Relationship between zero point of charge and solubility product for hydroxides of polyvalent cations

The zero point of charge (ZPC) of slightly soluble compounds is the pH at which their particles suspended in water have zero charge. The ZPC values of slightly soluble hydroxides were compared with their solubility product in the form of its negative logarithm, pKSP, and with th pH of their suspensions in pure water, pHSP, which is a function of pKSP. The ZPC-pKSP relation was nonlinear while the ZPC-pHSP relation was linear. Either equation can used to estimate the ZPC value of a hydroxide from its solubility product. The ZPC of a given hydroxide was higher than its pHSP because polyvalent cations are more extensively adsorbed and less extensively desorbed from the particle surface than the monovalent hydroxide ion. At the pHSP, there are equivalent amounts of the cation and of the hydroxide anion in solution, but the surface layer of the hydroxide particle contains an excess cation on an equivalent basis. This imbalance confers a positive charge to the particle. The solubility product of aluminum hydroxide, redetermined at 25 degrees by means of pH measurements, was 8 X 10(-33). Its ZPC, redetermined by microelectrophoresis, was 8.5 +/- 0.1.