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 hexacyanoferrate(III) was investigated in alkaline media using a spectrophotometric technique. The reaction shows first order in [Ru(VI)], a Michaelis-Menten-type dependence on [2-propanol], a fractional order in [Fe(CN)(6)(3-)] and a complicated variation on [OH-]. A reaction mechanism which involves two active catalytic species is proposed. Each of these species forms an intermediate complex with the substrate. These complexes decompose slowly, producing ruthenium(IV) complexes, which are reoxidized by hexacyanoferrate(III) in subsequent steps. The theoretical rate law obtained is in complete agreement with all the experimental observations. Copyright (C) 1999 John Wiley & Sons, Ltd.