NEW PHASES IN THE HYDROUS FERRIC SULFATE SYSTEM, A SUPPORTING ARGUMENT THAT THE MINERAL LAUSENITE IS OF FORMULA FE2(SO4)3∙5H2O AND THE CRYSTAL STRUCTURE REFINEMENT AND HYDROGEN BONDING SCHEME OF THE MINERALS QUENSTEDTITE AND ROMERITE
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A series of experiments were conducted to explore the hydration state of the mineral lausenite. The experiments of Posnjak and Merwin (1922) were recreated and the conclusion is reached that lausenite is of mineral formula Fe2(SO4)3∙5H2O, rather than Fe2(SO4)3∙6H2O as suggested by Posnjak and Merwin (1922). This conclusion is based on the X-ray diffraction data which found that the Posnjak and Merwin experiments produced a phase whose pattern matched that of the pentahydrate identified by Majzlan (2005). The refractive index data and morphology of this phase is also a match for the mineral described previously as a hexahydrate by Posnjak and Merwin (1922) and Lausen (1928). Synchrotron X-ray diffraction data was collected from a possible new phase in the hydrous ferric sulfate system. The data were analyzed and a unit cell was identified with monoclinic unit cell dimensions of a = 7.532(3)Å b = 12.551(6)Å c = 7.077(4)Å and β = 96.775(8)° with a unit cell volume of 664.4Å3. This phase was determined to grow only at temperatures above 85°C and at a RH of ~23%. The atomic structures of the minerals quenstedtite [Fe2(SO4)3∙11H2O] and romerite [Fe2+Fe3+2(SO4)4∙14H2O] are refined, hydrogen positions are identified and hydrogen bonding scheme is discussed. The weakest hydrogen bonds are found to occur between layers of differently coordinated tetrahedral groups in both romerite and quenstedtite. The transition from romerite to quenstedtite involves the oxidation of the ferrous iron in romerite converting into a Fe3+(SO4)∙5H2O cluster.