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To prevent scaling and to recycle aqueous solutions in industrial processes, the thermodynamic properties of the CaSO4-H2SO4-H2O system are studied by thermodynamic modeling with the Pitzer model. The published solubility data of calcium sulfate hydrates in sulfuric acid solutions were collected and reviewed critically. Then, the CaSO4-H2SO4-H2O system was modeled using the Pitzer activity coefficient approach from critically selected experimental data to obtain optimized parameters. The model reproduces the solubility data with good accuracy up to 5 m sulfuric acid at temperatures of 283.15-368.15, 283.15-473.15, and 298.15-398.15 K for gypsum (CaSO4·2H2O), anhydrite (CaSO4), and hemihydrate (CaSO4·0.5H2O), respectively. However, at temperatures above 398.15 K and sulfuric acid concentration above 0.5 mol/kg, the solubility of anhydrite predicted by our model deviates significantly from the literature data. Our model predicts that the solubility of anhydrite would first increase but then decrease in more concentrated sulfuric acid solutions, which is in disagreement with the experimental data showing constantly increasing solubilities as a function of increasing sulfuric acid concentration. This discrepancy has been discussed. The transformations of gypsum to anhydrite and hemihydrate were predicted in sulfuric acid solutions. With increasing H2SO4 concentration, the transformation temperatures of gypsum to anhydrite and hemihydrate will decrease. Thus, gypsum is stable at low temperatures in solutions of low H2SO4 concentrations and transforms to anhydrite at high temperatures and in concentrated H2SO4 solutions, while hemihydrate is always a metastable phase. Furthermore, the predicted results were compared with previous experimental studies to verify the accuracy of the model.