Influence of tetraalkylammonium cations on the electroreduction of nickel(II) in thiocyanate solutions

Influence of tetrabutyl-, tetrapentyl- and tetraisopentylammonium ions on the reduction of nickel(II) in thiocyanate solutions at the dropping mercury electrode has been investigated. These tetraalkylammonium ions, at their low concentrations, inhibit the reduction of nickel(II). However, at their high concentrations, the strong inhibiting effect disappers with the formation of a new wave corresponding to the reduction of a negatively charged nickel(II) thiocyanate complex, which is stabilized by the formation of ion pair with tetraalkylammonium cation. The variation of the reduction current with tetraalkalylammonium concentration was explained by taking into consideration both the change of the total charge of nickel(II) thocyanate complex involved in the reduction process and the simultaneous adsorption of tetraalkylammonium and thiocyanate ions on the mercury electrode.