The mechanism of the protonation of metal (hydr)oxides in aqueous solutions studied for various interfacial/surface ionization models and physicochemical parameters: a critical review and a novel approach.

The mechanism of the protonation of solid metal (hydr)oxides in aqueous media was investigated using simulation and experimental work. It was found that the apparent acidity/basicity of each kind of surface sites of metal (hydr)oxides in aqueous suspensions is strongly influenced by the overall surface charge of the (hydr)oxide and thus by the electrical potential smeared out at the interfacial region. Depending on its sign this increases or decreases the hydrogen ion concentration on the surface, thus promoting or hindering protonation. This is manifested by the shifts of the protonation peaks of the various kinds of sites with respect to the -pK values of the corresponding intrinsic protonation constants and the appearance of an extra peak in the d[H+cons,surf]/dpH vs. pH curves. Potentiometric titrations experiments performed for four technologically important oxides showed that the proposed protonation mechanism describes indeed the protonation of polycrystalline (hydr)oxides in aqueous media.