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Phosphine

1
Phosphine
This article is about the chemical. For the class of compounds used as ligands, see metal phosphine complex. For the
visual phenomenon, see phosphene.
"Phosphane" redirects here. For pentavalent organophosphorus compounds, see phosphorane.
Not to be confused with phosphene or phosgene.
Phosphine
Identifiers
CAS number
7803-51-2
[1]
 
PubChem
24404
[2]
ChemSpider
22814
[3]
 
EC number
232-260-8
[4]
UN number 2199
ChEBI
CHEBI:30278
[5]
 
RTECS number SY7525000
Jmol-3D images
Image 1
[6]
Properties
Molecular formula PH
3
Molar mass 33.99758 g/mol
Appearance colorless gas
Density 1.379 g/l, gas (25 •C)
Melting point €132.8 •C (€207.0 •F; 140.3 K)
Boiling point €87.7 •C (€125.9 •F; 185.5 K)
Solubility in water 31.2 mg/100 ml (17 •C)
Viscosity
1.1 x 10
€5
Pa s
Structure
Molecular shape Trigonal pyramidal
Phosphine
2
Dipole moment 0.58 D
Thermochemistry
Std molar
entropy S
o
298
210 J‚mol
€1
‚K
€1
Std enthalpy of
formation ƒ
f
H
o
298
5 kJ‚mol
€1
Hazards
MSDS
ICSC 0694
[7]
EU Index 015-181-00-1
EU classification Highly flammable (F+)
Very toxic (T+)
Corrosive (C)
Dangerous for the environment (N)
R-phrases R12, R17, R26, R34, R50
S-phrases (S1/2), S28, S36/37, S45, S61, S63
NFPA 704
Flash point flammable gas
Autoignition temperature 38 •C (100 •F; 311 K)
Explosive limits 1.8% • ?
Related compounds
Other cations Ammonia
Arsine
Stibine
Bismuthine
Related compounds Trimethylphosphine
Triphenylphosphine
Except where noted otherwise, data are given for materials in their standard state (at 25 •C (77 •F), 100 kPa)
 (verify)
[8]
 (what is:  / ?)
Infobox references
Phosphine (IUPAC name: phosphane) is the compound with the chemical formula PH
3
. It is a colorless,
flammable, toxic gas. Pure phosphine is odorless, but technical grade samples have a highly unpleasant odor like
garlic or rotting fish, due to the presence of substituted phosphine and diphosphane (P
2
H
4
). With traces of P
2
H
4
present, PH
3
is spontaneously flammable in air, burning with a luminous flame. Phosphines are also a group of
organophosphorus compounds with the formula R
3
P (R = organic derivative). Organophosphines are important in
catalysts where they complex to various metal ions; complexes derived from a chiral phosphine can catalyze
reactions to give chiral, enantioenriched products.
Phosphine
3
History
Perhaps because of its strong association with elemental phosphorus, phosphine was once regarded as a gaseous
form of the element, but Lavoisier (1789) recognised it as a combination of phosphorus with hydrogen and described
it as ‚hydruyet of phosphorus, or phosphuret of hydrogenƒ.Wikipedia:Citation needed
Th„nard (1845) used a cold trap to separate diphosphine from phosphine that had been generated from calcium
phosphide, thereby demonstrating that P
2
H
4
is responsible for spontaneous flammability associated with PH
3
, and
also for the characteristic orange/brown color that can form on surfaces, which is a polymerisation product. He
considered diphosphine„s formula to be PH
2
, and thus an intermediate between elemental phosphorus, the higher
polymers, and phosphine. Calcium phosphide (nominally Ca
3
P
2
) produces more P
2
H
4
than other phosphides because
of the preponderance of P-P bonds in the starting material.
Structure and properties
PH
3
is a trigonal pyramidal molecule with C
3v
molecular symmetry. The length of the P-H bond is 1.42 …, the
H-P-H bond angles are 93.5•. The dipole moment is 0.58 D, which increases with substitution of methyl groups in
the series: CH
3
PH
2
, 1.10 D; (CH
3
)
2
PH, 1.23 D; (CH
3
)
3
P, 1.19 D. In contrast, the dipole moments of amines
decrease with substitution, starting with ammonia, which has a dipole moment of 1.47 D. The low dipole moment
and almost orthogonal bond angles lead to the conclusion that in PH
3
the P-H bonds are almost entirely p†(P) •
s†(H) and phosphorus 3s orbital contributes little to the bonding between phosphorus and hydrogen in this molecule.
For this reason, the lone pair on phosphorus may be regarded as predominantly formed by the 3s orbital of
phosphorus. The upfield chemical shift of the phosphorus atom in the
31
P NMR spectrum accords with the
conclusion that the lone pair electrons occupy the 3s orbital (Fluck, 1973). This electronic structure leads to a lack of
nucleophilicity and an ability to form only weak hydrogen bonds.
The aqueous solubility of PH
3
is slight; 0.22 mL of gas dissolve in 1 mL of water. Phosphine dissolves more readily
in non-polar solvents than in water because of the non-polar P-H bonds. It acts as neither an acid nor a base in water.
Proton exchange proceeds via a phosphonium (PH
4
+
) ion in acidic solutions and via PH
2

at high pH, with
equilibrium constants K
b
= 4 ‡ 10
€28
and K
z
= 41.6 ‡ 10
€29
.
Phosphine burns producing a dense white cloud of phosphorus pentoxide:
2 PH
3
+ 4 O
2
… P
2
O
5
+ 3 H
2
O
Preparation and occurrence
Phosphine may be prepared in a variety of ways. Industrially it can be made by the reaction of white phosphorus
with sodium or potassium hydroxide, producing sodium or potassium hypophosphite as a by-product.
3KOH + P
4
+ 3H
2
O … 3KH
2
PO
2
+ PH
3
Alternatively the acid-catalyzed disproportioning of white phosphorus may be used, which yields phosphoric acid
and phosphine. Both routes have industrial significance; the acid route is preferred method if further reaction of the
phosphine to substituted phosphines is needed. The acid route requires purification and pressurizing. It can also be
made (as described above) by the hydrolysis of a metal phosphide, such as aluminium phosphide or calcium
phosphide. Pure samples of phosphine, free from P
2
H
4
, may be prepared using the action of potassium hydroxide on
phosphonium iodide (PH
4
I).
Phosphine is a constituent of the atmosphere at very low and highly variable concentrations. It may contribute
significantly to the global phosphorus biochemical cycle. The most likely source is reduction of phosphate in
decaying organic matter, possibly via partial reductions and disproportionations, since environmental systems do not
have known reducing agents of sufficient strength to directly convert phosphate to phosphine .
Phosphine
4
Phosphines
See also: metal phosphine complex
Related to a PH
3
is the class of organophosphorus compounds commonly called phosphines. These alkyl and aryl
derivatives of phosphine are analogous to organic amines. Common examples include triphenylphosphine
((C
6
H
5
)
3
P) and BINAP, both used as ligands in homogeneous catalysis or triisopropylphosphine. Phosphines are
easily oxidized to phosphine oxides as exemplified by the directed synthesis of a phospha-crown, the phosphorus
analogue of an aza crown where it is not possible to isolate the phosphine itself.
In step 1 diphosphinoethane coordinates to a ferrocene containing additional carbon monoxide ligands and an
acetonitrile ligand. The next step is a hydrophosphination with trivinylphosphine followed by alkylation with ethyl
bromide and hydrogenation with hydrogen over palladium on carbon. In the final step the iron template is removed
by bromine but oxidation of the phosphine groups is unavoidable.
When modified with suitable substituents as in certain (rare) diazaphospholenes (scheme 3) the polarity of the P-H
bond can be inverted (see: umpolung) and the resulting phosphine hydride can reduce a carbonyl group as in the
Phosphine
5
example of benzophenone in yet another way.
Applications
Organophosphorus chemistry
Phosphine is mainly consumed as an intermediate in organophosphorus chemistry. In an illustrative reaction,
formaldehyde adds in the presence of hydrogen chloride to give tetrakis(hydroxymethyl)phosphonium chloride,
which is used in textiles.
Microelectronics
Small amounts of phosphine are used as a dopant in the semiconductor industry, and a precursor for the deposition of
compound semiconductors.
Fumigant
For farm use, pellets of aluminium phosphide, calcium phosphide, or zinc phosphide release phosphine upon contact
with atmospheric water or rodents' stomach acid. These pellets also contain agents to reduce the potential for ignition
or explosion of the released phosphine.
Because the previously popular fumigant methyl bromide has been phased out in some countries under the Montreal
Protocol, phosphine is the only widely used, cost-effective, rapidly acting fumigant that does not leave residues on
the stored product. Pests with high levels of resistance toward phosphine have become common in Asia, Australia
and Brazil. High level resistance is also likely to occur in other regions, but has not been as closely monitored.
Genetic variants that contribute to high level resistance to phosphine have been identified in the dihydrolipoamide
dehydrogenase gene. Identification of this gene now allows rapid molecular identification of resistant insects.
Safety
Phosphine gas is more dense than air and hence may collect in low-lying areas. It can form explosive mixtures with
air and also self-ignite.
Phosphine can be absorbed into the body by inhalation. Direct contact with phosphine liquid • although unlikely to
occur • may cause frostbite, like other cryogenic liquids. The main target organ of phosphine gas is the respiratory
tract. According to the 2009 U.S. National Institute for Occupational Safety and Health (NIOSH) pocket guide, and
U.S. Occupational Safety and Health Administration (OSHA) regulation, the 8 hour average respiratory exposure
should not exceed 0.3 ppm. NIOSH recommends that the short term respiratory exposure to phosphine gas should
not exceed 1 ppm. The Immediately Dangerous to Life or Health level is 50 ppm. Overexposure to phosphine gas
causes nausea, vomiting, abdominal pain, diarrhea; thirst; chest tightness, dyspnea (breathing difficulty); muscle
pain, chills; stupor or syncope; pulmonary edema. Phosphine has been reported to have the odor of decaying fish or
garlic at concentrations below 0.3 ppm. The smell is normally restricted to laboratory areas or phosphine processing
since the smell comes from the way the phosphine is extracted from the environment. However, it may occur
elsewhere, such as in industrial waste landfills. Exposure to higher concentrations may cause olfactory fatigue.
In December 2013 three members of a family in Alcalˆ de Guada‰ra, Spain, died from phosphine inhalation. The
father had been accumulating caps from aluminum phosphide containers in their bathroom with the intention of
selling them for recycling. Combining with the humidity in the air the aluminum phosphide released phosphine gas
which caused the deaths.
On January 2014, a whole family in Jerusalem was poisoned from phosphine after a section of their apartment was
fumigated for pests, and some of the young children died from the poisoning.
Phosphine
6
References
[1] http:/ / www. commonchemistry.org/ ChemicalDetail.aspx?ref=7803-51-2
[2] http:/ / pubchem. ncbi. nlm.nih. gov/ summary/ summary. cgi?cid=24404
[3] http:/ / www. chemspider.com/ Chemical-Structure.22814. html
[4] http:/ / esis.jrc.ec.europa. eu/ lib/ einecs_IS_reponse. php?genre=ECNO& entree=232-260-8
[5] https:/ / www. ebi. ac. uk/ chebi/ searchId.do?chebiId=30278
[6] http:/ / chemapps.stolaf. edu/ jmol/ jmol.php?model=P
[7] http:/ / www. inchem. org/ documents/ icsc/ icsc/ eics0694. htm
[8] http:/ / en. wikipedia. org/ w/ index. php?title=Special:ComparePages& rev1=464205019& page2=Phosphine
Further reading
Š Fluck, E. (1973). "The Chemistry of Phosphine". Topics in Current Chemistry. Fortschritte der Chemischen
Forschung 35: 1•64. doi: 10.1007/BFb0051358 (http:/ / dx. doi. org/ 10. 1007/ BFb0051358).
ISBN 3-540-06080-4.
Š WHO (World Health Organisation) (1988). Phosphine and Selected Metal Phosphides (http:/ / www. inchem. org/
documents/ ehc/ ehc/ ehc73. htm). Environmental Health Criteria 73. Geneva: Joint sponsorship of UNEP, ILO
and WHO.
External links
Š International Chemical Safety Card 0694 (http:/ / www. inchem. org/ documents/ icsc/ icsc/ eics0694. htm)
Š CDC - Phosphine - NIOSH Workplace Safety and Health Topic (http:/ / www. cdc. gov/ niosh/ topics/ phosphine/
)
Article Sources and Contributors
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Article Sources and Contributors
Phosphine  Source: http://en.wikipedia.org/w/index.php?oldid=621455733  Contributors: 1YlGC6dsynvm, A. Carty, A876, AMVStecker, Adl9999, Anthonyhcole, Attilios, B07, Beetstra,
Benjah-bmm27, Bryan Derksen, Card, Carnildo, Chem-awb, ChemMater, Christopherlin, Cpiral, Curb Chain, DMacks, Darrien, DePiep, Deglr6328, Denelson83, Diglett11, DimaBorger,
Drbogdan, Dripp, DuncanHill, Edgar181, Edward, Ferkelparade, Freestyle-69, GRAHAMUK, GS3, Gauss, Giftlite, Gilliam, GoingBatty, Hellbus, Herbee, Hydro, Icairns, Ihope127, Ipatrol, Itub,
Ixfd64, JSquish, JZNIOSH, Japo, Jeffreywriter, Jim1138, Jmcmanus33061, John, John Nevard, Joshsteelersfan98, Jynto, Karlhahn, Kay Dekker, Keber, KnightRider, Kupirijo, KyleRGiggs,
Kzhr, La goutte de pluie, LegacyOfValor, Liamdavies, Lu‰s Felipe Braga, Magioladitis, Mancunion, Mark viking, Materialscientist, MiPe, Mikedelsol, Mikespedia, Mimihitam, Mortense,
Mstromb, Nbound, Nihiltres, Nirmos, Oatmeal batman, Obsidian Soul, Oktanyum, OldAlchemistElf, P.G.Antolinos, Pdcook, Physchim62, Pion, Pizza Puzzle, Polonium, Puppy8800, Purdygb,
Quantockgoblin, Quibik, Rich Farmbrough, Rifleman 82, Robbin' Knowledge, S0me l0ser, Shaddack, Shaliya waya, Shoefly, Shoy, Smartse, Smokefoot, StephenPratt, Stephenpratt, Steve Quinn,
Susurrus, TangParadise, Tgbguava, The High Fin Sperm Whale, Thricecube, Tkbx, Trusilver, UninvitedCompany, UnitedStatesian, V8rik, Valeg96, Vchorozopoulos, Vuo, WVhybrid, Walkerma,
Wavelength, Yyy, €•‚ƒ „…† ‡ ˆ ‰ , 114 anonymous edits
Image Sources, Licenses and Contributors
File:Monophosphan.svg  Source: http://en.wikipedia.org/w/index.php?title=File:Monophosphan.svg  License: Public Domain  Contributors: NEUROtiker
File:Phosphine-3D-balls.png  Source: http://en.wikipedia.org/w/index.php?title=File:Phosphine-3D-balls.png  License: Public Domain  Contributors: Ben Mills
File:Phosphine-underside-3D-vdW.png  Source: http://en.wikipedia.org/w/index.php?title=File:Phosphine-underside-3D-vdW.png  License: Public Domain  Contributors: Benjah-bmm27
File:Yes check.svg  Source: http://en.wikipedia.org/w/index.php?title=File:Yes_check.svg  License: Public Domain  Contributors: Anomie
File:X mark.svg  Source: http://en.wikipedia.org/w/index.php?title=File:X_mark.svg  License: Public Domain  Contributors: User:Gmaxwell
File:Phosphacrown.png  Source: http://en.wikipedia.org/w/index.php?title=File:Phosphacrown.png  License: GNU Free Documentation License  Contributors: Original uploader was V8rik at
en.wikipedia
File:Phosphine umpolung.png  Source: http://en.wikipedia.org/w/index.php?title=File:Phosphine_umpolung.png  License: GNU Free Documentation License  Contributors: Original uploader
was V8rik at en.wikipedia
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