Stibine

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Stibine
Stibine Stibine.png
Stibine
Stibine Stibine-3D-vdW.png
Stibine
Names
IUPAC name
Stibane
Other names
Antimony trihydride
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.149.507 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 620-578-3
795
PubChem CID
RTECS number
  • WJ0700000
UNII
UN number 2676
  • InChI=1S/Sb.3H Yes check.svgY
    Key: OUULRIDHGPHMNQ-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/Sb.3H/rH3Sb/h1H3
    Key: OUULRIDHGPHMNQ-LQMOCBGJAH
  • [SbH3]
Properties
SbH3
Molar mass 124.784 g/mol
AppearanceColourless gas
Odor unpleasant, like hydrogen sulfide
Density 5.48 g/L, gas
Melting point −88 °C (−126 °F; 185 K)
Boiling point −17 °C (1 °F; 256 K)
slightly soluble
Solubility in ethanolsoluble [1]
Vapor pressure >1 atm (20°C) [2]
Conjugate acid Stibonium
Structure
Trigonal pyramidal
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
Toxic, flammable
GHS labelling:
GHS-pictogram-flamme.svg GHS-pictogram-bottle.svg GHS-pictogram-skull.svg GHS-pictogram-silhouette.svg
Danger
H220, H370
P210, P260, P264, P270, P307+P311, P321, P377, P381, P403, P405, P501
NFPA 704 (fire diamond)
4
4
3
Flash point Flammable gas
Lethal dose or concentration (LD, LC):
100 ppm (mouse, 1 hr)
92 ppm (guinea pig, 1 hr)
40 ppm (dog, 1 hr) [3]
NIOSH (US health exposure limits):
PEL (Permissible)
TWA 0.1 ppm (0.5 mg/m3) [2]
REL (Recommended)
TWA 0.1 ppm (0.5 mg/m3) [2]
IDLH (Immediate danger)
5 ppm [2]
Related compounds
Related compounds
Ammonia
Phosphine
Arsine
Bismuthine
Triphenylstibine
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

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).

Contents

Preparation

SbH3 is generally prepared by the reaction of Sb3+ sources with H− equivalents: [4]

2 Sb2O3 + 3 LiAlH4 → 4 SbH3 + 1.5 Li2O + 1.5 Al2O3
4 SbCl3 + 3 NaBH4 → 4 SbH3 + 3 NaCl + 3 BCl3

Alternatively, sources of Sb3 react with protonic reagents (even water) to also produce this unstable gas:

Na3Sb + 3 H2O → SbH3 + 3 NaOH

Properties

The chemical properties of SbH3 resemble those for AsH3. [5] Typical for a heavy hydride (e.g. AsH3, H2Te, SnH4), SbH3 is unstable with respect to its elements. The gas decomposes slowly at room temperature but rapidly at 200 °C:

2 SbH3 → 3 H2 + 2 Sb

The decomposition is autocatalytic and can be explosive.

SbH3 is readily oxidized by O2 or even air:

2 SbH3 + 3 O2 → Sb2O3 + 3 H2O

SbH3 exhibits no basicity, but it can be deprotonated:

SbH3 + NaNH2 → NaSbH2 + NH3

Uses

Stibine is used in the semiconductor industry to dope silicon with small quantities of antimony via the process of chemical vapour deposition (CVD). It has also been used as a silicon dopant in epitaxial layers. Reports claim the use of SbH3 as a fumigant but its instability and awkward preparation contrast with the more conventional fumigant phosphine.

History

As stibine (SbH3) is similar to arsine (AsH3); it is also detected by the Marsh test. This sensitive test detects arsine generated in the presence of arsenic. [5] This procedure, developed circa 1836 by James Marsh, treats a sample with arsenic-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 arsenic is indicated by formation of a deposit in the heated part of the equipment. The formation of a black mirror deposit in the cool part of the equipment indicates the presence of antimony.

In 1837 Lewis Thomson and Pfaff independently discovered stibine. It took some time before the properties of the toxic gas could be determined, partly because a suitable synthesis was not available. In 1876 Francis Jones tested several synthesis methods, [6] but it was not before 1901 when Alfred Stock determined most of the properties of stibine. [7] [8]

Safety

SbH3 is an unstable flammable gas. It is highly toxic, with an LC50 of 100 ppm in mice.

Toxicology

The toxicity of stibine is distinct from that of other antimony compounds, but similar to that of arsine. [9] Stibine binds to the haemoglobin of red blood cells, causing them to be destroyed by the body. Most cases of stibine poisoning have been accompanied by arsine poisoning, although animal studies indicate that their toxicities are equivalent. The first signs of exposure, which can take several hours to become apparent, are headaches, vertigo, and nausea, followed by the symptoms of hemolytic anemia (high levels of unconjugated bilirubin), hemoglobinuria, and nephropathy.

See also

Related Research Articles

Antimony Chemical element, symbol Sb and atomic number 51

Antimony is a chemical element with the symbol Sb (from Latin: stibium) and atomic number 51. A lustrous gray metalloid, it is found in nature mainly as the sulfide mineral stibnite (Sb2S3). Antimony compounds have been known since ancient times and were powdered for use as medicine and cosmetics, often known by the Arabic name kohl. The earliest known description of the metal in the West was written in 1540 by Vannoccio Biringuccio.

Pnictogen Group 15 elements of the periodic table with valency 5

A pnictogen is any of the chemical elements in group 15 of the periodic table. Group 15 is also known as the nitrogen group or nitrogen family. It consists of the elements nitrogen (N), phosphorus (P), arsenic (As), antimony (Sb) and bismuth (Bi). Even though unconfirmed, the synthetic element moscovium (Mc) is predicted to be a pnictogen as well.

Marsh test

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.

Arsine Chemical compound

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. 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".

Antimony trioxide Chemical compound

Antimony(III) oxide is the inorganic compound with the formula Sb2O3. It is the most important commercial compound of antimony. It is found in nature as the minerals valentinite and senarmontite. Like most polymeric oxides, Sb2O3 dissolves in aqueous solutions with hydrolysis. A mixed arsenic-antimony oxide occurs in nature as the very rare mineral stibioclaudetite.

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.

Arsenous acid Chemical compound

Arsenous acid (or arsenious acid) is the inorganic compound with the formula H3AsO3. It is known to occur in aqueous solutions, but it has not been isolated as a pure material, although this fact does not detract from the significance of As(OH)3.

Metalorganic vapour-phase epitaxy Method of producing thin fils (polycrystalline and single crystal)

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 Chemical compound

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.

Aluminium arsenide Chemical compound

Aluminium arsenide is a semiconductor material with almost the same lattice constant as gallium arsenide and aluminium gallium arsenide and wider band gap than gallium arsenide. (AlAs) can form a superlattice with gallium arsenide (GaAs) which results in its semiconductor properties. Because GaAs and AlAs have almost the same lattice constant, the layers have very little induced strain, which allows them to be grown almost arbitrarily thick. This allows for extremely high performance high electron mobility, HEMT transistors, and other quantum well devices.

Diphenylchlorarsine Chemical compound

Diphenylchloroarsine (DA) is the organoarsenic compound with the formula (C6H5)2AsCl. It is highly toxic and was once used in chemical warfare. It is also an intermediate in the preparation of other organoarsenic compounds. The molecule consists of a pyramidal As(III) center attached to two phenyl rings and one chloride. It was also known as sneezing oil during World War I by the Allies.

Scheeles Green Highly toxic arsenic-based pigment

Scheele's Green, also called Schloss Green, is chemically a cupric hydrogen arsenite, CuHAsO
3
. It is chemically related to Paris Green. It is a yellowish-green pigment which in the past was used in some paints, but has since fallen out of use because of its toxicity and the instability of its color in the presence of sulfides and various chemical pollutants. Scheele's Green was invented in 1775 by Carl Wilhelm Scheele. By the end of the 19th century, it had virtually replaced the older green pigments based on copper carbonate.

Bismuthine Chemical compound of bismuth and hydrogen

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
3
F
. 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.

Trimethylarsine (abbreviated TMA or TMAs) is the chemical compound with the formula (CH3)3As, commonly abbreviated AsMe3 or TMAs. This organic derivative of arsine has been used as a source of arsenic in microelectronics industry, a building block to other organoarsenic compounds, and serves as a ligand in coordination chemistry. It has distinct "garlic"-like smell. Trimethylarsine had been discovered as early as 1854.

Ethenone Chemical compound

Ethenone is the formal name for ketene, an organic compound with formula C2H2O or H2C=C=O. It is the simplest member of the ketene class. It is an important reagent for acetylations.

Organoantimony chemistry is the chemistry of compounds containing a carbon to antimony (Sb) chemical bond. Relevant oxidation states are Sb(V) and Sb(III). The toxicity of antimony limits practical application in organic chemistry.

Cobalt tetracarbonyl hydride Chemical compound

Cobalt tetracarbonyl hydride is an organometallic compound with the formula HCo(CO)4. It is a volatile, yellow liquid that forms a colorless vapor and has an intolerable odor. The compound readily decomposes upon melt and in absentia of high CO partial pressures forms Co2(CO)8. Despite operational challenges associated with its handling, the compound has received considerable attention for its ability to function as a catalyst in hydroformylation. In this respect, HCo(CO)4 and related derivatives have received significant academic interest for their ability to mediate a variety of carbonylation (introduction of CO into inorganic compounds) reactions.

The Buchner–Curtius–Schlotterbeck reaction is the reaction of aldehydes or ketones with aliphatic diazoalkanes to form homologated ketones. It was first described by Eduard Buchner and Theodor Curtius in 1885 and later by Fritz Schlotterbeck in 1907. Two German chemists also preceded Schlotterbeck in discovery of the reaction, Hans von Pechmann in 1895 and Viktor Meyer in 1905. The reaction has since been extended to the synthesis of β-keto esters from the condensation between aldehydes and diazo esters. The general reaction scheme is as follows:

Pnictogen hydrides or hydrogen pnictides are binary compounds of hydrogen with pnictogen atoms covalently bonded to hydrogen.

References

  1. John Rumble (June 18, 2018). CRC Handbook of Chemistry and Physics (99th ed.). CRC Press. pp. 4–41. ISBN   978-1138561632.
  2. 1 2 3 4 NIOSH Pocket Guide to Chemical Hazards. "#0568". National Institute for Occupational Safety and Health (NIOSH).
  3. "Stibine". Immediately Dangerous to Life or Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
  4. 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): 2070–2072. doi:10.1021/ic50068a024.
  5. 1 2 Holleman, A. F.; Wiberg, E. (2001). Inorganic Chemistry. San Diego: Academic Press.
  6. Francis Jones (1876). "On Stibine". Journal of the Chemical Society. 29 (2): 641–650. doi:10.1039/JS8762900641.
  7. Alfred Stock; Walther Doht (1901). "Die Reindarstellung des Antimonwasserstoffes". Berichte der Deutschen Chemischen Gesellschaft. 34 (2): 2339–2344. doi:10.1002/cber.190103402166.
  8. Alfred Stock; Oskar Guttmann (1904). "Ueber den Antimonwasserstoff und das gelbe Antimon". Berichte der Deutschen Chemischen Gesellschaft. 37 (1): 885–900. doi:10.1002/cber.190403701148.
  9. "Fiche toxicologique n° 202 : Trihydrure d'antimoine" (PDF). Institut national de recherche et de sécurité (INRS). 1992.{{cite journal}}: Cite journal requires |journal= (help)