Abstract
The adsorption of triphenylarsine oxide (TASO) on the Hg electrode from methanolic and water-methanolic solutions of LiClO 4, is investigated by means of electrocapillary measurements. An analysis is carried out in terms of congruence of the experimental adsorption isotherm with respect to potential and electrode charge. At negative changes a satisfactory fit of Frumkin's isotherm with the experimental results is obtained when a negative interaction parameter, equal to −0.8, is used. At positive charges the increasing depression of the electrocapillary curves is attributed to changes within the adsorption layer, mainly involving the introduction of As δ+=O δ− groups into the double layer after the reorientation of TASO molecules and to a minor degree π-electron interactions. At these polarizations, although the field congruence of the adsorption isotherms seems to remain effective, it is shown that this congruence is only of an apparent nature. Finally, the various adsorption parameters are calculated and discussed.
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