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Names | |||
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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 | 100.029.151 | ||
EC Number |
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599 | |||
KEGG | |||
PubChem CID | |||
RTECS number |
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UNII | |||
UN number | 2188 | ||
CompTox Dashboard (EPA) | |||
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Properties | |||
AsH3 | |||
Molar mass | 77.9454 g/mol | ||
Appearance | Colourless gas | ||
Odor | Faint, garlic-like | ||
Density | 4.93 g/L, gas; 1.640 g/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) | ||
0.2 g/100 mL (20 °C) [1] 0.07 g/100 mL (25 °C) | |||
Solubility | soluble in chloroform, benzene | ||
Vapor pressure | 14.9 atm [1] | ||
Conjugate acid | Arsonium | ||
Structure | |||
Trigonal pyramidal | |||
0.20 D | |||
Thermochemistry | |||
Std molar entropy (S⦵298) | 223 J⋅K−1⋅mol−1 | ||
Std enthalpy of formation (ΔfH⦵298) | +66.4 kJ/mol | ||
Hazards | |||
Occupational safety and health (OHS/OSH): | |||
Main hazards | Extremely toxic, explosive, flammable, potential occupational carcinogen [1] | ||
GHS labelling: | |||
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) | |||
Flash point | −62 °C (−80 °F; 211 K) | ||
Explosive limits | 5.1–78% [1] | ||
Lethal dose or concentration (LD, LC): | |||
LD50 (median dose) | 2.5 mg/kg (intravenous) [2] | ||
LC50 (median concentration) |
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LCLo (lowest published) |
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NIOSH (US health exposure limits): | |||
PEL (Permissible) | TWA 0.05 ppm (0.2 mg/m3) [1] | ||
REL (Recommended) | C 0.002 mg/m3 [15-minute] [1] | ||
IDLH (Immediate danger) | 3 ppm [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). |
Arsine (IUPAC name: arsane) is an inorganic compound with the formula As H 3. This flammable, pyrophoric, and highly toxic pnictogen hydride gas is one of the simplest compounds of arsenic. [4] 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".
At its standard state, arsine is a colorless, denser-than-air gas that is slightly soluble in water (20% at 20 °C) [1] and in many organic solvents as well.[ citation needed ] Whereas arsine itself is odorless, [5] owing to its oxidation by air, it is possible to smell a slight garlic or fish-like scent when the compound is present above 0.5 ppm. [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 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. [7] Several other factors, such as humidity, presence of light and certain catalysts (namely alumina) facilitate the rate of decomposition. [8]
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. [9]
AsH3 is generally prepared by the reaction of As3+ sources with H− equivalents. [10]
As reported in 1775, Carl Scheele reduced arsenic(III) oxide with 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 and sodium arsenide are suitable precursors: [12]
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.
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.
This decomposition reaction is the basis of the Marsh test, which detects the elemental As.
Continuing the analogy to SbH3, AsH3 is readily oxidized by concentrated O2 or the dilute O2 concentration in air:
Arsine will react violently in presence of strong oxidizing agents, such as potassium permanganate, sodium hypochlorite, or nitric acid. [8]
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. [13]
A characteristic test for arsenic involves the reaction of AsH3 with Ag+, called 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" 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.
The acidic properties of the As–H bond are often exploited. Thus, AsH3 can be deprotonated:
Upon reaction with the aluminium trialkyls, AsH3 gives the trimeric [R2AlAsH2]3, where R = (CH3)3C. [15] 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]+. [16]
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. [8]
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.
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. [8] More importantly, AsH3 is used to make the semiconductor GaAs by chemical vapor deposition (CVD) at 700–900 °C:
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.
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. [17]
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. [4] This procedure, published in 1836 by James Marsh, [18] 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.
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. [19] [20]
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. [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 to arsenicosis.[ 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]
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. [22]
Country | Limit [23] |
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Argentina | Confirmed human carcinogen |
Australia | TWA 0.05 ppm (0.16 mg/m3) |
Belgium | TWA 0.05 ppm (0.16 mg/m3) |
Bulgaria | Confirmed human carcinogen |
British Columbia, Canada | TWA 0.005 ppm (0.02 mg/m3) |
Colombia | Confirmed human carcinogen |
Denmark | TWA 0.01 ppm (0.03 mg/m3) |
Egypt | TWA 0.05 ppm (0.2 mg/m3) |
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 0.05 ppm (0.2 mg/m3) |
Netherlands | MAC-TCG 0.2 mg/m3 |
New Zealand | TWA 0.05 ppm (0.16 mg/m3) |
Norway | TWA 0.003 ppm (0.01 mg/m3) |
Philippines | TWA 0.05 ppm (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 0.05 ppm (0.2 mg/m3) |
Sweden | TWA 0.02 ppm (0.05 mg/m3) |
Switzerland | MAK-week 0.05 ppm (0.16 mg/m3) |
Thailand | TWA 0.05 ppm (0.2 mg/m3) |
Turkey | TWA 0.05 ppm (0.2 mg/m3) |
United Kingdom | TWA 0.05 ppm (0.16 mg/m3) |
United States | 0.05 ppm (0.2 mg/m3) |
Vietnam | Confirmed human carcinogen |
In chemistry, a hydride is formally the anion of hydrogen (H−), a hydrogen atom with two electrons. The term is applied loosely. At one extreme, all compounds containing covalently bound H atoms are called hydrides: water (H2O) is a hydride of oxygen, ammonia is a hydride of nitrogen, etc. For inorganic chemists, hydrides refer to compounds and ions in which hydrogen is covalently attached to a less electronegative element. In such cases, the H centre has nucleophilic character, which contrasts with the protic character of acids. The hydride anion is very rarely observed.
Silane (Silicane) is an inorganic compound with chemical formula SiH4. It is a colourless, pyrophoric, toxic gas with a sharp, repulsive, pungent smell, somewhat similar to that of acetic acid. Silane is of practical interest as a precursor to elemental silicon. Silane with alkyl groups are effective water repellents for mineral surfaces such as concrete and masonry. Silanes with both organic and inorganic attachments are used as coupling agents. Silanes are commonly used to apply coatings to surfaces or as an adhesion promoter.
The Marsh test is a highly sensitive method in the detection of arsenic, especially useful in the field of forensic toxicology when arsenic was used as a poison. It was developed by the chemist James Marsh and first published in 1836. The method continued to be used, with improvements, in forensic toxicology until the 1970s.
Phosphine (IUPAC name: phosphane) is a colorless, flammable, highly toxic compound with the chemical formula PH3, classed as a pnictogen hydride. Pure phosphine is odorless, but technical grade samples have a highly unpleasant odor like rotting fish, due to the presence of substituted phosphine and diphosphane (P2H4). With traces of P2H4 present, PH3 is spontaneously flammable in air (pyrophoric), burning with a luminous flame. Phosphine is a highly toxic respiratory poison, and is immediately dangerous to life or health at 50 ppm. Phosphine has a trigonal pyramidal structure.
Ethylene oxide is an organic compound with the formula C2H4O. It is a cyclic ether and the simplest epoxide: a three-membered ring consisting of one oxygen atom and two carbon atoms. Ethylene oxide is a colorless and flammable gas with a faintly sweet odor. Because it is a strained ring, ethylene oxide easily participates in a number of addition reactions that result in ring-opening. Ethylene oxide is isomeric with acetaldehyde and with vinyl alcohol. Ethylene oxide is industrially produced by oxidation of ethylene in the presence of a silver catalyst.
Pentaborane(9) is an inorganic compound with the formula B5H9. It is one of the most common boron hydride clusters, although it is a highly reactive compound. Because of its high reactivity toward oxygen, it was once evaluated as rocket or jet fuel. Like many of the smaller boron hydrides, pentaborane is colourless, diamagnetic, and volatile. It is related to pentaborane(11).
Stibine (IUPAC name: stibane) is a chemical compound with the formula SbH3. A pnictogen hydride, this colourless, highly toxic gas is the principal covalent hydride of antimony, and a heavy analogue of ammonia. The molecule is pyramidal with H–Sb–H angles of 91.7° and Sb–H distances of 170.7 pm (1.707 Å). This gas has an offensive smell like hydrogen sulfide (rotten eggs).
Lithium hydride is an inorganic compound with the formula LiH. This alkali metal hydride is a colorless solid, although commercial samples are grey. Characteristic of a salt-like (ionic) hydride, it has a high melting point, and it is not soluble but reactive with all protic organic solvents. It is soluble and nonreactive with certain molten salts such as lithium fluoride, lithium borohydride, and sodium hydride. With a molar mass of 7.95 g/mol, it is the lightest ionic compound.
Hydrogen selenide is an inorganic compound with the formula H2Se. This hydrogen chalcogenide is the simplest and most commonly encountered hydride of selenium. H2Se is a colorless, flammable gas under standard conditions. It is the most toxic selenium compound with an exposure limit of 0.05 ppm over an 8-hour period. Even at extremely low concentrations, this compound has a very irritating smell resembling that of decayed horseradish or 'leaking gas', but smells of rotten eggs at higher concentrations.
Metalorganic vapour-phase epitaxy (MOVPE), also known as organometallic vapour-phase epitaxy (OMVPE) or metalorganic chemical vapour deposition (MOCVD), is a chemical vapour deposition method used to produce single- or polycrystalline thin films. It is a process for growing crystalline layers to create complex semiconductor multilayer structures. In contrast to molecular-beam epitaxy (MBE), the growth of crystals is by chemical reaction and not physical deposition. This takes place not in vacuum, but from the gas phase at moderate pressures. As such, this technique is preferred for the formation of devices incorporating thermodynamically metastable alloys, and it has become a major process in the manufacture of optoelectronics, such as Light-emitting diodes. It was invented in 1968 at North American Aviation Science Center by Harold M. Manasevit.
Germane is the chemical compound with the formula GeH4, and the germanium analogue of methane. It is the simplest germanium hydride and one of the most useful compounds of germanium. Like the related compounds silane and methane, germane is tetrahedral. It burns in air to produce GeO2 and water. Germane is a group 14 hydride.
Bismuthine (IUPAC name: bismuthane) is the chemical compound with the formula BiH3. As the heaviest analogue of ammonia (a pnictogen hydride), BiH3 is unstable, decomposing to bismuth metal well below 0 °C. This compound adopts the expected pyramidal structure with H–Bi–H angles of around 90°.
Perchloryl fluoride is a reactive gas with the chemical formula ClO
3F. It has a characteristic sweet odor that resembles gasoline and kerosene. It is toxic and is a powerful oxidizing and fluorinating agent. It is the acid fluoride of perchloric acid.
Aluminium hydride is an inorganic compound with the formula AlH3. Alane and its derivatives are part of a family of common reducing reagents in organic synthesis based around group 13 hydrides. In solution—typically in etherial solvents such tetrahydrofuran or diethyl ether—aluminium hydride forms complexes with Lewis bases, and reacts selectively with particular organic functional groups, and although it is not a reagent of choice, it can react with carbon-carbon multiple bonds. Given its density, and with hydrogen content on the order of 10% by weight, some forms of alane are, as of 2016, active candidates for storing hydrogen and so for power generation in fuel cell applications, including electric vehicles. As of 2006 it was noted that further research was required to identify an efficient, economical way to reverse the process, regenerating alane from spent aluminium product.
Beryllium hydride is an inorganic compound with the chemical formula n. This alkaline earth hydride is a colourless solid that is insoluble in solvents that do not decompose it. Unlike the ionically bonded hydrides of the heavier Group 2 elements, beryllium hydride is covalently bonded.
Zinc hydride is an inorganic compound with the chemical formula ZnH2. It is a white, odourless solid which slowly decomposes into its elements at room temperature; despite this it is the most stable of the binary first row transition metal hydrides. A variety of coordination compounds containing Zn–H bonds are used as reducing agents, however ZnH2 itself has no common applications.
Cadmium hydride is an inorganic compound with the chemical formula (CdH
2)
n. It is a solid, known only as a thermally unstable, insoluble white powder.
Titanium(IV) hydride is an inorganic compound with the empirical chemical formula TiH
4. It has not yet been obtained in bulk, hence its bulk properties remain unknown. However, molecular titanium(IV) hydride has been isolated in solid gas matrices. The molecular form is a colourless gas, and very unstable toward thermal decomposition. As such the compound is not well characterised, although many of its properties have been calculated via computational chemistry.
Pnictogen hydrides or hydrogen pnictides are binary compounds of hydrogen with pnictogen atoms covalently bonded to hydrogen.
An arsinide, arsanide, dihydridoarsenate(1−) or arsanyl compound is a chemical derivative of arsine, where one hydrogen atom is replaced with a metal or cation. The arsinide ion has formula AsH−2. It can be considered as a ligand with name arsenido or arsanido. Researchers are unenthusiastic about studying arsanyl compounds, because of the toxic chemicals, and their instability. The IUPAC names are arsanide and dihydridoarsenate(1−). For the ligand the name is arsanido. The neutral −AsH2 group is termed arsanyl.
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.