BONDING OF CHLOROPHENOLS ON IRON AND ALUMINUM-OXIDES

The adsorption of 10 chlorophenols on synthetic, naturally occurring iron and aluminum oxides was studied to elucidate the mechanism of binding and relative bond strength of the chlorine-substituted phenols on oxide surfaces. Surface-enhanced deprotonation of chlorophenols was identified by spectroscopic methods. Chlorophenolates were found to be chemisorbed on oxide surfaces via an inner-sphere coordination. Chlorophenols also bonded on oxides by weak physical forces (H bonding and condensation), but these types of weak bonding were identified only when adsorption occurred from the vapor phase onto dry surfaces. Physisorbed chlorophenols, unlike chemisorbed molecules, were readily removed from oxide surfaces by washing with water. Poorly crystallinzed iron and aluminum oxides showed similar mechanisms of chlorophenol binding, although the bond for chlorophenolate chemisorbed on iron oxide was stronger than that on aluminum oxide. Only physically adsorbed chlorophenols were detected on crystalline gibbsite, suggesting that the dominant (001) crystal face, with surface hydroxyl groups doubly coordinated to Al, was not specifically reactive with the chlorophenols. Chemisorption, however, was identified on the crystalline iron oxide, goethite. From the extent of perturbation of aromatic ring electrons, the surface bond strength for chlorophenolates on aluminum oxide was found to correlate with the Lewis basicity of the phenolate anions (the higher the pK(a) of the chlorophenols, the stronger the surface bond). Nevertheless, the amount of chlorophenol adsorbed on noncrystalline iron oxide at controlled pH of 5.4 was limited by the extent of deprotonation (the lower the pK(a), the more adsorption).