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{{chembox |
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{{chembox |
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| verifiedrevid = 447842430 |
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| verifiedrevid = 449655175 |
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| Name = Antimony trioxide |
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| ImageFile = Antimony trioxide.jpg |
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| Name = Antimony(III) oxide |
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| ImageFile = Antimony trioxide.jpg |
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| ImageSize = 200px |
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| ImageSize = 200px |
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| ImageName = Antimony trioxide |
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| ImageName = Antimony(III) oxide |
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| IUPACName = Antimony(III) oxide |
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| IUPACName = Antimony(III) oxide |
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| OtherNames = Antimony ]<br />Antimonous oxide<br />Flowers of Antimony<br />oxo-oxostibanyloxystibane |
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| OtherNames = Antimony ]<br />Antimonous oxide<br />Flowers of Antimony |
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| Section1 = {{Chembox Identifiers |
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|Section1={{Chembox Identifiers |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| ChemSpiderID = 25727 |
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| ChemSpiderID = 25727 |
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| UNII_Ref = {{fdacite|correct|FDA}} |
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| UNII_Ref = {{fdacite|correct|FDA}} |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| CASNo = 1309-64-4 |
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| CASNo = 1309-64-4 |
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| RTECS = CC5650000 |
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| RTECS = CC5650000 |
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| KEGG_Ref = {{keggcite|correct|kegg}} |
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| KEGG_Ref = {{keggcite|correct|kegg}} |
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| KEGG = C19192 |
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| KEGG = C19192 |
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| PubChem = 14794 |
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| EC_number = 215-474-6 |
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| Section2 = {{Chembox Properties |
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|Section2={{Chembox Properties |
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| Formula = Sb<sub>2</sub>O<sub>3</sub> |
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| Formula = Sb<sub>2</sub>O<sub>3</sub> |
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| MolarMass = 291.52 g/mol |
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| MolarMass = 291.518 g/mol |
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| Appearance = white solid |
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| Appearance = white solid |
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| Odor = odorless |
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| Density = 5.2 g/cm<sup>3</sup>, α-form |
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| Density = 5.2 g/cm<sup>3</sup>, α-form <br> 5.67 g/cm<sup>3</sup> β-form |
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| Solubility = 1.21 mg/100 mL (0 °C) <br> 1.80 mg/100 mL (20 °C) <br> 8.20 mg/100 mL (100 °C), with hydrolysis |
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| Solubility = {{val|370|37}} μg/L between 20.8 °C and 22.9 °C |
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| SolubleOther = insoluble |
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| SolubleOther = soluble in acid |
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| MeltingPt = 656 °C |
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| MeltingPtC = 656 |
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| BoilingPt = 1425 °C (sublimes) |
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| pKa = |
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| BoilingPtC = 1425 |
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| BoilingPt_notes = (sublimes) |
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| RefractIndex = 2.087 |
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| pKa = |
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| RefractIndex = 2.087, α-form <br> 2.35, β-form |
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| MagSus = {{val|-69.4e-6|u=cm<sup>3</sup>/mol}} |
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| Section3 = {{Chembox Structure |
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|Section3={{Chembox Structure |
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| Coordination = pyramidal |
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| Coordination = pyramidal |
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| CrystalStruct = ] (α)<570 °C<br />] (β) >570 °C |
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| CrystalStruct = ] (α) < 570 °C<br />] (β) > 570 °C |
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| Dipole = zero |
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| Dipole = zero |
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| Section7 = {{Chembox Hazards |
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| NFPA-H = 2 |
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| EUClass = Harmful ('''Xn''')<br />Carc. Cat. 3 |
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| NFPA-H = 2 |
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| NFPA-F = 0 |
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| NFPA-F = 0 |
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| NFPA-R = 0 |
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| GHSPictograms = {{GHS08}}<ref name="GESTIS">{{GESTIS|Name=Antimony trioxide|ZVG=3440|CAS=1309-64-4|Date=23 August 2017}}</ref> |
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| NFPA-R = 0 |
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| GHSSignalWord = Warning<ref name="GESTIS" /> |
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| RPhrases = {{R40}} |
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| HPhrases = {{H-phrases|351}}<ref name="GESTIS" /> |
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| SPhrases = {{S2}}, {{S22}}, {{S36/37}} |
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| PPhrases = {{P-phrases|281}}<ref name="GESTIS" /> |
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| LD50 = 7000 mg/kg, oral (rat) |
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| LD50 = 7000 mg/kg, oral (rat) |
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| REL = TWA 0.5 mg/m<sup>3</sup> (as Sb)<ref name=PGCH>{{PGCH|0036}}</ref> |
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| PEL = TWA 0.5 mg/m<sup>3</sup> (as Sb)<ref name=PGCH/> |
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| Section8 = {{Chembox Related |
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|Section8={{Chembox Related |
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| OtherAnions = ] |
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| OtherAnions = ]<br>]<br>] |
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| OtherCations = ]<br />] |
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| OtherCations = ]<br>]<br>]<br>] |
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| OtherCpds = ]<br />] |
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| OtherCompounds = ]<br />] |
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'''Antimony trioxide''' is the ] with the ] Sb<sub>2</sub>O<sub>3</sub>. It is the most important commercial compound of ]. It is found in nature as the minerals ] and ].<ref>Greenwood, N. N.; & Earnshaw, A. (1997). Chemistry of the Elements (2nd Edn.), Oxford:Butterworth-Heinemann. ISBN 0-7506-3365-4.</ref> Like most polymeric ]s, Sb<sub>2</sub>O<sub>3</sub> dissolves in aqueous solutions only with ]. |
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'''Antimony(III) oxide''' is the ] with the ] Sb<sub>2</sub>O<sub>3</sub>. It is the most important commercial compound of ]. It is found in nature as the minerals ] and senarmontite.<ref>Greenwood, N. N.; & Earnshaw, A. (1997). Chemistry of the Elements (2nd Edn.), Oxford:Butterworth-Heinemann. {{ISBN|0-7506-3365-4}}.</ref> Like most polymeric ]s, Sb<sub>2</sub>O<sub>3</sub> dissolves in aqueous solutions with ]. A mixed arsenic-antimony oxide occurs in nature as the very rare mineral stibioclaudetite.<ref>{{Cite web|url=https://www.mindat.org/min-32285.html|title = Stibioclaudetite}}</ref><ref>{{Cite web|url=https://www.ima-mineralogy.org/Minlist.htm|title=List of Minerals|date=21 March 2011}}</ref> |
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==Production and properties== |
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==Production and properties== |
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Global production of antimony trioxide in 2005 was 120,000 tonnes, an increase from 112,600 tonnes in 2002. China produces the largest share (47 %) followed by US/Mexico (22 %), Europe (17 %), Japan (10 %) and South Africa (2 %) and other countries (2%).<ref>http://ecb.jrc.ec.europa.eu/DOCUMENTS/Existing-Chemicals/RISK_ASSESSMENT/REPORT/datreport415.pdf Risk Assessment of Diantimony Trioxide</ref> |
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Global production of antimony(III) oxide in 2012 was 130,000 tonnes, an increase from 112,600 tonnes in 2002. China produces the largest share followed by US/Mexico, Europe, Japan and South Africa and other countries (2%).<ref>{{cite report|url=http://esis.jrc.ec.europa.eu/doc/risk_assessment/REPORT/datreport415.pdf |title=European Union Risk Assessment Report: DIANTIMONY TRIOXIDE (draft)|date=November 2008|location=Sweden|id=CAS No: 1309-64-4; EINECS No: 215-175-0|url-status=dead |archive-url=https://web.archive.org/web/20140106155610/http://esis.jrc.ec.europa.eu/doc/risk_assessment/REPORT/datreport415.pdf |archive-date=2014-01-06 }}</ref> |
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As of 2010, antimony(III) oxide was produced at four sites in the EU. It is produced via two routes, re-volatilizing of crude antimony(III) oxide and by oxidation of antimony metal. |
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Antimony trioxide is mainly produced via the smelting of ] ore, which is oxidised to crude Sb<sub>2</sub>O<sub>3</sub> using ] operating at approximately 850 to 1,000 °C. The transformation is described as follows: |
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Oxidation of antimony metal dominates in Europe. Several processes for the production of crude antimony(III) oxide or metallic antimony from virgin material. The choice of process depends on the composition of the ore and other factors. Typical steps include mining, crushing and grinding of ore, sometimes followed by ] and separation of the metal using pyrometallurgical processes (smelting or roasting) or in a few cases (e.g. when the ore is rich in precious metals) by hydrometallurgical processes. These steps do not take place in the EU but closer to the mining location. |
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:2 Sb<sub>2</sub>S<sub>3</sub> + 9 O<sub>2</sub> → 2 Sb<sub>2</sub>O<sub>3</sub> + 6 SO<sub>2</sub> |
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Crude Sb<sub>2</sub>O<sub>3</sub> is purified by ], which allows it to be separated from the more volatile ]. This step is relevant because antimony ores commonly contain significant amounts of arsenic. |
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===Re-volatilizing of crude antimony(III) oxide=== |
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Antimony oxide is also obtained via ], which can be obtained from stibnite. |
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Step 1) Crude stibnite is oxidized to crude antimony(III) oxide using furnaces operating at approximately 500 to 1,000 °C. The reaction is the following: |
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:2 Sb<sub>2</sub>S<sub>3</sub> + 3 CaCl<sub>2</sub> + 6 O<sub>2</sub> → 4 SbCl<sub>3</sub> + 3 CaSO<sub>4</sub> |
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:2 Sb<sub>2</sub>S<sub>3</sub> + 9 O<sub>2</sub> → 2 Sb<sub>2</sub>O<sub>3</sub> + 6 SO<sub>2</sub> |
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After fractional distillation to separate it from ], SbCl<sub>3</sub> can be hydrolyzed to the oxide: |
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Step 2) The crude antimony(III) oxide is purified by sublimation. |
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:2 SbCl<sub>3</sub> + 3 H<sub>2</sub>O → Sb<sub>2</sub>O<sub>3</sub> + 6 HCl |
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Intermediates in the hydrolysis include the oxychlorides SbOCl and Sb<sub>4</sub>O<sub>5</sub>Cl<sub>2</sub>. |
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===Oxidation of antimony metal=== |
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Although impractical for commercial purposes, Sb<sub>2</sub>O<sub>3</sub> can be prepared by burning elemental antimony in air: |
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Antimony metal is oxidized to antimony(III) oxide in furnaces. The reaction is exothermic. Antimony(III) oxide is formed through sublimation and recovered in bag filters. The size of the formed particles is controlled by process conditions in furnace and gas flow. The reaction can be schematically described by: |
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:4 Sb + 3 O<sub>2</sub> → 2 Sb<sub>2</sub>O<sub>3</sub> |
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:4 Sb + 3 O<sub>2</sub> → 2 Sb<sub>2</sub>O<sub>3</sub> |
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===Properties=== |
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===Properties=== |
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Antimony(III) oxide is an ]. It dissolves in aqueous ] solution to give the meta-antimonite NaSbO<sub>2</sub>, which can be isolated as the trihydrate. Antimony(III) oxide also dissolves in concentrated ] to give the corresponding salts, which hydrolyzes upon dilution with water.<ref name="InorgChem">{{cite book | title = Inorganic Chemistry | edition = 3rd | chapter = Chapter 15: The group 15 elements | author1 = Housecroft, C. E. | author2 = Sharpe, A. G. | publisher = Pearson | year = 2008 | isbn = 978-0-13-175553-6 | page = 481 }}</ref> With ], the trioxide is oxidized to ].<ref name="Handbook">{{cite book | title = Handbook of Inorganic Chemicals | author = Patnaik, P. | publisher = McGraw-Hill | year = 2002 | isbn = 0-07-049439-8 | page = 56 }}</ref> |
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Antimony trioxide is an ], dissolving in alkaline solution to give ]s and in acid solution to given a range of polyantimonous acids. It can be readily oxidized to antimony pentoxide and related antimony(V) compounds, but it is also easily reduced to antimony, sometimes with production of ]. |
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When heated with ], the oxide is reduced to ] metal. With other reducing agents such as ] or ], the unstable and very toxic gas ] is produced.<ref>{{ cite journal |author1=Bellama, J. M. |author2=MacDiarmid, A. G. | title = Synthesis of the Hydrides of Germanium, Phosphorus, Arsenic, and Antimony by the Solid-Phase Reaction of the Corresponding Oxide with Lithium Aluminum Hydride |journal = ] | year = 1968 | volume = 7 | issue = 10 | pages = 2070–2072 | doi = 10.1021/ic50068a024 }}</ref> When heated with ], a complex salt ], KSb(OH)<sub>2</sub>·C<sub>4</sub>H<sub>2</sub>O<sub>6</sub>, is formed.<ref name="Handbook" /> |
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==Structure== |
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==Structure== |
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The structure of Sb<sub>2</sub>O<sub>3</sub> depends on the temperature of the sample. Dimeric Sb<sub>4</sub>O<sub>6</sub> is the high temperature (1560 °C<!--seems high-->) gas.<ref name = "Wiberg&Holleman">Egon Wiberg, Arnold Frederick Holleman (2001) ''Inorganic Chemistry'', Elsevier ISBN 0123526515</ref> Sb<sub>4</sub>O<sub>6</sub> molecules are bicyclic cages, similar to the related oxide of phosphorus(III), ].<ref name = "Wells">Wells, A.F. (1984) Structural Inorganic Chemistry, Oxford: Clarendon Press. ISBN 0-19-855370-6.</ref> The cage structure is retained in a solid that crystallizes in a cubic habit. The Sb-O distance is 197.7 pm and the O-Sb-O angle of 95.6°.<ref>C. Svensson “Refinement of the crystal structure of cubic antimony trioxide, Sb<sub>2</sub>O<sub>3</sub>” Acta Crystographica, 1975, volume B31, pp. 2016-2018. {{doi|10.1107/S0567740875006759}}</ref> This form exists in nature as the ] ].<ref name = "Wells"/> Below 606 °C, the more stable form is ], consisting of pairs -Sb-O-Sb-O- chains that are linked by oxide bridges between the Sb centers. This form exists in nature as the mineral ].<ref name = "Wells"/> |
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The structure of Sb<sub>2</sub>O<sub>3</sub> depends on the temperature of the sample. Dimeric Sb<sub>4</sub>O<sub>6</sub> is the high temperature (1560 °C<!--seems high-->) gas.<ref name ="Wiberg&Holleman">{{ cite book |author1=Wiberg, E. |author2=Holleman, A. F. | year = 2001 | title = Inorganic Chemistry | publisher = Elsevier | isbn = 0-12-352651-5 }}</ref> Sb<sub>4</sub>O<sub>6</sub> molecules are bicyclic cages, similar to the related oxide of phosphorus(III), ].<ref name = "Wells">{{ cite book | author = Wells, A. F. | year = 1984 | title = Structural Inorganic Chemistry | location = Oxford | publisher = Clarendon Press | isbn = 0-19-855370-6 }}</ref> The cage structure is retained in a solid that crystallizes in a cubic habit. The Sb–O distance is 197.7 pm and the O–Sb–O angle of 95.6°.<ref>{{ cite journal | author = Svensson, C. | title = Refinement of the crystal structure of cubic antimony(III) oxide, Sb<sub>2</sub>O<sub>3</sub> | journal = Acta Crystallographica B | year = 1975 | volume = 31 | issue = 8 | pages = 2016–2018 | doi = 10.1107/S0567740875006759 | doi-access = }}</ref> This form exists in nature as the ] ].<ref name = "Wells"/> Above 606 °C, the more stable form is ], consisting of pairs of -Sb-O-Sb-O- chains that are linked by oxide bridges between the Sb centers. This form exists in nature as the mineral ].<ref name = "Wells"/> |
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{| class="wikitable" style="margin:1em auto; text-align:center;" |
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|<center>]</center>||<center>]</center>||<center>]</center> |
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|<center>Sb<sub>4</sub>O<sub>6</sub></center>||<center>senarmontite</center>||<center>valentinite</center> |
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|Sb<sub>4</sub>O<sub>6</sub>||senarmontite||valentinite |
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</center> |
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==Uses== |
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==Uses== |
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The annual consumption of antimony trioxide in the United States and Europe is approximately 10,000 and 25,000 ]s, respectively. The main application is for ]s in combination with halogenated materials. The combination of the halides and the antimony being key to the flame-retardant action for polymers, helping to form less flammable chars. Such flame retardants are found in electrical apparatus, textiles, leather, and coatings.<ref name=Ullmann>Sabina C. Grund, Kunibert Hanusch, Hans J. Breunig, Hans Uwe Wolf “Antimony and Antimony Compounds” in Ullmann's Encyclopedia of Industrial Chemistry 2006, Wiley-VCH, Weinheim. {{DOI| 10.1002/14356007.a03_055.pub2}}</ref> |
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The annual consumption of antimony(III) oxide in the United States and Europe is approximately 10,000 and 25,000 ]s, respectively. The main application is as ] synergist in combination with halogenated materials. The combination of the halides and the antimony is key to the flame-retardant action for polymers, helping to form less flammable chars. Such flame retardants are found in electrical apparatuses, textiles, leather, and coatings.<ref name=Ullmann>{{ Ullmann | author = Grund, S. C. |author2=Hanusch, K. |author3=Breunig, H. J. |author4=Wolf, H. U. | title = Antimony and Antimony Compounds | doi = 10.1002/14356007.a03_055.pub2 }}</ref> |
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Other applications: |
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Other applications: |
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*Antimony trioxide is an ] for ]es, ]s and ]s. |
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*Antimony(III) oxide is an ] for ]es, ]s and ]s. |
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*Some specialty ] contain antimony. |
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*Some specialty ] contain antimony. |
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*Antimony trioxide is a useful ] in the production of ] (PET plastic) and the ] of rubber. |
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*Antimony(III) oxide is a useful ] in the production of ] (PET plastic) and the ] of rubber. |
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*] for textiles, leather, polymers, and coatings. |
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==Safety== |
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==Safety== |
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Antimony(III) oxide has suspected carcinogenic potential for humans.<ref name=Ullmann/> Its ] is 0.5 mg/m<sup>3</sup>, as for most antimony compounds.<ref>{{ cite journal |author1=Newton, P. E. |author2=Schroeder, R. E. |author3=Zwick, L. |author4=Serex, T. | title = Inhalation Developmental Toxicity Studies In Rats With Antimony(III) oxide (Sb<sub>2</sub>O<sub>3</sub>) | journal = Toxicologist | year = 2004 | volume = 78 | issue = 1–S | pages = 38 }}</ref> Before 2021, no other human health hazards were identified for antimony(III) oxide, and no risks to human health and the environment were identified from the production and use of antimony trioxide in daily life. However, the 15th Report on Carcinogens released on December 21, 2021, by the ] categorised antimony(III) oxide as carcinogenic.<ref>{{Cite web |title=15th Report on Carcinogens |url=https://ntp.niehs.nih.gov/whatwestudy/assessments/cancer/roc |access-date=2023-06-15 |website=National Toxicology Program |language=en}}</ref> |
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The toxicity of Sb<sub>2</sub>O<sub>3</sub> is topical because it is a likely byproduct of the combustion of some materials "fireproofed" with antimony compounds. The oxides of arsenic, antimony, and bismuth are comparable in their toxicity, but their volatilities differ widely. Antimony trioxide has suspected carcinogenic potential for humans.<ref name=Ullmann/> Its ] is 0.5 mg/m<sup>3</sup>, as for most antimony compounds.<ref>Inhalation Developmental Toxicity Studies In Rats With Antimony Trioxide (Sb2O3). Newton PE; Schroeder RE; Zwick L; Serex T; Toxicologist 2004 Mar;78(1-S):38</ref> |
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==References== |
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==References== |
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==Further reading== |
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==Further reading== |
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* Institut national de recherche et de sécurité (INRS), ''Fiche toxicologique nº 198 : Trioxyde de diantimoine'', 1992. |
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* Institut national de recherche et de sécurité (INRS), ''Fiche toxicologique nº 198 : Trioxyde de diantimoine'', 1992. |
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* The Oxide Handbook, G.V. Samsonov, 1981, 2nd ed. IFI/Plenum, ISBN 0-306-65177-7 |
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* The Oxide Handbook, G.V. Samsonov, 1981, 2nd ed. IFI/Plenum, {{ISBN|0-306-65177-7}} |
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==External links== |
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==External links== |
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{{Antimony compounds}} |
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{{DEFAULTSORT:Antimony Trioxide}} |
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