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Allotropes of phosphorus

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White phosphorus (left), red phosphorus (center left and center right), and violet phosphorus (right)
White phosphorus and resultingallotropes

Elementalphosphoruscan exist in severalallotropes,the most common of which are white and red solids. Solid violet and black allotropes are also known. Gaseous phosphorus exists asdiphosphorusand atomic phosphorus.

White phosphorus[edit]

This section is about the chemistry of white phosphorus. For military applications, seewhite phosphorus munitions.
White phosphorus

White phosphorus sample with a chunk removed from the corner to expose un-oxidized material

Tetraphosphorus molecule
Names
IUPAC names
White phosphorus
Tetraphosphorus
Systematic IUPAC name
1,2,3,4-Tetraphosphatricyclo[1.1.0.02,4]butane
Other names
  • Molecular phosphorus
  • Yellow phosphorus
Identifiers
3D model (JSmol)
ChemSpider
UN number 1381
  • InChI=1S/P4/c1-2-3(1)4(1)2
    Key: OBSZRRSYVTXPNB-UHFFFAOYSA-N
  • P12P3P1P23
Properties
P4
Molar mass 123.895g·mol−1
Density 1.82 g/cm3
Melting point 44.1 °C; 111.4 °F; 317.3 K
Boiling point 280 °C; 536 °F; 553 K
Hazards
NFPA 704(fire diamond)
NFPA 704 four-colored diamondHealth 4: Very short exposure could cause death or major residual injury. E.g. VX gasFlammability 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. propaneInstability 2: Undergoes violent chemical change at elevated temperatures and pressures, reacts violently with water, or may form explosive mixtures with water. E.g. white phosphorusSpecial hazards (white): no code
4
4
2
Except where otherwise noted, data are given for materials in theirstandard state(at 25 °C [77 °F], 100 kPa).
White phosphorus crystal structure

White phosphorus,yellow phosphorusor simplytetraphosphorus(P4) exists asmoleculesof four phosphorusatomsin a tetrahedral structure, joined by six phosphorus—phosphorussingle bonds.Thetetrahedralarrangement results inring strainand instability.[1]Although both are called "white phosphorus", in fact two different crystal allotropes are known, interchanging reversibly at 195.2 K.[2]The element'sstandard stateis thebody-centered cubicα form, which is actuallymetastableunderstandard conditions.[1]The β form is believed to have ahexagonalcrystal structure.[2]

Molten and gaseous white phosphorus also retains the tetrahedral molecules, until 800 °C (1,500 °F; 1,100 K) when it starts decomposing toP
2molecules.[3]TheP
4molecule in the gas phase has a P-P bond length ofrg= 2.1994(3) Å as was determined bygas electron diffraction.[4]The β form of white phosphorus contains three slightly differentP
4molecules, i.e. 18 different P-P bond lengths — between 2.1768(5) and 2.1920(5) Å. The average P-P bond length is 2.183(5) Å.[3]

White phosphorus is a translucentwaxysolid that quickly yellows in light, and impure white phosphorus is for this reason called yellow phosphorus. It glows greenish in the dark (when exposed to oxygen) and is highlyflammableandpyrophoric(self-igniting) upon contact with air. It istoxic,causing severeliver damageon ingestion andphossy jawfrom chronic ingestion or inhalation. The odour of combustion of this form has a characteristic garlic smell, and samples are commonly coated with white "diphosphorus pentoxide",which consists ofP4O10tetrahedral with oxygen inserted between the phosphorus atoms and at their vertices. White phosphorus is only slightly soluble in water and can be stored under water. Indeed, white phosphorus is safe from self-igniting when it is submerged in water; due to this, unreacted white phosphorus can prove hazardous tobeachcomberswho may collect washed-up samples while unaware of their true nature.[5][6]P4is soluble inbenzene,oils,carbon disulfide,anddisulfur dichloride.

Production and applications[edit]

See also:Match

The white allotrope can be produced using several methods. In the industrial process,phosphate rockis heated in an electric or fuel-firedfurnacein the presence ofcarbonandsilica.[7]Elemental phosphorus is then liberated as a vapour and can be collected underphosphoric acid.An idealized equation for thiscarbothermal reactionis shown forcalcium phosphate(although phosphate rock contains substantial amounts offluoroapatite):

2 Ca3(PO4)2+ 6 SiO2+ 10 C → 6 CaSiO3+ 10 CO + P4

White phosphorus has an appreciablevapour pressureat ordinary temperatures. Thevapour densityindicates that the vapour is composed ofP4molecules up to about 800 °C. Above that temperature, dissociation intoP2molecules occurs.

Inbase,white phosphorus spontaneouslydisproportionatestophosphineand various phosphorusoxyacids.[8]

It ignites spontaneously in air at about 50 °C (122 °F), and at much lower temperatures if finely divided (due tomelting-point depression). Phosphorus reacts with oxygen, usually formingtwooxides depending on the amount of available oxygen:P4O6(phosphorus trioxide) when reacted with a limited supply of oxygen, andP4O10when reacted with excess oxygen. On rare occasions,P4O7,P4O8,andP4O9are also formed, but in small amounts. This combustion gives phosphorus(V) oxide:

P4+ 5 O2→ P4O10

Because of this property,white phosphorus is used as a weapon.

Phosphorus pentachlorideis prepared by the reaction of white phosphorus with excess of drychlorine.[9]

P4+ 10Cl2→ 4PCl5

It can also be prepared by the action ofsulfuryl chlorideon white phosphorus.[9]

P4+ 10SO2Cl2→ 4PCl5+ 10SO2

Other polyhedrane analogues[edit]

Although white phosphorus forms thetetrahedron,the simplest possiblePlatonic hydrocarbon,no other polyhedral phosphorus clusters are known.[10]White phosphorus converts to the thermodynamically-stabler red allotrope, but that allotrope is not isolated polyhedra.

Cubane,in particular, is unlikely to form,[10]and the closest approach is the half-phosphorus compoundP4(CH)4,produced fromphosphaalkynes.[11]Other clusters are more thermodynamically favorable, and some have been partially formed as components of larger polyelemental compounds.[10]

Red phosphorus[edit]

Red phosphorus
Red phosphorus structure

Red phosphorusmay be formed by heatingwhite phosphorusto 300 °C (570 °F) in the absence of air or by exposing white phosphorus tosunlight.Red phosphorus exists as anamorphousnetwork. Upon further heating, the amorphous red phosphorus crystallizes. Bulk red phosphorus does not ignite in air at temperatures below 240 °C (460 °F), whereas pieces of white phosphorus ignite at about 30 °C (86 °F).

Under standard conditions it is more stable than white phosphorus, but less stable than the thermodynamically stable black phosphorus. Thestandard enthalpy of formationof red phosphorus is −17.6 kJ/mol.[1]Red phosphorus is kinetically most stable.

It was first presented by Anton von Schrötter before the Vienna Academy of Sciences on December 9, 1847, although others had doubtlessly had this substance in their hands before, such as Berzelius.[12]

Applications[edit]

See also:Safety match

Red phosphorus can be used as a very effectiveflame retardant,especially inthermoplastics(e.g.polyamide) andthermosets(e.g.epoxy resinsorpolyurethanes). The flame retarding effect is based on the formation ofpolyphosphoric acid.Together with the organic polymer material, these acids create a char that prevents the propagation of the flames. The safety risks associated withphosphinegeneration andfriction sensitivityof red phosphorus can be effectively minimized by stabilization andmicro-encapsulation.For easier handling, red phosphorus is often used in form of dispersions or masterbatches in various carrier systems. However, for electronic/electrical systems, red phosphorus flame retardant has been effectively banned by major OEMs due to its tendency to induce premature failures.[13]One persistent problem is that red phosphorus in epoxy molding compounds induces elevated leakage current in semiconductor devices.[14]Another problem was acceleration ofhydrolysisreactions inPBTinsulating material.[15]

Red phosphorus can also be used in the illicit production ofmethamphetamineandKrokodil.

Red phosphorus can be used as an elementalphotocatalystfor hydrogen formation from the water.[16]They display a steady hydrogen evolution rates of 633 μmol/(h⋅g) by the formation of small-sized fibrous phosphorus.[17]

Violet or Hittorf's phosphorus[edit]

Violet phosphorus (right) by a sample of red phosphorus (left)
Violet phosphorus structure
Hitorff's phosphorus structure

Monoclinic phosphorus,orviolet phosphorus,is also known asHittorf's metallic phosphorus.[18][19]In 1865,Johann Wilhelm Hittorfheated red phosphorus in a sealed tube at 530 °C. The upper part of the tube was kept at 444 °C. Brilliant opaquemonoclinic,orrhombohedral,crystals sublimed as a result. Violet phosphorus can also be prepared by dissolving white phosphorus in moltenleadin a sealed tube at 500 °C for 18 hours. Upon slow cooling, Hittorf's allotropecrystallisesout. The crystals can be revealed by dissolving the lead in dilutenitric acidfollowed by boiling in concentratedhydrochloric acid.[20]In addition, afibrousform exists with similar phosphorus cages. The lattice structure of violet phosphorus was presented by Thurn and Krebs in 1969.[21]Imaginary frequencies, indicating the irrationalities or instabilities of the structure, were obtained for the reported violet structure from 1969.[22]The single crystal of violet phosphorus was also produced. The lattice structure of violet phosphorus has been obtained by single-crystalx-ray diffraction to be monoclinic with space group ofP2/n(13) (a= 9.210,b= 9.128,c= 21.893 Å,β= 97.776°,CSD-1935087). The optical band gap of the violet phosphorus was measured by diffuse reflectance spectroscopy to be around 1.7 eV. The thermal decomposition temperature was 52 °C higher than its black phosphorus counterpart. The violet phosphorene was easily obtained from both mechanical and solution exfoliation.

Reactions of violet phosphorus[edit]

Violet phosphorus does not ignite in air until heated to 300 °C and is insoluble in all solvents. It is not attacked byalkaliand only slowly reacts withhalogens.It can beoxidisedbynitric acidtophosphoric acid.

If it is heated in an atmosphere of inert gas, for examplenitrogenorcarbon dioxide,itsublimesand the vapour condenses as white phosphorus. If it is heated in avacuumand the vapour condensed rapidly, violet phosphorus is obtained. It would appear that violet phosphorus is apolymerof high relative molecular mass, which on heating breaks down intoP2molecules. On cooling, these would normallydimerizeto giveP4molecules (i.e. white phosphorus) but, in avacuum,they link up again to form the polymeric violet allotrope.

Black phosphorus[edit]

Black phosphorus ampoule
Black phosphorus
Black phosphorus structure

Black phosphorusis the thermodynamically stable form of phosphorus atroom temperature and pressure,with aheat of formationof −39.3 kJ/mol (relative to white phosphorus which is defined as the standard state).[1]It was first synthesized by heating white phosphorus under high pressures (12,000 atmospheres) in 1914. As a 2D material, in appearance, properties, and structure, black phosphorus is very much likegraphitewith both being black and flaky, a conductor of electricity, and having puckered sheets of linked atoms.[23]

Black phosphorus has anorthorhombicpleated honeycomb structure and is the least reactive allotrope, a result of its lattice of interlinked six-membered rings where each atom is bonded to three other atoms.[24][25]In this structure, each phosphorus atom has five outer shell electrons.[26]Black and red phosphorus can also take acubiccrystal lattice structure.[27]The first high-pressure synthesis of black phosphorus crystals was made by the Nobel prize winnerPercy Williams Bridgmanin 1914.[28]Metal salts catalyze the synthesis of black phosphorus.[29]

Black phosphorus based sensors exhibit several superior qualities over traditional materials used in piezoelectric or resistive sensors. Characterized by its unique puckered honeycomb lattice structure, black phosphorus provides exceptional carrier mobility. This property ensures its high sensitivity and mechanical resilience, making it an intriguing candidate forsensor technology.[30][31]

Phosphorene[edit]

Main article:phosphorene

The similarities to graphite also include the possibility of scotch-tape delamination (exfoliation), resulting inphosphorene,agraphene-like 2D material with excellent charge transport properties, thermal transport properties and optical properties. Distinguishing features of scientific interest include a thickness dependent band-gap, which is not found in graphene.[32]This, combined with a high on/off ratio of ~105makes phosphorene a promising candidate for field-effect transistors (FETs).[33]The tunable bandgap also suggests promising applications in mid-infrared photodetectors and LEDs.[34][35]Exfoliated black phosphorus sublimes at 400 °C in vacuum.[36]It gradually oxidizes when exposed to water in the presence of oxygen, which is a concern when contemplating it as a material for the manufacture of transistors, for example.[37][38]Exfoliated black phosphorus is an emerging anode material in the battery community, showing high stability andlithiumstorage.[39]

Ring-shaped phosphorus[edit]

Ring-shaped phosphorus was theoretically predicted in 2007.[40]The ring-shaped phosphorus was self-assembled inside evacuated multi-walled carbon nanotubes with inner diameters of 5–8 nm using a vapor encapsulation method. A ring with a diameter of 5.30 nm, consisting of 23P8and 23P2units with a total of 230 P atoms, was observed inside a multi-walled carbon nanotube with an inner diameter of 5.90 nm in atomic scale. The distance between neighboring rings is 6.4 Å.[41]

TheP6ring shaped molecule is not stable in isolation.

Blue phosphorus[edit]

Single-layer blue phosphorus was first produced in 2016 by the method ofmolecular beam epitaxyfrom black phosphorus as precursor.[42]

Diphosphorus[edit]

Main article:Diphosphorus
Structure of diphosphorus
Diphosphorus molecule

Thediphosphorusallotrope (P2) can normally be obtained only under extreme conditions (for example, fromP4at 1100 kelvin). In 2006, the diatomic molecule was generated in homogeneous solution under normal conditions with the use oftransition metalcomplexes(for example,tungstenandniobium).[43]

Diphosphorus is the gaseous form ofphosphorus,and the thermodynamically stable form between 1200 °C and 2000 °C. The dissociation of tetraphosphorus (P4) begins at lower temperature: the percentage ofP2at 800 °C is ≈ 1%. At temperatures above about 2000 °C, the diphosphorus molecule begins to dissociate into atomic phosphorus.

Phosphorus nanorods[edit]

P12nanorodpolymers were isolated from CuI-P complexes using low temperature treatment.[44]

Red/brown phosphorus was shown to be stable in air for several weeks and have properties distinct from those of red phosphorus.Electron microscopyshowed that red/brown phosphorus forms long, parallel nanorods with a diameter between 3.4Åand 4.7 Å.[44]

Properties[edit]

Properties of some allotropes of phosphorus[45][46]
Form white(α) white(β) violet black
Symmetry Body-centred cubic Triclinic Monoclinic Orthorhombic
Pearson symbol aP24 mP84 oS8
Space group I43m P1No. 2 P2/c No. 13 Cmca No. 64
Density(g/cm3) 1.828 1.88 2.36 2.69
Bandgap(eV) 2.1 1.5 0.34
Refractive index 1.8244 2.6 2.4

See also[edit]

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External links[edit]

White phosphorus
Retrieved from "https://en.wikipedia.org/w/index.php?title=Allotropes_of_phosphorus&oldid=1234239946#White_phosphorus"