World Library  
Flag as Inappropriate
Email this Article

Phosphine

Article Id: WHEBN0000264583
Reproduction Date:

Title: Phosphine  
Author: World Heritage Encyclopedia
Language: English
Subject: Chembox/testcases3, Chembox/testcases6, Zinc phosphide, Acetylene, Ammonia
Collection: Fumigants, Functional Groups, Industrial Gases, Phosphanes, Phosphine Complexes, Phosphorus Hydrides
Publisher: World Heritage Encyclopedia
Publication
Date:
 

Phosphine

Phosphine
Phosphine
Names
IUPAC name
Phosphane
Other names
Phosphamine
Phosphorus trihydride
Phosphorated hydrogen
Identifiers
 Y
ChEBI  Y
ChemSpider  Y
EC number 232-260-8
Jmol-3D images Image
PubChem
RTECS number SY7525000
UN number 2199
Properties
PH3
Molar mass 33.99758 g/mol
Appearance colorless gas
Odor faint, fish-like or garlic-like[1]
Density 1.379 g/l, gas (25 °C)
Melting point −132.8 °C (−207.0 °F; 140.4 K)
Boiling point −87.7 °C (−125.9 °F; 185.5 K)
31.2 mg/100 ml (17 °C)
Solubility soluble in alcohol, ether, CS2
slightly soluble in benzene, chloroform, ethanol
Vapor pressure 41.3 atm (20°C)[1]
2.144
Viscosity 1.1 x 10−5 Pa s
Structure
Trigonal pyramidal
0.58 D
Thermochemistry
210 J·mol−1·K−1[2]
5 kJ·mol−1[2]
Hazards
Safety data sheet ICSC 0694
Extremely Flammable F+ (F+)
Very Toxic T+ (T+)
Corrosive C (C)
Dangerous for the Environment (Nature) N (N)
R-phrases R50
S-phrases (S1/2), S28, S36/37, S45, S61, S63
NFPA 704
4
4
2
Flash point flammable gas
38 °C (100 °F; 311 K) see text
Explosive limits 1.79% – 98% [1]
Lethal dose or concentration (LD, LC):
LD50 (Median dose)
3.03 mg/kg (rat, oral)
11 ppm (rat, 4 hr)[3]
1000 ppm (mammal, 5 min)
270 ppm (mouse, 2 hr)
100 ppm (guinea pig, 4 hr)
50 ppm (cat, 2 hr)
2500 ppm (rabbit, 20 min)
1000 ppm (human, 5 min)[3]
US health exposure limits (NIOSH):
PEL (Permissible)
TWA 0.3 ppm (0.4 mg/m3)[1]
REL (Recommended)
TWA 0.3 ppm (0.4 mg/m3) ST 1 ppm (1 mg/m3)[1]
50 ppm[1]
Related compounds
Other cations
Ammonia
Arsine
Stibine
Bismuthine
Related compounds
Trimethylphosphine
Triphenylphosphine
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
 Y  (: Y/N?)

Phosphine (catalysts where they complex to various metal ions; complexes derived from a chiral phosphine can catalyze reactions to give chiral, enantioenriched products.

Contents

  • History 1
  • Structure and properties 2
  • Preparation and occurrence 3
  • Phosphines 4
  • Applications 5
    • Organophosphorus chemistry 5.1
    • Microelectronics 5.2
    • Fumigant 5.3
  • Safety 6
  • See also 7
  • References 8
  • Further reading 9
  • External links 10

History

Philippe Gengembre (1764-1838), a student of Lavoisier, first obtained phosphine in 1783 by heating phosphorus in an aqueous solution of potash (potassium carbonate).[4][5]

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 phosphure d'hydrogène (phosphide of hydrogen).[6]

In 1844, Paul Thénard, son of the French chemist Louis Jacques Thénard, used a cold trap to separate diphosphine from phosphine that had been generated from calcium phosphide, thereby demonstrating that P2H4 is responsible for spontaneous flammability associated with PH3, and also for the characteristic orange/brown color that can form on surfaces, which is a polymerisation product.[7] He considered diphosphine’s formula to be PH2, and thus an intermediate between elemental phosphorus, the higher polymers, and phosphine. Calcium phosphide (nominally Ca3P2) produces more P2H4 than other phosphides because of the preponderance of P-P bonds in the starting material.

The name "phosphine" first appeared in combined form in 1857.[8] The gas PH3 was named "phosphine" by 1865 (or earlier).[9]

Structure and properties

PH3 is a trigonal pyramidal molecule with C3v molecular symmetry. The length of the P-H bond is 1.42 Å, 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: CH3PH2, 1.10 D; (CH3)2PH, 1.23 D; (CH3)3P, 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 PH3 the P-H bonds are almost entirely pσ(P) – sσ(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 31P 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.[10]

The aqueous solubility of PH3 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 is technically amphoteric in water, but acid and base activity is poor. Proton exchange proceeds via a phosphonium (PH4+) ion in acidic solutions and via PH2 at high pH, with equilibrium constants Kb = 4 × 10−28 and Kz = 41.6 × 10−29.

Phosphine burns producing a dense white cloud of phosphorus pentoxide:

2 PH3 + 4 O2 → P2O5 + 3 H2O

Preparation and occurrence

Phosphine may be prepared in a variety of ways.[11] 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 + P4 + 3H2O → 3KH2PO2 + PH3

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 P2H4, may be prepared using the action of potassium hydroxide on phosphonium iodide (PH4I).

Phosphine is a constituent of the atmosphere at very low and highly variable concentrations.[12] It may contribute significantly to the global

  • International Chemical Safety Card 0694
  • CDC - Phosphine - NIOSH Workplace Safety and Health Topic

External links

  • Fluck, E. (1973). "The Chemistry of Phosphine". Topics in Current Chemistry. Fortschritte der Chemischen Forschung 35: 1–64.  
  • WHO (World Health Organisation) (1988). Phosphine and Selected Metal Phosphides. Environmental Health Criteria 73. Geneva: Joint sponsorship of UNEP, ILO and WHO. 

Further reading

  1. ^ a b c d e f "NIOSH Pocket Guide to Chemical Hazards #0505".  
  2. ^ a b Zumdahl, Steven S. (2009). Chemical Principles 6th Ed. Houghton Mifflin Company. p. A22.  
  3. ^ a b "Phosphine". Immediately Dangerous to Life and Health.  
  4. ^ Gengembre (1783) "Mémoire sur un nouveau gas obtenu, par l'action des substances alkalines, sur le phosphore de Kunckel" (Memoir on a new gas obtained by the action of alkaline substances on Kunckel's phosphorus), Mémoires de mathématique et de physique, 10 : 651-658.
  5. ^ For further information about the early history of phosphine, see:
    • The Encyclopaedia Britannica (1911 edition), vol. 21, p. 480: Phosphorus: Phosphine.
    • Thomas Thomson, A System of Chemistry, 6th ed. (London, England: Baldwin, Cradock, and Joy, 1820), vol. 1 , p. 272.
  6. ^ Note:
    • On p. 222 of his Traité élémentaire de chimie … , vol. 1, (Paris, France: Cuchet, 1789), Lavoisier calls the compound of phosphorus and hydrogen "phosphure d'hydrogène" (hydrogen phosphide). However, on p. 216, he calls the compound of hydrogen and phosphorus "Combinaison inconnue." (unknown combination), yet in a footnote, he says about the reactions of hydrogen with sulfur and with phosphorus: "Ces combinaisons ont lieu dans l'état de gaz & il en résulte du gaz hydrogène sulfurisé & phosphorisé." (These combinations occur in the gaseous state, and there results from them sulfurized and phosphorized hydrogen gas.)
    • In Robert Kerr's 1790 English translation of Lavoisier's Traité élémentaire de chimie … — namely, Lavoisier with Robert Kerr, trans., Elements of Chemistry … (Edinburgh, Scotland: William Creech, 1790) — Kerr translates Lavoisier's "phosphure d'hydrogène" as "phosphuret of hydrogen" (p. 204), and whereas Lavoisier — on p. 216 of his Traité élémentaire de chimie … — gave no name to the combination of hydrogen and phosphorus, Kerr calls it "hydruret of phosphorus, or phosphuret of hydrogen" (p. 198). Lavoisier's note about this compound — "Combinaison inconnue." — is translated: "Hitherto unknown." Lavoisier's footnote is translated as: "These combinations take place in the state of gas, and form, respectively, sulphurated and phosphorated oxygen gas." The word "oxygen" in the translation is an error because the original text clearly reads "hydrogène" (hydrogen). (The error was corrected in subsequent editions.)
  7. ^ Paul Thénard (1844) "Mémoire sur les combinaisons du phosphore avec l'hydrogène" (Memoir on the compounds of phosphorus with hydrogen), Comptes rendus, 18 : 652-655.
  8. ^ In 1857, Proceedings of the Royal Society of London, 8 : 523-527. From page 524: "The bases Me3P and E3P, the products of this reaction, which we propose to call respectively trimethylphosphine and triethylphosphine, … "
  9. ^ William Odling, A Course of Practical Chemistry Arranged for the Use of Medical Students, 2nd ed. (London, England: Longmans, Green, and Co., 1865), pp. 227, 230.
  10. ^ Sennikov, P. G. (1994). "Weak H-Bonding by Second-Row (PH3, H2S) and Third-Row (AsH3, H2Se) Hydrides". Journal of Physical Chemistry 98 (19): 4973–4981.  
  11. ^ Toy, A. D. F. (1973). The Chemistry of Phosphorus. Oxford, UK: Pergamon Press. 
  12. ^ Gassmann, G.; van Beusekom, J. E. E.; Glindemann, D. (1996). "Offshore atmospheric phosphine". Naturwissenschaften 83 (3): 129–131.  
  13. ^ Roels, J.; Verstraete, W. (2001). "Biological formation of volatile phosphorus compounds, a review paper". Bioresource Technology 79 (3): 243–250.  
  14. ^ Edwards, P. G.; Haigh, R.; Li, D.; Newman, P. D. (2006). "Template Synthesis of 1,4,7-Triphosphacyclononanes".  
  15. ^ Burck, S.; Gudat, D.; Nieger, M.; Du Mont, W.-W. (2006). "P-Hydrogen-Substituted 1,3,2-Diazaphospholenes: Molecular Hydrides".  
  16. ^ Bettermann, G.; Krause, W.; Riess, G.; Hofmann, T. (2002). "Phosphorus Compounds, Inorganic". Ullmann's Encyclopedia of Industrial Chemistry. Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH.  
  17. ^ Schlipalius, D. I., Valmas, N., Tuck, A. G., Jagadeesan, R., Ma, L., Kaur, R. et al. (2012). "A Core Metabolic Enzyme Mediates Resistance to Phosphine Gas". Science 338: 807–810.  
  18. ^ "NIOSH Emergency Response Card". CDC. Retrieved 2010-04-06. 
  19. ^ "NIOSH pocket guide". CDC. 2009-02-03. Retrieved 2010-04-06. 
  20. ^ "WHO (Data Sheets on Pesticides-No. 46): Phosphine". Inchem.org. Retrieved 2010-04-06. 
  21. ^ "NIOSH Alert: Preventing Phosphine Poisoning and Explosions during Fumigation". CDC. 1995-07-10. Retrieved 2010-04-06. 
  22. ^ [3]
  23. ^ [4]
  24. ^ "Two toddlers die after Jerusalem home sprayed for pests". Haaretz. 2014-01-22. Retrieved 2014-01-23. 
  25. ^ "Pesticide blamed in 8-month-old's death in Fort McMurray". CBC News. 2015-02-23. Retrieved 2015-02-23. 

References

See also

Deaths have resulted from accidental exposure to fumigation materials containing aluminum phosphide or phosphine.[22][23][24][25]

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.[18] 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.[19][20] 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.[21]

Phosphine gas is denser than air and hence may collect in low-lying areas. It can form explosive mixtures with air and also self-ignite.

Safety

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.[17] Identification of this gene now allows rapid molecular identification of resistant insects.

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.

Fumigant

Small amounts of phosphine are used as a dopant in the semiconductor industry, and a precursor for the deposition of compound semiconductors.[16]

Microelectronics

Phosphine is mainly consumed as an intermediate in hydrogen chloride to give tetrakis(hydroxymethyl)phosphonium chloride, which is used in textiles.

Organophosphorus chemistry

Applications

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 example of benzophenone in yet another way.[15]

Scheme 3. diazaphospholene phosphine hydride

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.

Scheme 4. Phosphacrown

Related to a PH3 is the class of amines. Common examples include triphenylphosphine ((C6H5)3P) 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[14] where it is not possible to isolate the phosphine itself.

Phosphines

[13]

This article was sourced from Creative Commons Attribution-ShareAlike License; additional terms may apply. World Heritage Encyclopedia content is assembled from numerous content providers, Open Access Publishing, and in compliance with The Fair Access to Science and Technology Research Act (FASTR), Wikimedia Foundation, Inc., Public Library of Science, The Encyclopedia of Life, Open Book Publishers (OBP), PubMed, U.S. National Library of Medicine, National Center for Biotechnology Information, U.S. National Library of Medicine, National Institutes of Health (NIH), U.S. Department of Health & Human Services, and USA.gov, which sources content from all federal, state, local, tribal, and territorial government publication portals (.gov, .mil, .edu). Funding for USA.gov and content contributors is made possible from the U.S. Congress, E-Government Act of 2002.
 
Crowd sourced content that is contributed to World Heritage Encyclopedia is peer reviewed and edited by our editorial staff to ensure quality scholarly research articles.
 
By using this site, you agree to the Terms of Use and Privacy Policy. World Heritage Encyclopedia™ is a registered trademark of the World Public Library Association, a non-profit organization.
 


Copyright © World Library Foundation. All rights reserved. eBooks from Project Gutenberg are sponsored by the World Library Foundation,
a 501c(4) Member's Support Non-Profit Organization, and is NOT affiliated with any governmental agency or department.