Studies on the Mechanism of the Electrolytic Formation of Perchlorate

Current‐potential curves of the electrolytic oxidation of chlorate were determined polarographically using a platinum microanode. The nature of the polarogram thus obtained was quite different from that of the usual oxidation‐reduction process. Two potential stages were found; the lower one is believed to be the potential of oxygen evolution and the higher one the potential of perchlorate formation. Probably the limiting current for the oxidation of water could also be seen in the polarogram.Electrolysis of chlorate solution at definite anodic potentials corresponding to the higher stage of the polarogram was carried out in order to confirm the results of the polarographic study. From these experiments, it was clear that the first step of perchlorate formation was probably the discharge of chlorate ion at higher potential than that of oxygen evolution.