Kinetics and mechanism of the Co(II)-assisted oxidation of L-ascorbic acid by dioxygen and nitrite in aqueous solution

Dalton Trans. 2009 Dec 21:(47):10541-9. doi: 10.1039/b906478h. Epub 2009 Oct 30.

Abstract

A detailed study of the oxidation of L-ascorbic acid by dioxygen and nitrite in water at pH 5.8 and 7.0, catalyzed by the octasulfophenyltetrapyrazinoporphyrazine complex of cobalt(II), was carried out using conventional spectrophotometric, low-temperature and high-pressure stopped-flow techniques. The Co(II) complex activates L-ascorbic acid through an intramolecular one-electron oxidation step that involves the reduction of the octasulfophenyltetrapyrazinoporphyrazine. The reaction rate strongly depends on pH due to the different redox behaviour of the L-ascorbic acid/ascorbate species present in solution. Kinetic parameters for the different reaction steps of the catalytic process were determined. The final product of the reaction between L-ascorbic acid and nitrite was found to be nitrous oxide.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Ascorbic Acid / chemistry*
  • Cobalt / chemistry*
  • Hydrogen-Ion Concentration
  • Kinetics
  • Nitrites / chemistry*
  • Organometallic Compounds / chemistry*
  • Oxidation-Reduction
  • Oxygen / chemistry*
  • Thermodynamics
  • Water / chemistry*

Substances

  • Nitrites
  • Organometallic Compounds
  • Water
  • Cobalt
  • Ascorbic Acid
  • Oxygen