Miscibility in the CaSO4·2H2O–CaSeO4·2H2O system: Implications for the crystallisation and dehydration behaviour

SeO42− ions can substitute for sulphate in the gypsum structure. In this work crystals of different Ca(SO4,SeO4)·2H2O solid solutions were precipitated by mixing a CaCl2 solution with solutions containing different ratios of Na2SO4 and Na2SeO4. The compositions of the precipitates were analysed by EDS and the cell parameters were determined by X-ray powder diffraction. Moreover, a comparative study on dehydration behaviour of selenate rich and sulfate rich Ca(SO4,SeO4)·2H2O solid solutions was carried out by thermogravimetry.The experimental results show that the Ca(SO4,SeO4)·2H2O solid solution presents a symmetric miscibility gap for compositions ranging from XCaSO4·2H2O = 0.23 to XCaSO4·2H2O = 0.77. By considering a regular solution model a Guggenheim parameter a0 = 2.238 was calculated. The solid phase activity coefficients obtained with this parameter were used to calculate a Lippmann diagram for the system Ca(SO4,SeO4)·2H2O–H2O.