Sodium Cyanide Acid Or Base
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Names | |||
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IUPAC names Arsenic trihydride | |||
Other names Arseniuretted hydrogen, | |||
Identifiers | |||
CAS Number |
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3D model (JSmol) |
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ChEBI |
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ChEMBL |
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ChemSpider |
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ECHA InfoCard | 100.029.151 | ||
EC Number |
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Gmelin Reference | 599 | ||
KEGG |
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PubChem CID |
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RTECS number |
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UNII |
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United nations number | 2188 | ||
CompTox Dashboard (EPA) |
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InChI
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SMILES
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Properties | |||
Chemical formula | AsHthree | ||
Molar mass | 77.9454g/mol | ||
Appearance | Colourless gas | ||
Aroma | Faint, garlic-like | ||
Density | 4.93grand/L, gas; 1.640k/mL (−64 °C) | ||
Melting point | −111.2 °C (−168.two °F; 162.0 K) | ||
Humid point | −62.five °C (−80.v °F; 210.7 Thousand) | ||
Solubility in water | 0.2g/100mL (xx °C)[1] 0.07g/100mL (25 °C) | ||
Solubility | soluble in chloroform, benzene | ||
Vapor pressure | 14.9atm[i] | ||
Conjugate acid | Arsonium | ||
Structure | |||
Molecular shape | Trigonal pyramidal | ||
Dipole moment | 0.20D | ||
Thermochemistry | |||
Std molar | 223J⋅Thousand−one⋅mol−1 | ||
Std enthalpy of | +66.fourkJ/mol | ||
Hazards | |||
Occupational rubber and health (OHS/OSH): | |||
Main hazards | Explosive, flammable, potential occupational carcinogen[1] | ||
GHS labelling: | |||
Pictograms | |||
Signal word | Danger | ||
Hazard statements | H220, H330, H373, H410 | ||
Precautionary statements | P210, P260, P271, P273, P284, P304+P340, P310, P314, P320, P377, P381, P391, P403, P403+P233, P405, P501 | ||
NFPA 704 (fire diamond) |
4 4 2 | ||
Flash signal | −62 °C (−fourscore °F; 211 K) | ||
Explosive limits | 5.1–78%[1] | ||
Lethal dose or concentration (LD, LC): | |||
LD50 (median dose) | two.vmg/kg (intravenous)[2] | ||
LCl (median concentration) |
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LCLo (lowest published) |
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NIOSH (US health exposure limits): | |||
PEL (Permissible) | TWA 0.05ppm (0.2mg/yard3)[i] | ||
REL (Recommended) | C 0.002mg/m3 [xv-minute][1] | ||
IDLH (Firsthand danger) | 3ppm[1] | ||
Related compounds | |||
Related hydrides | Ammonia; phosphine; stibine; bismuthine | ||
Supplementary data page | |||
Arsine (data page) | |||
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). Nverify (what is Y N ?) Infobox references |
Arsine (IUPAC proper noun: arsane) is an inorganic compound with the formula AsH3. This combustible, pyrophoric, and highly toxic pnictogen hydride gas is 1 of the simplest compounds of arsenic.[4] Despite its lethality, it finds some applications in the semiconductor manufacture and for the synthesis of organoarsenic compounds. The term arsine is normally used to describe a class of organoarsenic compounds of the formula AsHiii−tenRten, where R = aryl or alkyl. For example, As(C6H5)3, called triphenylarsine, is referred to as "an arsine".
General properties [edit]
At its standard state, arsine is a colorless, denser-than-air gas that is slightly soluble in water (twenty% at 20 °C)[1] and in many organic solvents besides.[ citation needed ] Whereas arsine itself is odorless,[v] owing to its oxidation past air, it is possible to odour a slight garlic or fish-like aroma when the compound is present above 0.5ppm.[6] This compound is kinetically stable: at room temperature information technology decomposes only slowly. At temperatures of ca. 230 °C, decomposition to arsenic and hydrogen is sufficiently rapid to be the basis of the Marsh Test (see below). Similar to stibine, the decomposition of arsine is autocatalytic, as the arsenic freed during the reaction acts as a catalyst for the aforementioned reaction.[7] Several other factors, such as humidity, presence of light and certain catalysts (namely alumina) facilitate the charge per unit of decomposition.[viii]
AsHiii is a pyramidal molecule with H–As–H angles of 91.8° and three equivalent As–H bonds, each of i.519 Å length.[9]
Discovery and synthesis [edit]
AsHiii is generally prepared by the reaction of Every bit3+ sources with H− equivalents.[10]
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- 4 AsClthree + 3 NaBHiv → 4 AsHiii + iii NaCl + iii BCl3
Every bit reported in 1775, Carl Scheele reduced arsenic(Iii) oxide with zinc in the presence of acid.[xi] This reaction is a prelude to the Marsh examination, described below.
Alternatively, sources of Asiii− react with protonic reagents to as well produce this gas. Zinc arsenide and sodium arsenide are suitable precursors:[12]
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- ZniiiAs2 + six H+ → two AsHiii + iii Zn2+
- Na3As + 3 HBr → AsHthree + 3 NaBr
Reactions [edit]
The understanding of the chemical backdrop of AsH3 is well developed and can be anticipated based on an average of the behavior of pnictogen counterparts, such as PH3 and SbHiii.
Thermal decomposition [edit]
Typical for a heavy hydride (e.chiliad., SbHiii, HtwoTe, SnH4), AsHthree is unstable with respect to its elements. In other words, AsH3 is stable kinetically but not thermodynamically.
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- 2 AsHiii → 3 H2 + two As
This decomposition reaction is the ground of the Marsh Examination described below, which detects the elemental As.
Oxidation [edit]
Continuing the analogy to SbH3, AsH3 is readily oxidized by full-bodied O2 or the dilute Otwo concentration in air:
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- ii AsH3 + 3 O2 → Equally2O3 + 3 HtwoO
Arsine will react violently in presence of strong oxidizing agents, such as potassium permanganate, sodium hypochlorite, or nitric acid.[8]
Precursor to metallic derivatives [edit]
AsH3 is used as a precursor to metallic complexes of "naked" (or "nearly naked") As. Illustrative is the dimanganese species [(CvH5)Mn(CO)2]iiAsH, wherein the Mn2AsH core is planar.[13]
Gutzeit examination [edit]
A characteristic test for arsenic involves the reaction of AsH3 with Ag+, chosen the Gutzeit test for arsenic.[14] Although this test has become obsolete in analytical chemistry, the underlying reactions further illustrate the affinity of AsH3 for "soft" metallic cations. In the Gutzeit exam, AsH3 is generated past reduction of aqueous arsenic compounds, typically arsenites, with Zn in the presence of HtwoAnd so4. The evolved gaseous AsHiii is and so exposed to AgNO3 either as pulverization or as a solution. With solid AgNO3, AsH3 reacts to produce yellow AgfourAsNO3, whereas AsH3 reacts with a solution of AgNO3 to give blackness Ag3Equally.
Acid-base reactions [edit]
The acidic properties of the As–H bail are often exploited. Thus, AsH3 can be deprotonated:
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- AsH3 + NaNHii → NaAsHtwo + NH3
Upon reaction with the aluminium trialkyls, AsHthree gives the trimeric [RtwoAlAsH2]iii, where R = (CHthree)3C.[xv] This reaction is relevant to the machinery by which GaAs forms from AsHthree (run into below).
AsH3 is generally considered non-bones, but it can be protonated past superacids to give isolable salts of the tetrahedral species [AsHfour]+.[16]
Reaction with halogen compounds [edit]
Reactions of arsine with the halogens (fluorine and chlorine) or some of their compounds, such as nitrogen trichloride, are extremely dangerous and can event in explosions.[viii]
Catenation [edit]
In contrast to the behavior of PH3, AsH3 does not form stable chains, although diarsine (or diarsane) H2As–AsH2, and even triarsane HiiEqually–As(H)–AsH2 have been detected. The diarsine is unstable above −100 °C.
Applications [edit]
Microelectronics applications [edit]
AsHiii is used in the synthesis of semiconducting materials related to microminiaturization and solid-country lasers. Related to phosphorus, arsenic is an n-dopant for silicon and germanium.[8] More than importantly, AsHiii is used to make the semiconductor GaAs by chemical vapor deposition (CVD) at 700–900 °C:
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- Ga(CH3)3 + AsH3 → GaAs + iii CH4
For microelectronic applications, arsine tin can exist provided via a sub-atmospheric gas source. In this blazon of gas package, the arsine is adsorbed on a solid microporous adsorbent within a gas cylinder. This method allows the gas to exist 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. For semiconductor manufacturing, this method is feasible, as processes such as ion implantation operate under high vacuum.
Chemical warfare [edit]
Since before WWII AsH3 was proposed as a possible chemical warfare weapon. The gas is colorless, well-nigh odorless, and ii.5 times denser than air, as required for a blanketing effect sought in chemical warfare. It is likewise lethal in concentrations far lower than those required to smell its garlic-like scent. In spite of these characteristics, arsine was never officially used as a weapon, considering of its loftier flammability and its lower efficacy when compared to the not-flammable culling phosgene. On the other hand, several organic compounds based on arsine, such every bit lewisite (β-chlorovinyldichloroarsine), adamsite (diphenylaminechloroarsine), Clark 1 (diphenylchloroarsine) and Clark 2 (diphenylcyanoarsine) have been finer developed for use in chemical warfare.[17]
Forensic science and the Marsh test [edit]
AsHthree is besides well known in forensic science considering it is a chemical intermediate in the detection of arsenic poisoning. The one-time (but extremely sensitive) Marsh test generates AsH3 in the presence of arsenic.[4] This procedure, published in 1836 past James Marsh,[18] is based upon treating an As-containing sample of a victim's body (typically the breadbasket contents) with As-costless zinc and dilute sulfuric acid: if the sample contains arsenic, gaseous arsine will form. The gas is swept into a glass tube and decomposed past means of heating around 250–300 °C. The presence of Every bit is indicated past formation of a deposit in the heated part of the equipment. On the other hand, the appearance of a blackness mirror deposit in the absurd part of the equipment indicates the presence of antimony (the highly unstable SbH3 decomposes even at low temperatures).
The Marsh examination was widely used by the end of the 19th century and the offset of the 20th; nowadays more sophisticated techniques such as atomic spectroscopy, inductively coupled plasma, and x-ray fluorescence analysis are employed in the forensic field. Though neutron activation analysis was used to observe trace levels of arsenic in the mid 20th century, it has since fallen out of use in modernistic forensics.
Toxicology [edit]
The toxicity of arsine is singled-out from that of other arsenic compounds. The primary road of exposure is by inhalation, although poisoning after skin contact has also been described. Arsine attacks hemoglobin in the ruddy claret cells, causing them to be destroyed by the body.[nineteen] [20]
The get-go signs of exposure, which tin can accept several hours to become apparent, are headaches, vertigo, and nausea, followed by the symptoms of haemolytic anaemia (high levels of unconjugated bilirubin), haemoglobinuria and nephropathy. In severe cases, the damage to the kidneys can be long-lasting.[1]
Exposure to arsine concentrations of 250 ppm is rapidly fatal: concentrations of 25–thirty ppm are fatal for thirty min exposure, and concentrations of x ppm can be fatal at longer exposure times.[three] Symptoms of poisoning appear afterwards 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 to arsenicosis.[ commendation needed ]
Arsine tin cause pneumonia in ii 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 e'er 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 tin can result in death.[21]
It is classified as an extremely hazardous substance in the United states of america 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 field to strict reporting requirements by facilities which produce, store, or employ it in significant quantities.[22]
Occupational exposure limits [edit]
Country | Limit[23] |
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Argentine republic | Confirmed human carcinogen |
Australia | TWA 0.05ppm (0.16 mg/thousand3) |
Belgium | TWA 0.05ppm (0.16 mg/m3) |
Bulgaria | Confirmed man 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.ii mg/grand3) |
France |
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Hungary | TWA 0.2 mg/m3STEL 0.8 mg/m3 |
Japan |
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Jordan | Confirmed human carcinogen |
Mexico | TWA 0.05ppm (0.2 mg/chiliad3) |
Netherlands | MAC-TCG 0.2 mg/grandthree |
New Zealand | TWA 0.05ppm (0.16 mg/k3) |
Norway | TWA 0.003ppm (0.01 mg/mthree) |
Philippines | TWA 0.05ppm (0.16 mg/m3) |
Poland | TWA 0.ii mg/m3 STEL 0.6 mg/thousandiii |
Russian federation | STEL 0.ane mg/miii |
Singapore | Confirmed human carcinogen |
South korea | TWA 0.05ppm (0.2 mg/g3) |
Sweden | TWA 0.02ppm (0.05 mg/chiliadiii) |
Switzerland | MAK-calendar week 0.05ppm (0.xvi mg/m3) |
Thailand | TWA 0.05ppm (0.2 mg/10003) |
Turkey | TWA 0.05ppm (0.2 mg/10003) |
Great britain | TWA 0.05ppm (0.16 mg/thouiii) |
United States | 0.05ppm (0.two mg/miii) |
Vietnam | Confirmed man carcinogen |
See also [edit]
- Cacodylic acid
- Cacodyl oxide
- Devarda's alloy, also used to produce arsine in the lab
- List of highly toxic gases
- Marsh exam, first used to clarify AsH3
- James Marsh, invented in 1836 the test now bearing his proper name
- Stibine
- Scheele's Green, a pigment popularly used in the early on 19th century
References [edit]
- ^ a b c d e f g h i NIOSH Pocket Guide to Chemical Hazards. "#0040". National Institute for Occupational Safety and Health (NIOSH).
- ^ Levvy, G.A. (1946). "The Toxicity of Arsine Administered by Intraperitoneal Injection". British Journal of Pharmacology and Chemotherapy. 1 (iv): 287–290. doi:10.1111/j.1476-5381.1946.tb00049.x. PMC1509744. PMID 19108099.
- ^ a b c "Arsine". Immediately Unsafe to Life or Health Concentrations (IDLH). National Plant for Occupational Prophylactic and Health (NIOSH).
- ^ a b Holleman, A. F.; Wiberg, E. (2001) Inorganic Chemistry Bookish Press: San Diego, ISBN 0-12-352651-5.
- ^ Greaves, Ian; Hunt, Paul (2010). "Ch. 5 Chemical Agents". Responding to Terrorism. A Medical Handbook. Elsevier. pp. 233–344. doi:x.1016/B978-0-08-045043-eight.00005-2. ISBN978-0-08-045043-8.
While arsine itself is odourless, its oxidation by air may produce a slight, garlic-like aroma. However, information technology is lethal in concentrations far lower than those required to produce this scent.
- ^ "Medical Management Guidelines for Arsine (AsHiii)". Bureau for Toxic Substances & Disease Registry.
- ^ Hartman, Robert James (1947). Briscoe, Herman Thompson (ed.). Colloid Chemistry (2 ed.). Houghton Mifflin Visitor. p. 124.
- ^ a b c d Institut National de Recherche et de Sécurité (2000). "Fiche toxicologique nº 53: Trihydrure d'arsenic" (PDF). Archived from the original (PDF) on 2006-11-26. Retrieved 2006-09-06 .
- ^ Nielsen H. H. (1952). "The Molecular Structure of Arsine". The Periodical of Chemical Physics. 20 (12): 1955–1956. Bibcode:1952JChPh..20.1955N. doi:ten.1063/one.1700347.
- ^ Bellama, J. M.; MacDiarmid, A. G. (1968). "Synthesis of the Hydrides of Germanium, Phosphorus, Arsenic, and Antimony past the Solid-Stage Reaction of the Corresponding Oxide with Lithium Aluminum Hydride". Inorganic Chemistry. 7 (10): 2070–2. doi:10.1021/ic50068a024.
- ^ Scheele, Carl Wilhelm (1775) "Om Arsenik och dess syra" Archived 2016-01-05 at the Wayback Auto (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. xxx. (a) This is the only [metal] of all whole- every bit well equally semi-metals that effervesces on digestion with arsenic acrid.) 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 most the opening [of the cylinder], the gases in [the] cylinder ignited with a bang; [the] flame [rushed] towards my manus, which became coated with [a] brown color, ... )
- ^ "Arsine" in Handbook of Preparative Inorganic Chemistry, 2nd ed., One thousand. Brauer (ed.), Academic Printing, 1963, NY, Vol. ane. p. 493.
- ^ Herrmann, Westward. A.; Koumbouris, B.; Schaefer, A.; Zahn, T.; Ziegler, M. L. (1985). "Generation and Complex Stabilization of Arsinidene and Diarsine Fragments by Metallic-Induced Degradation of Monoarsine". Chemische Berichte. 118 (half dozen): 2472–88. doi:ten.1002/cber.19851180624.
- ^ King, Eastward. J. (1959) Qualitative Analysis and Electrolytic Solutions Harcourt, Caryatid, and Earth; New York
- ^ Atwood, D. A.; Cowley, A. H.; Harris, P. R.; Jones, R. A.; Koschmieder, S. U.; Nunn, C. Chiliad.; Atwood, J. L.; Bott, South. G. (1993). "Cyclic Trimeric Hydroxy, Amido, Phosphido, and Arsenido Derivatives of aluminum and gallium. X-ray Structures of [tert-Bu2Ga(m-OH)]3 and [tert-BuiiGa(thou-NHtwo)]3". Organometallics. 12: 24–29. doi:ten.1021/om00025a010.
- ^ R. Minkwitz, R.; Kornath, A.; Sawodny, Due west.; Härtner, H. (1994). "Über die Darstellung der Pnikogenoniumsalze AsHfour +SbF6 −, AsH4 +AsFsix −, SbH4 +SbF6 −". Zeitschrift für Anorganische und Allgemeine Chemie. 620 (four): 753–756. doi:10.1002/zaac.19946200429.
- ^ Suchard, Jeffrey R. (March 2006). "CBRNE — Arsenicals, Arsine". EMedicine. Archived from the original on 2006-06-23. Retrieved 2006-09-05 .
- ^ Marsh, James (1836). "Account of a method of separating small quantities of arsenic from substances with which it may exist mixed". Edinburgh New Philosophical Periodical. 21: 229–236.
- ^ Fowler B. A.; Weissberg J. B. (1974). "Arsine poisoning". New England Periodical of Medicine. 300 (22): 1171–1174. doi:10.1056/NEJM197411282912207. PMID 4608634.
- ^ Hatlelid K. M. (1996). "Reactions of Arsine with Hemoglobine". Journal of Toxicology and Environmental Wellness Office A. 47 (two): 145–157. doi:x.1080/009841096161852. PMID 8598571.
- ^ "Collected Studies on the Pathology of War Gas Poisoning, from the Department of Bacteriology and Pathology, Medical Science Section, Chemic Warfare Service, under the direction of One thousand. C. Winternitz, major, M. C., U. Southward. A. Yale University Press". books.google.com. Yale University printing. 1920. Retrieved 28 September 2022.
- ^ "forty C.F.R.: Appendix A to Role 355—The List of Extremely Hazardous Substances and Their Threshold Planning Quantities" (PDF) (July 1, 2008 ed.). Authorities Press Function. Archived from the original (PDF) on Feb 25, 2012. Retrieved October 29, 2011.
- ^ "Arsine". RTECS. National Institute for Occupational Safety and Health (NIOSH). Archived from the original on 2017-06-08. Retrieved 2017-09-08 .
External links [edit]
- International Chemical Prophylactic Card 0222
- IARC Monograph "Arsenic and Arsenic Compounds"
- NIOSH Pocket Guide to Chemical Hazards
- Institut national de recherche et de sécurité (2000). "Trihydrure d'arsenic." Fiche toxicologique n° 53. Paris:INRS. (in French)
- Data on arsine from Air Liquide
Sodium Cyanide Acid Or Base,
Source: https://en.wikipedia.org/wiki/Arsine
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