Английская Википедия:Boron trioxide

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Шаблон:Chembox Boron trioxide or diboron trioxide is the oxide of boron with the formula Шаблон:Chem2. It is a colorless transparent solid, almost always glassy (amorphous), which can be crystallized only with great difficulty. It is also called boric oxide[1] or boria.[2] It has many important industrial applications, chiefly in ceramics as a flux for glazes and enamels and in the production of glasses.

Structure

Boron trioxide has three known forms, one amorphous and two crystalline.

Amorphous form

The amorphous form (g-Шаблон:Chem2) is by far the most common. It is thought to be composed of boroxol rings which are six-membered rings composed of alternating 3-coordinate boron and 2-coordinate oxygen.

Because of the difficulty of building disordered models at the correct density with many boroxol rings, this view was initially controversial, but such models have recently been constructed and exhibit properties in excellent agreement with experiment.[3][4] It is now recognized, from experimental and theoretical studies,[5][6][7][8][9] that the fraction of boron atoms belonging to boroxol rings in glassy Шаблон:Chem2 is somewhere between 0.73 and 0.83, with 0.75 = 3/4 corresponding to a 1:1 ratio between ring and non-ring units. The number of boroxol rings decays in the liquid state with increasing temperature.[10]

Crystalline α form

The crystalline form (α-Шаблон:Chem2) is exclusively composed of BO3 triangles. It crystal structure was initially believed to be the enantiomorphic space groups P31(#144) and P32(#145), like γ-glycine;[11][12] but was later revised to the enantiomorphic space groups P3121(#152) and P3221(#154) in the trigonal crystal system, like α-quartz[13]

Crystallization of α-Шаблон:Chem2 from the molten state at ambient pressure is strongly kinetically disfavored (compare liquid and crystal densities). It can be obtained with prologued annealing of the amorphous solid ~200 °C under at least 10 kbar of pressure.[14][15]

Crystalline β form

The trigonal network undergoes a coesite-like transformation to monoclinic β-Шаблон:Chem2 at several gigapascals (9.5 GPa).[16]

Preparation

Boron trioxide is produced by treating borax with sulfuric acid in a fusion furnace. At temperatures above 750 °C, the molten boron oxide layer separates out from sodium sulfate. It is then decanted, cooled and obtained in 96–97% purity.[17]

Another method is heating boric acid above ~300 °C. Boric acid will initially decompose into steam, (H2O(g)) and metaboric acid (HBO2) at around 170 °C, and further heating above 300 °C will produce more steam and diboron trioxide. The reactions are:

H3BO3 → HBO2 + H2O
2 HBO2Шаблон:Chem2 + H2O

Boric acid goes to anhydrous microcrystalline Шаблон:Chem2 in a heated fluidized bed.[18] Carefully controlled heating rate avoids gumming as water evolves.

Boron oxide will also form when diborane (B2H6) reacts with oxygen in the air or trace amounts of moisture:

2B2H6(g) + 3O2(g) → 2Шаблон:Chem2(s) + 6H2(g)
B2H6(g) + 3H2O(g) → Шаблон:Chem2(s) + 6H2(g)[19]

Reactions

Molten boron oxide attacks silicates. Containers can be passivated internally with a graphitized carbon layer obtained by thermal decomposition of acetylene.[20]

Applications

See also

References

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External links

Шаблон:Boron compounds Шаблон:Oxides Шаблон:Oxygen compounds Шаблон:Authority control