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Arsine

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Not to be confused witharcsineorursine.
Arsine
Skeletal formula of arsine
Ball-and-stick model of arsine
Ball-and-stick model of arsine
Spacefill model of arsine
Spacefill model of arsine
Arsenic, As
Hydrogen, H
Names
IUPAC names
Arsenic trihydride
Arsane
Trihydridoarsenic
Other names
Arseniuretted hydrogen,
Arsenous hydride,
Hydrogen arsenide
Arsenic hydride
Identifiers
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.029.151Edit this at Wikidata
EC Number
  • 232-066-3
599
KEGG
RTECS number
  • CG6475000
UNII
UN number 2188
  • InChI=1S/AsH3/h1H3checkY
    Key: RBFQJDQYXXHULB-UHFFFAOYSA-NcheckY
  • InChI=1/AsH3/h1H3
    Key: RBFQJDQYXXHULB-UHFFFAOYAH
  • [AsH3]
Properties
AsH3
Molar mass 77.9454g/mol
Appearance Colourless gas
Odor Faint, garlic-like
Density 4.93g/L, gas; 1.640g/mL (−64 °C)
Melting point −111.2 °C (−168.2 °F; 162.0 K)
Boiling point −62.5 °C (−80.5 °F; 210.7 K)
0.2g/100mL (20 °C)[1]
0.07g/100mL (25 °C)
Solubility soluble inchloroform,benzene
Vapor pressure 14.9atm[1]
Conjugate acid Arsonium
Structure
Trigonal pyramidal
0.20D
Thermochemistry
223J⋅K−1⋅mol−1
+66.4kJ/mol
Hazards
Occupational safety and health(OHS/OSH):
Main hazards
 Extremely toxic, explosive, flammable, potential occupational carcinogen[1]
GHSlabelling:
GHS02: FlammableGHS06: ToxicGHS08: Health hazardGHS09: Environmental hazard
Danger
H220,H330,H373,H410
P210,P260,P271,P273,P284,P304+P340,P310,P314,P320,P377,P381,P391,P403,P403+P233,P405,P501
NFPA 704(fire diamond)
NFPA 704 four-colored diamondHealth 4: Very short exposure could cause death or major residual injury. E.g. VX gasFlammability 4: Will rapidly or completely vaporize at normal atmospheric pressure and temperature, or is readily dispersed in air and will burn readily. Flash point below 23 °C (73 °F). E.g. propaneInstability 2: Undergoes violent chemical change at elevated temperatures and pressures, reacts violently with water, or may form explosive mixtures with water. E.g. white phosphorusSpecial hazards (white): no code
4
4
2
Flash point −62 °C (−80 °F; 211 K)
Explosive limits 5.1–78%[1]
Lethal doseor concentration (LD, LC):
2.5mg/kg (intravenous)[2]
  • 120ppm (rat, 10min)
  • 77ppm (mouse, 10min)
  • 201ppm (rabbit, 10min)
  • 108ppm (dog, 10min)[3]
  • 250ppm (human, 30min)
  • 300ppm (human, 5min)
  • 25ppm (human, 30min)[3]
NIOSH(US health exposure limits):
PEL(Permissible)
 TWA 0.05ppm (0.2mg/m3)[1]
REL(Recommended)
 C 0.002mg/m3[15-minute][1]
IDLH(Immediate danger)
 3ppm[1]
Related compounds
Relatedhydrides
 Ammonia;phosphine;stibine;bismuthine
Supplementary data page
Arsine (data page)
Except where otherwise noted, data are given for materials in theirstandard state(at 25 °C [77 °F], 100 kPa).

Arsine(IUPACname:arsane) is aninorganic compoundwith theformulaAsH3.This flammable,pyrophoric,and highly toxicpnictogen hydridegas is one of the simplest compounds ofarsenic.[4]Despite its lethality, it finds some applications in the semiconductor industry and for the synthesis oforganoarsenic compounds.The termarsineis commonly used to describe a class oforganoarseniccompounds of the formula AsH3−xRx,where R =aryloralkyl.For example, As(C6H5)3,calledtriphenylarsine,is referred to as "an arsine".

General properties[edit]

In its standard state arsine is a colorless, denser-than-air gas that is slightly soluble inwater(20% at 20 °C)[1]and in manyorganic solventsas well.[citation needed]Arsine itself is odorless,[5]but it oxidizes in air and this creates a slightgarlicor fish-like scent when the compound is present above 0.5ppm.[6]This compound is kinetically stable: at room temperature it decomposes only slowly. At temperatures of ca. 230 °C, decomposition to arsenic and hydrogen is sufficiently rapid to be the basis of theMarsh testfor arsenic presence. Similar tostibine,the decomposition of arsine is autocatalytic, as the arsenic freed during the reaction acts as a catalyst for the same reaction.[7]Several other factors, such ashumidity,presence of light and certaincatalysts(namelyalumina) facilitate the rate of decomposition.[8]

AsH3is atrigonal pyramidalmolecule with H–As–H angles of 91.8° and three equivalent As–H bonds, each of 1.519Ålength.[9]

Discovery and synthesis[edit]

AsH3is generally prepared by the reaction of As3+sources with H−equivalents.[10]

4 AsCl3+ 3 NaBH4→ 4 AsH3+ 3 NaCl + 3 BCl3

As reported in 1775,Carl Scheelereducedarsenic(III) oxidewith zinc in the presence of acid.[11]This reaction is a prelude to the Marsh test.

Alternatively, sources of As3−react with protonic reagents to also produce this gas. Zinc arsenide andsodium arsenideare suitable precursors:[12]

Zn3As2+ 6 H+→ 2 AsH3+ 3 Zn2+
Na3As + 3 HBr → AsH3+ 3 NaBr

Reactions[edit]

The understanding of the chemical properties of AsH3is well developed and can be anticipated based on an average of the behavior ofpnictogencounterparts, such asPH3andSbH3.

Thermal decomposition[edit]

Typical for a heavy hydride (e.g.,SbH3,H2Te,SnH4),AsH3is unstable with respect to its elements. In other words, it is stable kinetically but not thermodynamically.

2AsH3→ 3H2+ 2As

This decomposition reaction is the basis of the Marsh test, which detects elemental As.

Oxidation[edit]

Continuing the analogy to SbH3,AsH3is readilyoxidizedby concentrated O2or the dilute O2concentration in air:

2 AsH3+ 3 O2→ As2O3+ 3 H2O

Arsine will react violently in presence of strong oxidizing agents, such aspotassium permanganate,sodium hypochlorite,ornitric acid.[8]

Precursor to metallic derivatives[edit]

AsH3is used as a precursor to metal complexes of "naked" (or "nearly naked" ) arsenic. An example is the dimanganese species [(C5H5)Mn(CO)2]2AsH, wherein the Mn2AsH core is planar.[13]

Gutzeit test[edit]

A characteristic test for arsenic involves the reaction of AsH3with Ag+,called the Gutzeit test for arsenic.[14]Although this test has become obsolete inanalytical chemistry,the underlying reactions further illustrate the affinity of AsH3for "soft" metal cations. In the Gutzeit test, AsH3is generated by reduction of aqueous arsenic compounds, typicallyarsenites,with Zn in the presence of H2SO4.The evolved gaseous AsH3is then exposed to AgNO3either as powder or as a solution. With solid AgNO3,AsH3reacts to produce yellow Ag4AsNO3,whereas AsH3reacts with a solution of AgNO3to give black Ag3As.

Acid-base reactions[edit]

The acidic properties of the As–H bond are often exploited. Thus, AsH3can be deprotonated:

AsH3+ NaNH2→ NaAsH2+ NH3

Upon reaction with the aluminium trialkyls, AsH3gives the trimeric [R2AlAsH2]3,where R = (CH3)3C.[15]This reaction is relevant to the mechanism by which GaAs forms from AsH3(see below).

AsH3is generally considered non-basic, but it can be protonated bysuperacidsto give isolable salts of the tetrahedral species [AsH4]+.[16]

Reaction with halogen compounds[edit]

Reactions of arsine with thehalogens(fluorineandchlorine) or some of their compounds, such asnitrogen trichloride,are extremely dangerous and can result in explosions.[8]

Catenation[edit]

In contrast to the behavior of PH3,AsH3does not form stable chains, although diarsine (or diarsane) H2As–AsH2,and even triarsane H2As–As(H)–AsH2have been detected. The diarsine is unstable above −100 °C.

Applications[edit]

Microelectronics applications[edit]

AsH3is used in the synthesis of semiconducting materials related tomicroelectronicsandsolid-state lasers.Related tophosphorus,arsenic is ann-dopantfor silicon and germanium.[8]More importantly, AsH3is used to make thesemiconductorGaAsbychemical vapor deposition (CVD)at 700–900 °C:

Ga(CH3)3+ AsH3→ GaAs + 3 CH4

For microelectronic applications, arsine can be provided by a sub-atmospheric gas source (a source that supplies less than atmospheric pressure). In this type of gas package, the arsine is adsorbed on a solid microporous adsorbent inside a gas cylinder. This method allows the gas to be stored without pressure, significantly reducing the risk of an arsine gas leak from the cylinder. With this apparatus, arsine is obtained by applying vacuum to the gas cylinder valve outlet. Forsemiconductor manufacturing,this method is feasible, as processes such as ion implantation operate under high vacuum.

Chemical warfare[edit]

Since beforeWWIIAsH3was proposed as a possiblechemical warfareweapon. The gas is colorless, almost odorless, and 2.5 times denser than air, as required for a blanketing effect sought in chemical warfare. It is also lethal in concentrations far lower than those required to smell itsgarlic-like scent. In spite of these characteristics, arsine was never officially used as a weapon, because of its high flammability and its lower efficacy when compared to the non-flammable alternativephosgene.On the other hand, severalorganic compoundsbased on arsine, such aslewisite(β-chlorovinyldichloroarsine),adamsite(diphenylaminechloroarsine),Clark 1(diphenylchloroarsine) and Clark 2 (diphenylcyanoarsine) have been effectively developed for use in chemical warfare.[17]

Forensic science and the Marsh test[edit]

Main article:Marsh test

AsH3is well known inforensic sciencebecause it is a chemical intermediate in the detection of arsenic poisoning. The old (but extremely sensitive)Marsh testgenerates AsH3in the presence of arsenic.[4]This procedure, published in 1836 byJames Marsh,[18]is based upon treating an As-containing sample of a victim's body (typically the stomach contents) with As-freezincand dilutesulfuric acid:if the sample contains arsenic, gaseous arsine will form. The gas is swept into a glass tube and decomposed by means of heating around 250–300 °C. The presence of As is indicated by formation of a deposit in the heated part of the equipment. On the other hand, the appearance of a black mirror deposit in thecoolpart of the equipment indicates the presence of antimony (the highly unstableSbH3decomposes even at low temperatures).

The Marsh test was widely used by the end of the 19th century and the start of the 20th; nowadays more sophisticated techniques such asatomic spectroscopy,inductively coupled plasma,andx-ray fluorescenceanalysis are employed in the forensic field. Thoughneutron activationanalysis was used to detect trace levels of arsenic in the mid 20th century, it has since fallen out of use in modern forensics.

Toxicology[edit]

For the toxicology of other arsenic compounds, seeArsenic,Arsenic trioxide,andArsenic poisoning.

The toxicity of arsine is distinct from that of other arsenic compounds. The main route of exposure is by inhalation, although poisoning after skin contact has also been described. Arsine attackshemoglobinin thered blood cells,causing them to be destroyed by the body.[19][20]

The first signs of exposure, which can take several hours to become apparent, areheadaches,vertigo,andnausea,followed by the symptoms ofhaemolytic anaemia(high levels of unconjugatedbilirubin),haemoglobinuriaandnephropathy.In severe cases, the damage to thekidneyscan be long-lasting.[1]

Exposure to arsine concentrations of 250 ppm is rapidly fatal: concentrations of 25–30 ppm are fatal for 30 min exposure, and concentrations of 10 ppm can be fatal at longer exposure times.[3]Symptoms of poisoning appear after exposure to concentrations of 0.5 ppm. There is little information on the chronic toxicity of arsine, although it is reasonable to assume that, in common with other arsenic compounds, a long-term exposure could lead toarsenicosis.[citation needed]

Arsine can cause pneumonia in two different ways either the "extensive edema of the acute stage may become diffusely infiltrated with polymorphonuclear leucocytes, and the edema may change to ringed with leucocytes, their epithelium degenerated, their walls infiltrated, and each bronchiole the center of a small focus or nodule of pneumonic consolidation", and In the second Case "the areas involved are practically always the anterior tips of the middle and upper lobes, while the posterior portions of these lobes and the whole of the lower lobes present an air-containing and emphysematous condition, sometimes with slight congestion, sometimes with none." which can result in death.[21]

Pneumonia forming

It is classified as anextremely hazardous substancein 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.[22]

Occupational exposure limits[edit]

Country Limit[23]
Argentina Confirmed human carcinogen
Australia TWA0.05ppm (0.16 mg/m3)
Belgium TWA 0.05ppm (0.16 mg/m3)
Bulgaria Confirmed human carcinogen
British Columbia, Canada TWA 0.005ppm (0.02 mg/m3)
Colombia Confirmed human carcinogen
Denmark TWA 0.01ppm (0.03 mg/m3)
Egypt TWA 0.05ppm (0.2 mg/m3)
France
  • VME 0.05ppm (0.2 mg/m3)
  • VLE 0.2ppm (0.8 mg/m3)
Hungary TWA 0.2 mg/m3STEL 0.8 mg/m3
Japan
  • Occupational exposure limit 0.01ppm (0.032 mg/m3)
  • Continuous 0.1ppm (0.32 mg/m3)
Jordan Confirmed human carcinogen
Mexico TWA 0.05ppm (0.2 mg/m3)
Netherlands MAC-TCG 0.2 mg/m3
New Zealand TWA 0.05ppm (0.16 mg/m3)
Norway TWA 0.003ppm (0.01 mg/m3)
Philippines TWA 0.05ppm (0.16 mg/m3)
Poland TWA 0.2 mg/m3STEL 0.6 mg/m3
Russia STEL 0.1 mg/m3
Singapore Confirmed human carcinogen
South Korea TWA 0.05ppm (0.2 mg/m3)
Sweden TWA 0.02ppm (0.05 mg/m3)
Switzerland MAK-week 0.05ppm (0.16 mg/m3)
Thailand TWA 0.05ppm (0.2 mg/m3)
Turkey TWA 0.05ppm (0.2 mg/m3)
United Kingdom TWA 0.05ppm (0.16 mg/m3)
United States 0.05ppm (0.2 mg/m3)
Vietnam Confirmed human carcinogen

See also[edit]

References[edit]

  1. ^abcdefghiNIOSH Pocket Guide to Chemical Hazards."#0040".National Institute for Occupational Safety and Health(NIOSH).
  2. ^Levvy, G.A. (1946)."The Toxicity of Arsine Administered by Intraperitoneal Injection".British Journal of Pharmacology and Chemotherapy.1(4): 287–290.doi:10.1111/j.1476-5381.1946.tb00049.x.PMC1509744.PMID19108099.
  3. ^abc"Arsine".Immediately Dangerous to Life or Health Concentrations (IDLH).National Institute for Occupational Safety and Health(NIOSH).
  4. ^abHolleman, A. F.; Wiberg, E. (2001)Inorganic ChemistryAcademic Press: San Diego,ISBN0-12-352651-5.
  5. ^Greaves, Ian; Hunt, Paul (2010). "Ch. 5 Chemical Agents".Responding to Terrorism. A Medical Handbook.Elsevier. pp. 233–344.doi:10.1016/B978-0-08-045043-8.00005-2.ISBN978-0-08-045043-8.While arsine itself is odourless, its oxidation by air may produce a slight, garlic-like scent. However, it is lethal in concentrations far lower than those required to produce this smell.
  6. ^"Medical Management Guidelines for Arsine (AsH3) ".Agency for Toxic Substances & Disease Registry. Archived fromthe originalon January 24, 2012.
  7. ^Hartman, Robert James (1947). Briscoe, Herman Thompson (ed.).Colloid Chemistry(2 ed.). Houghton Mifflin Company. p. 124.
  8. ^abcdInstitut National de Recherche et de Sécurité (2000).Fiche toxicologique nº 53: Trihydrure d'arsenic(PDF)(Report) (in French). Archived fromthe original(PDF)on 2006-11-26.Retrieved2006-09-06.
  9. ^Nielsen, H. H. (1952). "The Molecular Structure of Arsine".The Journal of Chemical Physics.20(12): 1955–1956.Bibcode:1952JChPh..20.1955N.doi:10.1063/1.1700347.
  10. ^Bellama, J. M.; MacDiarmid, A. G. (1968). "Synthesis of the Hydrides of Germanium, Phosphorus, Arsenic, and Antimony by the Solid-Phase Reaction of the Corresponding Oxide with Lithium Aluminum Hydride".Inorganic Chemistry.7(10): 2070–2.doi:10.1021/ic50068a024.
  11. ^Scheele, Carl Wilhelm (1775)"Om Arsenik och dess syra"Archived2016-01-05 at theWayback Machine(On arsenic and its acid),Kongliga Vetenskaps Academiens Handlingar(Proceedings of the Royal Scientific Academy [of Sweden]),36:263-294. From p. 290:"Med Zinck. 30. (a) Denna år den endaste af alla så hela som halfva Metaller, som i digestion met Arsenik-syra effervescerar."(With zinc. 30. (a) This is the only [metal] of all whole- as well as semi-metals that effervesces on digestion with arsenic acid.) Scheele collected the arsine and put a mixture of arsine and air into a cylinder. From p. 291:"3:0, Då et tåndt ljus kom når o̊pningen, tåndes luften i kolfven med en småll, lågan for mot handen, denna blef o̊fvedragen med brun fårg,..."(3:0, Then as [the] lit candle came near the opening [of the cylinder], the gases in [the] cylinder ignited with a bang; [the] flame [rushed] towards my hand, which became coated with [a] brown color,... )
  12. ^"Arsine" inHandbook of Preparative Inorganic Chemistry,2nd ed., G. Brauer (ed.), Academic Press, 1963, NY, Vol. 1. p. 493.
  13. ^Herrmann, W. A.; Koumbouris, B.; Schaefer, A.; Zahn, T.; Ziegler, M. L. (1985). "Generation and Complex Stabilization of Arsinidene and Diarsine Fragments by Metal-Induced Degradation of Monoarsine".Chemische Berichte.118(6): 2472–88.doi:10.1002/cber.19851180624.
  14. ^King, E. J. (1959)Qualitative Analysis and Electrolytic SolutionsHarcourt, Brace, and World; New York
  15. ^Atwood, D. A.; Cowley, A. H.; Harris, P. R.; Jones, R. A.; Koschmieder, S. U.; Nunn, C. M.; Atwood, J. L.; Bott, S. G. (1993). "Cyclic Trimeric Hydroxy, Amido, Phosphido, and Arsenido Derivatives of aluminum and gallium. X-ray Structures of [tert-Bu2Ga(m-OH)]3and [tert-Bu2Ga(m-NH2)]3".Organometallics.12:24–29.doi:10.1021/om00025a010.
  16. ^R. Minkwitz, R.; Kornath, A.; Sawodny, W.; Härtner, H. (1994). "Über die Darstellung der Pnikogenoniumsalze AsH4+SbF6−,AsH4+AsF6−,SbH4+SbF6−".Zeitschrift für Anorganische und Allgemeine Chemie(in German).620(4): 753–756.doi:10.1002/zaac.19946200429.
  17. ^Suchard, Jeffrey R. (March 2006)."CBRNE — Arsenicals, Arsine".EMedicine.Archivedfrom the original on 2006-06-23.Retrieved2006-09-05.
  18. ^Marsh, James (1836)."Account of a method of separating small quantities of arsenic from substances with which it may be mixed".Edinburgh New Philosophical Journal.21:229–236.
  19. ^Fowler B. A.; Weissberg J. B. (1974). "Arsine poisoning".New England Journal of Medicine.300(22): 1171–1174.doi:10.1056/NEJM197411282912207.PMID4608634.
  20. ^Hatlelid K. M. (1996). "Reactions of Arsine with Hemoglobine".Journal of Toxicology and Environmental Health Part A.47(2): 145–157.Bibcode:1996JTEHA..47..145H.doi:10.1080/009841096161852.PMID8598571.
  21. ^"Collected Studies on the Pathology of War Gas Poisoning, from the Department of Bacteriology and Pathology, Medical Science Section, Chemical Warfare Service, under the direction of M. C. Winternitz, major, M. C., U. S. A. Yale University Press".books.google.com.Yale University press. 1920.Retrieved28 September2022.
  22. ^40 C.F.R.: Appendix A to Part 355—The List of Extremely Hazardous Substances and Their Threshold Planning Quantities(PDF)(Report) (July 1, 2008 ed.).Government Printing Office.Archived fromthe original(PDF)on February 25, 2012.RetrievedOctober 29,2011.
  23. ^"Arsine".RTECS.National Institute for Occupational Safety and Health (NIOSH).Archivedfrom the original on 2017-06-08.Retrieved2017-09-08.

External links[edit]

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