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Jarosite–butlerite intergrowths in non-stoichiometric jarosites: crystal chemistry of monoclinic natrojarosite–hydroniumjarosite phases

Published online by Cambridge University Press:  05 July 2018

I. E. Grey ,
N. V. Y. Scarlett ,
P. Bordet  and
H. E. A. Brand
I. E. Grey*
Affiliation:
CSIRO Process Science and Engineering, Box 312 Clayton South, Victoria 3169, Australia
N. V. Y. Scarlett
Affiliation:
CSIRO Process Science and Engineering, Box 312 Clayton South, Victoria 3169, Australia
P. Bordet
Affiliation:
Institut Néel, CNRS and Université Joseph Fourier, BP166, 38042 Grenoble, France
H. E. A. Brand
Affiliation:
CSIRO Process Science and Engineering, Box 312 Clayton South, Victoria 3169, Australia Bragg Institute, ANSTO, Locked Bag 2001 Kirawee DC, NSW 2232, Australia
*
*E-mail: ian.grey@csiro.au
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Abstract

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 Å 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 H2O molecules, with one of the H2O molecules coming from deprotonation of H3O+. The general formula, based on intergrowth of stoichiometric jarosite and non-stoichiometric, butlerite-like regions, is [(Na,H3O)Fe3(SO4)2(OH)6]1–y[(H2O)Fe2(SO4)2(OH)2(H2O)4]y.

Keywords

monoclinic jarositesnon-stoichiometric jarositessynchrotron Rietveld refinements
Type
Research Article
Information
Mineralogical Magazine , Volume 75 , Issue 6 , December 2011 , pp. 2775 - 2791
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2011

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