Abstract
Kinetic measurements of CH 3NO 2 electroreduction in aqueous solutions of pH values ranging from 1 to 9 were carried out with the polarographic technique under different experimental conditions. In particular, different concentrations of the supporting electrolytes NaClO 4 and NaCl, which are nonspecifically adsorbed at the potentials investigated, or else of the specifically adsorbed electrolyte KI, were employed to change the potential d at the outer Helmholtz plane and/or the charge density q i at the inner Helmholtz plane. The effects of these changes between pH 4 and 9 are consistent with a rate-determining protonation step C H 3 N O 2 − → ( + H + ) C H 3 N O 2 H taking place within the compact layer. As pH is gradually decreased from 4 to 1, double-layer effects are satisfactorily interpreted by assuming that the control of the overall electrode process passes from the above protonation step to the electron-transfer step CH 3NO 2+ e→CH 3NO 2 −, again occurring within the compact layer.
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