Abstract
The irreversible adsorption of SO 2 on Pt(111) electrodes has been studied in acid media by means of cyclic voltammetry and in situ FT–IRRA Spectroscopy. The resulting adsorbed residue presents a characteristic vibrational band at 1220 cm −1 (0.65 V) either in 0.5 M HClO 4 or 0.5 M HCl. In the potential region of constant coverage (0.65–1.0 V) the bandcentre frequency increases linearly with potential at a tuning rate of 65–75 cm −1 V −1. This shift may result from mixed contributions from Stark and/or backbonding effects. Below 0.65 V, the abrupt decrease in band frequency can be linked to the weakening of the dipole–dipole coupling effect resulting from the decrease in SO 2 surface coverage. From the vibrational data for SO 2–transition metal complexes and with the aid of the surface selection rule, the band at 1220–1240 cm −1 can be assigned to the asymmetric stretching mode of undissociated SO 2, bound to the surface via S and one of the O atoms in a η 2-bridging configuration.
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