Abstract
The uncatalyzed oxidation of dimethyl sulfoxide (DMSO) by Ce(IV) involves complex formation between them in nitric acid medium which yields final products. The orders in [Ce(IV)] and [DMSO] were one and fractional, respectively. With Ag(I) as catalyst, an Ag(I)-DMSO adduct is proposed. This adduct reacts with Ce(IV) bimolecularly to give a Ag(II)-DMSO adduct which finally yields the products. The rates exhibit fractional order in [Ag(I)] as well as [DMSO] and first order in [Ce(IV)].
Abstract
Некатализированное окисление диметилсульфоксида (DMSO) с помощью Ce(IV) происходит через образование комплекса между ними в среде азотной кислоты, что и приводит к обарзованию конечных продуктов. Порядок реакции по [Ce(IV)] равен единице, а по [DMSO]—дробный. В случае Ag(I) как катализатора, полагается образование аддукта Ag(I)−DMSO. Этот аддукт реагирует с Ce(IV) бимолекулярно, давая аддукт Ag(II)−DMSO, который уже и приводит к конечным продуктам. Реакция имеет дробный порядок как по [Ag(I)], так и по [DMSO], и первый порядок по [Ce(IV)].
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Rajeshwar Rao, S., Jagannadham, V. Ag(I) catalyzed and uncatalyzed oxidation of dimethyl sulfoxide by ceric nitrate in nitric acid medium: A kinetic study. React Kinet Catal Lett 27, 239–244 (1985). https://doi.org/10.1007/BF02070450
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DOI: https://doi.org/10.1007/BF02070450