Arsenic trichloride: Difference between revisions
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| verifiedrevid = 438487761 |
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| Name = Arsenic trichloride |
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| ImageFile = Arsenic-trichloride-3D-balls.png |
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| SMILES = Cl[As](Cl)Cl |
| SMILES = Cl[As](Cl)Cl |
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| InChIKey = OEYOHULQRFXULB-UHFFFAOYAG |
| InChIKey = OEYOHULQRFXULB-UHFFFAOYAG |
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| StdInChIKey = OEYOHULQRFXULB-UHFFFAOYSA-N |
| StdInChIKey = OEYOHULQRFXULB-UHFFFAOYSA-N |
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| CASNo = 7784-34-1 |
| CASNo = 7784-34-1 |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| PubChem = 24570 |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| ChemSpiderID=22974 |
| ChemSpiderID=22974 |
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| RTECS = CG1750000 |
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| UNNumber = 1560 |
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| EC_number = 232-059-5 |
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| UNII = 5XW39M1300 |
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|Section2={{Chembox Properties |
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| Formula = AsCl<sub>3</sub> |
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| MolarMass = 181.28 g/mol |
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| Appearance = colourless oily liquid |
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| Density = 2.163 g/cm<sup>3</sup>, liquid |
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| Solubility = Hydrolyzes |
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| SolubleOther = soluble in [[ethanol|alcohol]], [[diethyl ether|ether]], [[hydrochloric acid|HCl]], [[hydrobromic acid|HBr]], [[chloroform]], [[carbon tetrachloride|CCl<sub>4</sub>]]<ref name="crc">{{cite book |author1=John Rumble |title=CRC Handbook of Chemistry and Physics |date=June 18, 2018 |publisher=CRC Press |isbn=978-1138561632 |pages=4–41|edition=99th |language=English}}</ref> |
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| MeltingPtC = −16.2 |
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| BoilingPtC = 130.2 |
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| RefractIndex = 1.6006 |
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| Viscosity = 9.77 x 10<sup>−6</sup> Pa s |
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| MagSus = -79.9·10<sup>−6</sup> cm<sup>3</sup>/mol |
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|Section7={{Chembox Hazards |
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| MainHazards = Very toxic, carcinogen, corrosive, decomposes on contact with water releasing [[hydrochloric acid|HCl]] |
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| EUClass = Very Toxic ('''T+''')<br/>Dangerous for the environment ('''N''') <!-- Index No. 033-002-00-5 --> |
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| GHSPictograms = {{GHS05}}{{GHS06}}{{GHS08}}{{GHS09}} |
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| GHSSignalWord = Danger |
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| SPhrases = {{S1/2}}, {{S20/21}}, {{S28}}, {{S45}}, {{S60}}, {{S61}} |
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| HPhrases = {{H-phrases|301|310|314|331|350|410}} |
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| PPhrases = {{P-phrases|201|202|260|261|262|264|270|271|273|280|281|301+310|301+330+331|302+350|303+361+353|304+340|305+351+338|308+313|310|311|321|322|330|361|363|391|403+233|405|501}} |
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| NFPA-R = 0 |
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| NFPA-H = 4 |
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| NFPA-R = 1 |
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| LD50 = 48 mg/kg |
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| LCLo = 100 mg/m<sup>3</sup> (cat, 1 hr)<br/>200 mg/m<sup>3</sup> (cat, 20 min)<br/>338 ppm (rat, 10 min)<ref>{{IDLH|7440382|Arsenic (inorganic compounds, as As)}}</ref> |
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| IDLH = Ca [5 mg/m<sup>3</sup> (as As)]<ref name=PGCH>{{PGCH|0038}}</ref> |
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| REL = Ca C 0.002 mg/m<sup>3</sup> [15-minute]<ref name=PGCH/> |
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| PEL = [1910.1018] TWA 0.010 mg/m<sup>3</sup><ref name=PGCH/> |
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|Section8={{Chembox Related |
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| OtherAnions = [[Arsenic trioxide]], [[Arsenic trifluoride]] |
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| OtherCations = [[Antimony trichloride]] |
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| OtherFunction = |
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| OtherFunction_label = |
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| OtherCompounds = }} |
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'''Arsenic trichloride''' is an [[inorganic compound]] with the formula AsCl<sub>3</sub>, also known as arsenous chloride or butter of arsenic. This poisonous oil is colourless, although impure samples may appear yellow. It is an intermediate in the manufacture of [[organoarsenic compound]]s.<ref name=Ullmann>Sabina C. Grund, Kunibert Hanusch, Hans Uwe Wolf "Arsenic and Arsenic Compounds" in Ullmann's Encyclopedia of Industrial Chemistry, VCH-Wiley, 2008, Weinheim.{{ |
'''Arsenic trichloride''' is an [[inorganic compound]] with the formula AsCl<sub>3</sub>, also known as '''arsenous chloride''' or '''butter of arsenic'''. This poisonous oil is colourless, although impure samples may appear yellow. It is an intermediate in the manufacture of [[organoarsenic compound]]s.<ref name=Ullmann>Sabina C. Grund, Kunibert Hanusch, Hans Uwe Wolf "Arsenic and Arsenic Compounds" in ''Ullmann's Encyclopedia of Industrial Chemistry'', VCH-Wiley, 2008, Weinheim.{{doi|10.1002/14356007.a03_113.pub2}}</ref> |
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==Structure== |
==Structure== |
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AsCl<sub>3</sub> is a pyramidal molecule with C<sub>3v</sub> [[symmetry group|symmetry]]. The As-Cl bond is 2.161 Å and the angle Cl-As-Cl is 98° |
AsCl<sub>3</sub> is a pyramidal molecule with C<sub>3v</sub> [[symmetry group|symmetry]]. The As-Cl bond is 2.161 Å and the angle Cl-As-Cl is 98° 25'±30.<ref>P. Kisliuk; C. H. Townes. "The Microwave Spectra and Molecular Structure of Phosphorus and Arsenic Trichloride". ''J. Chem. Phys.'' 1950, 18.</ref><ref>Jean Galy; Renee Enjalbertl Pierre Lecante; Andrzej Burian "AsCl<sub>3</sub>: From the crystalline to the liquid state. XRD (176< T (K) < 250) and WAXS (295K) studies" ''Inorg. Chem'' 2002, volume 41, pp. 693–698.{{doi|10.1021/ic0102788}}</ref> AsCl<sub>3</sub> has four normal modes of vibration: ν1(A<sub>1</sub>) 416, ν2(A<sub>1</sub>) 192, ν3 393, and ν4(E) 152 cm<sup>−1</sup>.<ref>Klapoetke, Thomas M. "The vibrational spectrum of arsenic trichloride" ''Main Group Metal Chemistry'' 1997, volume 20, pp. 81–83.</ref> |
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Arsenic trichloride contains predominantly [[covalent bond]]s, which explains its low melting point. |
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==Synthesis== |
==Synthesis== |
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: As<sub>2</sub>O<sub>3</sub> + 6 HCl → 2 AsCl<sub>3</sub> + 3 H<sub>2</sub>O |
: As<sub>2</sub>O<sub>3</sub> + 6 HCl → 2 AsCl<sub>3</sub> + 3 H<sub>2</sub>O |
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It can also be prepared by chlorination of arsenic at |
It can also be prepared by chlorination of arsenic at 80–85 °C, but this method requires elemental arsenic.<ref name=Ullmann/> |
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: 2 As + 3 Cl<sub>2</sub> → 2 AsCl<sub>3</sub> |
: 2 As + 3 Cl<sub>2</sub> → 2 AsCl<sub>3</sub> |
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Arsenic trichloride can |
Arsenic trichloride can be prepared by the reaction of arsenic oxide and sulfur monochloride. This method requires simple apparatus and proceeds efficiently:<ref>R. C. Smith, "Manufacture of Arsenic trichloride" ''The Journal of Industrial and Engineering Chemistry'' 1919, volume 11, pp. 109–110. {{doi|10.1021/ie50110a009}}</ref> |
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: 2 As<sub>2</sub>O<sub>3</sub> + 6 S<sub>2</sub>Cl<sub>2</sub> → 4 AsCl<sub>3</sub> + 3 SO<sub>2</sub> + 9 S |
: 2 As<sub>2</sub>O<sub>3</sub> + 6 S<sub>2</sub>Cl<sub>2</sub> → 4 AsCl<sub>3</sub> + 3 SO<sub>2</sub> + 9 S |
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A convenient laboratory method is refluxing arsenic(III) oxide with [[thionyl chloride]]:<ref>{{cite journal |first1=S. K.| last1=Pandey |first2=A. |last2=Steiner |first3=H. W. |last3=Roesky |title=Arsenic(III) chloride | journal=Inorganic Syntheses | year=1997|volume=31|page=148-150|doi=10.1002/9780470132623.ch24}}</ref> |
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: 2 As<sub>2</sub>O<sub>3</sub> + 3 SOCl<sub>2</sub> → 2 AsCl<sub>3</sub> + 3 SO<sub>2</sub> |
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Arsenic trichloride can also be prepared by the reaction of hydrochloric acid and arsenic(III) sulfide. |
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:As<sub>2</sub>S<sub>3</sub> + 6 HCl → 2 AsCl<sub>3</sub> + 3 H<sub>2</sub>S |
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==Reactions== |
==Reactions== |
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[[Hydrolysis]] |
[[Hydrolysis]] gives [[arsenous acid]] and [[hydrochloric acid]]: |
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: AsCl<sub>3</sub> + 3 H<sub>2</sub>O → As(OH)<sub>3</sub> + 3 HCl |
: AsCl<sub>3</sub> + 3 H<sub>2</sub>O → As(OH)<sub>3</sub> + 3 HCl |
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Although AsCl<sub>3</sub> is less moisture sensitive than PCl<sub>3</sub>, it still fumes in moist air.<ref>Holleman, A. F.; Wiberg, E. |
Although AsCl<sub>3</sub> is less moisture sensitive than PCl<sub>3</sub>, it still fumes in moist air.<ref>Holleman, A. F.; Wiberg, E. ''Inorganic Chemistry'' Academic Press: San Diego, 2001. {{ISBN|0-12-352651-5}}.</ref> |
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AsCl<sub>3</sub> undergoes redistribution upon treatment with As<sub>2</sub>O<sub>3</sub> to give the [[inorganic polymer]] AsOCl. With chloride sources, AsCl<sub>3</sub> |
AsCl<sub>3</sub> undergoes redistribution upon treatment with As<sub>2</sub>O<sub>3</sub> to give the [[inorganic polymer]] AsOCl. With chloride sources, AsCl<sub>3</sub> also forms salts containing the anion [AsCl<sub>4</sub>]<sup>−</sup>. Reaction with [[potassium bromide]] and potassium iodide give [[arsenic tribromide]] and [[arsenic triiodide]], respectively. |
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AsCl<sub>3</sub> is useful in organoarsenic chemistry, for example [[triphenylarsine]] is derived from AsCl<sub>3</sub>:<ref name=Shriner>{{OrgSynth | author = Shriner, R. L. |
AsCl<sub>3</sub> is useful in organoarsenic chemistry, for example [[triphenylarsine]] is derived from AsCl<sub>3</sub>:<ref name=Shriner>{{OrgSynth | author = Shriner, R. L. |author2=Wolf, C. N. | title = Tetraphenylarsonium Chloride Hydrochloride | collvol = 4 | collvolpages = 910 | year = 1963 | prep = cv4p0910}}. Describes the preparation of As(C<sub>6</sub>H<sub>5</sub>)<sub>3</sub>.</ref> |
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:AsCl<sub>3</sub> + 6 Na + |
:AsCl<sub>3</sub> + 6 Na + C<sub>6</sub>H<sub>5</sub>Cl → As(C<sub>6</sub>H<sub>5</sub>)<sub>3</sub> + 6 NaCl |
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The chemical weapons called [[Lewisite]]s are prepared by the addition of arsenic trichloride to acetylene: |
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:{{chem2|AsCl3 + C2H2 -> ClCH\dCHAsCl2}} |
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==Safety== |
==Safety== |
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Inorganic arsenic compounds are highly toxic,<ref name=Ullmann/> and AsCl<sub>3</sub> especially so because of its volatility and solubility (in water). |
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It is classified as an [[List of extremely hazardous substances|extremely hazardous substance]] in the United States as defined in Section 302 of the U.S. [[Emergency Planning and Community Right-to-Know Act]] (42 U.S.C. 11002), and is subject to strict reporting requirements by facilities which produce, store, or use it in significant quantities.<ref name="gov-right-know">{{Cite report | publisher = [[United States Government Publishing Office|Government Printing Office]] | title = 40 C.F.R.: Appendix A to Part 355—The List of Extremely Hazardous Substances and Their Threshold Planning Quantities | url = http://edocket.access.gpo.gov/cfr_2008/julqtr/pdf/40cfr355AppA.pdf | edition = July 1, 2008 | access-date = October 29, 2011 | archive-url = https://web.archive.org/web/20120225051612/http://edocket.access.gpo.gov/cfr_2008/julqtr/pdf/40cfr355AppA.pdf | archive-date = February 25, 2012 | url-status = dead }}</ref> |
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==References== |
==References== |
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{{Arsenic compounds}} |
{{Arsenic compounds}} |
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{{Chlorides}} |
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[[Category:Arsenic(III) compounds]] |
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[[Category:Chlorides]] |
[[Category:Chlorides]] |
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[[ar:كلوريد الزرنيخ الثلاثي]] |
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[[cs:Chlorid arsenitý]] |
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[[de:Arsen(III)-chlorid]] |
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[[el:Τριχλωριούχο αρσενικό]] |
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[[it:Tricloruro di arsenico]] |
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[[nl:Arseen(III)chloride]] |
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[[pl:Chlorek arsenu(III)]] |
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[[pt:Tricloreto de arsênio]] |
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[[ru:Хлорид мышьяка(III)]] |
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[[fi:Arseenitrikloridi]] |
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[[sv:Arseniktriklorid]] |