Specific adsorption of simple organic acids on metal(hydr)oxides: a radiotracer approach

The pH dependence of adsorption of (14)C-labeled benzoic and oxalic acids on gamma-Al(2)O(3) and hematite was studied in acid medium in the presence of 0.5 mol dm(-3) NaClO(4) supporting electrolyte. It was found that the adsorption of the organic species starts at pH values where the protonation of the oxide surface takes place. In the case of benzoic acid the extent of adsorption with decreasing pH goes through a sharp maximum at a pH value not far from the pK (4.2) of the acid, while in the case of oxalic acid only a small decrease can be observed at very low pH values (pH<1). In indirect radiotracer studies using (35)S-labeled sulfate ions it was shown that the competitive adsorption of formic, malonic, maleic, and oxalic acids with sulfate ions depends on pH and the effect of the organic acid on the anion adsorption becomes pronounced at pH values about and above the pK of the acid. On the basis of these observations and considerations concerning the dissociation of the organic acids studied it is assumed that the specific adsorption of the anionic form of the acids takes place. It is, however, emphasized that the negative charge of the anions, consequently the electrostatic forces, do not play significant role in the adsorption.