MECHANISM OF ANODIC-OXIDATION OF CHLORATE TO PERCHLORATE ON PLATINUM-ELECTRODES

The kinetics and mechanism of the anodic oxidation of chlorate to perchlorate on platinum electrodes have been investigated. The current efficiency for perchlorate formation and the electrode potential have been determined as a function of current density for various solution compositions, flow rates and pHs at 50 degrees C. The results have been compared with theoretical relations between the ratio of the current efficiencies for perchlorate and oxygen formation, the electrode potential, the concentration of chlorate at the electrode surface and the current density for various possible mechanisms. It is concluded that the formation of an adsorbed hydroxyl radical is the first step in the overall electrode reaction. The mechanism proposed for the ClO4 perchlorate and oxygen formation is: H2O --> (OH)(ad) + H+ + e(-) ClO3- + (OH)(ad) --> ClO4- + H+ + e(-) 2(OH)(ad) --> O-ad + H2O 20(ad) reversible arrow O-2 The ratio between the current efficiency for perchlorate and that for oxygen formation is determined by the rate of the electrode reaction involving ClO3- and that for the combination reaction of (OH)(ad).