Phosphine
IUPAC name	Phosphane
Other names	Phosphine Phosphamine Phosphorus hydride Phosphorated hydrogen
Identifiers
CAS number	7803-51-2
Properties
Molecular formula	PH3
Molar mass	34.00 g/mol
Appearance	colorless gas
Density	1.379 g/l, gas (25 °C)
Melting point	−134 °C A phosphene is an entoptic phenomenon characterized by the sensation of seeing light. ... Image File history File links Download high resolution version (640x700, 9 KB) File links The following pages on the English Wikipedia link to this file (pages on other projects are not listed): Phosphine User:Benjah-bmm27/Old gallery ... Image File history File links Download high resolution version (1600x901, 251 KB) File links The following pages on the English Wikipedia link to this file (pages on other projects are not listed): Phosphine User:Benjah-bmm27/Old gallery ... Image File history File links Download high resolution version (1148x1100, 264 KB) File links The following pages on the English Wikipedia link to this file (pages on other projects are not listed): Phosphine User:Benjah-bmm27/Gallery User:Benjah-bmm27/Old gallery User:Ben Mills/Gallery User:Benjah-bmm27/Gallery... IUPAC nomenclature is a system of naming chemical compounds and of describing the science of chemistry in general. ... CAS registry numbers are unique numerical identifiers for chemical compounds, polymers, biological sequences, mixtures and alloys. ... A chemical formula is a concise way of expressing information about the atoms that constitute a particular chemical compound. ... Molar mass is the mass of one mole of a chemical element or chemical compound. ... For other uses, see Density (disambiguation). ... The melting point of a crystalline solid is the temperature range at which it changes state from solid to liquid. ...
Boiling point	−87.8 °C Italic text This article is about the boiling point of liquids. ...
Solubility in water	31.2 mg/100 ml (17 °C)
Structure
Molecular shape	Trigonal pyramidal
Dipole moment	0.58 D
Hazards
EU classification	Highly flammable (F+) Very toxic (T+) Dangerous for the environment (N)
NFPA 704	Solubility is a chemical property referring to the ability for a given substance, the solute, to dissolve in a solvent. ... Impact from a water drop causes an upward rebound jet surrounded by circular capillary waves. ... four sp³ orbitals three sp² orbitals In chemistry, hybridisation or hybridization (see also spelling differences) is the concept of mixing atomic orbitals to form new hybrid orbitals suitable for the qualitative description of atomic bonding properties. ... The Earths magnetic field, which is approximately a dipole. ... The debye (symbol: D) is a non-SI and non-CGS unit of electrical dipole moment. ... Council Directive 67/548/EEC of 27 June 1967 on the approximation of laws, regulations and administrative provisions relating to the classification, packaging and labelling of dangerous substances (as amended) is the main European Union law concerning chemical safety. ... NFPA 704 is a standard maintained by the U.S. National Fire Protection Association. ... Image File history File links NFPA_704. ... 4 3 2
R-phrases	R12, R17, R26, R34, R50
S-phrases	(S1/2), S28, S36/37, S45, S61, S63
Flash point	flammable gas
Autoignition temperature	38 °C (see text)
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, 100 kPa) Infobox disclaimer and references

Phosphine is the common name for phosphorus hydride (PH₃), also known by the IUPAC name phosphane and, occasionally, phosphamine. It is a colorless, flammable gas with a boiling point of −88 °C at standard pressure. Pure phosphine is odorless, but technical grade phosphine has a highly unpleasant odor like garlic or rotting fish, due to the presence of substituted phosphine and diphosphine (P₂H₄). Phosphines are also a group of substituted phosphines, with the structure R₃P, where other functional groups replace hydrogens. They are important in catalysts where they complex to various metal ions; a chiral metal phosphine complex can catalyze a reaction to give chiral products. R-phrases are defined in Annex III of European Union Directive 67/548/EEC: Nature of special risks attributed to dangerous substances and preparations. ... S-phrases are defined in Annex IV of European Union Directive 67/548/EEC: Safety advice concerning dangerous substances and preparations. ... For other uses, see Flash point (disambiguation). ... The autoignition temperature, or the ignition temperature of a substance is the lowest temperature at which a chemical will spontaneously ignite in a normal atmosphere, without an external source of ignition, such as a flame or spark. ... This article is about the electrically charged particle. ... For other uses, see Ammonia (disambiguation). ... Arsine, the simplest compound of arsenic, is AsH3. ... Stibine is a colourless gas formed by the reaction of certain antimony compounds with water or reducing agents. ... Bimuthine is the highly unstable molecule BiH3. ... Trimethylphosphine is the chemical compound with the formula P(CH3)3, commonly abbreviated PMe3. ... Triphenylphosphine (in Europe: triphenylphosphane) is a common organophosphorus compound with the formula P(C6H5)3 - often abbreviated to PPh3 or Ph3P. It is widely used in the synthesis of organic and organometallic compounds. ... The plimsoll symbol as used in shipping In chemistry, the standard state of a material is its state at 1 bar (100 kilopascals exactly). ... The International Union of Pure and Applied Chemistry (IUPAC) is an international non-governmental organization devoted to the advancement of chemistry. ... Temperature and air pressure can vary from one place to another on the Earth, and can also vary in the same place with time. ... Binomial name L. Allium sativum L., commonly known as garlic, is a species in the onion family Alliaceae. ... The term chiral (pronounced ) is used to describe an object which is non-superimposable on its mirror image. ...

Phosphine is highly toxic; it can easily kill in relatively low concentrations. Because of this, the gas is used for pest control by fumigation. For farm use, it is often sold in the form of aluminium phosphide, calcium phosphide, or zinc phosphide pellets, which yield phosphine on contact with atmospheric water or rodents' stomach acid. These pellets also contain other chemicals which evolve ammonia which helps to reduce the potential for spontaneous ignition or explosion of the phosphine gas. They may also contain other agents, such as methanethiol, to give the gas a detectable garlic smell to help warn against its presence in the atmosphere. For other uses, see Toxin (disambiguation). ... A cropduster spreading pesticide. ... Fumigation is a method of pest control that completely fills an area with gaseous pesticides to suffocate or poison the pests within. ... Agriculture (from Agri Latin for ager (a field), and culture, from the Latin cultura cultivation in the strict sense of tillage of the soil. A literal reading of the English word yields tillage of the soil of a field.) is the production of food, feed, fiber and other goods by... Aluminium phosphide (AlP) is a compound of aluminium and phosphorus. ... Calcium phosphide is a chemical that has uses in incendiary bombs. ... Zinc phosphide (Zn3P2) is an inorganic chemical compound. ... For other uses, see Ammonia (disambiguation). ... This article is about the chemical reaction combustion. ... Methanethiol (also known as methyl mercaptan) is a colorless gas with a smell like rotten cabbage. ...

Phosphine is also used as a dopant in the semiconductor industry, and a precursor for the deposition of compound semiconductors. Recently high purity tertiary butyl phosphine (TBP) has been developed as a less hazardous liquid alternative to highly toxic phosphine gas, for application in Metalorganic Vapor Phase Epitaxy (MOVPE) of III-V compound semiconductors. A dopant, also called doping agent and dope, is an impurity element added to a semiconductor lattice in low concentrations in order to alter the optical/electrical properties of the semiconductor. ... A semiconductor is a solid whose electrical conductivity is in between that of a conductor and that of an insulator, and can be controlled over a wide range, either permanently or dynamically. ... A Compound semiconductor is composed of elements from two or more different groups of the chemical periodic table, e. ... Metalorganic vapour phase epitaxy (MOVPE) is a chemical vapour deposition method of epitaxial growth of materials, especially semiconductors from the pyrolysis of organic compounds containing the required chemical elements. ... A Compound semiconductor is composed of elements from two or more different groups of the chemical periodic table, e. ...

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 by describing it as “hydruyet of phosphorus, or phosphuret of hydrogen”. General Name, symbol, number phosphorus, P, 15 Chemical series nonmetals Group, period, block 15, 3, p Appearance waxy white/ red/ black/ colorless Standard atomic weight 30. ... Antoine-Laurent de Lavoisier (August 26, 1743 - May 8, 1794) was a French nobleman prominent in the histories of chemistry, finance, biology, and economics. ...

Ernst von Meyer (1891) described the early history of phosphine research thus: "The discovery of phosphuretted hydrogen (PH₃) by Gengembre in 1783, and the examination of it by Pelletier (who was the first to prepare it pure), only became fruitful after Humphry Davy’s investigations; and the last-named elucidated the composition of this gas, and pointed out its analogy to ammonia, this being emphasised still more sharply by H. Rose later on." Pelletier is the name of several people: David Pelletier, Canadian skater Delphine Pelletier, French triathalete Gérard Pelletier, Canadian journalist Jacques Peletier du Mans, French humanist, poet and mathematician Jean Pelletier, Canadian politician Jean-Jacques Pelletier, Canadian philosopher and author Joel Pelletier, Los Angeles-based artist/musician Madeleine Pelletier, French... Sir Humphry Davy, 1st Baronet, FRS (17 December 1778 – 29 May 1829) was a British chemist and physicist. ... For other uses, see Ammonia (disambiguation). ...

Thénard (1845) 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 colour that can form on surfaces, which is a polymerisation product. 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. Louis Jacques Thénard. ... Vacuum systems For the vacuum device, see cryopump In vacuum applications a cold trap is a device that condenses a vapor into either a liquid or a solid. ... Calcium phosphide is a chemical that has uses in incendiary bombs. ...

Structure and properties

PH₃ is a trigonal pyramidal molecule with C_3v molecular symmetry. The length of the P-H bond 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 the lone pair contributes only a little to the molecular orbitals. The high positive chemical shift of the P atom in³¹P NMR spectrum accords with the conclusion that the lone pair electrons occupy the 3s orbital and so are close to the P atom (Fluck, 1973). This electronic structure leads to a lack of nucleophilicity and an inability to form hydrogen bonds. Molecular symmetry in chemistry describes symmetry in molecules and the classification of molecules in groups based on symmetry. ... In molecular geometry, bond length or bond distance is the distance between two bonded atoms in a molecule. ... An angstrom, angström, or Ã¥ngström (symbol Ã…) is a unit of length. ... Geometry of the water molecule Molecules have fixed equilibrium geometries--bond lengths and angles--that are dictated by the laws of quantum mechanics. ... This article describes the unit of angle. ... This article is about the electromagnetic phenomenon. ... Substitution in the context of organic chemistry has the general meaning of replacing an atom, a functional group, or a substituent in a molecule. ... Methyl group In chemistry, a methyl group is a hydrophobic alkyl functional group derived from methane (CH4). ... For other uses, see Ammonia (disambiguation). ... In chemistry, a molecular orbital is a region in which an electron may be found in a molecule. ... In chemistry, a nucleophile (literally nucleus lover) is a reagent which is attracted to centres of positive charge. ... In chemistry, a hydrogen bond is a type of attractive intermolecular force that exists between two partial electric charges of opposite polarity. ...

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 acts as neither an acid nor a base in water. Proton exchange proceeds via a phosphonium (PH₄⁺) ion in acidic solutions and via PH₂^- at high pH, with equilibrium constants K_b = 4 x 10^-28 and K_z = 41.6 x 10^-29. Solubility is a chemical property referring to the ability for a given substance, the solute, to dissolve in a solvent. ... In chemistry, the phosphonium cation is a positively charged polyatomic ion with the chemical formula PH4+, resulting from protonation of phosphine. ...

Chemistry

Phosphine may be prepared in a variety of ways^[2]. Industrially it can be made by the reaction of white phosphorus with sodium hydroxide, producing sodium hypophosphite and sodium phosphite as a by-product. Alternatively the acid-catalyzed disproportioning of white phosphorus may be used, which yields phosphoric acid and phosphine. Both routes have industrial significance, with the acid route as the preferred method if further reaction of the phosphine to substituted phosphines is needed. This latter step 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). General Name, symbol, number phosphorus, P, 15 Chemical series nonmetals Group, period, block 15, 3, p Appearance waxy white/ red/ black/ colorless Standard atomic weight 30. ... Flash point Non-flammable. ... Sodium hypophosphite (NaPO2H2) is the sodium salt of hypophosphorous acid. ... The phosphite ion is a polyatomic ion with phosphorus as its central atom. ... General Name, symbol, number phosphorus, P, 15 Chemical series nonmetals Group, period, block 15, 3, p Appearance waxy white/ red/ black/ colorless Standard atomic weight 30. ... This article is about orthophosphoric acid. ... Aluminium phosphide (AlP) is a compound of aluminium and phosphorus. ... Calcium phosphide is a chemical that has uses in incendiary bombs. ... The chemical compound potassium hydroxide, (KOH) sometimes known as caustic potash, potassa, potash lye, and potassium hydrate, is a metallic base. ...

Phosphines

Related to PH₃ is the class of compounds commonly called phosphines. These are alkyl or aryl derivatives of phosphine, just as amines can be regarded as derivatives of ammonia. Common examples include triphenylphosphine ((C₆H₅)₃P) and BINAP, both used as phosphine ligands in metal complexes such as Wilkinson's catalyst. Metal phosphine complexes are catalysts for reactions such as the Sonogashira coupling. Most of these phosphines, with the exception of triphenyl phosphine, are made from pressurized, purified phosphine gas as described above. The general structure of an amine Amines are organic compounds and a type of functional group that contain nitrogen as the key atom. ... For other uses, see Ammonia (disambiguation). ... Triphenylphosphine (in Europe: triphenylphosphane) is a common organophosphorus compound with the formula P(C6H5)3 - often abbreviated to PPh3 or Ph3P. It is widely used in the synthesis of organic and organometallic compounds. ... (S)- and (R)-BINAP Ball and stick model of BINAP viewed as above In organic chemistry, BINAP, an acronym used for 2,2-bis(diphenylphosphino)-1,1-binaphthyl, is an important chiral ligand widely used in asymmetric synthesis. ... In chemistry, a ligand is an atom, ion, or molecule (see also: functional group) that generally donates one or more of its electrons through a coordinate covalent bond to, or shares its electrons through a covalent bond with, one or more central atoms or ions (these ligands act as a... Synthesis of copper(II)-tetraphenylporphine, a metal complex, from tetraphenylporphine and copper(II) acetate monohydrate. ... Wilkinsons catalyst 1 is the common name for chlorotris(triphenylphosphine)rhodium(I), named after the late organometallic chemist and 1973 Nobel Laureate, Sir Geoffrey Wilkinson. ... It has been suggested that this article or section be merged into Catalysis. ... In organic chemistry, a Sonogashira coupling is a coupling reaction of terminal alkynes with aryl or vinyl halides. ... Triphenyl phosphine is a cheap and air stable phosphine which has three phenyl groups attached to a phosphorus atom in the centre of the molecule. ...

A large industrial application of phosphine is found in the production of tetrakis(hydroxymethyl) phosphonium salts, made by passing phosphine gas through a solution of formaldehyde and a mineral acid such as hydrochloric acid. These find application as flame retardants for textile ("Proban") and as biocides. In chemistry, the phosphonium cation is a positively charged polyatomic ion with the chemical formula PH4+, resulting from protonation of phosphine. ... The chemical compound formaldehyde (also known as methanal) is a gas with a pungent smell. ... Headline text Happy Hannukah and a happy new year!! POOP e Butt ... The chemical compound hydrochloric acid is the aqueous (water-based) solution of hydrogen chloride gas (HCl). ... Flame retardants are materials that inhibit or resist the spread of fire. ... A biocide is a chemical substance capable of killing different forms of living organisms used in fields such as medicine, agriculture, forestry, and mosquito control. ...

Phosphine is often confused with phosgene, (COCl₂) which has a similar-sounding name but contains no phosphorus. Phosgene is a highly toxic chemical compound with the formula COCl2. ...

Use as a fumigant

Phosphine is highly toxic to organisms undergoing oxidative respiration, but is non toxic to organisms kept under low oxygen (<1%) or that can anaerobically respire (i.e. ferment). Because of these characteristics, phosphine is widely used as a fumigant of metabolically dormant stored products such as grain. The toxicity of phosphine kills insect pests that might infest the grain, but does not affect the viability of the dormant grain. The Electron Transport Chain. ... It has been suggested that this article or section be merged with Fermentation (food). ... Fumigation is a method of pest control that completely fills an area with gaseous pesticides to suffocate or poison the pests within. ... Dormancy is a arrested plant growth. ... This article is about cereals in general. ...

Because continued use of the previously widely used fumigant methyl bromide has been banned under the Montreal Protocol, phosphine is the only widely used, cost effective, rapidly acting fumigant that does not leave residues on the stored product. Given the heavy reliance on phosphine as a means of protecting grain from insect infestation, it is disturbing to note that pests developing high levels of resistance toward phosphine have become commonplace in many countries of Asia and in Australia as well. Active research in Australia into the mode of action of phosphine and the mechanisms whereby insects acquire resistance is being carried out by the CSIRO in Canberra, QDPI&F in Queensland and the University of Queensland. Fumigation is a method of pest control that completely fills an area with gaseous pesticides to suffocate or poison the pests within. ... The chemical compound bromomethane is an organic halogen compound with formula BrCH3. ... The largest Antarctic ozone hole recorded as of September 2000 For other similarly-named agreements, see Montreal Protocol (disambiguation). ... The Commonwealth Scientific and Industrial Research Organisation (CSIRO) is the national government body for scientific research in Australia. ... The University of Queensland (UQ) is the longest-established university in the state of Queensland, Australia, a member of Australias Group of Eight, and the Sandstone Universities. ...

See also

• Phosphine oxide - OPR₃
• Phosphinite - P(OR)R₂
• Phosphonite - P(OR)₂R
• Phosphite - P(OR)₃
• Phosphinate - OP(OR)R₂
• Phosphonate - OP(OR)₂R
• Phosphate - OP(OR)₃

Phosphine oxide, organophosphorus compounds with the fromula - OPR3 Phosphine - PR3 Phosphinite - P(OR)R2 Phosphonite - P(OR)2R Phosphite - P(OR)3 Phosphinate - OP(OR)R2 Phosphonate - OP(OR)2R Phosphate - OP(OR)3 ... Phosphinite, an organophosphorus compounds with the fromula P(OR)R2 Phosphine - PR3 Phosphine oxide - OPR3 Phosphonite - P(OR)2R Phosphite - P(OR)3 Phosphinate - OP(OR)R2 Phosphonate - OP(OR)2R Phosphate - OP(OR)3 ... Phosphonite, organophosphorus compounds with the fromula P(OR)2R Phosphine - PR3 Phosphine oxide - OPR3 Phosphinite - P(OR)R2 Phosphite - P(OR)3 Phosphinate - OP(OR)R2 Phosphonate - OP(OR)2R Phosphate - OP(OR)3 ... The phosphite ion is a polyatomic ion with phosphorus as its central atom. ... Phosphinate, organophosphorus compounds with the fromula OP(OR)R2 Phosphine - PR3 Phosphine oxide - OPR3 Phosphinite - P(OR)R2 Phosphonite - P(OR)2R Phosphite - P(OR)3 Phosphonate - OP(OR)2R Phosphate - OP(OR)3 ... Phosphonates or Phosphonic acids are organic compounds containing one or more C-PO(OH)2 groups. ... A phosphate, in inorganic chemistry, is a salt of phosphoric acid. ...

References

1. E. Fluck, The chemistry of phosphine, Topics in Current Chemistry Vol. 35, 64 pp, 1973.
2. A.D.F. Toy, The Chemistry of Phosphorus, Pergamon Press, Oxford, UK, 1973.
3. WHO (World Health Organisation), Phosphine and selected metal phosphides, Environmental Health Criteria. Published under the joint sponsorship of UNEP, ILO and WHO, Geneva, Vol. 73, 100 pp, 1988.

External links

• International Chemical Safety Card 0694