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Chemicals/Phosphoruses

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White phosphorus is under water on the left, with red phosphorus (center images), and violet phosporus right. Credit: Materialscientist.{{free media}}

Phosphorus has several allotropes that exhibit strikingly diverse properties.[1] The two most common allotropes are white phosphorus and red phosphorus.[2]

Emissions

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Phosphorus spectrum is for emission lines between 400 nm - 700 nm. Credit: McZusatz.{{free media}}

Visuals

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Main resource: Radiation astronomy/Visuals
White phosphorus and resulting allotropes, including violet phosphorus, are indicated. Credit: UserXresu.{{free media}}

"The P species in the titania lattice should be the dominant group responsive to visible light, whereas the P species on the surface could retard the phase transition of anatase to rutile and increase the surface area and adsorption capability."[3]

"The P species in the titania lattice should be the dominant group responsive to the visible light activity, although P species on the surface could retard the phase transition of anatase to rutile, and increase the surface area and adsorption capability, consequently enhancing the photocatalytic activity."[3]

White phosphoruses

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A chunk of white phosphorus in water is shown. Credit: W. Oelen.{{free media}}

From the perspective of applications and chemical literature, the most important form of elemental phosphorus is white phosphorus, often abbreviated as WP, is a soft, waxy solid which consists of tetrahedral P
4 molecules, in which each atom is bound to the other three atoms by a formal single bond, this P
4 tetrahedron is also present in liquid and gaseous phosphorus up to the temperature of 800 °C (1,470 °F) when it starts decomposing to P
2 molecules.[4] The P
4 molecule in the gas phase has a P-P bond length of rg = 2.1994(3) Å as was determined by gas electron diffraction.[5] The nature of bonding in this P
4 tetrahedron can be described by spherical aromaticity or cluster bonding, that is the electrons are highly delocalized. This has been illustrated by calculations of the magnetically induced currents, which sum up to 29 nA/T, much more than in the archetypical aromatic molecule benzene (11 nA/T).[5]

White phosphorus exists in two crystalline forms: α (alpha) and β (beta): at room temperature, the α-form is stable, more common, has cubic crystal structure and at 195.2 K (−78.0 °C), transforms into β-form.[6]

The β-form has hexagonal crystal structure and differ in terms of the relative orientations of the constituent P4 tetrahedra.[6][7] The β form of white phosphorus contains three slightly different P
4 molecules, i.e. 18 different P-P bond lengths between 2.1768(5) and 2.1920(5) Å, with the average P-P bond length is 2.183(5) Å.[4]

White phosphorus is the least stable, the most reactive, the most volatile, the least dense and the most toxic of the allotropes which gradually changes to red phosphorus, transformation is accelerated by light and heat, and samples of white phosphorus almost always contain some red phosphorus and accordingly appear yellow.[8]

For this reason, white phosphorus that is aged or otherwise impure (e.g., weapons-grade, not lab-grade WP) is also called yellow phosphorus, when exposed to oxygen, white phosphorus glows in the dark with a very faint tinge of green and blue, is highly flammable and pyrophoric (self-igniting) upon contact with air, has a characteristic garlic smell, and samples are commonly coated with white "phosphorus pentoxide", which consists of P
4O
10 tetrahedra with oxygen inserted between the phosphorus atoms and at their vertices, is insoluble in water but soluble in carbon disulfide.[8]

Black phosphoruses

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Crystals of Black Phosphorus are in a sealed ampoule. Credit: Alshaer666.{{free media}}

Black phosphorus is the thermodynamically stable form of phosphorus at room temperature and pressure, with a standard enthalpy of formation (heat of formation) of -39.3 kJ/mol (relative to white phosphorus which is defined as the standard state).[9]

As a 2D material, in appearance, properties, and structure, black phosphorus is very much like graphite with both being black and flaky, a conductor of electricity, and having puckered sheets of linked atoms.[10]

Black phosphorus has an orthorhombic pleated 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.[11][12] In this structure, each phosphorous atom has 5 outer shell electrons.[13] Black and red phosphorus can also take a cubic crystal lattice structure.[14] The first high-pressure synthesis of black phosphorus crystals was made in 1914.[15] Metal salts catalyze the synthesis of black phosphorus.[16]

Violets

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Main resource: Radiation astronomy/Violets
Violet phosphorus sample is shown. Credit: Michal Sobkowski.{{free media}}

Violet phosphorus is a form of phosphorus that can be produced by day-long annealing of red phosphorus above 550 °C, when phosphorus was recrystallised from molten lead, a red/purple form is obtained, sometimes known as "Hittorf's phosphorus" (or violet or α-metallic phosphorus).[17]

Blues

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Main resource: Radiation astronomy/Blues

Single-layer blue phosphorus was first produced by the method of molecular beam epitaxy from black phosphorus as precursor.[18]

Yellows

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Main resource: Radiation astronomy/Yellows
White phosphorus under water turns yellow when exposed to light. Credit: BXXXD.{{free media}}

White phosphorus is a translucent waxy solid that quickly becomes yellow when exposed to light.

Reds

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Main resource: Radiation astronomy/Reds
Red phosphorus in an ampoule is shown. Credit: Tomihahndorf.{{free media}}

Under standard conditions red phosphorus is more stable than white phosphorus, but less stable than the thermodynamically stable black phosphorus, with a standard enthalpy of formation of red phosphorus is -17.6 kJ/mol.[9]

P12 nanorod polymers were isolated from CuI-P complexes using low temperature treatment.[19]

Electron microscopy showed that red/brown phosphorus forms long, parallel nanorods with a diameter between 3.4 Å and 4.7 Å.[19]

Plasmas

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Gases

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Gaseous phosphorus exists as diphosphorus and atomic phosphorus.

The diphosphorus allotrope (P2) can normally be obtained only under extreme conditions (for example, from P4 at 1100 kelvin): the diatomic molecule was generated in homogeneous solution under normal conditions with the use of transition metal complexes (for example, tungsten and niobium).[20]

Liquids

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The P
4 tetrahedron is present in liquid phosphorus.[4]

Solids

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White phosphorus is a soft, waxy solid which consists of tetrahedral P
4 molecules.[4]

Properties of some allotropes of phosphorus[1][21]
Form white(α) white(β) violet black
Symmetry Body-centred cubic Triclinic Monoclinic Orthorhombic
Pearson symbol aP24 mP84 oS8
Space group I43m P1 No.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

Alloys

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Phosphorus is an important component in steel production, in the making of phosphor bronze, and in many other related products.[22][23]

Phosphorus is added to metallic copper during its smelting process to react with oxygen present as an impurity in copper and to produce phosphorus-containing copper (CuOFP) alloys with a higher hydrogen embrittlement resistance than normal copper.[24]

Minerals

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Phosphate minerals contain the tetrahedrally coordinated phosphate (PO43−) anion along sometimes with arsenate (AsO43−) and vanadate (VO43−) substitutions, and chloride (Cl−), fluoride (F−), and hydroxide (OH−) anions that also fit into the crystal structure.

Allabogdanites

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Allabogdanite is a very rare phosphide mineral with formula (Fe,Ni)
2P, found in 1994 in the Onello meteorite.[25][26] It was described for an occurrence in the Onello meteorite in the Onello River basin, Sakha Republic; Yakutia, Russia; associated with taenite, schreibersite, kamacite, graphite and awaruite.[26] It was named for Russian geologist Alla Bogdanova.[27]

In June 2021 terrestrial allabogdanite was discovered in a sedimentary formation, located in the Negev desert of Israel, just southwest of the Dead Sea.[28]

Iron–Nickel–Chromium–Cobalt–Phosphorus

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"Grain size varies from 98 to 530 lm with an average of *150 lm. Minor [elements] oxidation [from an iron–nickel–chromium–cobalt–phosphorus alloy] is evidenced by the presence of a light brown and blue surface layer composed of very fine-grained (<1 lm) crystals on the surface."[29] "[T]he oxidation of minor elements in metallic alloys in the early solar system" is indicated to possess at instances a blue surface layer.[29]

Schreibersites

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Slice is from the Gebel Kamil Meteorite with schreibersite rimmed by kamacite. Credit: Butcherbird.{{free media}}

Schreibersite is generally a rare iron nickel phosphide mineral, (Fe,Ni)3P, though common in iron-nickel meteorites, where the only known occurrence of the mineral on Earth is located on Disko Island in Greenland.[30]

Another name used for the mineral is rhabdite that forms tetragonal crystals with perfect 001 cleavage; color ranges from bronze to brass yellow to silver white; density is 7.5 and a hardness of 6.5 – 7; opaque with a metallic luster and a dark gray streak; named after the Austrian scientist Carl Franz Anton Ritter von Schreibers (1775–1852), who was one of the first to describe it from iron meteorites.[31]

Schreibersite is reported from the Magura Meteorite, Arva-(present name – Orava), Slovak Republic; the Sikhote-Alin Meteorite in eastern Russia; the São Julião de Moreira Meteorite, Viana do Castelo, Portugal; the Gebel Kamil (meteorite) in Egypt; and numerous other locations including the Moon.[32]

Schreibersite and other meteoric phosphorus bearing minerals may be the ultimate source for the phosphorus that is so important for life on Earth.[33][34][35] Pyrophosphite is a possible precursor to pyrophosphate, the molecule associated with adenosine triphosphate (ATP), a co-enzyme central to energy metabolism in all life on Earth, produced by subjecting a sample of schreibersite to a warm, acidic environment typically found in association with volcanic activity, activity that was far more common on the primordial Earth, possibly representing "chemical life", a stage of evolution which may have led to the emergence of fully biological life as exists today.[36]

Phosphorites

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Peloidal phosphorite, Phosphoria Formation, Simplot Mine, Idaho. 4.6 cm wide. Credit: James St. John.{{free media}}
Fossiliferous peloidal phosphorite, (4.7 cm across), is from Yunnan Province, China. Credit: James St. John.{{free media}}

The Phosphoria Formation is the most famous phosphorite unit in America. On a global scale, phosphorite deposition was at its maximum, volumetrically, during the Neoproterozoic and Cambrian (see Zhongyicun Member phosphorite specimen).

The fossiliferous peloidal phosphorite comes from just south of Ercaicun, ~4 km WSW of Haikou, Kunming City Prefecture, east-central Yunnan Province, southwestern China. This rock was deposited not long after the Cambrian Explosion (the sudden, evolutionary appearance of abundant fossil life near the Precambrian-Cambrian boundary).

On a global scale, phosphorite deposition was at its maximum, volumetrically, during the Neoproterozoic and Cambrian.

Glaciology

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"Phosphorus has been shown to be deficient in glacial environments, and thus is one of the limits on microbial growth and activity."[37]

Resources

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See also

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References

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  1. ↑ 1.0 1.1 A. Holleman; N. Wiberg (1985). "XV 2.1.3". Lehrbuch der Anorganischen Chemie (33rd ed.). de Gruyter. 
  2. ↑ Abundance. ptable.com
  3. ↑ 3.0 3.1 Renyang Zheng; Li Lin; Jinglin Xie; Yuexiang Zhu; Youchang Xie (September 10, 2008). "State of Doped Phosphorus and Its Influence on the Physicochemical and Photocatalytic Properties of P-doped Titania". Journal of Physical Chemistry C 112 (39): 15502-9. doi:10.1021/jp806121m. http://pubs.acs.org/doi/abs/10.1021/jp806121m?prevSearch=%2522dominant%2Bgroup%2522&searchHistoryKey=. Retrieved 2012-03-16. 
  4. ↑ 4.0 4.1 4.2 4.3 Simon, Arndt; Borrmann, Horst; Horakh, Jörg (1997). "On the Polymorphism of White Phosphorus". Chemische Berichte 130 (9): 1235–1240. doi:10.1002/cber.19971300911. 
  5. ↑ 5.0 5.1 Cossairt, Brandi M.; Cummins, Christopher C.; Head, Ashley R.; Lichtenberger, Dennis L.; Berger, Raphael J. F.; Hayes, Stuart A.; Mitzel, Norbert W.; Wu, Gang (2010-06-01). "On the Molecular and Electronic Structures of AsP3 and P4". Journal of the American Chemical Society 132 (24): 8459–8465. doi:10.1021/ja102580d. ISSN 0002-7863. PMID 20515032. http://dx.doi.org/10.1021/ja102580d. 
  6. ↑ 6.0 6.1 Welford C. Roberts; William R. Hartley (1992-06-16). Drinking Water Health Advisory: Munitions (illustrated ed.). CRC Press, 1992. p. 399. 
  7. ↑ Marie-Thérèse Averbuch-Pouchot; A. Durif (1996). Topics in Phosphate Chemistry. World Scientific, 1996. p. 3. 
  8. ↑ 8.0 8.1 Greenwood, N. N.; & Earnshaw, A. (1997). Chemistry of the Elements (2nd Edn.), Oxford:Butterworth-Heinemann. ISBN 0-7506-3365-4.
  9. ↑ 9.0 9.1 Housecroft, C. E.; Sharpe, A. G. (2004). Inorganic Chemistry (2nd ed.). Prentice Hall. p. 392. ISBN 978-0-13-039913-7.
  10. ↑ Korolkov, Vladimir V.; Timokhin, Ivan G.; Haubrichs, Rolf; Smith, Emily F.; Yang, Lixu; Yang, Sihai; Champness, Neil R.; Schröder, Martin et al. (2017-11-09). "Supramolecular networks stabilise and functionalise black phosphorus". Nature Communications 8 (1): 1385. doi:10.1038/s41467-017-01797-6. ISSN 2041-1723. PMID 29123112. PMC 5680224. //www.ncbi.nlm.nih.gov/pmc/articles/PMC5680224/. 
  11. ↑ Brown, A.; Rundqvist, S. (1965). "Refinement of the crystal structure of black phosphorus". Acta Crystallographica 19 (4): 684–685. doi:10.1107/S0365110X65004140. 
  12. ↑ Cartz, L.; Srinivasa, S. R.; Riedner, R. J.; Jorgensen, J. D.; Worlton, T. G. (1979). "Effect of pressure on bonding in black phosphorus". The Journal of Chemical Physics 71 (4): 1718. doi:10.1063/1.438523. 
  13. ↑ Ling, Xi; Wang, Han; Huang, Shengxi; Xia, Fengnian; Dresselhaus, Mildred S. (2015-03-27). "The renaissance of black phosphorus". Proceedings of the National Academy of Sciences 112 (15): 4523–4530. doi:10.1073/pnas.1416581112. ISSN 0027-8424. PMID 25820173. PMC 4403146. //www.ncbi.nlm.nih.gov/pmc/articles/PMC4403146/. 
  14. ↑ Ahuja, Rajeev (2003). "Calculated high pressure crystal structure transformations for phosphorus". Physica Status Solidi B 235 (2): 282–287. doi:10.1002/pssb.200301569. 
  15. ↑ Bridgman, P. W. (1914-07-01). "Two New Modifications of Phosphorus". Journal of the American Chemical Society 36 (7): 1344–1363. doi:10.1021/ja02184a002. ISSN 0002-7863. https://zenodo.org/record/1428993. 
  16. ↑ Lange, Stefan; Schmidt, Peer; Nilges, Tom (2007). "Au
    3    SnP
    7     Black Phosphorus: An Easy Access to Black Phosphorus". Inorganic Chemistry 46 (10): 4028–35. doi:10.1021/ic062192q. PMID 17439206.     
  17. ↑ Berger, L. I. (1996). Semiconductor materials. CRC Press. p. 84]. https://archive.org/details/semiconductormat0000berg. 
  18. ↑ Zhang, Jia Lin; Zhao, Songtao and 10 others (30 June 2016). "Epitaxial Growth of Single Layer Blue Phosphorus: A New Phase of Two-Dimensional Phosphorus". Nano Letters 16 (8): 4903–4908. doi:10.1021/acs.nanolett.6b01459. PMID 27359041. 
  19. ↑ 19.0 19.1 Pfitzner, A; Bräu, Mf; Zweck, J; Brunklaus, G; Eckert, H (Aug 2004). "Phosphorus nanorods – two allotropic modifications of a long-known element". Angewandte Chemie International Edition in English 43 (32): 4228–31. doi:10.1002/anie.200460244. PMID 15307095. 
  20. ↑ Piro, Na; Figueroa, Js; Mckellar, Jt; Cummins, Cc (2006). "Triple-bond reactivity of diphosphorus molecules". Science 313 (5791): 1276–9. doi:10.1126/science.1129630. PMID 16946068. 
  21. ↑ Berger, L. I. (1996). Semiconductor materials. CRC Press. p. 84. ISBN 978-0-8493-8912-2. https://archive.org/details/semiconductormat0000berg. 
  22. ↑ Roland W. Scholz, ed (2014-03-12). Sustainable Phosphorus Management: A Global Transdisciplinary Roadmap. Springer Science & Business Media. p. 175. ISBN 978-9400772502. 
  23. ↑ Mel Schwartz (2016-07-06). Encyclopedia and Handbook of Materials, Parts and Finishes. CRC Press. ISBN 978-1138032064. 
  24. ↑ Joseph R. Davisz, ed (January 2001). Copper and Copper Alloys. ASM International. p. 181. 
  25. ↑ Britvin, Sergey N.; Rudashevsky, Nikolay S.; Krivovichev, Sergey V.; Burns, Peter C.; Polekhovsky, Yury S. (2002). "Allabogdanite, (Fe,Ni)
    2    P, a new mineral from the Onello meteorite: The occurrence and crystal structure". American Mineralogist 87 (8–9): 1245–1249. doi:10.2138/am-2002-8-924.     
  26. ↑ 26.0 26.1 Mindat
  27. ↑ Webmineral data
  28. ↑ Britvin, Sergey N.; Vereshchagin, Oleg S.; Shilovskikh, Vladimir V.; Krzhizhanovskaya, Maria G.; Gorelova, Liudmila A.; Vlasenko, Natalia S.; Pakhomova, Anna S.; Zaitsev, Anatoly N. et al. (2021). "Discovery of terrestrial allabogdanite (Fe,Ni)2P, and the effect of Ni and Mo substitution on the barringerite-allabogdanite high-pressure transition". American Mineralogist 106 (6): 944–952. doi:10.2138/am-2021-7621. https://bib-pubdb1.desy.de/record/449035. 
  29. ↑ 29.0 29.1 Dante S. Lauretta; Britney E. Schmidt (April 1, 2009). "Oxidation of Minor Elements from an Iron–Nickel–Chromium–Cobalt–Phosphorus Alloy in 17.3% CO2–H2 gas mixtures at 700–1000 °C". Oxidation of Metals 71 (3-4): 219-35. doi:10.1007/s11085-009-9140-7. http://link.springer.com/article/10.1007/s11085-009-9140-7. Retrieved 2013-06-01. 
  30. ↑ "Power behind primordial soup discovered", Eurekalert, April 4, 2013
  31. ↑ Schreibersite. Webmineral
  32. ↑ Hunter R. H.; Taylor L. A. (1982). "Rust and schreibersite in Apollo 16 highland rocks – Manifestations of volatile-element mobility". Lunar and Planetary Science Conference, 12th, Houston, TX, March 16–20, 1981, Proceedings. Section 1. (A82-31677 15–91). New York and Oxford: Pergamon Press. pp. 253–259. Bibcode: 1982LPSC...12..253H. 
  33. ↑ Report of U of A Extra-terrestrial Phosphorus
  34. ↑ "5.2.3. The Origin of Phosphorus". The Limits of Organic Life in Planetary Systems. National Academies Press. 2007. p. 56. ISBN 978-0309104845. http://books.nap.edu/openbook.php?record_id=11919&page=56. 
  35. ↑ Sasso, Anne (January 3, 2005) Life's Fifth Element Came From Meteors. Discover Magazine.
  36. ↑ Bryant, D. E.; Greenfield, D.; Walshaw, R. D.; Johnson, B. R. G.; Herschy, B.; Smith, C.; Pasek, M. A.; Telford, R. et al. (2013). "Hydrothermal modification of the Sikhote-Alin iron meteorite under low pH geothermal environments. A plausibly prebiotic route to activated phosphorus on the early Earth". Geochimica et Cosmochimica Acta 109: 90–112. doi:10.1016/j.gca.2012.12.043. 
  37. ↑ Marek Stibal; Martyn Tranter; Jon Telling; Liane G. Benning (2008). "Speciation, phase association and potential bioavailability of phosphorus on a Svalbard glacier". Biogeochemistry 90 (1): 1-13. doi:10.1007/s10533-008-9226-3. http://link.springer.com/article/10.1007/s10533-008-9226-3. Retrieved 2014-06-24. 
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