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Bismuth(III) oxide : ウィキペディア英語版
Bismuth(III) oxide

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Bismuth(III) oxide is perhaps the most industrially important compound of bismuth. It is also a common starting point for bismuth chemistry. It is found naturally as the mineral bismite (monoclinic) and sphaerobismoite (tetragonal, much more rare), but it is usually obtained as a by-product of the smelting of copper and lead ores. Bismuth trioxide is commonly used to produce the "Dragon's eggs" effect in fireworks, as a replacement of red lead.〔
==Structure==
The structures adopted by Bi2O3 differ substantially from those of arsenic(III) oxide, As2O3, and antimony(III) oxide, Sb2O3.〔Wells, A.F. (1984) ''Structural Inorganic Chemistry''. 5th. London, England: Oxford University Press. ISBN 0-19-855370-6〕
Bismuth oxide, Bi2O3 has five crystallographic polymorphs. The room temperature phase, α-Bi2O3 has a monoclinic crystal structure. There are three high temperature phases, a tetragonal β-phase, a body-centred cubic γ-phase, a cubic δ-Bi2O3 phase and an ε- phase.
The room temperature α-phase has a complex structure with layers of oxygen atoms with layers of bismuth atoms between them. The bismuth atoms are in two different environments which can be described as distorted 6 and 5 coordinate respectively.
β-Bi2O3 has a structure related to fluorite.〔
γ-Bi2O3 has a structure related to that of Bi12SiO20 (a sillenite), where a fraction of the Bi atoms occupy the position occupied by SiIV, and may be written as Bi12Bi0.8O19.2.
δ- Bi2O3 has a defective fluorite-type crystal structure in which two of the eight oxygen sites in the unit cell are vacant.
ε- Bi2O3 has a structure related to the α- and β- phases but as the structure is fully ordered it is an ionic insulator. It can be prepared by hydrothermal means and transforms to the α- phase at 400 °C.〔
The monoclinic α-phase transforms to the cubic δ-Bi2O3 when heated above 729 °C, which remains the structure until the melting point, 824 °C, is reached. The behaviour of Bi2O3 on cooling from the δ-phase is more complex, with the possible formation of two intermediate metastable phases; the tetragonal β-phase or the body-centred cubic γ-phase. The γ-phase can exist at room temperature with very slow cooling rates, but α- Bi2O3 always forms on cooling the β-phase. Even though when formed by heat, it reverts to α- Bi2O3 when the temperature drops back below 727 °C, δ-Bi2O3 can be formed directly through electrodeposition and remain relatively stable at room temperature, in an electrolyte of bismuth compounds that is also rich in sodium or potassium hydroxide so as to have a pH near 14.

抄文引用元・出典: フリー百科事典『 ウィキペディア(Wikipedia)
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