COMPARATIVE-STUDY OF THE ADSORPTION OF ORGANIC-LIGANDS ON ALUMINUM-OXIDE BY TITRATION CALORIMETRY

Ligand adsorption on delta-Al2O3 at pH 8 was examined for a series of organic ligands (aromatic acids, monochlorophenols and aliphatic acids) including both monodentate and bidentate ligands. Adsorption isotherms for the aromatic acids exhibited saturation at high dissolved ligand concentrations; saturation was not observed (over the concentration range examined) for the chlorophenols. Small, though measurable, amounts of heat were evolved on reaction of the aromatic acids, the monochlorophenols and propionate (but not of the longer chain fatty acids) with the oxide surface; overall ligand adsorption reactions were exothermic (DELTAH(obs) < 0). For adsorption of (partially or fully) protonated ligands. the favorable DELTAH(obs) was due largely to the exothermic proton transfer reaction between phenolic hydroxyl groups of the ligands and hydroxide ions displaced from the oxide surface. The enthalpy corresponding to the ligand-exchange reaction of surface hydroxyl groups for the various ligands (as fully deprotonated species), DELTAH(corr), appeared to be related to the ligand structure. The surface ligand-exchange reaction was more exothermic for the dicarboxylic acid phthalate than for the monocarboxylic acids benzoate or propionate or for salicylate and was endothermic for the chlorophenols.