Impedance study of formic acid oxidation on platinum electrodes

The electrooxidation of formic acid on polycrystalline platinum electrodes in sulphuric acid is studied by a dynamic impedance method. Impedance spectra in the frequency range 0.7 Hz to 20 kHz, assembled from ac voltammograms, are interpreted in terms of a mechanism with three adsorbed species, although one of these may be free sites. The spectra show evidence for incipient oscillations in two potential regions, and observed oscillations were related to these spectra. The zeroes of the interfacial impedance were directly extracted from suitable equivalent circuits in distinct potential regions where oscillations may be triggered. The observation of only real zeroes of the interfacial impedance eliminates the possibility of pure potentiostatic oscillations arising from chemical reasons alone, and therefore potential is an essential variable.