This work presents chemical modeling of solubilities of metal sulfates in aqueous solutions of sulfuric acid at high temperatures. Calculations were compared with experimental solubility measurements of hematite (Fe2O3) in aqueous ternary and quaternary systems of H2SO4, MgSO4 and Al-2(SO4)(3) at high temperatures. A hybrid model of ion-association and electrolyte non-random two liquid (ENRTL) theory was employed to fit solubility data in three ternary systems H2SO4-MgSO4-H2O, H2SO4-Al-2(SO4)(3)-H2O at 235-270degreesC and H2SO4-Fe-2(SO4)(3)-H2O at 150-270degreesC. Employing the Aspen Plus(TM) property program, the electrolyte NRTL local composition model was used for calculating activity coefficients of the ions Al3+, Mg2+ Fe3+ and SO42-, HSO4-, OH-, H3O+, respectively, as well as molecular species. The solid phases were hydronium alunite (H3O)Al-3(SO4)(2)(OH)(6), hematite Fe2O3 and magnesium sulfate monohydrate (MgSO4).H2O which were employed as constraint precipitation solids in calculating the metal sulfate solubilities. A correlation for the equilibrium constants of the association reactions of complex species versus temperature was implemented. Based on the maximum-likelihood principle, the binary interaction energy parameters for the ionic species as well as the coefficients for equilibrium constants of the reactions were obtained simultaneously using the solubility data of the ternary systems. Following that, the solubilities of metal sulfates in the quaternary systems H2SO4-Fe-2(SO4)(3)-MgSO4-H2O, H2SO4-Fe-2(SO4)(3)-Al-2(SO4)(3)-H2O at 250degreesC and H2SO4-Al-2(SO4)(3)-MgSO4-H2O at 230-270degreesC were predicted. The calculated results were in excellent agreement with the experimental data. (C) 2004 Elsevier B.V. All rights reserved.