Title: Kinetics of Oxidation of Carbonyl Compounds by Peroxomonosulfate. Acetaldehyde, Propionaldehyde, and Butyraldehyde
Abstract: Abstract A kinetic study of oxidation of acetaldehyde, propionaldehyde, and butyraldehyde by peroxomonosulfate (PMS) in the presence of H+ ion has been carried out. The reaction shows first order dependence each on [PMS] and [Aldehyde]. The reaction shows inverse first order over a particular concentration range of H+ ion and beyond that first order dependence is observed with respect to [H+]. The inverse hydrogen ion dependence on kobsd may be due to the higher reactivity of SO52− than HSO5− with aldehydes. The increase in kobsd with increase in [H+] beyond certain [H+] can be explained by the formation of protonated carbonyl compounds. The Taft’s plot gives ρ* value of ≈5.0 indicating that the reaction is nucleophilic substitution at the carbonyl carbon which then rearranges to products.