co^II complex distribution. It was found that sulphate inhibits and bromide accelerates the oxidation process. Possible oxidation routes are discussed. The oxidation process is limited to some extent by O₂ transport from the air to the bulk solution.     

Kinetics of reduction of hydroxycuprate(III) in KOH solution

The solution of an unstable copper(III) complex, hydroxycuprate(III) i.e. Cu(OH)^– ₄, has been obtained by oxidising a copper anode in 0.5–3 M KOH solution. The kinetics of the copper(III) reduction in KOH solution has been studied spectrophotometrically and is first order with respect to copper(III), and the pseudo-first order rate constant increases as the KOH concentration increases. The kinetic data is explained by a scheme according to which a Cu^III intermediate, in equilibrium with Cu(OH)^– ₄, reacts with OH^–. On the basis of the kinetic data, the molar absorptivity of the Cu(OH)^– ₄ solution has been determined.