An Analysis of the Voltammetric Adsorption Waves of Methyl Viologen

Abstract
The electrochemical behavior of 1,1′-dimethyl-4,4′-bipyridinium dichloride (methyl viologen, MV) is complicated with the strong adsorption of both the oxidized (MV2+) and the reduced (MV+·) forms of MV on a mercury electrode. MV2+ adsorbs on the electrode with a flat orientation at more positive potentials than the potential of zero charge of the mercury electrode. MV+· adsorbs on the electrode with a vertical orientation at more negative potentials than the formal potential of the MV2+⁄+· couple, (E0′)MV. It is probable that the change in the orientation of the adsorbed MV+· from flat to vertical with the increase in the MV+· concentration in the vicinity of the (E0′)MV leads to a strongly attractive interaction between the adsorbed MV+· molecules and a sharp voltammetric adsorption peak results at higher concentrations of MV2+.

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