期刊
MINERALOGICAL MAGAZINE
卷 75, 期 6, 页码 2775-2791出版社
MINERALOGICAL SOC
DOI: 10.1180/minmag.2011.075.6.2775
关键词
monoclinic jarosites; non-stoichiometric jarosites; synchrotron Rietveld refinements
类别
资金
- Australian Synchrotron, Victoria, Australia [FI2736]
- ANSTO
Monoclinic, non-stoichiometric natrojarosite-hydroniumjarosite solid solution phases have been synthesized hydrothermally over a range of temperatures, starting compositions and reaction times, and have been characterized using Rietveld refinement of synchrotron X-ray diffraction data, and chemical and thermal analyses. The H atom locations have been obtained from refinement of neutron diffraction data on a deuterated sample. The results confirm a direct relationship between the monoclinic distortion and the ordering of iron site vacancies in one of two independent iron sites. Ordering of iron vacancies gives rise to domains containing butlerite-like 7 angstrom chains of corner-connected octahedra and tetrahedra. The formation of these chains within (100) planes results in an expansion of the monoclinic a lattice parameter and a contraction of the c parameter relative to stoichiometric jarosites. The results support a recent model for iron deficiency, whereby an iron vacancy is compensated by the replacement of four coordinated OH(-) ions by H(2)O molecules, with one of the H(2)O molecules coming from deprotonation of H(3)O(+). The general formula, based on intergrowth of stoichiometric jarosite and non-stoichiometric, butlerite-like regions, is [(Na,H(3)O)Fe(3) (SO(4))(2)(OH)(6)](1-y)[H(2)O)Fe(2)(SO(4))(2)(OH)(2)(H(2)O)(4)](y).
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