关键词: 二羟基二过碘酸合镍(Ⅳ), 乙二胺, 氧化还原, 动力学及机理

Abstract: The kinetics of oxidation of ethylenediamine(en)by dihydroxydiperiodatonickelate(Ⅳ) complex 0.40) at 20-35℃. The reaction rate showed first-order dependence in oxidant and positive fractional order dependence in ethylenediamine. The pseudo first-order ([en]>> [DDN]) rate constant kobs increases with the increase of [OH^-] and decreases with the increase of [IO₄^-], which implies that before the ratedetermining step there is a preequilibrium in which one of the periodate ligands of the oxidant is deprotonated and the other is dissociated, and dihydroxymonoperiodate (Ⅳ) complex (DMN ) is the reactive species. In addition, no salt effect and no free radical was observed, which indicates that an innersphere one-step two-electron transfer mechanism without free radical intermediate may be in operation. Based on the experimental results a mechanism involving a preequilibrium of an adduct formation between the [Ni(OH)₂(HIO₆)]_2- and ethylenediamine has been proposed. The rate equation derived from the mechanism can be used to explain all the experimental results satisfactorily and the preequilibrium constants, rate constant of the rate-determining step together with the activation parameters were evaluated.

Key words: Dihydroxydiperodatonickelate(Ⅳ), Ethylenediamine, Oxidation and reduction, Kinetics and mechanism