Kinetic study of ruthenium (VI)-catalyzed oxidation of 2-propanol by alkaline hexacyanoferrate (III)

The kinetics of Ru(VI)-catalyzed oxidation of 2-propanol by hexacyanoferrat e(III) was investigated in alkaline media using a spectrophotometric techni que. The reaction shows first order in [Ru(VI)], a Michaelis-Menten-type de pendence on [2-propanol], a fractional order in [Fe(CN)(6)(3-)] and a compl icated variation on [OH-]. A reaction mechanism which involves two active c atalytic species is proposed. Each of these species forms an intermediate c omplex with the substrate. These complexes decompose slowly, producing ruth enium(IV) complexes, which are reoxidized by hexacyanoferrate(III) in subse quent steps. The theoretical rate law obtained is in complete agreement wit h all the experimental observations. Copyright (C) 1999 John Wiley & Sons, Ltd.