Studies on the oxygen atom transfer reactions of peroxomonosulfate: Oxidation of glycolic acid

✍ Scribed by S. Shailaja; M. S. Ramachandran

• Publisher: John Wiley and Sons
• Year: 2009
• Tongue: English
• Weight: 118 KB
• Volume: 41
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.20388

✦ Synopsis

Abstract

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. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 41: 160–167, 2009