Formation and transformation of five different phases in the CaSO4-H2O system:: Crystal structure of the subhydrate β-CaSO4•0.5H2O and soluble anhydrite CaSO4

At least five crystalline-phases can be found in the CaSO4-H2O system, which are gypsum CaSO4 center dot 2H(2)O, the subhydrates alpha- and beta-CaSO4 center dot 0.5H(2)O, and the soluble and insoluble anhydrite CaSO4. The formation of these five phases in the CaSO4-H2O system and their transformations were investigated by in situ time-resolved synchrotron radiation powder X-ray diffraction (SR-PXD) in this study. Furthermore, revised structural models for beta-CaSO4 center dot 0.5H(2)O and soluble anhydrite CaSO4 are presented. The hydration of alpha-CaSO4 center dot 0.5H(2)O was studied at 25 degrees C and showed that the reaction with H2O started immediately after mixing the two reactants and that the formation of CaSO4 center dot 2H(2)O was coupled to the depletion of alpha-CaSO4 center dot 0.5H(2)O. The thermal decomposition of CaSO4 center dot 2H(2)O was investigated in the temperature range of 25-500 degrees C and showed the fon-nation of alpha-CaSO4 center dot 0.5H(2)O followed by the formation of soluble anhydrite AIII-CaSO4, which was gradually converted to insoluble anhydrite AII-CaSO4. The thermal decomposition of alpha-CaSO4 center dot 0.5D(2)O was investigated in the temperature range of 25-500 degrees C and showed successive phase transformations to beta-CaSO4 center dot 0.5D(2)O, soluble anhydrite AIII-CaSO4, and insoluble anhydrite AII-CaS04. The two polymorphs of anhydrite coexist in the investigated temperature range of 200-500 degrees C. The hydrothermal decomposition of CaSO4 center dot 2H(2)O was investigated in the temperature range of 25-200 degrees C using a 1 M HNO3 or a 1 M LiCl solution, and in both experiments, CaSO4 center dot 2H(2)O was converted to alpha-CaSO4 center dot 0.5H(2)O and further to insoluble anhydrite AII-CaSO4. A structural model for beta-CaSO4 center dot 0.5H(2)O is proposed on the basis of SR-PXD data and a trigonal unit cell (in hexagonal setting) a = 6.93145(3), c = 12.736 17(4) angstrom, Z = 6, and space group P3(1). A structural model for soluble anhydrite AIII-CaSO4 is also proposed on the basis of powder neutron diffraction data, and a hexagonal unit cell parameters are a = 6.9687(1), c = 6.3004(1) angstrom, Z = 3, and space group P6(2)22.