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Hydroniumjarosite, (H3O)+Fe3(SO4)2(OH)6, from Cerros Pintados, Chile: Single-crystal X-ray diffraction and vibrational spectroscopic study

Published online by Cambridge University Press:  05 July 2018

J. Plášil ,
R. Škoda ,
K. Fejfarová ,
J. Čejka ,
A. V. Kasatkin ,
M. Dušek ,
D. Talla ,
L. Lapčák ,
V. Machovič  and
M. Dini
J. Plášil*
Affiliation:
Institute of Physics ASCR, v.v.i., Na Slovance 2, Prague 8, CZ–182 21, Czech Republic
R. Škoda
Affiliation:
Department of Geological Sciences, Masaryk University, Kotlářská 2, Brno, CZ–611 37, Czech Republic
K. Fejfarová
Affiliation:
Institute of Physics ASCR, v.v.i., Na Slovance 2, Prague 8, CZ–182 21, Czech Republic
J. Čejka
Affiliation:
Department of Mineralogy and Petrology, National Museum, Cirkusová 1740, Prague 9, CZ–193 00, Czech Republic
A. V. Kasatkin
Affiliation:
V/O "Almazjuvelirexport", Ostozhenka str., 22, block 1, 119034 Moscow, Russia
M. Dušek
Affiliation:
Institute of Physics ASCR, v.v.i., Na Slovance 2, Prague 8, CZ–182 21, Czech Republic
D. Talla
Affiliation:
Department of Geological Sciences, Masaryk University, Kotlářská 2, Brno, CZ–611 37, Czech Republic Institut für Mineralogie und Kristallographie, Althanstrabe 14, 1090–Wien, Austria
L. Lapčák
Affiliation:
Institute of Chemical Technology, Prague, Technická 5, Prague 6, CZ–166 28, Czech Republic
V. Machovič
Affiliation:
Institute of Chemical Technology, Prague, Technická 5, Prague 6, CZ–166 28, Czech Republic Institute of Rock Structures and Mechanics ASCR, v.v.i., V Holešovičkách 41, Prague 8, CZ–182 09, Czech Republic
M. Dini
Affiliation:
Pasaje San Agustin 4045, La Serena, Chile
*
E-mail: [email protected]
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Abstract

The natural hydroniumjarosite sample from Cerros Pintados (Chile) was investigated by electron microprobe, single-crystal X-ray diffraction and vibrational spectroscopy (Infrared and Raman). The chemical composition of studied specimens (wt.%, mean of seven analyses) obtained from electron microprobe (in wt.%): Na2O 1.30, K2O 0.23, CaO 0.04, Fe2O3 50.49, Al2O3 0.37, SiO2 0.33, SO3 33.88, H2O (calculated on the basis of Σ(OH–+H3O+) deduced from the charge balance) 13.32, total 99.98, corresponds to the empirical formula (H3O)0.77+(Na0.20K0.02)∑0.22(Fe2.95Al0.03)∑2.98 (OH)6.12[(SO4)1.97(SiO4)0.03]∑2.00 (calculated on the basis of S + Si = 2 a.p.f.u. (atoms per formula unit)). The studied hydroniumjarosite is trigonal, with space group Rm, with a = 7.3408(2), c = 17.0451(6) Å and V = 795.46(4) Å3. The refined structure architecture is consistent with known jarosite-series minerals, including synthetic hydroniumjarosite. However, in the current study the presence of H3O+ is well documented in difference Fourier maps, where characteristic positive difference Fourier maxima, with apparent trigonal symmetry, were localized in the vicinity of the O4 atom in the channel-voids of the structure. The structure of natural hydroniumjarosite, including the H atoms, was refined to R1 = 0.0166 for 2113 unique observed reflections, with Iobs>3σ(I). The present structure model, which includes the position of the H atom within the hydronium ion, is discussed with regard to the vibration spectroscopy results and earlier published density-functional theory (DFT) calculations for the alunite-like structure containing H3O+.

Keywords

hydroniumjarositeH3O+crystal structureX-ray diffractionvibrational spectroscopy
Type
Research Article
Information
Mineralogical Magazine , Volume 78 , Issue 3 , June 2014 , pp. 535 - 547
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2014

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