Stibine

Stibine
Names
IUPAC name
Stibane
Other names
Antimony trihydride
Identifiers
7803-52-3 
ChEBI CHEBI:30288 Yes
ChemSpider 8992 Yes
Jmol-3D images Image
Properties
SbH3
Molar mass 124.784 g/mol
Appearance Colourless gas
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 other solvents Insoluble
Structure
Molecular shape Trigonal pyramidal
Hazards
EU classification Harmful (Xn)
Dangerous for
the environment (N)
R-phrases R20/22 R50/53
S-phrases (S2) S61
NFPA 704
Flammability code 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., propane Health code 4: Very short exposure could cause death or major residual injury. E.g., VX gas Reactivity code 2: Undergoes violent chemical change at elevated temperatures and pressures, reacts violently with water, or may form explosive mixtures with water. E.g., phosphorus Special hazards (white): no codeNFPA 704 four-colored diamond
4
4
2
Flash point Flammable gas
US health exposure limits (NIOSH):
TWA 0.1 ppm (0.5 mg/m3)[1]
Related compounds
Related compounds
 Ammonia,
Phosphine,
Arsine
Bismuthine
Triphenylstibine
Except where noted otherwise, data is given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
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Infobox references

Stibine is the chemical compound with the formula SbH3. This colourless 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 1.707 Å (170.7 pm). This gas has an offensive smell like hydrogen sulfide (rotten eggs).

Preparation

SbH3 is generally prepared by the reaction of Sb3+ sources with H− equivalents:[2]

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.[3] 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 very similar to arsine (AsH3), it is also detected by the Marsh test. This sensitive test detects arsine generated in the presence of arsenic.[3] This procedure, developed around 1836 by James Marsh, is based upon treating 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,[4] but it was not before 1901 when Alfred Stock determined most of the properties of stibine.[5][6]

Safety

SbH3 is an unstable flammable gas. It is highly toxic, with an LC50 of 100 ppm in mice. Fortunately, SbH3 is so unstable that it is rarely encountered outside of laboratories.

Toxicology

For the toxicology of other antimony compounds, see Antimony trioxide.

The toxicity of stibine is distinct from that of other antimony compounds, but similar to that of arsine.[7] 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

  1. ↑ "NIOSH Pocket Guide to Chemical Hazards #0568". National Institute for Occupational Safety and Health (NIOSH).
  2. ↑ 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.
  3. ↑ 3.0 3.1 Holleman, A. F.; Wiberg, E. (2001). Inorganic Chemistry. San Diego: Academic Press.
  4. ↑ Francis Jones (1876). "On Stibine". Journal of the Chemical Society 29 (2): 641–650. doi:10.1039/JS8762900641.
  5. ↑ Alfred Stock; Walther Doht (1901). "Die Reindarstellung des Antimonwasserstoffes". Berichte der Deutschen Chemischen Gesellschaft 34 (2): 2339–2344. doi:10.1002/cber.190103402166.
  6. ↑ 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.
  7. ↑ "Fiche toxicologique n° 202 : Trihydrure d'antimoine" (PDF). Institut national de recherche et de sécurité (INRS). 1992.

External links