Stibine

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Stibine
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  Antimony, Sb
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  Hydrogen, H
Names
IUPAC name
Stibane
Other names
Antimony trihydride
Hydrogen antimonide
Identifiers
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3D model (JSmol)
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EC Number Page Template:Plainlist/styles.css has no content.
795
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UN number 2676
  • InChI=1S/Sb.3H checkY
    Key: OUULRIDHGPHMNQ-UHFFFAOYSA-N checkY
  • InChI=1/Sb.3H/rH3Sb/h1H3
    Key: OUULRIDHGPHMNQ-LQMOCBGJAH
  • [SbH3]
Properties
Page Module:Chem2/styles.css has no content.SbH3
Molar mass 124.784 g·mol−1
Appearance Colourless gas
Odor garlic-like
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 ethanol soluble[1]
Vapor pressure >1 atm (20°C)[2]
Structure
Trigonal pyramidal
Hazards
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NFPA 704 four-colored diamondHealth 4: Very short exposure could cause death or major residual injury. E.g. VX gasFlammability 4: Will rapidly or completely vaporize at normal atmospheric pressure and temperature, or is readily dispersed in air and will burn readily. Flash point below 23 °C (73 °F). E.g. propaneInstability 3: Capable of detonation or explosive decomposition but requires a strong initiating source, must be heated under confinement before initiation, reacts explosively with water, or will detonate if severely shocked. E.g. hydrogen peroxideSpecial hazards (white): no code
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
Hydrogen telluride
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Template:Chembox Footer/trackingTemplate:Short description

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). The smell of this compound from usual sources (like from reduction of antimony compounds) is reminiscent of arsine, i.e. garlic-like. The term stibine is also used for the class of organoantimony(III) compounds of the formula SbH3−xRx, where R is a aryl group or alkyl group.

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. Oxidation of by oxygen (air) gives the element:

Page Module:Chem2/styles.css has no content.SbH3 + 0.75 O2 → Sb + 1.5 H2O

Oxidation at low temperature give the metastable yellow allotrope,[6]

SbH3 can be deprotonated:

SbH3 + NaNH2 → NaSbH2 + NH3

The salt Page Module:Chem2/styles.css has no content.NaSbH2 is called sodium stibinide, and contains the stibinide anion Page Module:Chem2/styles.css has no content.SbH2.

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,[7] but it was not before 1901 when Alfred Stock determined most of the properties of stibine.[8][9]

Safety

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

Toxicology

Script error: No such module "For". The toxicity of stibine is distinct from that of other antimony compounds, but similar to that of arsine.[10] 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

References

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  1. ^ Page Module:Citation/CS1/styles.css has no content.John Rumble (June 18, 2018). CRC Handbook of Chemistry and Physics (99th ed.). CRC Press. pp. 4–41. ISBN 978-1138561632.
  2. ^ a b c d Page Module:Citation/CS1/styles.css has no content.NIOSH Pocket Guide to Chemical Hazards. "#0568". National Institute for Occupational Safety and Health (NIOSH).
  3. ^ Page Module:Citation/CS1/styles.css has no content."Stibine". Immediately Dangerous to Life or Health Concentrations. National Institute for Occupational Safety and Health.
  4. ^ Page Module:Citation/CS1/styles.css has no content.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. ^ a b Page Module:Citation/CS1/styles.css has no content.Holleman, A. F.; Wiberg, E. (2001). Inorganic Chemistry. San Diego: Academic Press.
  6. ^ Page Module:Citation/CS1/styles.css has no content.Stock, Alfred; Guttmann, Oskar (1904). "Ueber den Antimonwasserstoff und das gelbe Antimon". Berichte der Deutschen Chemischen Gesellschaft. 37: 885–900. doi:10.1002/cber.190403701148.
  7. ^ Page Module:Citation/CS1/styles.css has no content.Francis Jones (1876). "On Stibine". Journal of the Chemical Society. 29 (2): 641–650. doi:10.1039/JS8762900641.
  8. ^ Page Module:Citation/CS1/styles.css has no content.Alfred Stock; Walther Doht (1901). "Die Reindarstellung des Antimonwasserstoffes". Berichte der Deutschen Chemischen Gesellschaft. 34 (2): 2339–2344. doi:10.1002/cber.190103402166.
  9. ^ Page Module:Citation/CS1/styles.css has no content.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.
  10. ^ Page Module:Citation/CS1/styles.css has no content."Fiche toxicologique n° 202 : Trihydrure d'antimoine" (PDF). Institut national de recherche et de sécurité (INRS). 1992. {{cite journal}}: Cite journal requires |journal= (help)

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