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Complex hydrogen bonding and thermal behaviour over a wide temperature range of kainite KMg(SO4)Cl⋅2.75H2O

Published online by Cambridge University Press:  18 February 2022

Artem S. Borisov ,
Oleg I. Siidra Open the ORCID record for Oleg I. Siidra [Opens in a new window] ,
Valery L. Ugolkov ,
Alexey N. Kuznetsov Open the ORCID record for Alexey N. Kuznetsov [Opens in a new window] ,
Vera A. Firsova ,
Dmitri O. Charkin ,
Natalia V. Platonova Open the ORCID record for Natalia V. Platonova [Opens in a new window]  and
Igor V. Pekov
Artem S. Borisov
Affiliation:
Department of Crystallography, St. Petersburg State University, University emb. 7/9, 199034, St. Petersburg, Russia Institute of Silicate Chemistry, Russian Academy of Sciences, Adm. Makarova emb. 2, 199034, St. Petersburg, Russia
Oleg I. Siidra*
Affiliation:
Department of Crystallography, St. Petersburg State University, University emb. 7/9, 199034, St. Petersburg, Russia Institute of Silicate Chemistry, Russian Academy of Sciences, Adm. Makarova emb. 2, 199034, St. Petersburg, Russia
Valery L. Ugolkov
Affiliation:
Institute of Silicate Chemistry, Russian Academy of Sciences, Adm. Makarova emb. 2, 199034, St. Petersburg, Russia
Alexey N. Kuznetsov
Affiliation:
Kurnakov Institute of General and Inorganic Chemistry RAS, Leninskii prosp., 31, 119991, Moscow, Russia Department of Inorganic Chemistry, Faculty of Chemistry, Moscow State University, Vorobievy Gory, 119991, Moscow, Russia
Vera A. Firsova
Affiliation:
Institute of Silicate Chemistry, Russian Academy of Sciences, Adm. Makarova emb. 2, 199034, St. Petersburg, Russia
Dmitri O. Charkin
Affiliation:
Department of Inorganic Chemistry, Faculty of Chemistry, Moscow State University, Vorobievy Gory, 119991, Moscow, Russia
Natalia V. Platonova
Affiliation:
X-ray Diffraction Resource Center, St. Petersburg State University, University emb. 7/9, 199034, St. Petersburg, Russia
Igor V. Pekov
Affiliation:
Department of Mineralogy, Faculty of Geology, Moscow State University, Vorobievy Gory, 119991, Moscow, Russia
*
*Author for correspondence: Oleg I. Siidra, Email: o.siidra@spbu.ru
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Abstract

Kainite, KMg(SO4)Cl⋅2.75H2O, is one of the most common hydrated sulfate minerals, and it plays an important role as a source of potassium. However, its properties and structure have, to date, been insufficiently studied. In our present work, kainite was investigated using multiple techniques, including single-crystal and powder X-ray diffraction, thermogravimetry, differential scanning calorimetry (DSC), and infrared spectroscopy (IR). The mineral is monoclinic, C2/m, a = 19.6742(2), b = 16.18240(10), c = 9.49140(10) Å, β = 94.8840(10)°, V = 3010.86(5) Å3 and Z = 16. The structure was refined to R1 = 0.0230 for 3080 unique observed reflections with |Fo| ≥ 4σF. The complex hydrogen bonding system for kainite is described for the first time. The structure of kainite contains seven symmetrically independent sites occupied by water molecules, six of which are strongly bonded to Mg2+ cations while the seventh resides in the framework cavities. The acceptors of the hydrogen bonds are either chloride anions, neighbouring water molecules or oxygens atoms of sulfate groups. A bifurcated hydrogen bond was described for one of the water molecules. Based on the analysis of the crystal structure, we have confirmed and propose the correct formula for kainite as KMg(SO4)Cl⋅2.75H2O. The thermal studies of kainite in the temperature range of –150°C to +600°C indicate its stability to 190°C. The decomposition products are K2Mg2(SO4)3, KCl and K2SO4. The thermal expansion was calculated, which for kainite has a character typical for monoclinic crystals and similar to the compressibility tensor described earlier.

Keywords

kainitesulfatesX-ray diffractionhydrogen bondingbifurcated hydrogen bondthermal expansion
Type
Article
Information
Mineralogical Magazine , Volume 86 , Issue 1 , February 2022 , pp. 37 - 48
Copyright
Copyright © The Author(s), 2022. Published by Cambridge University Press on behalf of The Mineralogical Society of Great Britain and Ireland

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Footnotes

Associate Editor: Juraj Majzlan

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