Arsine (IUPAC name: arsane) is an inorganic compound with the Chemical formula arsenichydrogen3. This flammable, pyrophoric, and highly toxic pnictogen hydride gas is one of the simplest compounds of arsenic.
General properties
In its standard state arsine is a colorless, denser-than-air gas that is slightly soluble in water (2% at 20 °C)
[ and in many as well. Arsine itself is odorless,]
AsH3 is a trigonal pyramidal molecule with H–As–H angles of 91.8° and three equivalent As–H bonds, each of 1.519 Å length.
Discovery and synthesis
AsH3 is generally prepared by the reaction of As3+ sources with H− equivalents.
- :4 AsCl3 + 3 NaBH4 → 4 AsH3 + 3 NaCl + 3 BCl3
As reported in 1775, Carl Scheele reduced arsenic(III) oxide with zinc in the presence of acid.[Scheele, Carl Wilhelm (1775) "Om Arsenik och dess syra" (On arsenic and its acid), Kongliga Vetenskaps Academiens Handlingar (Proceedings of the Royal Scientific Academy of), 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 gases in the cylinder ignited with a bang; the flame rushed towards my hand, which became coated with a brown color, ... )] This reaction is a prelude to the Marsh test.
Alternatively, sources of As3− react with protonic reagents to also produce this gas. Zinc arsenide and sodium arsenide are suitable precursors:["Arsine" in Handbook of Preparative Inorganic Chemistry, 2nd ed., G. Brauer (ed.), Academic Press, 1963, NY, Vol. 1. p. 493.]
- :Zn3As2 + 6 H+ → 2 AsH3 + 3 Zn2+
- :Na3As + 3 HBr → AsH3 + 3 NaBr
Reactions
The understanding of the chemical properties of AsH3 is well developed and can be anticipated based on an average of the behavior of pnictogen counterparts, such as phosphine and stibine.
Thermal decomposition
Typical for a heavy hydride (e.g., stibine, , ), is unstable with respect to its elements. In other words, it is stable kinetically but not thermodynamically.
- :
This decomposition reaction is the basis of the Marsh test, which detects elemental As.
Oxidation
Continuing the analogy to SbH3, AsH3 is readily oxidation by concentrated O2 or the dilute O2 concentration in air:
- :2 AsH3 + 3 O2 → As2O3 + 3 H2O
Arsine will react violently in presence of strong oxidizing agents, such as potassium permanganate, sodium hypochlorite, or nitric acid.
Precursor to metallic derivatives
AsH3 is used as a precursor to metal complexes of "naked" (or "nearly naked") arsenic. An example is the dimanganese species (C5H5)Mn(CO)22AsH, wherein the Mn2AsH core is planar.
Gutzeit test
A characteristic test for arsenic involves the reaction of AsH3 with Ag+, called the Gutzeit test for arsenic.[King, E. J. (1959) Qualitative Analysis and Electrolytic Solutions Harcourt, Brace, and World; New York] Although this test has become obsolete in analytical chemistry, the underlying reactions further illustrate the affinity of AsH3 for "soft" metal cations. In the Gutzeit test, AsH3 is generated by reduction of aqueous arsenic compounds, typically , with Zn in the presence of H2SO4. The evolved gaseous AsH3 is then exposed to AgNO3 either as powder or as a solution. With solid AgNO3, AsH3 reacts to produce yellow Ag4AsNO3, whereas AsH3 reacts with a solution of AgNO3 to give black Ag3As.
Acid-base reactions
The acidic properties of the As–H bond are often exploited. Thus, AsH3 can be deprotonated:
- :AsH3 + NaNH2 → NaAsH2 + NH3
Upon reaction with the aluminium trialkyls, AsH3 gives the trimeric R2AlAsH23, where R = (CH3)3C.
AsH3 is generally considered non-basic, but it can be protonated by to give isolable salts of the tetrahedral species AsH4+.
Reaction with halogen compounds
Reactions of arsine with the (fluorine and chlorine) or some of their compounds, such as nitrogen trichloride, are extremely dangerous and can result in explosions.
Catenation
In contrast to the behavior of PH3, AsH3 does not form stable chains, although diarsine (or diarsane) H2As–AsH2, and even triarsane H2As–As(H)–AsH2 have been detected. The diarsine is unstable above −100 °C.
Applications
Microelectronics applications
AsH3 is used in the synthesis of semiconducting materials related to microelectronics and solid-state lasers. Related to phosphorus, arsenic is an n-dopant for silicon and germanium.
- :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. For semiconductor manufacturing, this method is feasible, as processes such as ion implantation operate under high vacuum.
Chemical warfare
Since before WWII AsH3 was proposed as a possible chemical warfare weapon. 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 its garlic-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 alternative phosgene. On the other hand, several based on arsine, such as lewisite (β-chlorovinyldichloroarsine), adamsite (diphenylaminechloroarsine), Clark 1 (diphenylchloroarsine) and Clark 2 (diphenylcyanoarsine) have been effectively developed for use in chemical warfare.
Forensic science and the Marsh test
AsH3 is well known in forensic science because it is a chemical intermediate in the detection of arsenic poisoning. The old (but extremely sensitive) Marsh test generates AsH3 in the presence of arsenic.[Holleman, A. F.; Wiberg, E. (2001) Inorganic Chemistry Academic Press: San Diego, .] This procedure, published in 1836 by James Marsh,
The Marsh test was widely used by the end of the 19th century and the start 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 detect trace levels of arsenic in the mid 20th century, it has since fallen out of use in modern forensics.
Toxicology
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 attacks hemoglobin in the red blood cells, causing them to be destroyed by the body.
The first signs of exposure, which can take several hours to become apparent, are , 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 can be long-lasting.[
]
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.
Arsine can cause pneumonia in two different ways; in the first, extensive edema of the acute stage becomes diffusely infiltrated with leucocytes and the edema may become a cellular exudate over large areas of the lung, with little anatomical relationship to the bronchi. In the second, the smaller bronchi and bronchioles may become ringed with leucocytes and their epithelium degenerated and walls penetrated, each becoming the center of a small nodule of pneumonia. Either case can result in death.
It is classified as an 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.
Occupational exposure limits
See also
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Cacodylic acid
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Cacodyl oxide
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Devarda's alloy, also used to produce arsine in the lab
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List of highly toxic gases
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Scheele's Green, a pigment popularly used in the early 19th century
External links
