A pyrogenic alumina (type C, Degussa) was studied. The original product contains chlorine impurity (similar to1 x 10(-4) mol/g), the hydrolysis of bound chlorine results in acidic species in aqueous suspension. Heat treatment at 1000 degreesC proved to be an effective purification. Potentiometric acid-base titration was used to characterize the surface charging of alumina in electrolyte solutions (KNO3, KCl). This method can measure only the H+/OH- depletion in bulk liquid phase. Trace amounts of impurity and additional acid-base reactions, such as dissolution of solid, affect the net H+/OH- consumption. We analyzed these effects on proton adsorption curves. The fitting (FITEQL) of titration data for purified alumina in KNO3 solutions between pH similar to5 and similar to9 is good enough with assuming surface charging reactions only and using any surface complexation model. In KCI solutions, however, only the triple layer model resulted in an acceptable optimization, presumably because of the specific adsorption of Cl- ions. Outside these material-specific limits of pH, asymmetric proton binding curves appear which are often interpreted as a result of specific ion adsorption or surface site heterogeneity. In fact, the dissolution of the amphoteric solid plays the governing role, especially below pH similar to4.5. The experimental curves over the range of pH 3-10 can be fitted well, if the partial dissolution of alumina and the solution equilibria of mononucleus A1-species formation with literature log K values are inserted into the model, in addition to the surface complexation. The assumed chemical model can be supported only by an independent analysis of equilibrium liquid phase. The concentration of aluminum in the equilibrium supernatants with different pH values between similar to4 and similar to 10 were measured by means of the inductively coupled plasma method. The measured amounts coincide strikingly well, especially in the alkaline region, with the calculated total concentration of A1 species, which provide indisputable evidence for the reality of the assumed chemical model.