Английская Википедия:Arsine

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Arsine (IUPAC name: arsane) is an inorganic compound with the formula AsH3. This flammable, pyrophoric, and highly toxic pnictogen hydride gas is one of the simplest compounds of arsenic.[1] Despite its lethality, it finds some applications in the semiconductor industry and for the synthesis of organoarsenic compounds. The term arsine is commonly used to describe a class of organoarsenic compounds of the formula AsH3−xRx, where R = aryl or alkyl. For example, As(C6H5)3, called triphenylarsine, is referred to as "an arsine".

General properties

At its standard state, arsine is a colorless, denser-than-air gas that is slightly soluble in water (20% at 20 °C)[2] and in many organic solvents as well.Шаблон:Citation needed Whereas arsine itself is odorless,[3] owing to its oxidation by air, it is possible to smell a slight garlic or fish-like scent when the compound is present above 0.5Шаблон:Nbspppm.[4] 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 the Marsh test. Similar to stibine, the decomposition of arsine is autocatalytic, as the arsenic freed during the reaction acts as a catalyst for the same reaction.[5] Several other factors, such as humidity, presence of light and certain catalysts (namely alumina) facilitate the rate of decomposition.[6]

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.[7]

Discovery and synthesis

AsH3 is generally prepared by the reaction of As3+ sources with H equivalents.[8]

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.[9] 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:[10]

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 PH3 and SbH3.

Thermal decomposition

Typical for a heavy hydride (e.g., SbH3, H2Te, SnH4), AsH3 is unstable with respect to its elements. In other words, AsH3 is stable kinetically but not thermodynamically.

2 AsH3 → 3 H2 + 2 As

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

Oxidation

Continuing the analogy to SbH3, AsH3 is readily oxidized 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.[6]

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)2]2AsH, wherein the Mn2AsH core is planar.[11]

Gutzeit test

A characteristic test for arsenic involves the reaction of AsH3 with Ag+, called the Gutzeit test for arsenic.[12] 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 arsenites, 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 [R2AlAsH2]3, where R = (CH3)3C.[13] This reaction is relevant to the mechanism by which GaAs forms from AsH3 (see below).

AsH3 is generally considered non-basic, but it can be protonated by superacids to give isolable salts of the tetrahedral species [AsH4]+.[14]

Reaction with halogen compounds

Reactions of arsine with the halogens (fluorine and chlorine) or some of their compounds, such as nitrogen trichloride, are extremely dangerous and can result in explosions.[6]

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.[6] More importantly, AsH3 is used to make the semiconductor GaAs by chemical vapor deposition (CVD) at 700–900 °C:

Ga(CH3)3 + AsH3 → GaAs + 3 CH4

For microelectronic applications, arsine can be provided via a sub-atmospheric gas source. 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 organic compounds 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.[15]

Forensic science and the Marsh test

Шаблон:Main AsH3 is also 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.[1] This procedure, published in 1836 by James Marsh,[16] is based upon treating an As-containing sample of a victim's body (typically the stomach contents) with As-free zinc and dilute sulfuric 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 the cool part of the equipment indicates the presence of antimony (the highly unstable SbH3 decomposes 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 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

Шаблон:For

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.[17][18]

The first signs of exposure, which can take 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.[2]

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.[19] 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 to arsenicosis.Шаблон: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.[20]

Файл:Pneumonia forming around bronchioles.png
Pneumonia forming

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.[21]

Occupational exposure limits

Country Limit[22]
Argentina Confirmed human carcinogen
Australia TWA 0.05Шаблон:Nbspppm (0.16 mg/m3)
Belgium TWA 0.05Шаблон:Nbspppm (0.16 mg/m3)
Bulgaria Confirmed human carcinogen
British Columbia, Canada TWA 0.005Шаблон:Nbspppm (0.02 mg/m3)
Colombia Confirmed human carcinogen
Denmark TWA 0.01Шаблон:Nbspppm (0.03 mg/m3)
Egypt TWA 0.05Шаблон:Nbspppm (0.2 mg/m3)
France Шаблон:Unbulleted list
Hungary TWA 0.2 mg/m3STEL 0.8 mg/m3
Japan Шаблон:Unbulleted list
Jordan Confirmed human carcinogen
Mexico TWA 0.05Шаблон:Nbspppm (0.2 mg/m3)
Netherlands MAC-TCG 0.2 mg/m3
New Zealand TWA 0.05Шаблон:Nbspppm (0.16 mg/m3)
Norway TWA 0.003Шаблон:Nbspppm (0.01 mg/m3)
Philippines TWA 0.05Шаблон:Nbspppm (0.16 mg/m3)
Poland TWA 0.2 mg/m3 STEL 0.6 mg/m3
Russia STEL 0.1 mg/m3
Singapore Confirmed human carcinogen
South Korea TWA 0.05Шаблон:Nbspppm (0.2 mg/m3)
Sweden TWA 0.02Шаблон:Nbspppm (0.05 mg/m3)
Switzerland MAK-week 0.05Шаблон:Nbspppm (0.16 mg/m3)
Thailand TWA 0.05Шаблон:Nbspppm (0.2 mg/m3)
Turkey TWA 0.05Шаблон:Nbspppm (0.2 mg/m3)
United Kingdom TWA 0.05Шаблон:Nbspppm (0.16 mg/m3)
United States 0.05Шаблон:Nbspppm (0.2 mg/m3)
Vietnam Confirmed human carcinogen

See also

References

Шаблон:Reflist

External links

Шаблон:Arsenic compounds Шаблон:Arsenides Шаблон:Hydrides by group Шаблон:Chemical agents

Шаблон:Authority control

  1. 1,0 1,1 Holleman, A. F.; Wiberg, E. (2001) Inorganic Chemistry Academic Press: San Diego, Шаблон:ISBN.
  2. 2,0 2,1 Ошибка цитирования Неверный тег <ref>; для сносок PGCH не указан текст
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  9. Scheele, Carl Wilhelm (1775) "Om Arsenik och dess syra" Шаблон:Webarchive (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, ... )
  10. "Arsine" in Handbook of Preparative Inorganic Chemistry, 2nd ed., G. Brauer (ed.), Academic Press, 1963, NY, Vol. 1. p. 493.
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  12. King, E. J. (1959) Qualitative Analysis and Electrolytic Solutions Harcourt, Brace, and World; New York
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