Abstract
Kinetic measurements of CH3NO2 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 NaClO4 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 qi at the inner Helmholtz plane. The effects of these changes between pH 4 and 9 are consistent with a rate-determining protonation step CH3NO2−→(+H+)CH3NO2H 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 CH3NO2+e→CH3NO2−, again occurring within the compact layer.
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