Electron transfer between trans-dihydroxotetraoxoosmate(VIII) and thiosulfate. A kinetic study in aqueous alkaline media

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 where K_Os 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 S₂O and its decomposition constant. The K_Os, 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 S₂O, followed by a rate-determining decomposition of the complex with concomitant electron transfer.