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{{otheruses4|chemical element}}
[[Image:CalinescuG.jpg|thumb|200px|George Călinescu]]
{{Infobox phosphorus}}
'''Phosphorus''', ({{IPAEng|ˈfɒsfərəs}}), is the [[chemical element]] that has the symbol '''P''' and [[atomic number]] 15. The name comes from the {{lang-el|''φώς''}} (meaning "light") and ''φόρος'' (meaning "bearer"). A [[Valency (chemistry)|multivalent]] [[nonmetal]] of the [[nitrogen group]], phosphorus is commonly found in inorganic [[phosphate minerals|phosphate rocks]].


Due to its high reactivity, phosphorus is gay haha fuck it never found as a free element in nature on Earth. One form of phosphorus (white phosphorus) emits a faint glow upon exposure to [[oxygen]] &mdash; hence its Greek derivation, Φωσφόρος meaning "light-bearer" (Latin ''[[Lucifer]]''), the planet [[Venus]] as "[[Hesperus|Morning Star]]".
'''George Călinescu''' ([[June 19]], [[1899]], [[Bucharest]] - [[March 12]], [[1965]], [[Otopeni]]) was a [[Romania]]n literary critic, historian, Academician and journalist, and writer of [[Classicism|classicist]] and [[Humanism|humanist]] tendencies. He is currently considered one of the most important Romanian literary critics of all time, alongside [[Titu Maiorescu]] and [[Eugen Lovinescu]], and one of the outstanding figures of Romanian letters in the 20th century.
==Biography==
===Early childhood===
George Călinescu was born Gheorghe Vişan on the [[14 June 1899]] as the son of a housekeeper, Maria Vişan; the child was brought up by his mother's employers, Constantin Călinescu, a worker for [[Romanian State Railways]], and his wife Maria, in their house in Bucharest. The Călinescu family, along with their housekeeper and the child, moved first to [[Botoşani]], then to [[Iaşi]], where Gheorghe Vişan, the future writer, matriculated at the Şcoala "Carol I." In [[1907]], Maria Vişan accepted the Călinescu's offer to formally adopt her son, who then took the name Gheorghe Călinescu.


Phosphorus is a component of [[DNA]] and [[RNA]], as well as [[Adenosine triphosphate|ATP]], and is an essential element for all [[living cell]]s. The most important commercial use of phosphorus-based chemicals is the production of [[fertilizer]]s.
===Education===
Călinescu spent his first two years of primary school at Iaşi's ''Colegiul Carol I'', the other two in Bucharest at the ''Şcoala Cuibul cu barză'', then moved on to the Gimnazie ''Dimitrie Cantemir'' before finishing his secondary studies at the Liceul ''Gheorghe Lazăr.'' He remained in Bucharest for his university studies, gaining his "license" in literature from the Faculty of Letters and Philosophy of Bucharest in [[1923]] with a thesis on [[Carducci]]'s humanism. During his studies in Bucharest, Călinescu was profoundly marked by his collaboration with two professors: the Italian scholar [[Ramiro Ortiz]] and the Romanian historian [[Vasile Pârvan]].


Phosphorus compounds are also widely used in [[explosive material|explosives]], [[nerve agents]], friction [[match]]es, [[firework]]s, [[pesticide]]s, [[toothpaste]] and [[detergent]]s.
===A Model: Ramiro Ortiz===
[[Ramiro Ortiz]], who taught Italian language and literature at the Faculty of Letters and Philosophy, exercised a seminal influence over Călinescu's development. Călinescu developed a strong friendship with Ortiz; years later, he would give Ortiz credit for helping him "seize" a literary education of extraordinary quality. Under Ortiz's guidance Călinescu made his first translations from Italian; during his student days he translated [[Giovanni Papini]]'s autobiographical novel ''Un uomo finito'' and a novella from [[Boccaccio]]'s ''[[Decameron]].'' Again with Ortiz's help, he began work at the literary review ''Roma'', the first issue appearing in January 1921, and travelled to Italy with his university colleagues. Călinescu's first book was written in Italian under the title ''Alcuni missionari catolici italiani nella Moldavia nei secoli XVII e XVIII,'' which appeared in 1925 and treated the Vatican's counter-reformationary propaganda efforts in Baroque Moldavia with heavy reliance on unpublished sources found in the Vatican Archives.


== Characteristics==
===Another Model: Vasile Pârvan===
===Allotropes===
If in Bucharest, alongside Ramiro Ortiz, Călinescu realized his vocation as a creative artist and scholar, his attention in Rome was focused on Vasile Pârvan, the director of the [[Accademia di Romania]]. Călinescu was captivated by Pârvan's erudition and work ethic, but also by his existential philosophy. Călinescu would always return to this "spiritual father" whenever the difficulties of life seemed to bring him to his knees. Călinescu observed that while Pârvan's natural aptitude was fairly common, his tendency to exercise all the powers of his mind in the ascetic pursuit of an intellectual ideal was transformed into an existential philosophy: Life is transitory, but man can defeat death and oblivion through creation, thus leaving a permanent record of a temporary existence. Călinescu later said, "even if not everyone is in a position to become a Pârvan, everyone can see in him a model, that is to say a way in which he too can accomplish the same renunciations."
{{main|Allotropes of phosphorus}}
Phosphorus is an excellent example of an element that exhibits [[allotropy]], as its various allotropes have strikingly different properties.


The two most common allotropes are white phosphorus and red phosphorus. A third form, scarlet phosphorus, is obtained by allowing a solution of white phosphorus in carbon disulfide to evaporate in sunlight. A fourth allotrope, black phosphorus, is obtained by heating white phosphorus under very high pressures (12,000 atmospheres). In appearance, properties and structure it is very like graphite, being black and flaky, a conductor of electricity and has puckered sheets of linked atoms. Another allotrope is [[diphosphorus]] - which is highly reactive.
===Rediscovery of Romanian literature===
In 1926, following his stay in Rome, Călinescu rented a house in Bucharest, obtained a position at the Liceul Gheorghe Şincai, and began to read his work to the literary circle forming around Eugen Lovinescu. In 1929, he married Alice Vera, the daughter of minor Bucharest landlords. The highly amusing story of their first meeting would be richly described in Călinescu's novel ''Cartea nunţii.'' With the help of other writers he also edited the review ''Sinteza'' in 1927 and published two editions of his own review, ''Capricorn'', in 1930. The minor adventure of having his own review resulted in financial disaster, but within its pages he first worked out a method for applying his insights to Romanian literature. A more fertile experience resulted from his collaboration at ''Viaţa românească'', the review published by critic [[Garabet Ibrăileanu]], which helped him to his definitive decision to become a professor of Romanian literature in 1931. In 1933, working for the ''Advărul literar şi artistic,'' he inaugurated his celebrated column ''Cronica mizantropului,'' which would later give its title to his collected essays.


[[Image:White phosphrous molecule.jpg|left|175px]]
===Doctorate in literature - and beyond===
[[White phosphorus]] ({{chem|P|4}}) exists as individual molecules made up of four atoms in a [[tetrahedral]] arrangement, resulting in very high [[ring strain]] and instability. It contains 6 single bonds.
In 1936, Călinescu received his doctorate in literature from the University of Iaşi with a thesis on ''Avatarii faraonului Tla'', a posthumous work of [[Mihai Eminescu]] whose value he was the first to publicize. In fact, this thesis was an extract from Călinescu's earlier work, ''Opera lui Mihai Eminescu'', which he wrote out longhand in five copies and sent to the members of the Examination Committee. Afterwards he was named Lecturer in Romanian Literature at the Faculty of Letters of the University of Iaşi, after having won the competition for the post with the maximum possible score. In 1945, he transferred to the University of Bucharest, from which point he collaborated on the prestigious ''Revistă a Fundaţiilor Regale'', edited by [[Alexandru Rosetti]] and [[Camil Petrescu]], until the abdication of the King in 1947. After 1947, he was published consistently in such reviews as ''Gazeta literară'' (later to become ''România literară'') and ''Contemporanul'', also collaborating on ''Roma'', ''Universul literar'', ''Viaţa literară'', ''Sburătorul'', and ''Gândirea''.


White phosphorus is a white, waxy transparent solid. This allotrope is thermodynamically unstable at normal condition and will gradually change to red phosphorus. This transformation, which is accelerated by light and heat, makes white phosphorus almost always contain some red phosphorus and therefore appear yellow. For this reason, it is also called yellow phosphorus. It glows greenish in the dark (when exposed to oxygen), is highly [[flammable]] and [[pyrophoricity|pyrophoric]] (self-igniting) upon contact with air as well as [[toxicity|toxic]] (causing severe liver damage on ingestion). The incendiary bomb [[Napalm]] relies, among others, on this principle to spontaneously ignite. The odour of combustion of this form has a characteristic garlic smell, and samples are commonly coated with white "(di)[[phosphorus pentoxide]]", which consists of P<sub>4</sub>O<sub>10</sub> tetrahedra with oxygen inserted between the phosphorus atoms and at their vertices. White phosphorus is insoluble in water but soluble in carbon disulfide.
===Under Communism===
Călinescu was deposed from his position at the Faculty of Letters of the University of Bucharest after the establishment in power of the [[Communist Party of Romania]]. He was considered a political liability despite having shown evidence of democratic, left-leaning tendencies throughout the interwar period. In the 1950's, however, he became director of the ''Institutul de Teorie literară şi Folclor'' and coordinated the institute's publication, ''Studii şi cercetări de istorie literară şi folclor'', from 1952 to 1965. He was reinvited to his post at the Faculty of Letters only in 1961; in the meantime, he produced numerous writings on wide-ranging subjects, from the aesthetic of folk tales to the history of Spanish literature.
The white allotrope can be produced using several different methods. In one process, [[calcium]] phosphate, which is derived from phosphate rock, is heated in an electric or fuel-fired furnace in the presence of [[carbon]] and [[silica]]<ref name="threlfall"/>. Elemental phosphorus is then liberated as a vapour and can be collected under [[phosphoric acid]]. This process is similar to the first synthesis of phosphorus from calcium phosphate in urine.


Red phosphorus may be formed by heating white phosphorus to 250°C (482°F) or by exposing white phosphorus to sunlight. Phosphorus after this treatment exists as an [[amorphous]] network of atoms which reduces strain and gives greater stability; further heating results in the red phosphorus becoming crystalline. Red phosphorus does not catch fire in air at temperatures below 240°C, whereas white phosphorus ignites at about 30°C.
==Research, criticism, writings==
Călinescu was the author of several fundamental texts of Romanian literary history (''Viaţa lui Mihai Eminescu, Opera lui Mihai Eminescu,'' and ''Viaţa lui Ion Creanga'' among others). After 1945, he published significant writings on world literature (including ''Impresii asupra literaturii spaniole,'' and ''Scriitori străini''.) His study ''Estetica basmului'', devoted to the poetics of Romanian folk tales, underlined the range of his interests. From 1932 to 1962, he published monographs, in separate volumes, on such writers as Eminescu, fabulist [[Ion Creangă]], realist novelist [[Nicolae Filimon]], and poet [[Grigore Alexandrescu]], fictionalized biographies, scholarly studies, and essays. He continued presiding over numerous academic and radio conferences and writing thousands of critical reviews until his death in 1965.


In 1865 [[Hittorf]] discovered that when phosphorus was recrystallized from molten [[lead]], a red/purple form is obtained. This purple form is sometimes known as "Hittorf's phosphorus." In addition, a fibrous form exists with similar phosphorus cages. Below is shown a chain of phosphorus atoms which exhibits both the purple and fibrous forms.
===Novelist, poet, and dramatist===
Călinescu produced heavily descriptive realist novels in the mode of [[Honoré de Balzac]], often with obvious polemical undertones lurking beneath their apparently objective style. The novel he considered his best, ''Enigma Otiliei'', narrates an unhappy love story; ''Cartea nunţii'' is a disquisition on marriage; and ''Bietul Ioanide'' and ''Scrinul negru'' present the problems of intellectuals, all against the backdrop of interwar and immediate postwar Romania. Călinescu also wrote poems (''Lauda lucrurilor'') and plays (''Şun, mit mongol'') while continuing to practice journalism, although ''Cronicile mizantropului'' abruptly became ''Cronicile optimistului'' after the Communists seized power in 1947.


[[Image:Hittoff phosphorus chain.jpg|400px]]
===Civic and political activity under Communism===
An intellectual with liberal-left ideas who nonetheless proved flexible enough to write praises of the King under Carol's dictatorship, Călinescu outwardly adhered to the new Communist ideology after 1947, likely noting the practical advantages of such a shift in loyalties.


One of the forms of red/black phosphorus is a [[cubic]] solid.<ref>{{cite journal
He made numerous research trips to the [[Soviet Union]] (''Kiev, Moscova, Leningrad'' appeared in 1949) and the [[People's Republic of China]] (''Am fost în China nouă'', in 1953), publishing his impressions in the two volumes above.
| author = Ahuja, R.
| year = 2003
| title = Calculated high pressure crystal structure transformations for phosphorus
| journal = [[Physica Status Solidi]] Section B
| volume = 235
| issue = 2
| pages = 282–287
| doi = 10.1002/pssb.200301569
}}</ref>


Black phosphorus has an [[Orthorhombic crystal system|orthorhombic]] structure (C<sub>mca</sub>) and is the least reactive allotrope. It consists of many six-membered rings which are interlinked. Each atom is bonded to three other atoms.<ref name="Brown">{{cite journal | author = A. Brown, S. Runquist | journal = [[Acta Crystallogr.]] | volume = 19 | year = 1965 | pages = 684 | doi = 10.1107/S0365110X65004140 | title = Refinement of the crystal structure of black phosphorus}}</ref><ref>{{cite journal | author = Cartz, L.;Srinivasa, S.R.;Riedner, R.J.;Jorgensen, J.D.;Worlton, T.G. | journal = [[Journal of Chemical Physics]] | year = 1979 | volume = 71 | pages = 1718–1721 | doi = 10.1063/1.438523 | title = Effect of pressure on bonding in black phosphorus}}</ref> A recent synthesis of black phosphorus using metal salts as catalysts has been reported.<ref>{{cite journal | author = Stefan Lange, Peer Schmidt, and Tom Nilges | journal = [[Inorg. Chem.]] | year = 2007 | volume = 46 | pages = 4028 | doi = 10.1021/ic062192q | title = Au3SnP7@Black Phosphorus: An Easy Access to Black Phosphorus}}</ref>
From 1948 to 1953 Călinescu was mistrusted and marginalized, despite being named to the Academy of the Romanian People's Republic in 1949; even after destalinization began in the [[Soviet Union]] in 1953, the Romanian establishment continued to favor the "wooden-tongued," [[socialist realist]] models the Soviets had begun to abandon. Călinescu's total inability to write convincingly in this style resulted in his continued perception as a reactionary conservative. Nonetheless, he was invited to resume his columns on a permanent basis in 1956, marking the beginning of his rehabilitation. Before the end of his life, all of his works, with the exception of his monumental ''Istoria'', were issued in new editions; ''Istoria'' would appear (to great acclaim) only in the 1980's, through the efforts of Călinescu's assistant Alexandru Piru.


The diphosphorus allotrope (P<sub>2</sub>) can be obtained normally only under extreme conditions (for example, from P<sub>4</sub> at 1100 kelvin). Nevertheless, some advancements were obtained in generating the diatomic molecule in homogeneous solution, under normal conditions with the use by some transitional metal complexes (based on, for example, [[tungsten]] and [[niobium]]).<ref>{{cite journal | journal = [[Science (journal)|Science]] | volume = 313 | issue = 5791 | pages = 1276 | doi = 10.1126/science.1129630 | title = Triple-Bond Reactivity of Diphosphorus Molecules | year = 2006 | author = Piro, N. A. | pmid = 16946068}}</ref>
===Final years of life===
[[Image:Schwarzer Phosphor2.svg|left|200px]]
In November 1964, George Călinescu was diagnosed with cirrhosis of the liver and sent for treatment to the sanatorium at Otopeni. On [[12 March 1965]], in the middle of the night, he died - leaving behind, in the words of Geo Bogza, "a body of work fundamental to the Romanian people."


===Post-Communist reputation===
=== Glow ===
The chemical element [[phosphorus]] ([[Greek language|Greek]]. ''phosphoros'', meaning "light bearer") was discovered by [[Germany|German]] alchemist [[Hennig Brand]] in 1669. Working in [[Hamburg]], Brand attempted to distill some kind of "life essence" from his urine, and in the process produced a white material that glowed in the dark. However, phosphorus itself is ''not'' a [[phosphor]]; it is highly reactive and gives-off a faint [[chemiluminescence|chemiluminescent]] glow upon uniting with [[oxygen]]. The glow observed by Brand was actually caused by the very slow burning of the phosphorus, but as he saw no flame nor felt any heat he did not recognize it as burning.
After 1989 there began a period in which Călinescu's civic activity under the Communist regime was called into question, and in which he was accused of collaborating with the authorities, notably by his former assistant Adrian Marino. A veritable "trial by press" resulted in which all of his works and activities were systematically reevaluated, proving Călinescu's perennial value and ability to offer new generations new perspectives on his own times and the whole history of Romanian literature.


The mechanism for that glow was not fully described until 1974.<ref name="shockinghistory">Emsley, John (2000). ''The Shocking History of Phosphorus''. London: Macmillan. ISBN 0-330-39005-8</ref> It was known from early times that the glow would persist for a time in a stoppered jar but then cease. [[Robert Boyle]] in the 1680s ascribed it to "debilitation" of the air; in fact, it is oxygen being consumed. By the 18th century, it was known that in pure oxygen phosphorus does not glow at all;<ref>[http://nobelprize.org/chemistry/laureates/1956/press.html Nobel Prize in Chemistry 1956 - Presentation Speech], by Professor A. Ölander (committee member)</ref> there is only a range of [[partial pressure]] at which it does. Heat can be applied to drive the reaction at higher pressures.<ref>[http://www.lateralscience.co.uk/phos/index.html Phosphorus Topics page, at Lateral Science]</ref>


In 1974, the glow was explained by R. J. van Zee and A. U. Khan.<ref name="shockinghistory"/> A reaction with oxygen takes place at the surface of the solid (or liquid) phosphorus, forming the short-lived molecules HPO and P<sub>2</sub>O<sub>2</sub> that both emit visible light. The reaction is slow and only very little of the intermediates is required to produce the luminescence, hence the extended time the glow continues in a stoppered jar.
==Works of George Călinescu==


Although the term [[phosphorescence]] is derived from phosphorus, the reaction which gives phosphorus its glow is properly called luminescence (glowing by its own reaction, in this case [[chemoluminescence]]), not phosphorescence (re-emitting light that previously fell on it).
===Studies in foreign languages===
* ''Alcuni missionari catolici italiani nella Moldavia nella secoli XVII e XVIII'' (On Some Italian Catholic Missionaries in the Moldavia of the 17th and 18th Centuries), 1925.


=== Isotopes ===<!-- This section is linked from [[Silicon]] -->
===Studies on aesthetics and world literature===
{{main|Isotopes of phosphorus}}
* ''Principii de estetică'' (Principles of Aesthetics), 1939.
{{Expand-section|date=January 2008}}<!-- add about 31P -->
* ''Impresii asupra literaturii spaniole'' (Impressions on Spanish Literature), 1946.
[[Radioactive decay|Radioactive]] [[isotope]]s of phosphorus include
* ''Sensul clasicismului'' (The Meaning of Classicism), 1946.
* <sup>32</sup>P; a [[beta particle|beta]]-emitter (1.71 MeV) with a [[half-life]] of 14.3 days which is used routinely in life-science laboratories, primarily to produce [[radiolabel]]ed DNA and RNA [[probe]]s, ''e.g.'' for use in [[Northern blot]]s or [[Southern blot]]s. Because the high energy beta particles produced penetrate skin and [[cornea]]s, and because any <sup>32</sup>P ingested, inhaled, or absorbed is readily incorporated into bone and [[nucleic acid]]s, [[Occupational Safety and Health Administration]] in the Unites States, and similar institutions in other developed countries require that a [[lab coat]], [[rubber glove|disposable gloves]], and [[safety glasses]] or [[goggle]]s be worn when working with <sup>32</sup>P, and that working directly over an open container be avoided in order to protect the eyes. [[Monitoring]] personal, clothing, and surface contamination is also required. In addition, due to the high energy of the beta particles, [[radiation shield|shielding]] this radiation with the normally used dense materials (''e.g.'' [[lead]]), gives rise to secondary emission of [[X-ray]]s via a process known as [[Bremsstrahlung]], meaning [[braking radiation]]. Therefore shielding must be accomplished with low density materials, ''e.g.'' [[Plexiglas]], [[Lucite]], [[plastic]], [[wood]], or [[water]].<ref>http://www.oseh.umich.edu/TrainP32.pdf</ref>
* ''Studii şi conferinţe'' (Studies and Conferences), 1956.
* <sup>33</sup>P; a beta-emitter (0.25 MeV) with a half-life of 25.4 days. It is used in life-science laboratories in applications in which lower energy beta emissions are advantageous such as DNA sequencing.
* ''Scriitori străini'' (Foreign Writers), 1967.


===Poetry===
=== Occurrence ===
:''See also [[:category:Phosphate minerals|Phosphate minerals]].''
* ''Poesii'' (Poetry), 1937.
* ''Lauda lucrurilor'' (In Praise of Things), 1963.


Due to its reactivity with air and many other oxygen-containing substances, phosphorus is not found free in nature but it is widely distributed in many different [[mineral]]s.
==Drama==
* ''Şun, mit mongol sau Calea neturburată'' (Şun, a Mongol Myth), 1940.
* ''Ludovic al XIX-lea'' (Louis the Nineteenth), 1964.
* ''Teatru'' (Theatre), 1965.


Phosphate rock, which is partially made of [[apatite]] (an impure tri-calcium phosphate mineral), is an important commercial source of this element. About 50 per cent of the global phosphorus reserves are in the Arab nations.<ref>http://www.anba.com.br/ingles/noticia.php?id=17288</ref> Large deposits of apatite are located in [[China]], [[Russia]], [[Morocco]], [[Florida]], [[Idaho]], [[Tennessee]], [[Utah]], and elsewhere. [[Albright and Wilson]] in the United Kingdom and their [[Niagara Falls]] plant, for instance, were using phosphate rock in the 1890s and 1900s from [[Connetable]], Tennessee and Florida; by 1950 they were using phosphate rock mainly from Tennessee and North Africa<ref name="threlfall"/>. In the early 1990s Albright and Wilson's purified wet phosphoric acid business was being affected by phosphate rock sales by China and the entry of their long standing Moroccan phosphate suppliers into the purified wet phosphoric acid business.<ref name="podger">Podger, Hugh, (2002). ''Albright & Wilson: The Last 50 Years''. Studley: Brewin Books. ISBN 1-85858-223-7</ref>
==Novels==
* ''Cartea nunţii'' (The Book of the Wedding), 1933.
* ''Enigma Otliei'' (Otilia's Secret), 1938.
* ''Trei nuvele'' (Three Novellas), 1949.
* ''Bietul Ioanide'' (Poor Ioanide), 1953.
* ''Scrinul negru'' (The Black Chest of Drawers), 1965.


In 2007, at the current rate of consumption, the supply of phosphorus was estimated to run out in 345 years.<ref>{{cite journal | date=[[May 26]], [[2007]] | journal = New Scientist | volume = 194 | issue = 2605 | pages = 38–39 | issn = 0262 4079 | title = How Long Will it Last? }}</ref> However, scientists are now claiming that a "Peak Phosphorus" will occur in 30 years and that "At current rates, reserves will be depleted in the next 50 to 100 years."<ref>{{cite news | url = http://business.timesonline.co.uk/tol/business/industry_sectors/natural_resources/article4193017.ece | title = Scientists warn of lack of vital phosphorus as biofuels raise demand | date = 2008-06-23 | author = Leo Lewis | publisher = [[The Times]]}}</ref>
==History and literary criticism==
* ''Viaţa lui Mihai Eminescu'' (The Life of Mihai Eminescu), 1932.
* ''Opera lui Mihai Eminescu'' (The Works of Mihai Eminescu), 1934.
* ''Viaţa lui Ion Creangă'' (The Life of Ion Creangă), 1938.
* ''Istoria literaturii române de la origini până în prezent'' (The History of Romanian Literature from its Origins to the Present), 1941.
* ''Istoria literaturii române. Compendiu'' (The History of Romanian Literature. A Compendium), 1945.
* ''Universul poeziei'' (The Universe of Poetry), 1947.
* ''Nicolae Filimon'', 1959.
* ''Gr. M. Alecsandrescu'', 1962.
* ''Ion Creangă; Viaţa şi opera'' (Ion Creangă; His Life and Works), 1964.
* ''Vasile Alecsandri'', 1965.


==Journalism==
== Compounds ==
{{Expand-section|date=January 2008}}
* ''Cronicile optimistului'' (The Chronicles of an Optimist), 1964.
''See also [[:Category:Phosphorus compounds|Phosphorus compounds]]''
* ''Ulysse'' (Ulysses), 1967.
<div style="-moz-column-count:3; column-count:3;">
* [[Hydride]]: [[Phosphine|PH<sub>3</sub>]]
* [[Halide]]s: [[Phosphorus pentabromide|PBr<sub>5</sub>]], [[Phosphorus tribromide|PBr<sub>3</sub>]], [[Phosphorus trichloride|PCl<sub>3</sub>]], [[Phosphorus triiodide|PI<sub>3</sub>]]
* [[Oxide]]s:[[Phosphorus trioxide|P<sub>4</sub>O<sub>6</sub>]], [[Phosphorus pentoxide|P<sub>4</sub>O<sub>10</sub>]]
* [[Sulfide]]s: [[Phosphorus pentasulfide|P<sub>2</sub>S<sub>5</sub>]], [[Phosphorus sesquisulfide|P<sub>4</sub>S<sub>3</sub>]]
* [[Acid]]s: [[Hypophosphorous acid|H<sub>3</sub>PO<sub>2</sub>]], [[Phosphoric acid|H<sub>3</sub>PO<sub>4</sub>]]
* [[Phosphate]]s: [[Ammonium phosphate|(NH<sub>4</sub>)<sub>3</sub>PO<sub>4</sub>]], [[Tricalcium phosphate|Ca<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub>)]], [[Iron(III) phosphate|FePO<sub>4</sub>]], [[Iron(II) phosphate|Fe<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub>]], [[Trisodium phosphate|Na<sub>3</sub>PO<sub>4</sub>]], [[Calcium dihydrogen phosphate|Ca(H<sub>2</sub>PO<sub>4</sub>)<sub>2</sub>]], [[Monopotassium phosphate|KH<sub>2</sub>PO<sub>4</sub>]]
* [[Phosphide]]s: [[Calcium phosphide|Ca<sub>3</sub>P<sub>2</sub>]], [[Gallium(III) phosphide|GaP]], [[Zinc phosphide|Zn<sub>3</sub>P<sub>2</sub>]] [[Copper phosphide|Cu<sub>3</sub>P]]
* [[Organophosphorus]] and [[organophosphate]]s: [[Lawesson's reagent]], [[Parathion]], [[Sarin]], [[Soman]], [[Tabun (nerve agent)|Tabun]], [[Triphenyl phosphine]], [[VX (nerve agent)|VX]] nerve gas
</div>


=== As an exception to the octet rule ===
==Travel journals==
{{Details|Octet rule}}
* ''Kiev, Moscova, Leningrad'' (Kiev, Moscow, Leningrad), 1949.
* ''Am fost în China nouă'' (I've Been to the New China), 1953.


The simple [[Lewis structure]] for the [[trigonal bipyramid molecular geometry|trigonal bipyramidal]] [[phosphorus pentachloride|PCl<sub>5</sub>]] molecule contains five [[covalent bonds]], implying a [[hypervalent molecule]] with ten valence electrons contrary to the [[octet rule]].
==External links==
*{{imdb name|id=0130023}}


An alternate description of the bonding, however, respects the octet rule by using [[3-center-4-electron bond|3-center-4-electron (3c-4e) bonds]]. In this model the octet on the P atom corresponds to six electrons which form three Lewis (2c-2e) bonds to the three equatorial Cl atoms, plus the two electrons in the 3-centre Cl-P-Cl bonding molecular orbital for the two axial Cl electrons. The two electrons in the corresponding nonbonding molecular orbital are not included because this orbital is localized on the two Cl atoms and does not contribute to the [[electron density]] on P.
{{DEFAULTSORT:Calinescu, George}}
[[Category:People from Bucharest]]
[[Category:Romanian biographers]]
[[Category:Romanian literary critics]]
[[Category:Romanian essayists]]
[[Category:Romanian novelists]]
[[Category:University of Bucharest faculty]]
[[Category:Burials at Bellu]]
[[Category:1899 births]]
[[Category:1965 deaths]]


However, it should always be remembered that the octet rule is not some universal rule of chemical bonding, and while many compounds obey it, there are many elements (the majority, in fact) to which it just does not apply.
{{Romania-bio-stub}}
{{Euro-writer-stub}}


== Applications ==
[[es:George Călinescu]]
* Phosphorus being an essential plant nutrient, finds its major use as a constituent of fertilizers for [[agriculture]] and farm production in the form of concentrated phosphoric acids, which can consist of 70% to 75% P<sub>2</sub>O<sub>5</sub>. Global demand for fertilizers led to large increase in [[phosphate]] (PO<sub>4</sub><sup>3-</sup>) production in the second half of the 20th century.
[[fr:George Calinescu]]
* Phosphorus is widely used to make [[organophosphorus compound]]s, through the intermediates [[phosphorus chlorides]] and the two phosphorus sulfides: [[phosphorus pentasulfide]], and [[phosphorus sesquisulfide]].<ref name="threlfall"/> Organophosphorus compounds have many applications, including in [[plasticizers]], [[flame retardant]]s, [[pesticide]]s, [[extraction agent]]s, and water treatment.
[[pl:George Călinescu]]
* Phosphorus is also an important component in [[steel]] production, in the making of [[phosphor bronze]], and in many other related products.
[[ro:George Călinescu]]
* Phosphates are utilized in the making of special [[glass]]es that are used for [[sodium lamp]]s.
[[ru:Кэлинеску, Джордже]]
* Bone-ash, [[calcium phosphate]], is used in the production of fine china.
* [[Sodium tripolyphosphate]] made from phosphoric acid is used in laundry detergents in some countries, but banned for this use in others.
* Phosphoric acid made from elemental phosphorus is used in food applications such as some soda beverages. The acid is also a starting point to make food grade phosphates.<ref name="threlfall">Threlfall, R.E., (1951). ''100 years of Phosphorus Making: 1851 - 1951''. Oldbury: [[Albright and Wilson]] Ltd</ref> These include mono-calcium phosphate which is employed in [[baking powder]] and [[sodium tripolyphosphate]] and other sodium phosphates<ref name="threlfall"/>. Among other uses these are used to improve the characteristics of processed meat and cheese. Others are used in toothpaste.<ref name="threlfall"/> [[Trisodium phosphate]] is used in cleaning agents to [[water softener|soften water]] and for preventing pipe/boiler tube [[corrosion]].
* [[white phosphorus incendiary|White phosphorus]], called "WP" (slang term "Willie Peter") is used in [[military]] applications as [[incendiary device|incendiary bomb]]s, for [[smoke-screen]]ing as smoke pots and [[smoke bomb]]s, and in [[tracer ammunition]].
* Red phosphorus is essential for manufacturing matchbook strikers, flares,<ref name="threlfall"/> safety matches, pharmaceutical grade and street [[methamphetamine]], and is used in [[cap gun]] caps.
* Phosphorus sesquisulfide is used in heads of strike-anywhere matches.<ref name="threlfall"/>
* In trace amounts, phosphorus is used as a [[dopant]] for [[N-type semiconductor]]s.
* <sup>32</sup>P and <sup>33</sup>P are used as radioactive tracers in biochemical laboratories (see [[#Isotopes|Isotopes]]).

== Biological role ==
Phosphorus is a key element in all known forms of [[life]]. Inorganic phosphorus in the form of the phosphate PO<sub>4</sub><sup>3-</sup> plays a major role in biological molecules such as DNA and RNA where it forms part of the structural framework of these molecules. Living cells also use phosphate to transport cellular energy via [[adenosine triphosphate]] (ATP). Nearly every cellular process that uses energy obtains it in the form of ATP. ATP is also important for [[phosphorylation]], a key regulatory event in cells. [[Phospholipid]]s are the main structural components of all cellular membranes. [[Calcium phosphate]] salts assist in stiffening [[bone]]s.

An average adult human contains a little less than 1 kg of phosphorus, about 85% of which is present in bones and teeth in the form of [[apatite]], and the remainder inside cells in soft tissues. A well-fed adult in the industrialized world consumes and excretes about 1-3 g of phosphorus per day in the form of phosphate. Only about 0.1% of body phosphate circulates in the blood, but this amount reflects the amount of phosphate available to soft tissue cells.

In medicine, low phosphate syndromes are caused by malnutrition, by failure to absorb phosphate, and by metabolic syndromes which draw phosphate from the blood or pass too much of it into the urine. All are characterized by [[hypophosphatemia]] (see article for medical details). Symptoms of low phosphate include muscle and neurological dysfunction, and disruption of muscle and blood cells due to lack of ATP. Too much phosphate can lead to diarrhea and calcification (hardening) of organs and soft tissue, and can interfere with the body's ability to use iron, calcium, magnesium, and zinc.<ref>Anderson JJB. Calcium, phosphorus, and human bone development. J Nutr. 1996; 126: 1153.

</ref>

Phosphorus is an essential [[macromineral]] for plants, which is studied extensively in [[edaphology]] in order to understand plant uptake from [[soil]] systems. In [[ecological]] terms, phosphorus is often a [[limiting factor]] in many environments; i.e. the availability of phosphorus governs the rate of growth of many organisms. In [[ecosystems]] an excess of phosphorus can be problematic, especially in aquatic systems, see [[eutrophication]] and [[algal blooms]].

== History ==
Phosphorus ([[Greek language|Greek]] ''phosphoros'' was the ancient name for the planet [[Venus (planet)|Venus]], but in [[Greek mythology]], Hesperus and Eosphorus could be confused with Phosphorus) was discovered by German [[alchemy|alchemist]] [[Hennig Brand]] in 1669 through a preparation from [[urine]], which contains considerable quantities of dissolved phosphates from normal metabolism. Working in [[Hamburg]], Brand attempted to create the infamous [[Philosopher's stone]] through the [[distillation]] of some [[salt]]s by evaporating urine, and in the process produced a white material that glowed in the dark and burned brilliantly. Since that time, phosphorescence has been used to describe substances that shine in the dark without burning.

Phosphorus was recognized as a chemical element at the emergence of the [[Atomic_theory#Modern_atomic_theory|atomic theory]] that gradually occurred in the late part of the 18th century and the early 19th century, and was formulated by [[John Dalton]].

Phosphorus was first made commercially, for the match industry, in the 19th century, by distilling off phosphorus vapor from precipitated phosphates heated in a [[retort]].<ref name="threlfall"/> The precipitated phosphates were made from ground-up bones that had been de-greased and treated with strong acids.<ref name="threlfall"/> This process became obsolete in the late 1890s when the [[electric arc furnace]] was adapted to reduce phosphate rock.<ref name="threlfall"/>

Early matches used white phosphorus in their composition, which was dangerous due to its toxicity. Murders, suicides and accidental [[poison]]ings resulted from its use. (An apocryphal tale tells of a woman attempting to murder her husband with white phosphorus in his food, which was detected by the stew giving off luminous steam).<ref name="shockinghistory"/> In addition, exposure to the vapours gave match workers a [[necrosis]] of the bones of the jaw, the infamous "[[phossy jaw]]." When a safe process for manufacturing red phosphorus was discovered, with its far lower flammability and toxicity, laws were enacted, under the [[Berne Convention]] (1906), requiring its adoption as a safer alternative for match manufacture.

The electric furnace method allowed production to increase to the point where phosphorus could be used in weapons of war.<ref name="shockinghistory"/><ref name="threlfall"/> In [[World War I]] it was used in incendiaries, [[smoke screen]]s and tracer bullets.<ref name="threlfall"/> A special incendiary bullet was developed to shoot at [[hydrogen]]-filled [[Zeppelin]]s over [[United Kingdom|Britain]] (hydrogen being highly [[inflammable]] if it can be ignited).<ref name="threlfall"/> During [[World War II]], [[Molotov cocktail]]s of [[benzene]] and phosphorus were distributed in Britain to specially selected civilians within the British resistance operation, for defence; and phosphorus incendiary bombs were used in war on a large scale. Burning phosphorus is difficult to extinguish and if it splashes onto human skin it has horrific effects (see [[#Precautions|precautions]] below). People covered in it have been known to commit suicide due to the torment.

Today phosphorus production is larger than ever. It is used as a precursor for various chemicals,<ref>{{cite journal|title=The American Phosphorus Industry|author =Aall C. H.|journal =Industrial & Engineering Chemistry|year= 1952|volume =44|doi =10.1021/ie50511a018|issue=7|pages=1520–1525}}</ref> in particular the herbicide [[glyphosate]] sold under the brand name [[Roundup]]. Production of white phosphorus takes place at large facilities and it is transported heated in liquid form. Some major accidents have occurred during transportation, train derailments at [[Brownston, Nebraska]] and [[Miamisburg, Ohio]] led to large fires. The worst accident in recent times was an environmental one in 1968 when phosphorus spilled into the sea from a plant at [[Placentia Bay, Newfoundland]].

=== Spelling and etymology===
According to the Oxford English Dictionary the correct spelling of the element is '''phosphorus'''. The word '''phosphorous''' is the adjectival form of the P<sup>3+</sup> valency: so, just as [[sulfur]] forms sulfur'''ous''' and sulfur'''ic''' compounds, phosphor'''us''' forms phosphor'''ous''' compounds (see e.g. [[phosphorous acid]]) and P<sup>5+</sup> valency phosphor'''ic''' compounds (see e.g. [[Phosphoric acids and phosphates]]).

== Precautions ==
[[Image:Hazard F.svg|left|100px]]
[[Image:Skull and crossbones.svg|right|80px]]

Organic compounds of phosphorus form a wide class of materials, some of which are extremely toxic. [[Fluorophosphate]] [[ester]]s are among the most potent [[neurotoxin]]s known. A wide range of organophosphorus compounds are used for their toxicity to certain organisms as [[pesticides]] ([[herbicides]], [[insecticides]], [[fungicides]], etc.) and [[weapon]]ized as nerve agents. Most inorganic phosphates are relatively nontoxic and essential nutrients. For environmentally adverse effects of phosphates see [[eutrophication]] and [[algal bloom]]s.

The white phosphorus allotrope should be kept under water at all times as it presents a significant [[fire]] hazard due to its extreme reactivity with atmospheric oxygen, and it should only be manipulated with forceps since contact with [[skin]] can cause severe burns. Chronic white phosphorus poisoning leads to necrosis of the jaw called "[[phossy jaw]]". Ingestion of white phosphorus may cause a medical condition known as "Smoking Stool Syndrome". <ref>[http://www.emedicine.com/EMERG/topic918.htm emedicine.com] CBRNE - Incendiary Agents, White Phosphorus (Smoking Stool Syndrome)</ref>

When the white form is exposed to sunlight or when it is heated in its own vapour to 250°C, it is transmuted to the red form, which does not phosphoresce in air. The red allotrope does not spontaneously ignite in air and is not as dangerous as the white form. Nevertheless, it should be handled with care because it reverts to white phosphorus in some temperature ranges and it also emits highly [[toxic]] fumes that consist of phosphorus [[oxide]]s when it is heated.

Upon exposure to elemental phosphorus, in the past it was suggested to wash the affected area with 2% [[copper sulfate]] solution to form harmless compounds that can be washed away. According to the recent ''US Navy's Treatment of Chemical Agent Casualties and Conventional Military Chemical Injuries: FM8-285: Part 2 Conventional Military Chemical Injuries'', "Cupric (copper(II)) sulfate has been used by U.S. personnel in the past and is still being used by some nations. However, copper sulfate is toxic and its use will be discontinued. Copper sulfate may produce kidney and cerebral toxicity as well as intravascular hemolysis."<ref>[http://www.vnh.org/FM8285/Chapter/chapter9.html US Navy's Treatment of Chemical Agent Casualties and Conventional Military Chemical Injuries: FM8-285: Part 2 Conventional Military Chemical Injuries]</ref>

[[Image:Phosphorus explosion.gif|thumb|Phosphorus explosion]]
The manual suggests instead "a bicarbonate solution to neutralize phosphoric acid, which will then allow removal of visible WP. Particles often can be located by their emission of smoke when air strikes them, or by their phosphorescence in the dark. In dark surroundings, fragments are seen as luminescent spots." Then, "Promptly debride the burn if the patient's condition will permit removal of bits of WP which might be absorbed later and possibly produce systemic poisoning. DO NOT apply oily-based ointments until it is certain that all WP has been removed. Following complete removal of the particles, treat the lesions as thermal burns." As white phosphorus readily mixes with oils, any oily substances or ointments are not recommended until the area is thoroughly cleaned and all white phosphorus removed.

Further warnings of toxic effects and recommendations for treatment can be found in the ''Emergency War Surgery NATO Handbook: Part I: Types of Wounds and Injuries: Chapter III: Burn Injury: Chemical Burns And White Phosphorus injury''.<ref>[http://www.brooksidepress.org/Products/OperationalMedicine/DATA/operationalmed/Manuals/NATOEWS/ch03/03ChemicalBurns.html Emergency War Surgery NATO Handbook: Part I: Types of Wounds and Injuries: Chapter III: Burn Injury: Chemical Burns And White Phosphorus injury].</ref>

=== US DEA List I status ===
Phosphorus can reduce elemental [[iodine]] to [[hydroiodic acid]], which is a reagent effective for reducing [[ephedrine]] or [[pseudoephedrine]] to methamphetamine.<ref>{{cite journal | author = Skinner, H.F. | year = 1990 | title = Methamphetamine synthesis via hydriodic acid/red phosphorus reduction of ephedrine | journal = [[Forensic Science International]] | volume = 48 | issue = 2 | pages = 123–134 | doi = 10.1016/0379-0738(90)90104-7}}</ref> For this reason, two allotropes of elemental phosphorus—red phosphorus and white phosphorus—were designated by the [[United States of America|United States]] [[Drug Enforcement Administration]] as [[DEA list of chemicals|List I precursor chemicals]] under [[Code of Federal Regulations|21 CFR 1310.02]] effective November 17, 2001.<ref name="66 CFR 52670">[http://frwebgate.access.gpo.gov/cgi-bin/getdoc.cgi?dbname=2001_register&docid=01-26013-filed 66 FR 52670—52675.] 17 October 2001.</ref> As a result, in the United States, handlers of red phosphorus or white phosphorus are subject to stringent regulatory controls pursuant to the [[Controlled Substances Act]] in order to reduce diversion of these substances for use in clandestine production of controlled substances.<ref name="66 CFR 52670"/><ref name="21 CFR 1309">[http://www.access.gpo.gov/nara/cfr/waisidx_06/21cfr1309_06.html 21 CFR 1309]</ref><ref name="CSA">[http://www.usdoj.gov/dea/pubs/csa.html 21 USC, Chapter 13 (Controlled Substances Act)]</ref>

== References ==
{{reflist}}

== External links ==
{{commons}}
* [http://periodic.lanl.gov/elements/15.html Los Alamos National Laboratory &ndash; Phosphorus]
* [http://www.webelements.com/webelements/elements/text/P/index.html WebElements.com: Phosphorus]
* [http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=PubMed&list_uids=946251&dopt=Abstract; Entrez PubMed: Acute Yellow Phosphorus Poisoning]
* [http://www.emedicine.com/EMERG/topic918.htm eMedicine.com: Article on White Phophorus as used as weapon]
* [http://www.phosphorus-recovery.tu-darmstadt.de Website of the Technische Universität Darmstadt and the CEEP about Phosphorus Recovery]
{{Clear}}
{{Compact periodic table}}

[[Category:Chemical elements]]
[[Category:DEA List I chemicals]]
[[Category:Dietary minerals]]
[[Category:Nonmetals]]
[[Category:Pnictogens]]
[[Category:Phosphorus|*]]
[[Category:Pyrotechnic fuels]]

[[af:Fosfor]]
[[ar:فوسفور]]
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[[es:Fósforo]]
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[[fur:Fosfar]]
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[[ko:인]]
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[[ta:பாஸ்பரஸ்]]
[[te:భాస్వరము]]
[[th:ฟอสฟอรัส]]
[[vi:Phốtpho]]
[[tg:Фосфор]]
[[tr:Fosfor]]
[[uk:Фосфор]]
[[ur:فاسفورس]]
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Revision as of 15:05, 10 October 2008

This article is about chemical element. For other uses, see Phosphorus (disambiguation).
Phosphorus, 15P
Forms of phosphorus
Waxy white
Light red
Dark red and violet
Black
Phosphorus
Pronunciation/ˈfɒsfərəs/ ​(FOS-fər-əs)
Allotropeswhite, red, violet, black and others (see Allotropes of phosphorus)
Appearancewhite, red and violet are waxy, black is metallic-looking
Standard atomic weight Ar°(P)
Abundance
in the Earth's crust5.2 (silicon = 100)
Phosphorus in the periodic table
Hydrogen Helium
Lithium Beryllium Boron Carbon Nitrogen Oxygen Fluorine Neon
Sodium Magnesium Aluminium Silicon Phosphorus Sulfur Chlorine Argon
Potassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton
Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon
Caesium Barium Lanthanum Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury (element) Thallium Lead Bismuth Polonium Astatine Radon
Francium Radium Actinium Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium Darmstadtium Roentgenium Copernicium Nihonium Flerovium Moscovium Livermorium Tennessine Oganesson
N
↑
P
↓
As
silicon ← phosphorus → sulfur
Atomic number (Z)15
Groupgroup 15 (pnictogens)
Periodperiod 3
Block  p-block
Electron configuration[Ne] 3s2 3p3
Electrons per shell2, 8, 5
Physical properties
Phase at STPsolid
Melting pointwhite: 317.3 K ​(44.15 °C, ​111.5 °F)
red: ∼860 K (∼590 °C, ∼1090 °F)[3]
Boiling pointwhite: 553.7 K ​(280.5 °C, ​536.9 °F)
Sublimation pointred: ≈689.2–863 K ​(≈416–590 °C, ​≈780.8–1094 °F)
violet: 893 K (620 °C, 1148 °F)
Density (near r.t.)white: 1.823 g/cm3
red: ≈2.2–2.34 g/cm3
violet: 2.36 g/cm3
black: 2.69 g/cm3
Heat of fusionwhite: 0.66 kJ/mol
Heat of vaporizationwhite: 51.9 kJ/mol
Molar heat capacitywhite: 23.824 J/(mol·K)
Vapor pressure (white)
P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 279 307 342 388 453 549
vapor pressure (red)
P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 455 489 529 576 635 704
Atomic properties
Oxidation states−3, −2, −1, 0,[4] +1,[5] +2, +3, +4, +5 (a mildly acidic oxide)
ElectronegativityPauling scale: 2.19
Ionization energies
  • 1st: 1011.8 kJ/mol
  • 2nd: 1907 kJ/mol
  • 3rd: 2914.1 kJ/mol
  • (more)
Covalent radius107±3 pm
Van der Waals radius180 pm
Color lines in a spectral range
Spectral lines of phosphorus
Other properties
Natural occurrenceprimordial
Crystal structureα-white: ​body-centered cubic (bcc) (cI232)
Lattice constant
Body-centred cubic crystal structure for α-white: phosphorus
a = 1.869 nm (at 20 °C)[6]
Crystal structureblack: ​orthorhombic (oS8)
Lattice constants
Orthorhombic crystal structure for black: phosphorus
a = 0.33137 nm
b = 1.0477 nm
c = 0.43755 nm (at 20 °C)[6]
Thermal conductivitywhite: 0.236 W/(m⋅K)
black: 12.1 W/(m⋅K)
Magnetic orderingwhite, red, violet, black: diamagnetic[7]
Molar magnetic susceptibility−20.8×10−6 cm3/mol (293 K)[8]
Bulk moduluswhite: 5 GPa
red: 11 GPa
CAS Number7723-14-0 (red)
12185-10-3 (white)
History
DiscoveryHennig Brand (1669)
Recognised as an element byAntoine Lavoisier[9] (1777)
Isotopes of phosphorus
Main isotopes Decay
abun­dance half-life (t1/2) mode pro­duct
31P 100% stable
32P trace 14.269 d β− 32S
33P trace 25.35 d β− 33S
 Category: Phosphorus
| references

Phosphorus, (/ˈfɒsfərəs/), is the chemical element that has the symbol P and atomic number 15. The name comes from the [φώς] Error: {{Lang-xx}}: text has italic markup (help) (meaning "light") and φόρος (meaning "bearer"). A multivalent nonmetal of the nitrogen group, phosphorus is commonly found in inorganic phosphate rocks.

Due to its high reactivity, phosphorus is gay haha fuck it never found as a free element in nature on Earth. One form of phosphorus (white phosphorus) emits a faint glow upon exposure to oxygen — hence its Greek derivation, Φωσφόρος meaning "light-bearer" (Latin Lucifer), the planet Venus as "Morning Star".

Phosphorus is a component of DNA and RNA, as well as ATP, and is an essential element for all living cells. The most important commercial use of phosphorus-based chemicals is the production of fertilizers.

Phosphorus compounds are also widely used in explosives, nerve agents, friction matches, fireworks, pesticides, toothpaste and detergents.

Characteristics

Allotropes

Main article: Allotropes of phosphorus

Phosphorus is an excellent example of an element that exhibits allotropy, as its various allotropes have strikingly different properties.

The two most common allotropes are white phosphorus and red phosphorus. A third form, scarlet phosphorus, is obtained by allowing a solution of white phosphorus in carbon disulfide to evaporate in sunlight. A fourth allotrope, black phosphorus, is obtained by heating white phosphorus under very high pressures (12,000 atmospheres). In appearance, properties and structure it is very like graphite, being black and flaky, a conductor of electricity and has puckered sheets of linked atoms. Another allotrope is diphosphorus - which is highly reactive.

White phosphorus (P
4) exists as individual molecules made up of four atoms in a tetrahedral arrangement, resulting in very high ring strain and instability. It contains 6 single bonds.

White phosphorus is a white, waxy transparent solid. This allotrope is thermodynamically unstable at normal condition and will gradually change to red phosphorus. This transformation, which is accelerated by light and heat, makes white phosphorus almost always contain some red phosphorus and therefore appear yellow. For this reason, it is also called yellow phosphorus. It glows greenish in the dark (when exposed to oxygen), is highly flammable and pyrophoric (self-igniting) upon contact with air as well as toxic (causing severe liver damage on ingestion). The incendiary bomb Napalm relies, among others, on this principle to spontaneously ignite. The odour of combustion of this form has a characteristic garlic smell, and samples are commonly coated with white "(di)phosphorus pentoxide", which consists of P4O10 tetrahedra with oxygen inserted between the phosphorus atoms and at their vertices. White phosphorus is insoluble in water but soluble in carbon disulfide.

The white allotrope can be produced using several different methods. In one process, calcium phosphate, which is derived from phosphate rock, is heated in an electric or fuel-fired furnace in the presence of carbon and silica[10]. Elemental phosphorus is then liberated as a vapour and can be collected under phosphoric acid. This process is similar to the first synthesis of phosphorus from calcium phosphate in urine.

Red phosphorus may be formed by heating white phosphorus to 250°C (482°F) or by exposing white phosphorus to sunlight. Phosphorus after this treatment exists as an amorphous network of atoms which reduces strain and gives greater stability; further heating results in the red phosphorus becoming crystalline. Red phosphorus does not catch fire in air at temperatures below 240°C, whereas white phosphorus ignites at about 30°C.

In 1865 Hittorf discovered that when phosphorus was recrystallized from molten lead, a red/purple form is obtained. This purple form is sometimes known as "Hittorf's phosphorus." In addition, a fibrous form exists with similar phosphorus cages. Below is shown a chain of phosphorus atoms which exhibits both the purple and fibrous forms.

One of the forms of red/black phosphorus is a cubic solid.[11]

Black phosphorus has an orthorhombic structure (Cmca) and is the least reactive allotrope. It consists of many six-membered rings which are interlinked. Each atom is bonded to three other atoms.[12][13] A recent synthesis of black phosphorus using metal salts as catalysts has been reported.[14]

The diphosphorus allotrope (P2) can be obtained normally only under extreme conditions (for example, from P4 at 1100 kelvin). Nevertheless, some advancements were obtained in generating the diatomic molecule in homogeneous solution, under normal conditions with the use by some transitional metal complexes (based on, for example, tungsten and niobium).[15]

Glow

The chemical element phosphorus (Greek. phosphoros, meaning "light bearer") was discovered by German alchemist Hennig Brand in 1669. Working in Hamburg, Brand attempted to distill some kind of "life essence" from his urine, and in the process produced a white material that glowed in the dark. However, phosphorus itself is not a phosphor; it is highly reactive and gives-off a faint chemiluminescent glow upon uniting with oxygen. The glow observed by Brand was actually caused by the very slow burning of the phosphorus, but as he saw no flame nor felt any heat he did not recognize it as burning.

The mechanism for that glow was not fully described until 1974.[16] It was known from early times that the glow would persist for a time in a stoppered jar but then cease. Robert Boyle in the 1680s ascribed it to "debilitation" of the air; in fact, it is oxygen being consumed. By the 18th century, it was known that in pure oxygen phosphorus does not glow at all;[17] there is only a range of partial pressure at which it does. Heat can be applied to drive the reaction at higher pressures.[18]

In 1974, the glow was explained by R. J. van Zee and A. U. Khan.[16] A reaction with oxygen takes place at the surface of the solid (or liquid) phosphorus, forming the short-lived molecules HPO and P2O2 that both emit visible light. The reaction is slow and only very little of the intermediates is required to produce the luminescence, hence the extended time the glow continues in a stoppered jar.

Although the term phosphorescence is derived from phosphorus, the reaction which gives phosphorus its glow is properly called luminescence (glowing by its own reaction, in this case chemoluminescence), not phosphorescence (re-emitting light that previously fell on it).

Isotopes

Main article: Isotopes of phosphorus

Radioactive isotopes of phosphorus include

  • 32P; a beta-emitter (1.71 MeV) with a half-life of 14.3 days which is used routinely in life-science laboratories, primarily to produce radiolabeled DNA and RNA probes, e.g. for use in Northern blots or Southern blots. Because the high energy beta particles produced penetrate skin and corneas, and because any 32P ingested, inhaled, or absorbed is readily incorporated into bone and nucleic acids, Occupational Safety and Health Administration in the Unites States, and similar institutions in other developed countries require that a lab coat, disposable gloves, and safety glasses or goggles be worn when working with 32P, and that working directly over an open container be avoided in order to protect the eyes. Monitoring personal, clothing, and surface contamination is also required. In addition, due to the high energy of the beta particles, shielding this radiation with the normally used dense materials (e.g. lead), gives rise to secondary emission of X-rays via a process known as Bremsstrahlung, meaning braking radiation. Therefore shielding must be accomplished with low density materials, e.g. Plexiglas, Lucite, plastic, wood, or water.[19]
  • 33P; a beta-emitter (0.25 MeV) with a half-life of 25.4 days. It is used in life-science laboratories in applications in which lower energy beta emissions are advantageous such as DNA sequencing.

Occurrence

See also Phosphate minerals.

Due to its reactivity with air and many other oxygen-containing substances, phosphorus is not found free in nature but it is widely distributed in many different minerals.

Phosphate rock, which is partially made of apatite (an impure tri-calcium phosphate mineral), is an important commercial source of this element. About 50 per cent of the global phosphorus reserves are in the Arab nations.[20] Large deposits of apatite are located in China, Russia, Morocco, Florida, Idaho, Tennessee, Utah, and elsewhere. Albright and Wilson in the United Kingdom and their Niagara Falls plant, for instance, were using phosphate rock in the 1890s and 1900s from Connetable, Tennessee and Florida; by 1950 they were using phosphate rock mainly from Tennessee and North Africa[10]. In the early 1990s Albright and Wilson's purified wet phosphoric acid business was being affected by phosphate rock sales by China and the entry of their long standing Moroccan phosphate suppliers into the purified wet phosphoric acid business.[21]

In 2007, at the current rate of consumption, the supply of phosphorus was estimated to run out in 345 years.[22] However, scientists are now claiming that a "Peak Phosphorus" will occur in 30 years and that "At current rates, reserves will be depleted in the next 50 to 100 years."[23]

Compounds

See also Phosphorus compounds

As an exception to the octet rule

Further information: Octet rule

The simple Lewis structure for the trigonal bipyramidal PCl5 molecule contains five covalent bonds, implying a hypervalent molecule with ten valence electrons contrary to the octet rule.

An alternate description of the bonding, however, respects the octet rule by using 3-center-4-electron (3c-4e) bonds. In this model the octet on the P atom corresponds to six electrons which form three Lewis (2c-2e) bonds to the three equatorial Cl atoms, plus the two electrons in the 3-centre Cl-P-Cl bonding molecular orbital for the two axial Cl electrons. The two electrons in the corresponding nonbonding molecular orbital are not included because this orbital is localized on the two Cl atoms and does not contribute to the electron density on P.

However, it should always be remembered that the octet rule is not some universal rule of chemical bonding, and while many compounds obey it, there are many elements (the majority, in fact) to which it just does not apply.

Applications

Biological role

Phosphorus is a key element in all known forms of life. Inorganic phosphorus in the form of the phosphate PO43- plays a major role in biological molecules such as DNA and RNA where it forms part of the structural framework of these molecules. Living cells also use phosphate to transport cellular energy via adenosine triphosphate (ATP). Nearly every cellular process that uses energy obtains it in the form of ATP. ATP is also important for phosphorylation, a key regulatory event in cells. Phospholipids are the main structural components of all cellular membranes. Calcium phosphate salts assist in stiffening bones.

An average adult human contains a little less than 1 kg of phosphorus, about 85% of which is present in bones and teeth in the form of apatite, and the remainder inside cells in soft tissues. A well-fed adult in the industrialized world consumes and excretes about 1-3 g of phosphorus per day in the form of phosphate. Only about 0.1% of body phosphate circulates in the blood, but this amount reflects the amount of phosphate available to soft tissue cells.

In medicine, low phosphate syndromes are caused by malnutrition, by failure to absorb phosphate, and by metabolic syndromes which draw phosphate from the blood or pass too much of it into the urine. All are characterized by hypophosphatemia (see article for medical details). Symptoms of low phosphate include muscle and neurological dysfunction, and disruption of muscle and blood cells due to lack of ATP. Too much phosphate can lead to diarrhea and calcification (hardening) of organs and soft tissue, and can interfere with the body's ability to use iron, calcium, magnesium, and zinc.[24]

Phosphorus is an essential macromineral for plants, which is studied extensively in edaphology in order to understand plant uptake from soil systems. In ecological terms, phosphorus is often a limiting factor in many environments; i.e. the availability of phosphorus governs the rate of growth of many organisms. In ecosystems an excess of phosphorus can be problematic, especially in aquatic systems, see eutrophication and algal blooms.

History

Phosphorus (Greek phosphoros was the ancient name for the planet Venus, but in Greek mythology, Hesperus and Eosphorus could be confused with Phosphorus) was discovered by German alchemist Hennig Brand in 1669 through a preparation from urine, which contains considerable quantities of dissolved phosphates from normal metabolism. Working in Hamburg, Brand attempted to create the infamous Philosopher's stone through the distillation of some salts by evaporating urine, and in the process produced a white material that glowed in the dark and burned brilliantly. Since that time, phosphorescence has been used to describe substances that shine in the dark without burning.

Phosphorus was recognized as a chemical element at the emergence of the atomic theory that gradually occurred in the late part of the 18th century and the early 19th century, and was formulated by John Dalton.

Phosphorus was first made commercially, for the match industry, in the 19th century, by distilling off phosphorus vapor from precipitated phosphates heated in a retort.[10] The precipitated phosphates were made from ground-up bones that had been de-greased and treated with strong acids.[10] This process became obsolete in the late 1890s when the electric arc furnace was adapted to reduce phosphate rock.[10]

Early matches used white phosphorus in their composition, which was dangerous due to its toxicity. Murders, suicides and accidental poisonings resulted from its use. (An apocryphal tale tells of a woman attempting to murder her husband with white phosphorus in his food, which was detected by the stew giving off luminous steam).[16] In addition, exposure to the vapours gave match workers a necrosis of the bones of the jaw, the infamous "phossy jaw." When a safe process for manufacturing red phosphorus was discovered, with its far lower flammability and toxicity, laws were enacted, under the Berne Convention (1906), requiring its adoption as a safer alternative for match manufacture.

The electric furnace method allowed production to increase to the point where phosphorus could be used in weapons of war.[16][10] In World War I it was used in incendiaries, smoke screens and tracer bullets.[10] A special incendiary bullet was developed to shoot at hydrogen-filled Zeppelins over Britain (hydrogen being highly inflammable if it can be ignited).[10] During World War II, Molotov cocktails of benzene and phosphorus were distributed in Britain to specially selected civilians within the British resistance operation, for defence; and phosphorus incendiary bombs were used in war on a large scale. Burning phosphorus is difficult to extinguish and if it splashes onto human skin it has horrific effects (see precautions below). People covered in it have been known to commit suicide due to the torment.

Today phosphorus production is larger than ever. It is used as a precursor for various chemicals,[25] in particular the herbicide glyphosate sold under the brand name Roundup. Production of white phosphorus takes place at large facilities and it is transported heated in liquid form. Some major accidents have occurred during transportation, train derailments at Brownston, Nebraska and Miamisburg, Ohio led to large fires. The worst accident in recent times was an environmental one in 1968 when phosphorus spilled into the sea from a plant at Placentia Bay, Newfoundland.

Spelling and etymology

According to the Oxford English Dictionary the correct spelling of the element is phosphorus. The word phosphorous is the adjectival form of the P3+ valency: so, just as sulfur forms sulfurous and sulfuric compounds, phosphorus forms phosphorous compounds (see e.g. phosphorous acid) and P5+ valency phosphoric compounds (see e.g. Phosphoric acids and phosphates).

Precautions

Organic compounds of phosphorus form a wide class of materials, some of which are extremely toxic. Fluorophosphate esters are among the most potent neurotoxins known. A wide range of organophosphorus compounds are used for their toxicity to certain organisms as pesticides (herbicides, insecticides, fungicides, etc.) and weaponized as nerve agents. Most inorganic phosphates are relatively nontoxic and essential nutrients. For environmentally adverse effects of phosphates see eutrophication and algal blooms.

The white phosphorus allotrope should be kept under water at all times as it presents a significant fire hazard due to its extreme reactivity with atmospheric oxygen, and it should only be manipulated with forceps since contact with skin can cause severe burns. Chronic white phosphorus poisoning leads to necrosis of the jaw called "phossy jaw". Ingestion of white phosphorus may cause a medical condition known as "Smoking Stool Syndrome". [26]

When the white form is exposed to sunlight or when it is heated in its own vapour to 250°C, it is transmuted to the red form, which does not phosphoresce in air. The red allotrope does not spontaneously ignite in air and is not as dangerous as the white form. Nevertheless, it should be handled with care because it reverts to white phosphorus in some temperature ranges and it also emits highly toxic fumes that consist of phosphorus oxides when it is heated.

Upon exposure to elemental phosphorus, in the past it was suggested to wash the affected area with 2% copper sulfate solution to form harmless compounds that can be washed away. According to the recent US Navy's Treatment of Chemical Agent Casualties and Conventional Military Chemical Injuries: FM8-285: Part 2 Conventional Military Chemical Injuries, "Cupric (copper(II)) sulfate has been used by U.S. personnel in the past and is still being used by some nations. However, copper sulfate is toxic and its use will be discontinued. Copper sulfate may produce kidney and cerebral toxicity as well as intravascular hemolysis."[27]

Phosphorus explosion

The manual suggests instead "a bicarbonate solution to neutralize phosphoric acid, which will then allow removal of visible WP. Particles often can be located by their emission of smoke when air strikes them, or by their phosphorescence in the dark. In dark surroundings, fragments are seen as luminescent spots." Then, "Promptly debride the burn if the patient's condition will permit removal of bits of WP which might be absorbed later and possibly produce systemic poisoning. DO NOT apply oily-based ointments until it is certain that all WP has been removed. Following complete removal of the particles, treat the lesions as thermal burns." As white phosphorus readily mixes with oils, any oily substances or ointments are not recommended until the area is thoroughly cleaned and all white phosphorus removed.

Further warnings of toxic effects and recommendations for treatment can be found in the Emergency War Surgery NATO Handbook: Part I: Types of Wounds and Injuries: Chapter III: Burn Injury: Chemical Burns And White Phosphorus injury.[28]

US DEA List I status

Phosphorus can reduce elemental iodine to hydroiodic acid, which is a reagent effective for reducing ephedrine or pseudoephedrine to methamphetamine.[29] For this reason, two allotropes of elemental phosphorus—red phosphorus and white phosphorus—were designated by the United States Drug Enforcement Administration as List I precursor chemicals under 21 CFR 1310.02 effective November 17, 2001.[30] As a result, in the United States, handlers of red phosphorus or white phosphorus are subject to stringent regulatory controls pursuant to the Controlled Substances Act in order to reduce diversion of these substances for use in clandestine production of controlled substances.[30][31][32]

References

  1. ^ "Standard Atomic Weights: Phosphorus". CIAAW. 2013.
  2. ^ Prohaska, Thomas; Irrgeher, Johanna; Benefield, Jacqueline; Böhlke, John K.; Chesson, Lesley A.; Coplen, Tyler B.; Ding, Tiping; Dunn, Philip J. H.; Gröning, Manfred; Holden, Norman E.; Meijer, Harro A. J. (2022-05-04). "Standard atomic weights of the elements 2021 (IUPAC Technical Report)". Pure and Applied Chemistry. doi:10.1515/pac-2019-0603. ISSN 1365-3075.
  3. ^ Phosphorus at the Encyclopædia Britannica
  4. ^ Wang, Yuzhong; Xie, Yaoming; Wei, Pingrong; King, R. Bruce; Schaefer, Iii; Schleyer, Paul v. R.; Robinson, Gregory H. (2008). "Carbene-Stabilized Diphosphorus". Journal of the American Chemical Society. 130 (45): 14970–1. doi:10.1021/ja807828t. PMID 18937460.
  5. ^ Ellis, Bobby D.; MacDonald, Charles L. B. (2006). "Phosphorus(I) Iodide: A Versatile Metathesis Reagent for the Synthesis of Low Oxidation State Phosphorus Compounds". Inorganic Chemistry. 45 (17): 6864–74. doi:10.1021/ic060186o. PMID 16903744.
  6. ^ a b Arblaster, John W. (2018). Selected Values of the Crystallographic Properties of Elements. Materials Park, Ohio: ASM International. ISBN 978-1-62708-155-9.
  7. ^ Lide, D. R., ed. (2005). "Magnetic susceptibility of the elements and inorganic compounds". CRC Handbook of Chemistry and Physics (PDF) (86th ed.). Boca Raton (FL): CRC Press. ISBN 0-8493-0486-5.
  8. ^ Weast, Robert (1984). CRC, Handbook of Chemistry and Physics. Boca Raton, Florida: Chemical Rubber Company Publishing. pp. E110. ISBN 0-8493-0464-4.
  9. ^ cf. "Memoir on Combustion in General" Mémoires de l'Académie Royale des Sciences 1777, 592–600. from Henry Marshall Leicester and Herbert S. Klickstein, A Source Book in Chemistry 1400–1900 (New York: McGraw Hill, 1952)
  10. ^ a b c d e f g h i j k l m n Threlfall, R.E., (1951). 100 years of Phosphorus Making: 1851 - 1951. Oldbury: Albright and Wilson Ltd
  11. ^ Ahuja, R. (2003). "Calculated high pressure crystal structure transformations for phosphorus". Physica Status Solidi Section B. 235 (2): 282–287. doi:10.1002/pssb.200301569.
  12. ^ A. Brown, S. Runquist (1965). "Refinement of the crystal structure of black phosphorus". Acta Crystallogr. 19: 684. doi:10.1107/S0365110X65004140.
  13. ^ Cartz, L.;Srinivasa, S.R.;Riedner, R.J.;Jorgensen, J.D.;Worlton, T.G. (1979). "Effect of pressure on bonding in black phosphorus". Journal of Chemical Physics. 71: 1718–1721. doi:10.1063/1.438523.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  14. ^ Stefan Lange, Peer Schmidt, and Tom Nilges (2007). "Au3SnP7@Black Phosphorus: An Easy Access to Black Phosphorus". Inorg. Chem. 46: 4028. doi:10.1021/ic062192q.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  15. ^ Piro, N. A. (2006). "Triple-Bond Reactivity of Diphosphorus Molecules". Science. 313 (5791): 1276. doi:10.1126/science.1129630. PMID 16946068.
  16. ^ a b c d Emsley, John (2000). The Shocking History of Phosphorus. London: Macmillan. ISBN 0-330-39005-8
  17. ^ Nobel Prize in Chemistry 1956 - Presentation Speech, by Professor A. Ölander (committee member)
  18. ^ Phosphorus Topics page, at Lateral Science
  19. ^ http://www.oseh.umich.edu/TrainP32.pdf
  20. ^ http://www.anba.com.br/ingles/noticia.php?id=17288
  21. ^ Podger, Hugh, (2002). Albright & Wilson: The Last 50 Years. Studley: Brewin Books. ISBN 1-85858-223-7
  22. ^ "How Long Will it Last?". New Scientist. 194 (2605): 38–39. May 26, 2007. ISSN 0262-4079. {{cite journal}}: Check date values in: |date= (help)
  23. ^ Leo Lewis (2008-06-23). "Scientists warn of lack of vital phosphorus as biofuels raise demand". The Times.
  24. ^ Anderson JJB. Calcium, phosphorus, and human bone development. J Nutr. 1996; 126: 1153.
  25. ^ Aall C. H. (1952). "The American Phosphorus Industry". Industrial & Engineering Chemistry. 44 (7): 1520–1525. doi:10.1021/ie50511a018.
  26. ^ emedicine.com CBRNE - Incendiary Agents, White Phosphorus (Smoking Stool Syndrome)
  27. ^ US Navy's Treatment of Chemical Agent Casualties and Conventional Military Chemical Injuries: FM8-285: Part 2 Conventional Military Chemical Injuries
  28. ^ Emergency War Surgery NATO Handbook: Part I: Types of Wounds and Injuries: Chapter III: Burn Injury: Chemical Burns And White Phosphorus injury.
  29. ^ Skinner, H.F. (1990). "Methamphetamine synthesis via hydriodic acid/red phosphorus reduction of ephedrine". Forensic Science International. 48 (2): 123–134. doi:10.1016/0379-0738(90)90104-7.
  30. ^ a b 66 FR 52670—52675. 17 October 2001.
  31. ^ 21 CFR 1309
  32. ^ 21 USC, Chapter 13 (Controlled Substances Act)

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