Tetravalent metal phosphates (M = Zr, Ti, and Sn) were prepared and characterized by XRD, surface properties, and TG-DTA. The cation exchange and sorption behavior of these metal phosphates toward transition metal ions such as Cu2+, Co2+, and Ni2+ have been studied comparatively as a function of temperature and concentration. The adsorption process was found to increases with increase in temperature and concentration. The selectivity order for alpha-titanium and alpha-tin phosphates is Cu2+ > Co2+ > Ni2+, whereas for a-zirconium phosphate it is Cu2+ > Ni2+ > Co2+. The ion exchange capacity of alpha-titanium phosphate is greater than those of other phosphates, which is explained on the basis of the surface behavior, disorderness of the system, degree of hydrolysis of incoming guest adsorbate metal ions, and structural steric hindrance of the exchangers during adsorption and sorption. The distribution coefficient, Gibbs free energy, enthalpy, and entropy values indicate that the ion-exchange processes are spontaneous. (C) 2003 Elsevier Inc. All rights reserved.