Unusual kinetic behavior in cathodic H2 evolution from KF.2HF melts at mild-steel and alloy electrodes

Apart from its interest as a "model" process for kinetic studies of gas-evolving electrode reactions, the cathodic hydrogen evolution reaction (her) is involved in several processes that are of importance in applied electrochemistry, e.g., as the cathodic co-reactions in the commercial production of C12 and F2, in electrolyses for production of hydrogen, in electrochemical hydrogenation and, indirectly, as the partial process in corrosion of base metals in the absence of oxygen. The present paper reports several aspects of the unusual behavior of the her that is involved as the co-reaction to electrolytic production of F2 from KF/HF melts using carbon anodes and Fe or mild-steel cathodes. Anomalous anodic polarization behavior that arises in electrolytic generation of F2 from KF/HF melts at carbon electrodes is well known. It is characterized by very high Tafel slopes associated with "CF" film formation and by sluggish F2 bubble disengagement from the electrode. Interest in such effects has, however, tended to overshadow rather similar, so-called "hyper polarization" effects that also arise in the cathodic reaction, but for different reasons. The origins and nature of such effects are described and characterized in the present paper, and comparisons are made between behavior of Hz evolution from KF.2HF and that from the aquo-system analogue, KOH.2H2O. An important aspect is the very different interfacial behavior in KF/HF or KF.2HF melts from that in the corresponding aquo-system. Effects of As-species in HF feeds is investigated in terms of electro catalysis and poisoning effects on the her