The kinetics of oxidation of glycolic acid, an α-hydroxy acid, by peroxomonosulfate (PMS) was studied in the presence of Ni(II) and Cu(II) ions and in acidic pH range 4.05-5.89. The metal glycolate, not the glycolic acid (GLYCA), is oxidized by PMS. The rate is first order in [PMS] and metal ion concentrations. The oxidation of nickel glycolate is zero-order in [GLYCA] and inverse first order in [H + ]. The increase of [GLYCA] decreases the rate in copper glycolate, and the rate constants initially increase and then remain constant with pH. The results suggest that the metal glycolate ML + reacts with PMS through a metal-peroxide intermediate, which transforms slowly into a hydroperoxide intermediate by the oxygen atom transfer to hydroxyl group of the chelated GLYCA. The effect of hydrogen ion concentrations on k obs suggests that the structure of the metal-peroxide intermediates may be different in Ni(II) and Cu(II) glycolates. C

No abstract

No abstract

shows that the electron-donating methyl group in lactic acid enhances the nucleophilic interaction of the α-hydroxyl group. A suitable mechanistic scheme is also proposed.

No abstract