Boron trioxide

Boron trioxide
Names
	IUPAC name Diboron trioxide
	Other names boron oxide, diboron trioxide, boron sesquioxide, boric oxide, boria; Boric anhydride
Identifiers
CAS Number	1303-86-2 ;
3D model (JSmol)	Interactive image;
ChEBI	CHEBI:30163 ;
ChemSpider	452485 ;
ECHA InfoCard	100.013.751
EC Number	215-125-8;
Gmelin Reference	11108
PubChem CID	518682;
RTECS number	ED7900000;
UNII	483W67CPF4 ;
CompTox Dashboard (EPA)	DTXSID7034387 ;
	InChI InChI=1S/B2O3/c3-1-5-2-4 Key: JKWMSGQKBLHBQQ-UHFFFAOYSA-N ; InChI=1/B2O3/c3-1-5-2-4 Key: JKWMSGQKBLHBQQ-UHFFFAOYAI;
	SMILES O=BOB=O;
Properties
Chemical formula	B2O3
Molar mass	69.6182 g/mol
Appearance	white, glassy solid
Density	2.460 g/cm3, liquid;; 2.55 g/cm3, trigonal;; 3.11–3.146 g/cm3, monoclinic
Melting point	450 °C (842 °F; 723 K) (trigonal) ; 510 °C (tetrahedral)
Boiling point	1,860 °C (3,380 °F; 2,130 K) , sublimes at 1500 °C
Solubility in water	1.1 g/100mL (10 °C) ; 3.3 g/100mL (20 °C) ; 15.7 g/100mL (100 °C)
Solubility	partially soluble in methanol
Acidity (pKa)	~ 4
Magnetic susceptibility (χ)	−39.0·10−6 cm3/mol
Thermochemistry
Heat capacity (C)	66.9 J/(mol⋅K)
Std molar; entropy (S⦵298)	80.8 J/(mol⋅K)
Std enthalpy of; formation (ΔfH⦵298)	−1254 kJ/mol
Gibbs free energy (ΔfG⦵)	−832 kJ/mol
Hazards
	Occupational safety and health (OHS/OSH):
Main hazards	Irritant
	GHS labelling:
Pictograms
Signal word	Danger
Hazard statements	H360FD
Precautionary statements	P201, P202, P281, P308+P313, P405, P501
NFPA 704 (fire diamond)	2 0 0
Flash point	noncombustible
	Lethal dose or concentration (LD, LC):
LD50 (median dose)	3163 mg/kg (oral, mouse)
	NIOSH (US health exposure limits):
PEL (Permissible)	TWA 15 mg/m3
REL (Recommended)	TWA 10 mg/m3
IDLH (Immediate danger)	2000 mg/m3
Supplementary data page
	Boron trioxide (data page)
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). verify (what is ?) Infobox references

Boron trioxide or diboron trioxide is the oxide of boron with the formula B₂O₃. It is a colorless transparent solid, almost always glassy (amorphous), which can be crystallized only with great difficulty. It is also called boric oxide^[6] or boria.^[7] 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-B₂O₃) 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.^[8]^[9] It is now recognized, from experimental and theoretical studies,^[10]^[11]^[12]^[13]^[14] that the fraction of boron atoms belonging to boroxol rings in glassy B₂O₃ 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.^[15]

Crystalline α form

The crystalline form (α-B₂O₃) 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;^[16]^[17] but was later revised to the enantiomorphic space groups P3₁21(#152) and P3₂21(#154) in the trigonal crystal system, like α-quartz^[18]

Crystallization of α-B₂O₃ 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.^[19]^[1]

Crystalline β form

The trigonal network undergoes a coesite-like transformation to monoclinic β-B₂O₃ at several gigapascals (9.5 GPa).^[20]

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.^[3]

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 HBO₂ → B₂O₃ + H₂O

Boric acid goes to anhydrous microcrystalline B₂O₃ in a heated fluidized bed.^[21] 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) → 2B₂O₃(s) + 6H₂(g)

B₂H₆(g) + 3H₂O(g) → B₂O₃(s) + 6H₂(g)^[22]

Reactions

Molten boron oxide attacks silicates. Containers can be passivated internally with a graphitized carbon layer obtained by thermal decomposition of acetylene.^[23]

Applications

Major component of borosilicate glass
Fluxing agent for glass and enamels^{[citation needed]}
An additive used in glass fibres (optical fibres)
The inert capping layer in the Liquid Encapsulation Czochralski process for the production of gallium arsenide single crystal
As an acid catalyst in organic synthesis
As a starting material for the production of other boron compounds, such as boron carbide

References

^ ^a ^b Gurr, G. E.; Montgomery, P. W.; Knutson, C. D.; Gorres, B. T. (1970). "The Crystal Structure of Trigonal Diboron Trioxide". Acta Crystallographica B. 26 (7): 906–915. doi:10.1107/S0567740870003369.
^ High temperature corrosion and materials chemistry: proceedings of the Per Kofstad Memorial Symposium. Proceedings of the Electrochemical Society. The Electrochemical Society. 2000. p. 496. ISBN 978-1-56677-261-7.
^ ^a ^b Patnaik, P. (2003). Handbook of Inorganic Chemical Compounds. McGraw-Hill. p. 119. ISBN 978-0-07-049439-8. Retrieved 2009-06-06.
^ ^a ^b ^c ^d NIOSH Pocket Guide to Chemical Hazards. "#0060". National Institute for Occupational Safety and Health (NIOSH).
^ "Boron oxide". Immediately Dangerous to Life or Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
^ L. McCulloch (1937): "A Crystalline Boric Oxide". Journal of the American Chemical Society, volume 59, issue 12, pages 2650–2652. doi:10.1021/ja01291a05
^ I.Vishnevetsky and M.Epstein (2015): "Solar carbothermic reduction of alumina, magnesia and boria under vacuum". Solar Energy, volume 111, pages 236-251 doi:10.1016/j.solener.2014.10.039
^ Ferlat, G.; Charpentier, T.; Seitsonen, A. P.; Takada, A.; Lazzeri, M.; Cormier, L.; Calas, G.; Mauri. F. (2008). "Boroxol Rings in Liquid and Vitreous B₂O₃ from First Principles". Phys. Rev. Lett. 101 (6): 065504. Bibcode:2008PhRvL.101f5504F. doi:10.1103/PhysRevLett.101.065504. PMID 18764473.
^ Ferlat, G.; Seitsonen, A. P.; Lazzeri, M.; Mauri, F. (2012). "Hidden polymorphs drive vitrification in B₂O₃". Nature Materials Letters. 11 (11): 925–929. arXiv:1209.3482. Bibcode:2012NatMa..11..925F. doi:10.1038/NMAT3416. PMID 22941329. S2CID 11567458.
^ Hung, I.; et al. (2009). "Determination of the bond-angle distribution in vitreous B₂O₃ by rotation (DOR) NMR spectroscopy". Journal of Solid State Chemistry. 182 (9): 2402–2408. Bibcode:2009JSSCh.182.2402H. doi:10.1016/j.jssc.2009.06.025.
^ Soper, A. K. (2011). "Boroxol rings from diffraction data on vitreous boron trioxide". J. Phys.: Condens. Matter. 23 (36): 365402. Bibcode:2011JPCM...23.5402S. doi:10.1088/0953-8984/23/36/365402. PMID 21865633. S2CID 5291179.
^ Joo, C.; et al. (2000). "The ring structure of boron trioxide glass". Journal of Non-Crystalline Solids. 261 (1–3): 282–286. Bibcode:2000JNCS..261..282J. doi:10.1016/s0022-3093(99)00609-2.
^ Zwanziger, J. W. (2005). "The NMR response of boroxol rings: a density functional theory study". Solid State Nuclear Magnetic Resonance. 27 (1–2): 5–9. doi:10.1016/j.ssnmr.2004.08.004. PMID 15589722.
^ Micoulaut, M. (1997). "The structure of vitreous B₂O₃ obtained from a thermostatistical model of agglomeration". Journal of Molecular Liquids. 71 (2–3): 107–114. doi:10.1016/s0167-7322(97)00003-2.
^ Alderman, O. L. G. Ferlat, G. Baroni, A. Salanne, M. Micoulaut, M. Benmore, C. J. Lin, A. Tamalonis, A. Weber, J. K. R. (2015). "Liquid B2O3 up to 1700K: X-ray diffraction and boroxol ring dissolution" (PDF). Journal of Physics: Condensed Matter. 27 (45): 455104. Bibcode:2015JPCM...27S5104A. doi:10.1088/0953-8984/27/45/455104. PMID 26499978. S2CID 21783488.{{cite journal}}: CS1 maint: multiple names: authors list (link)
^ Gurr, G. E.; Montgomery, P. W.; Knutson, C. D.; Gorres, B. T. (1970). "The crystal structure of trigonal diboron trioxide". Acta Crystallographica B. 26 (7): 906–915. doi:10.1107/S0567740870003369.
^ Strong, S. L.; Wells, A. F.; Kaplow, R. (1971). "On the crystal structure of B₂O₃". Acta Crystallographica B. 27 (8): 1662–1663. doi:10.1107/S0567740871004515.
^ Effenberger, H.; Lengauer, C. L.; Parthé, E. (2001). "Trigonal B₂O₃ with Higher Space-Group Symmetry: Results of a Reevaluation". Monatshefte für Chemie. 132 (12): 1515–1517. doi:10.1007/s007060170008. S2CID 97795834.
^ Aziz, M. J.; Nygren, E.; Hays, J. F.; Turnbull, D. (1985). "Crystal Growth Kinetics of Boron Oxide Under Pressure". Journal of Applied Physics. 57 (6): 2233. Bibcode:1985JAP....57.2233A. doi:10.1063/1.334368.
^ Brazhkin, V. V.; Katayama, Y.; Inamura, Y.; Kondrin, M. V.; Lyapin, A. G.; Popova, S. V.; Voloshin, R. N. (2003). "Structural transformations in liquid, crystalline and glassy B₂O₃ under high pressure". JETP Letters. 78 (6): 393–397. Bibcode:2003JETPL..78..393B. doi:10.1134/1.1630134. S2CID 189764568.
^ Kocakuşak, S.; Akçay, K.; Ayok, T.; Koöroğlu, H. J.; Koral, M.; Savaşçi, Ö. T.; Tolun, R. (1996). "Production of anhydrous, crystalline boron oxide in fluidized bed reactor". Chemical Engineering and Processing. 35 (4): 311–317. doi:10.1016/0255-2701(95)04142-7.
^ AirProducts (2011). "Diborane Storage & Delivery" (PDF). Archived from the original (PDF) on 2015-02-04. Retrieved 2013-08-21. {{cite journal}}: Cite journal requires |journal= (help)
^ Morelock, C. R. (1961). "Research Laboratory Report #61-RL-2672M". General Electric. {{cite journal}}: Cite journal requires |journal= (help)

External links

[a1-1] Gurr, G. E.; Montgomery, P. W.; Knutson, C. D.; Gorres, B. T. (1970). "The Crystal Structure of Trigonal Diboron Trioxide". Acta Crystallographica B. 26 (7): 906–915. doi:10.1107/S0567740870003369.

[2] High temperature corrosion and materials chemistry: proceedings of the Per Kofstad Memorial Symposium. Proceedings of the Electrochemical Society. The Electrochemical Society. 2000. p. 496. ISBN 978-1-56677-261-7.

[patnaik-3] Patnaik, P. (2003). Handbook of Inorganic Chemical Compounds. McGraw-Hill. p. 119. ISBN 978-0-07-049439-8. Retrieved 2009-06-06.

[PGCH-4] NIOSH Pocket Guide to Chemical Hazards. "#0060". National Institute for Occupational Safety and Health (NIOSH).

[5] "Boron oxide". Immediately Dangerous to Life or Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).

[mccu1937-6] L. McCulloch (1937): "A Crystalline Boric Oxide". Journal of the American Chemical Society, volume 59, issue 12, pages 2650–2652. doi:10.1021/ja01291a05

[vish2015-7] I.Vishnevetsky and M.Epstein (2015): "Solar carbothermic reduction of alumina, magnesia and boria under vacuum". Solar Energy, volume 111, pages 236-251 doi:10.1016/j.solener.2014.10.039

[ferl2008-8] Ferlat, G.; Charpentier, T.; Seitsonen, A. P.; Takada, A.; Lazzeri, M.; Cormier, L.; Calas, G.; Mauri. F. (2008). "Boroxol Rings in Liquid and Vitreous B₂O₃ from First Principles". Phys. Rev. Lett. 101 (6): 065504. Bibcode:2008PhRvL.101f5504F. doi:10.1103/PhysRevLett.101.065504. PMID 18764473.

[ferl2012-9] Ferlat, G.; Seitsonen, A. P.; Lazzeri, M.; Mauri, F. (2012). "Hidden polymorphs drive vitrification in B₂O₃". Nature Materials Letters. 11 (11): 925–929. arXiv:1209.3482. Bibcode:2012NatMa..11..925F. doi:10.1038/NMAT3416. PMID 22941329. S2CID 11567458.

[hung2009-10] Hung, I.; et al. (2009). "Determination of the bond-angle distribution in vitreous B₂O₃ by rotation (DOR) NMR spectroscopy". Journal of Solid State Chemistry. 182 (9): 2402–2408. Bibcode:2009JSSCh.182.2402H. doi:10.1016/j.jssc.2009.06.025.

[soper2011-11] Soper, A. K. (2011). "Boroxol rings from diffraction data on vitreous boron trioxide". J. Phys.: Condens. Matter. 23 (36): 365402. Bibcode:2011JPCM...23.5402S. doi:10.1088/0953-8984/23/36/365402. PMID 21865633. S2CID 5291179.

[jooc2000-12] Joo, C.; et al. (2000). "The ring structure of boron trioxide glass". Journal of Non-Crystalline Solids. 261 (1–3): 282–286. Bibcode:2000JNCS..261..282J. doi:10.1016/s0022-3093(99)00609-2.

[zwan2005-13] Zwanziger, J. W. (2005). "The NMR response of boroxol rings: a density functional theory study". Solid State Nuclear Magnetic Resonance. 27 (1–2): 5–9. doi:10.1016/j.ssnmr.2004.08.004. PMID 15589722.

[mico1997-14] Micoulaut, M. (1997). "The structure of vitreous B₂O₃ obtained from a thermostatistical model of agglomeration". Journal of Molecular Liquids. 71 (2–3): 107–114. doi:10.1016/s0167-7322(97)00003-2.

[alde2015-15] Alderman, O. L. G. Ferlat, G. Baroni, A. Salanne, M. Micoulaut, M. Benmore, C. J. Lin, A. Tamalonis, A. Weber, J. K. R. (2015). "Liquid B2O3 up to 1700K: X-ray diffraction and boroxol ring dissolution" (PDF). Journal of Physics: Condensed Matter. 27 (45): 455104. Bibcode:2015JPCM...27S5104A. doi:10.1088/0953-8984/27/45/455104. PMID 26499978. S2CID 21783488.{{cite journal}}: CS1 maint: multiple names: authors list (link)

[gurr1970-16] Gurr, G. E.; Montgomery, P. W.; Knutson, C. D.; Gorres, B. T. (1970). "The crystal structure of trigonal diboron trioxide". Acta Crystallographica B. 26 (7): 906–915. doi:10.1107/S0567740870003369.

[stro1971-17] Strong, S. L.; Wells, A. F.; Kaplow, R. (1971). "On the crystal structure of B₂O₃". Acta Crystallographica B. 27 (8): 1662–1663. doi:10.1107/S0567740871004515.

[effe2001-18] Effenberger, H.; Lengauer, C. L.; Parthé, E. (2001). "Trigonal B₂O₃ with Higher Space-Group Symmetry: Results of a Reevaluation". Monatshefte für Chemie. 132 (12): 1515–1517. doi:10.1007/s007060170008. S2CID 97795834.

[aziz1985-19] Aziz, M. J.; Nygren, E.; Hays, J. F.; Turnbull, D. (1985). "Crystal Growth Kinetics of Boron Oxide Under Pressure". Journal of Applied Physics. 57 (6): 2233. Bibcode:1985JAP....57.2233A. doi:10.1063/1.334368.

[braz2003-20] Brazhkin, V. V.; Katayama, Y.; Inamura, Y.; Kondrin, M. V.; Lyapin, A. G.; Popova, S. V.; Voloshin, R. N. (2003). "Structural transformations in liquid, crystalline and glassy B₂O₃ under high pressure". JETP Letters. 78 (6): 393–397. Bibcode:2003JETPL..78..393B. doi:10.1134/1.1630134. S2CID 189764568.

[akca1996-21] Kocakuşak, S.; Akçay, K.; Ayok, T.; Koöroğlu, H. J.; Koral, M.; Savaşçi, Ö. T.; Tolun, R. (1996). "Production of anhydrous, crystalline boron oxide in fluidized bed reactor". Chemical Engineering and Processing. 35 (4): 311–317. doi:10.1016/0255-2701(95)04142-7.

[AIRP2011-22] AirProducts (2011). "Diborane Storage & Delivery" (PDF). Archived from the original (PDF) on 2015-02-04. Retrieved 2013-08-21. {{cite journal}}: Cite journal requires |journal= (help)

[more1961-23] Morelock, C. R. (1961). "Research Laboratory Report #61-RL-2672M". General Electric. {{cite journal}}: Cite journal requires |journal= (help)

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