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Electron transfer to trans ‐dihydroxotetraoxoosmate(VIII). II. Kinetics of the oxidation of dimethylsulfoxide in aqueous alkaline media
Author(s) -
Neogi G.,
Acharya S.,
Panda R. K.,
Ramaswamy D.
Publication year - 1983
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550150904
Subject(s) - chemistry , kinetics , nucleophile , aqueous solution , reaction rate constant , ion , electron transfer , outer sphere electron transfer , aqueous medium , inorganic chemistry , medicinal chemistry , photochemistry , catalysis , organic chemistry , physics , quantum mechanics
The kinetics of the oxidation of dimethylsulfoxide by oxohydroxoosmate(VIII) complex ions in alkaline media follow pseudo‐first‐order disappearance in Os(VIII). The values of the observed pseudo‐first‐order rate constant are linearly dependent on initial dimethylsulfoxide concentrations in a fortyfold range, and increase with increasing [OH − ], leveling off at higher relative [OH − ]. The results are interpreted in terms of outer sphere interactions involving dimethylsulfoxide and various species of the Os(VIII) complex. The more nucleophilic dihydroxotetraoxoosmate(VIII) ion reacts about 50 times faster than the trihydroxotrioxoosmate(VIII) species.