Voltammetric Study of Reduction Processes in Rhodium(+3)–Selenium(+4) Acidic Mixtures

Using square‐wave voltammetry and linear scan voltammetry, some reduction processes, that take place on the hanging mercury drop electrode (HMDE) in rhodium(+3)–selenium(+4) mixtures, were studied in highly acidic sulfate, chloride and perchlorate solutions. The special attention was paid to the peak located at ?1.1 V, that reflects catalytic hydrogen evolution on the rhodium islets, and its changes under the influence of added selenium(+4), or selenium(?2) produced at the electrode. It can be concluded that addition of selenite to a dilute rhodium solution has the similar effect as the increase of rhodium(+3) concentration, making the catalytic hydrogen evolution more pronounced, probably by changing the properties of metal clusters on the mercury drop. If so, the effect could be of some practical importance in production of rhodium deposits on other surfaces, too.