Electrochemical oxidation of oxalate ion in the presence of fluoride ion, and radical analysis by ESR

The problem at hand is the electrochemical oxidation of oxalate ion, which is accelerated by fluoride ion at a platinum anode. The hypothesis that fluoride ion traps incipient hydroxyl radicals as hydroxyfluoride radical anions was not supported by ESR experiments in which hydroxyl radicals were generated in the presence of the spin trap α-(4-pyridyl-1-oxide) N-tert-butyl-nitrone with and without the addition of fluoride ion. The electrochemical oxidation of oxalate at constant current followed current controlled kinetics both at a platinum anode, as observed previously, and at a boron-doped diamond anode, but the rate of the latter reaction was indifferent to the presence of fluoride ion. We propose that the competition of fluoride and hydroxide ions for the Pt/PtOn surface inhibits the dimerization reactions that lead to oxygen evolution; the displacement of oxygen evolution to more positive potentials overcomes the overpotential for the oxidation of oxalate at this anode. Fluoride ion has no influence on the oxidation of oxalate at BDD because oxygen evolution inherently occurs at more positive potentials at this anode.