Stibine

Stibine
	; Antimony, Sb Hydrogen, H
Names
	IUPAC name Stibane
	Other names Antimony trihydride ; Hydrogen antimonide
Identifiers
CAS Number	7803-52-3 ;
3D model (JSmol)	Interactive image;
ChEBI	CHEBI:30288 ;
ChemSpider	8992 ;
ECHA InfoCard	100.149.507
EC Number	620-578-3;
Gmelin Reference	795
PubChem CID	9359;
RTECS number	WJ0700000;
UNII	0VKZ97K3UB ;
UN number	2676
CompTox Dashboard (EPA)	DTXSID601014341 ;
	InChI InChI=1S/Sb.3H Key: OUULRIDHGPHMNQ-UHFFFAOYSA-N ; InChI=1/Sb.3H/rH3Sb/h1H3 Key: OUULRIDHGPHMNQ-LQMOCBGJAH;
	SMILES [SbH3];
Properties
Chemical formula	SbH3
Molar mass	124.784 g/mol
Appearance	Colourless 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)
Solubility in water	slightly soluble
Solubility in ethanol	soluble
Vapor pressure	>1 atm (20°C)
Conjugate acid	Stibonium
Structure
Molecular shape	Trigonal pyramidal
Hazards
	Occupational safety and health (OHS/OSH):
Main hazards	Extremely toxic, flammable and highly reactive
	GHS labelling:
Pictograms
Signal word	Danger
Hazard statements	H220, H330, H370
Precautionary statements	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):
LCLo (lowest published)	100 ppm (mouse, 1 hr); 92 ppm (guinea pig, 1 hr); 40 ppm (dog, 1 hr)
	NIOSH (US health exposure limits):
PEL (Permissible)	TWA 0.1 ppm (0.5 mg/m3)
REL (Recommended)	TWA 0.1 ppm (0.5 mg/m3)
IDLH (Immediate danger)	5 ppm
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). verify (what is ?) Infobox references

Stibine (IUPAC name: stibane) is a chemical compound with the formula Sb H₃. 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.

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

The salt NaSbH₂ is called sodium stibinide, and contains the stibinide anion SbH−2.

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.

References

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

External links

International Chemical Safety Card 0776
NIOSH Pocket Guide to Chemical Hazards
"Fiche toxicologique n° 202 : Trihydrure d'antimoine" (PDF). Institut national de recherche et de sécurité (INRS). 1992. {{cite journal}}: Cite journal requires |journal= (help)

[crc-1] John Rumble (June 18, 2018). CRC Handbook of Chemistry and Physics (99th ed.). CRC Press. pp. 4–41. ISBN 978-1138561632.

[PGCH-2] 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.

[Holleman-5] 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)

[1]

[2]

[3]

[4]

[5]

[6]

[7]

[8]

[9]