Abstract
Polythermic single-crystal X-ray studies of chalcocyanite CuSO4, dolerophanite Cu2OSO4, and kamchatkite KCu3O(SO4)2Cl have established their melting points as well as peculiarities of their thermal expansion. Association of oxocentered and sulfate tetrahedra in dolerophanite and kamchatkite leads to the formation of rigid tetrahedral “backbones” only slightly sensitive to thermal variations. Rigid complexes can also be distinguished in the structure of chalcocyanite, if we consider only the system of the shortest and strongest Cu–O and S–O bonds. The anisotropy of the thermal expansion can be explained by either rigid complexes drifting parallel to each other (as in dolerophanite and chalcocyanite), or radial and angular distortions in the polyhedra of alkali cations. The presence of a tetrahedrally coordinated additional oxygen atom in the structure of dolerophanite and kamchatkite leads to an increase in the principal eigenvalues. The demonstrated rigidity of the sulfate tetrahedra in studied anhydrous copper sulfate minerals explains the absence of phase transitions up to the melting temperatures. The variation of chemical composition leads to changes in their thermal decomposition points. Chlorine-containing kamchatkite decomposes at the lowest temperature of 590(5) K, next are chalcocyanite 675(10) K, and dolerophanite 925(10) K.
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Acknowledgements
We are grateful to Pietro Vignola and one anonymous reviewer for their valuable comments that led to improvement of the initial version of the manuscript. Technical support by the St. Petersburg State University X-ray Diffraction Resource Centre is gratefully acknowledged.
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The research was supported within the scientific task # 0081-2022-0002.
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All authors have equally contributed to the work described. EVN, OIS, DOC, SKF: MS preparation and analysis of the data. EVN, OIS, LRZ: HT single-crystal X-ray diffraction and interpretation. OIS, EVN: sampling of minerals from the Yadovitaya fumarole.
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Nazarchuk, E.V., Siidra, O.I., Filatov, S.K. et al. Thermal expansion of anhydrous copper sulfate minerals determined by single crystal X-ray diffraction: chalcocyanite CuSO4, dolerophanite Cu2OSO4 and kamchatkite KCu3O(SO4)2Cl. Phys Chem Minerals 50, 11 (2023). https://doi.org/10.1007/s00269-023-01236-7
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DOI: https://doi.org/10.1007/s00269-023-01236-7