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Electron transfer between trans-dihydroxotetraoxoosmate(VIII) and thiosulfate. A kinetic study in aqueous alkaline media
Authors:Rama Krushna Panda  Gautam Neogi  D Ramaswamy
Abstract:The kinetics of oxidation of thiosulfate to tetrathionate by trans-dihydroxotetraoxoosmate(VIII) in aqueous alkaline media have been studied. The oxidation follows a rate expression equation image where KOs is the formation constant of trans-dihydroxotetraoxoosmate (VIII), and K2 and k3, respectively, represent the formation constants of the intermediate complex involving Os(VIII) and S2Ourn:x-wiley:05388066:media:KIN550131002:tex2gif-stack-1 and its decomposition constant. The KOs, K2, and k3 values have been computed to be (19.5 ± 3) dm3/mol, (6.12 ± 0.5) and (3.32 ± 0.3) × 10?1 dm3/mol s at 303 K, and I = 0.32 mol/dm3, respectively. The rate law is consistent with a mechanism envisaging the equilibrium formation of an intermediate complex involving Os(VIII) and S2Ourn:x-wiley:05388066:media:KIN550131002:tex2gif-stack-2, followed by a rate-determining decomposition of the complex with concomitant electron transfer.
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