Abstract
The system Fe2O3-SO3-H2O contains the most important minerals of acid mine drainage (AMD), iron oxides, and iron sulfates. For geochemical modeling of the AMD systems, reliable thermodynamic data for these phases are needed. In this work, we have determined thermodynamic data for the most acidic sulfates rhomboclase [(H5O2)Fe(SO4)2⋅2H2O or (H3O)Fe(SO4)2⋅3H2O] and the phase (H3O)Fe(SO4)2. The actual compositions of the studied phases are (H3O)1.34Fe(SO4)2.17(H2O)3.06 (molecular mass of 344.919 g/mol) and (H3O)1.34Fe(SO4)2.17 (289.792 g/mol). Structural details for both phases were refined from synchrotron powder X-ray diffraction data. Enthalpies of formation were determined by acid-solution calorimetry. Low-temperature heat capacity was measured for rhomboclase by relaxation calorimetry but a critical analysis of entropies for several oxysalts showed that these data are too high. Entropies for both phases were estimated from a Kopp-rule algorithm. The enthalpies of formation and entropies were combined with previously published temperature-relative humidity brackets to generate an internally consistent thermodynamic data set for rhomboclase: ΔfH° = –3202.03 kJ/mol, S° = 378.7 J/(mol⋅K); and for (H3O)1.34Fe(SO4)2.17 : ΔfH° = –2276.25 kJ/mol, S° = 253.2 J/(mol⋅K). Solubility experiments at room temperature and at T = 4 °C agree well with previously reported data in the system Fe2O3-SO3-H2O. An inspection of the extended Pitzer model for Fe3+-SO4 solutions shows that this model reproduces the general topology of the phase diagram, but the position of the calculated solubility curves deviates substantially from the experimental data. Solid-state 2H MAS NMR spectra on deuterated rhomboclase show two isotropic chemical shifts δiso(2H) = of 8 ± 1 and 228 ± 1 ppm, assigned to
Acknowledgments
We thank two anonymous reviewers for their constructive comments. We are thankful to Tina Block and Artur Banaszewski for the sample preparation. This project was financially supported by a Deutsche Forschungsgemeinschaft (DFG) grant MA 3927/21-1. We acknowledge the ANKA Angströmquelle Karlsruhe for the provision of the beamtime at the PDIFF beamline and Stephen Doyle for the support during the measurements at the beamline. U.G.N. acknowledges the Villum Foundation for a “Villum Young Investigator Programme” (grants VKR022364). E.G. is grateful for financial support from Oticon Fonden. We acknowledge the support of the Canada Foundation for Innovation, the Atlantic Innovation Fund, and other partners that fund the Facilities for Materials Characterization at Dalhousie University, managed by the Institute for Research in Materials.
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