Kinetics of oxidation of organic compounds by silver(II) in aqueous perchloric acid solution. IV. Aliphatic alcohols

Abstract

AbstractThe kinetics and mechanism of the silver(II) oxidation of methanol, ethanol, 1‐propanol, 1‐methyl‐ ethanol, 1‐butanol, 2‐methyl‐1‐propanol, 2‐butanol, 2‐methyl‐2‐propanol, D4‐methanol, and D6‐methanol have been investigated at 8.0 and 20.0°C in aqueous perchloric acid media (1.00 ≤ [HClO4] ≤ 4.00M; μ = 4.0M). The kinetics were monitored by following the disappearance of Ag(II) with a spectrophotometric stopped‐flow technique. The reactions are first order in each reactant and involve both Ag2+ and AgOH+ species. No kinetic or spectroscopic evidence for complex formation between reactants was obtained. The results are discussed with reference to electron density on the OH or αC‐H substrate sites and to the isotopic hydrogen/deuterium rate quotients found for methanol and ethanol.