The surface-enhanced Raman spectra (SERS) provide information about the extent of protonation of the species adsorbed at the silver/aqueous solution interface. The compounds investigated were 4-pyridylcarbinol (1), 4-acetylpyridine (2), 3-pyridinecarboxaldehyde (3), isonicotinic acid (4), isonicotinamide (5), 4-benzoylpyridine (6), 4-(aminomethyl)pyridine (7) and 4-aminopyridine (8). For 1, the fraction of the adsorbed species which was protonated at -0.20 V vs. SCE varied with pH in a manner indicating stronger adsorption of the neutral than the cationic form. The fraction protonated increased at more negative potentials. Similar results were obtained with 3. For all compounds but 4, bands due to the unprotonated species near 1600 cm-1 and for the ring-protonated species near 1640 cm-1 were seen in the SERS spectra.
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