The effect of size and location of adsorbed intermediates in the double layer on the tafel slope the reduction of hydroxylamine on the dropping mercury electrode

The reduction of hydroxylamine on the dropping mercury electrode was studied. Kinetic parameters were determined from measurements at the foot of the polarographic wave. Tafel plots were extended to higher current densities with the use of the Koutecký correction.This molecule was chosen as an example of a relatively small species for which the effect of competition with water is small and the importance of the location of the adsorbed intermediate in the double layer can be demonstrated. The experimentally observed value of b = 96 ± 3 mV (combined with reaction orders of unity both with respect to hydroxylamine and hydrogen ions) was found to be consistent with the notion of an adsorbed intermediate whose reduction is brought about by a potential difference φ_M - φ_x, where φ_x has an intermediate value between φ_M and φ_s. These results were compared with earlier results found in a study of the reduction of nitroalkanes under similar conditions.The advantages of making measurements on the DME at the foot of the polarographic wave are emphasized.