Thermal expansion of anhydrous copper sulfate minerals determined by single crystal X-ray diffraction: chalcocyanite CuSO4, dolerophanite Cu2OSO4 and kamchatkite KCu3O(SO4)2Cl

IF 1.2 4区 地球科学 Q4 MATERIALS SCIENCE, MULTIDISCIPLINARY
Evgeny V. Nazarchuk, Oleg I. Siidra, Stanislav K. Filatov, Dmitri O. Charkin, Lada R. Zhdanova
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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.

Abstract Image

用单晶x射线衍射测定无水硫酸铜矿物:黄铜矿cuo4、白云石Cu2OSO4和堪察凯特kcu30 (SO4)2Cl的热膨胀
对黄铜矿CuSO4、白云石Cu2OSO4和堪察凯特kcu30 (SO4)2Cl的多热单晶x射线研究确定了它们的熔点和热膨胀特性。在白云石和堪察石中,氧中心和硫酸盐四面体的结合导致刚性四面体“骨架”的形成,对热变化仅轻微敏感。如果我们只考虑最短和最强的Cu-O和S-O键的系统,那么在黄铜矿的结构中也可以区分出刚性配合物。热膨胀的各向异性可以用相互平行漂移的刚性配合物(如在白云石和黄铜矿中)或碱阳离子多面体的径向和角度扭曲来解释。白云石和堪察石结构中四面体配位附加氧原子的存在导致了主特征值的增加。所研究的无水硫酸铜矿物中硫酸盐四面体的刚性解释了在熔融温度之前没有相变的原因。化学成分的变化导致其热分解点的变化。含氯堪察石的最低分解温度为590(5)K,其次是黄铜矿675(10)K,白云石925(10)K。
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来源期刊
Physics and Chemistry of Minerals
Physics and Chemistry of Minerals 地学-材料科学:综合
CiteScore
2.90
自引率
14.30%
发文量
43
审稿时长
3 months
期刊介绍: Physics and Chemistry of Minerals is an international journal devoted to publishing articles and short communications of physical or chemical studies on minerals or solids related to minerals. The aim of the journal is to support competent interdisciplinary work in mineralogy and physics or chemistry. Particular emphasis is placed on applications of modern techniques or new theories and models to interpret atomic structures and physical or chemical properties of minerals. Some subjects of interest are: -Relationships between atomic structure and crystalline state (structures of various states, crystal energies, crystal growth, thermodynamic studies, phase transformations, solid solution, exsolution phenomena, etc.) -General solid state spectroscopy (ultraviolet, visible, infrared, Raman, ESCA, luminescence, X-ray, electron paramagnetic resonance, nuclear magnetic resonance, gamma ray resonance, etc.) -Experimental and theoretical analysis of chemical bonding in minerals (application of crystal field, molecular orbital, band theories, etc.) -Physical properties (magnetic, mechanical, electric, optical, thermodynamic, etc.) -Relations between thermal expansion, compressibility, elastic constants, and fundamental properties of atomic structure, particularly as applied to geophysical problems -Electron microscopy in support of physical and chemical studies -Computational methods in the study of the structure and properties of minerals -Mineral surfaces (experimental methods, structure and properties)
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