Abstract
MnIII is stabilized by pyrophosphate in weakly acidic solutions. The nature of the complex formed was elucidated spectrophotometrically. The kinetics of MnIII oxidation of thiocyanate in pyrophosphate medium was investigated over the pH range 2–3. The oxidation followed first order kinetics with [MnIII]. The effects of varying [MnIII], [NCS−], added MnII and metal ions, pH, total [P2Of7p4−] and added ClOf4p−, Cl− and SOf4p2− were studied. The order in [NCS−] was unity, and increasing [H+] increased the rate. Retardations with added P2Of7p4− and MnII were observed. Complexation of NCS− as K2Zn(NCS)4 decreased the reactivity without any change in overall mechanism. The dependence of the reaction rate on temperature was examined, and activation parameters were computed from Arrhenius and Eyring plots. A mechanism consistent with the results is proposed.
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