Arsenic trioxide

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Arsenic trioxide
As4O6-molecule-from-arsenolite-xtal-3D-balls.png
Arsenic trioxide.jpg
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
DrugBank
ECHA InfoCard 100.014.075 OOjs UI icon edit-ltr-progressive.svg
35185
KEGG
PubChem CID
  • InChI=1S/As4O6/c5-1-6-3-8-2(5)9-4(7-1)10-3
    Key: KTTMEOWBIWLMSE-UHFFFAOYSA-N
  • O1[As]2O[As]3O[As]1O[As](O2)O3
Properties
As4O6
Molar mass 395.680 g·mol−1
Appearancewhite solid
Density 3.74 g/cm3
Melting point 312.2 °C (594.0 °F; 585.3 K)
Boiling point 465 °C (869 °F; 738 K)
20 g/L (25 °C)
(see text)
Hazards
GHS labelling:
GHS-pictogram-acid.svg GHS-pictogram-skull.svg GHS-pictogram-silhouette.svg GHS-pictogram-pollu.svg
Danger
H300, H314, H350, H410
P201, P202, P260, P264, P270, P273, P280, P301+P330+P331, P303+P361+P353, P304+P340+P310, P305+P351+P338+P310, P308+P313, P363, P391, P405, P501
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Arsenic trioxide is the inorganic compound with the formula As4O6. [1] As an industrial chemical, its major uses include the manufacture of wood preservatives, pesticides, and glass. For medical purposes, it is sold under the brand name Trisenox among others [2] [3] when used as a medication to treat a type of cancer known as acute promyelocytic leukemia. [4] For this use it is given by injection into a vein. [4]

Contents

Arsenic trioxide was approved for medical use in the United States in 2000. [4] It is on the World Health Organization's List of Essential Medicines. [5] Approximately 50,000 tonnes were produced in 1991. [6] Due to its toxicity, a number of countries have regulations around its manufacture and sale. [7]

Uses

Arsenic trioxide is the dominant form of arsenic for commercial applications. Industrial uses include usage as a precursor to forestry products, in colorless glass production, and in electronics. Being the main compound of arsenic, the trioxide is the precursor to elemental arsenic, arsenic alloys, and arsenide semiconductors. Bulk arsenic-based compounds sodium arsenite and sodium cacodylate are derived from the trioxide. [6]

A variety of applications exploit arsenic's toxicity, including the use of the oxide as a wood preservative. Copper arsenates, such as chromated copper arsenate, are derived from arsenic trioxide. These compounds were once used on a large scale as wood preservatives in the U.S. and Malaysia, but are now banned in many parts of the world. This practice remains controversial. [6] When combined with copper(II) acetate, arsenic trioxide gives the vibrant green pigment known as Paris green, which finds some use as an insecticide. [8]

Medical

Historical

Despite the well known toxicity of arsenic, arsenic trioxide was used in traditional Chinese medicine, where it is known as pi-shuang (Chinese :砒霜; pinyin :pīshuāng; lit.'arsenic frost'). Some discredited patent medicines, e.g., Fowler's solution, contained derivatives of arsenic oxide. [9]

Modern

Arsenic trioxide is used to treat a type of cancer known as acute promyelocytic leukemia (APL). [4] It may be used both in cases that are unresponsive to other agents, such as all-trans retinoic acid (ATRA) or as part of the initial treatment of newly diagnosed cases. [4] This initial treatment may include combination therapy of arsenic trioxide with all-trans retinoic acid (ATRA). [10] [11]

Production and occurrence

Historic arsenic mine Sankt Blasen, Austria St.BlasenArsenikstollen5.jpg
Historic arsenic mine Sankt Blasen, Austria

Arsenic trioxide can be generated via routine processing of arsenic compounds including the oxidation (combustion) of arsenic and arsenic-containing minerals in air. Illustrative is the roasting of orpiment, a typical arsenic sulfide ore.

2 As2S3 + 9 O2 → 2 As2O3 + 6 SO2

Smelting and related ore processing often generate arsenic trioxide, which poses a risk to the environment. For example, the Giant Mine in Canada processed substantial amounts of arsenopyrite-contaminated gold ores.

Most arsenic oxide is, however, obtained as a volatile by-product of the processing of other ores. For example, arsenopyrite, a common impurity in gold- and copper-containing ores, liberates arsenic trioxide upon heating in air. The processing of such minerals has led to numerous cases of poisonings, [12] and after the mine is closed, the leftover trioxide waste will present environmental hazard (as was the case with the Giant Mine, for example). Only in China are arsenic ores intentionally mined. [6]

In the laboratory, it is prepared by hydrolysis of arsenic trichloride: [13]

2 AsCl3 + 3 H2O → As2O3 + 6 HCl

As2O3 occurs naturally as two minerals, arsenolite (cubic) and claudetite (monoclinic). Both are relatively rare secondary minerals found in oxidation zones of As-rich ore deposits.

Reactions

Acid-base reactions

Arsenic trioxide is an amphoteric oxide, and its aqueous solutions are weakly acidic. Thus, it dissolves readily in alkaline solutions to give arsenites: [14]

As2O3 + 6 NaOH → 2 Na3AsO3 + 3 H2O

Arsenic trioxide is less soluble in acids, although it will dissolve in hydrochloric acid. [15] [ page needed ]

When treated with anhydrous HF and HCl, arsenic trioxide converts to the corresponding trihalide. [16] The tribromide and triiodide are made using concentrated hydrobromic acid and hydroiodic acid, respectively: [17]

As2O3 + 6 HX → 2 AsX3 + 3 H2O (X = F, Cl, Br, I)

Redox reactions

Only with strong oxidizing agents such as ozone, hydrogen peroxide, and nitric acid does it yield arsenic pentoxide, As2O5 or its corresponding acid: [16] : 601 

2 HNO3 + As2O3 + 2 H2O → 2 H3AsO4 + N2O3

In terms of its resistance to oxidation, arsenic trioxide differs from phosphorus trioxide, which readily combusts to phosphorus pentoxide.[ clarification needed ]

Reduction gives elemental arsenic or arsine (AsH3) depending on conditions: [16] : 593–594 

As2O3 + 6 Zn + 12 HNO3 → 2 AsH3 + 6 Zn(NO3)2 + 3 H2O

This reaction is used in the Marsh test. [18]

Precursor to organoarsenic compounds

Arsenic trioxide has played a special role as entry to organoarsenic chemistry. In the 18th century it was found that combining arsenic trioxide and four equivalents of potassium acetate (CH3CO2K) gives a product called "Cadet's fuming liquid", which is often considered the first organometallic compound. Cadet's fuming liquid is a derivative of cacodylic acid, ((CH3)2As)2O and cacodyl, ((CH3)2As)2. [19]

Arsenic trioxide reacts with phenyl magnesium bromide as described by the following idealized equation: [15]

As2O3 + 4 C6H5MgBr → [(C6H5)2As]2O + 3 MgO + MgBr2

Metal derivatives

Like many other oxides, arsenic trioxide condenses with transition metal oxyanions to give polyoxometallates. Many such clusters have been characterized by X-ray crystallography. [20] It reacts with aqueous copper(II) acetate to give Cu2(O2CCH3)(As3O6), known as Paris green.. [21]

Structure

In the gas phase below 800 °C (1,470 °F), arsenic trioxide has the formula As4O6 and is isostructural with P4O6 . Above 800 °C (1,470 °F)As4O6 dissociation into molecular As2O3, with the same structure as N2O3 , becomes significant. Three crystalline forms (polymorphs) are known: a high temperature (over 110 °C (230 °F)) cubic form, containing molecular As4O6, and two related polymeric forms. [22] [ page needed ] The polymers, which both crystallize as monoclinic crystals, feature sheets of pyramidal AsO3 units that share O atoms. [23] [ page needed ] One of the polymeric forms (presumably I, as II was not known at the time) is apparently [24] the most stable form.

Arsenolite-xtal-3D-balls-D.png Claudetite-I-layer-3D-balls.png Claudetite-II-layer-3D-balls.png
arsenolite
(cubic)
claudetite I
(monoclinic)
claudetite II
(monoclinic)

The liquid state is agreed to be polymeric,[ by whom? ] and can form a glass; the liquid and glass have bonding of the same general type as the polymeric crystalline forms. [25]

Safety

As with other inorganic arsenic compounds, arsenic trioxide is toxic to living organisms. Arsenic trioxide is readily absorbed by the digestive system. Ingestion of as little as 0.1 grams can be fatal. [6]

Chronic arsenic poisoning is known as arsenicosis. This disorder affects workers in smelters, in populations whose drinking water contains high levels of arsenic (0.3–0.4 ppm), and in patients treated for long periods with arsenic-based pharmaceuticals. Long-term ingestion of arsenic trioxide either in drinking water or as a medical treatment can lead to skin cancer. Reproductive problems (high incidences of miscarriage, low birth weight, congenital deformations) have also been indicated in one study of women exposed to arsenic trioxide dust as employees or neighbours of a copper foundry.

In the U.S., the OSHA 1910.1018 occupational permissible exposure limit for inorganic arsenic compounds in breathing zone air is 0.010 mg/m3.

In Austria, there lived the so-called "arsenic eaters of Styria", who ingested doses far beyond the lethal dose of arsenic trioxide without any apparent harm. Arsenic is thought to enable strenuous work at high altitudes, e.g. in the Alps. [26] [27] [28] [29]

References

  1. ↑ Sun H (2010). Biological Chemistry of Arsenic, Antimony and Bismuth. John Wiley & Sons. p. 295. ISBN   9780470976227. Archived from the original on 14 April 2023. Retrieved 18 March 2023.
  2. ↑ "Trisenox- arsenic trioxide injection, solution". DailyMed. 30 June 2022. Archived from the original on 3 February 2024. Retrieved 3 February 2024.
  3. ↑ "Trisenox EPAR". European Medicines Agency. 10 August 2010. Archived from the original on 16 August 2023. Retrieved 3 February 2024.
  4. 1 2 3 4 5 "Arsenic Trioxide Monograph for Professionals". Drugs.com. Archived from the original on 15 November 2019. Retrieved 15 November 2019.
  5. ↑ World Health Organization (2023). The selection and use of essential medicines 2023: web annex A: World Health Organization model list of essential medicines: 23rd list (2023). Geneva: World Health Organization. hdl: 10665/371090 . WHO/MHP/HPS/EML/2023.02.
  6. 1 2 3 4 5 Grund SC, Hanusch K, Wolf HU. "Arsenic and Arsenic Compounds". Ullmann's Encyclopedia of Industrial Chemistry . Weinheim: Wiley-VCH. doi:10.1002/14356007.a03_113.pub2. ISBN   978-3-527-30673-2.
  7. ↑ Consolidated List of Products Whose Consumption And/or Sale Have Been Banned, Withdrawn, Severely Restricted Or Not Approved by Governments: Chemicals (PDF). United Nations Publications. 2009. p. 24. ISBN   9789211302196.
  8. ↑ Richardson, H. Wayne (2000). "Copper Compounds". Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.a07_567. ISBN   978-3-527-30385-4.
  9. ↑ Gibaud S, Jaouen G (2010). "Arsenic-Based Drugs: From Fowler's Solution to Modern Anticancer Chemotherapy". Medicinal Organometallic Chemistry. Topics in Organometallic Chemistry. Vol. 32. pp. 1–20. Bibcode:2010moc..book....1G. doi:10.1007/978-3-642-13185-1_1. ISBN   978-3-642-13184-4.
  10. ↑ Zhu J, Chen Z, Lallemand-Breitenbach V, de Thé H (September 2002). "How acute promyelocytic leukaemia revived arsenic". Nature Reviews. Cancer. 2 (9): 705–713. doi:10.1038/nrc887. PMID   12209159. S2CID   2815389.
  11. ↑ "Drug Approval Package: Trisenox (Arsenic Trioxide) NDA #21-248". U.S. Food and Drug Administration (FDA). 12 July 2001. Archived from the original on 3 February 2024. Retrieved 3 February 2024.
  12. ↑ "Giant Mine – Northwest Territories Region – Indian and Northern Affairs Canada". Archived from the original on 27 June 2006. Retrieved 28 August 2007.
  13. ↑ P. W. Schenk (1963). "Diarsenic Trioxide". In G. Brauer (ed.). Handbook of Preparative Inorganic Chemistry, 2nd Ed. Vol. 1. NY,NY: Academic Press. p. 600.
  14. ↑ A. Wayne Ruddy, Edgar B. Starkey (1946). "P-Nitrophenylarsonic Acid". Organic Syntheses. 26: 60. doi:10.15227/orgsyn.026.0060.
  15. 1 2 Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. doi:10.1016/C2009-0-30414-6. ISBN   978-0-08-037941-8.
  16. 1 2 3 W. Kwasnik; P.W. Schenk (1963). "4, 10". In G. Brauer (ed.). Handbook of Preparative Inorganic Chemistry, 2nd Ed. Vol. 1. NY,NY: Academic Press. p. 197, 596.
  17. ↑ Tanaka, Susumu; Konishi, Masafumi; Imoto, Hiroaki; Nakamura, Yuma; Ishida, Masatoshi; Furuta, Hiroyuki; Naka, Kensuke (2020). "Fundamental Study on Arsenic(III) Halides (AsX3; X = Br, I) toward the Construction of C3-Symmetrical Monodentate Arsenic Ligands". Inorganic Chemistry. 59 (14): 9587–9593. doi:10.1021/acs.inorgchem.0c00598. PMID   32515950.
  18. ↑ Hempel, Sandra (2013). "James Marsh and the poison panic". The Lancet. 381 (9885): 2247–2248. doi: 10.1016/S0140-6736(13)61472-5 . PMID   23819157. S2CID   36011702.
  19. ↑ Seyferth, Dietmar (2001). "Cadet's Fuming Arsenical Liquid and the Cacodyl Compounds of Bunsen". Organometallics. 20 (8): 1488–1498. doi:10.1021/om0101947.
  20. ↑ Kondinski, Aleksandar; Rasmussen, Maren; Mangelsen, Sebastian; Pienack, Nicole; Simjanoski, Viktor; Näther, Christian; Stares, Daniel L.; Schalley, Christoph A.; Bensch, Wolfgang (2022). "Composition-driven archetype dynamics in polyoxovanadates". Chemical Science. 13 (21): 6397–6412. doi:10.1039/D2SC01004F. PMC   9159092 . PMID   35733899.
  21. ↑ Pertlik, F. (1977). "Die Kristallstruktur von Cu2As3O6CH3COO". Zeitschrift für Kristallographie. 145 (1–2): 35–45. Bibcode:1977ZK....145...35P. doi:10.1524/zkri.1977.145.1-2.35.
  22. ↑ Wells, Alexander Frank (1991). Structural inorganic chemistry (5th ed.). Oxford: Clarendon press. ISBN   0-19-855370-6.
  23. ↑ Holleman AF, Wiberg E (2001). Inorganic Chemistry. San Diego: Academic Press. ISBN   0-12-352651-5.
  24. ↑ Pokrovski, Gleb; Gout, Robert; Schott, Jacques; Zotov, Alexandre; Harrichoury, Jean-Claude (1996). "Thermodynamic properties and stoichiometry of as (III) hydroxide complexes at hydrothermal conditions". Geochimica et Cosmochimica Acta. 60 (5): 739. Bibcode:1996GeCoA..60..737P. doi:10.1016/0016-7037(95)00427-0.
  25. ↑ Yannopoulos, S. N.; Papatheodorou, G. N.; Fytas, G. (1 December 1999). "Light-scattering study of slow and fast dynamics in a strong inorganic glass former". Physical Review B. 60 (22): 15131–15142. Bibcode:1999PhRvB..6015131Y. doi:10.1103/PhysRevB.60.15131.
  26. ↑ "Arsenic Eaters". The New York Times . 26 July 1885. Archived from the original on 27 July 2018. Retrieved 27 July 2018.
  27. ↑ Allesch RM (1959). Arsenik. Seine Geschichte in Österreich. Archiv für vaterländische Geschichte und Topographie. Vol. 54. Klagenfurt: Kleinmayr.
  28. ↑ Przygoda G, Feldmann J, Cullen WR (2001). "The arsenic eaters of Styria: a different picture of people who were chronically exposed to arsenic". Applied Organometallic Chemistry. 15 (6): 457–462. doi:10.1002/aoc.126.
  29. ↑ Whorton JC (2010). The Arsenic Century . Oxford University Press. pp.  270–273. ISBN   978-0-19-960599-6.
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