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Thermodynamics of arsenates, selenites, and sulfates in the oxidation zone of sulfide ores. X. thermal stability and dehydration features of synthetic analogs of the cobaltomenite–ahlfeldite solid solution series

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Abstract

The aim of this study is the experimental investigation of the synthetic analogs of cobaltomenite, CoSeO3 • 2H2O, ahlfeldite, NiSeO3 • 2H2O, members of the cobaltomenite–ahlfeldite solid solution series (Ni x Co1–x )SeO3 • 2H2O, and singularities of their dehydration and dissociation. The intermediate members of the cobaltomenite (CoSeO3 • 2H2O)–ahlfeldite (NiSeO3 • 2H2O) series have been synthesized and studied with a combination of X-ray diffraction, scanning electron microscopy, and the simultaneous application of thermogravimetry (TG) and differential scanning calorimetry (DSC) within the temperature range from 25 to 640°C. The complete solid solution series corresponds to the monoclinic space group P21/n. Unit-cell dimensions decrease in all crystallographic directions as the amount of Ni increases. The angle β increases from 98.82(1) (cobaltomenite) to 99.05(1)° (ahlfeldite). It has been established that CoSeO3 • 2H2O and NiSeO3 • 2H2O dehydrate at 120–340°C through two stages apparently corresponding, to the formation of intermediate hydrated species CoSeO3 • H2O and NiSeO3 • 1/3H2O. The reaction enthalpies for each dehydration stage of CoSeO3 • 2H2O and NiSeO3 • 2H2O have been determined. Changes of the unit-cell dimensions and dehydration temperatures are rationalized in terms of the Co and Ni site occupancy in the structure of the cobaltomenite–ahlfeldite solid-solution series members.

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Authors and Affiliations

  1. St. Petersburg State University, Universitetskaya nab. 7/9, St. Petersburg, 199034, Russia

    M. V. Charykova, E. L. Fokina, V. G. Krivovichev, O. S. Yakovenko, E. V. Klimova & V. V. Semenova

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  1. M. V. Charykova
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  2. E. L. Fokina
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  3. V. G. Krivovichev
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  4. O. S. Yakovenko
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  5. E. V. Klimova
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  6. V. V. Semenova
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Correspondence to M. V. Charykova.

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Original Russian Text © M.V. Charykova, E.L. Fokina, V.G. Krivovichev, O.S. Yakovenko, E.V. Klimova, V.V. Semenova, 2014, published in Zapiski Rossiiskogo Mineralogicheskogo Obshchestva, 2014, No. 3, pp. 72–84.

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Charykova, M.V., Fokina, E.L., Krivovichev, V.G. et al. Thermodynamics of arsenates, selenites, and sulfates in the oxidation zone of sulfide ores. X. thermal stability and dehydration features of synthetic analogs of the cobaltomenite–ahlfeldite solid solution series. Geol. Ore Deposits 57, 570–578 (2015). https://doi.org/10.1134/S107570151507003X

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