Galvanostatic dissolution of mercury from the surface of glassy carbon into thiocyanate solution

The galvanostatic dissolution of mercury from the surface of glassy carbon into a thiocyanate solution proceeds in accord with theoretical assumptions, as manifested by the constant product of the dissolution current and transition time. Under certain relations between the amount of oxidised mercury and concentration of thiocyanate at the electrode surface, however, a small part of the mercury dissolves at more positive potentials than correspond to the Nernst equation. This dissolution can be accompanied by potential oscillations. The anomalous behaviour is elucidated by the concept about coverage of a certain part of mercury with a film of sparingly soluble compounds of SCN- ions with mercury. This film is formed at the end of the galvanostatic dissolution on certain places of the electrode surface covered with mercury droplets, where SCN- ions are much exhausted as a result of a high current density.