White phosphorus

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White phosphorus
Weisser Phosphor.JPG
White phosphorus sample with a chunk removed from the corner to expose un-oxidized material
Tetraphosphorus-liquid-2D-dimensions.png
Tetraphosphorus molecule
Names
IUPAC names
White phosphorus
Tetraphosphorus
Systematic IUPAC name
1,2,3,4-Tetraphosphatricyclo[1.1.0.02,4]butane
Other names
  • Molecular phosphorus
  • Yellow phosphorus
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.107.967 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
UN number 1381
  • InChI=1S/P4/c1-2-3(1)4(1)2
    Key: OBSZRRSYVTXPNB-UHFFFAOYSA-N
  • P12P3P1P23
Properties
P4
Molar mass 123.895 g·mol−1
Density 1.82 g/cm3
Melting point 44.1 °C; 111.4 °F; 317.3 K
Boiling point 280 °C; 536 °F; 553 K
Hazards
NFPA 704 (fire diamond)
NFPA 704.svgHealth 4: Very short exposure could cause death or major residual injury. E.g. VX gasFlammability 4: Will rapidly or completely vaporize at normal atmospheric pressure and temperature, or is readily dispersed in air and will burn readily. Flash point below 23 °C (73 °F). E.g. propaneInstability 2: Undergoes violent chemical change at elevated temperatures and pressures, reacts violently with water, or may form explosive mixtures with water. E.g. white phosphorusSpecial hazards (white): no code
4
4
2
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

White phosphorus, yellow phosphorus, or simply tetraphosphorus (P4) is an allotrope of phosphorus. It is a translucent waxy solid that quickly yellows in light (due to its photochemical conversion into red phosphorus) [1] , and impure white phosphorus is for this reason called yellow phosphorus. White phosphorus is the first allotrope of phosphorus, and in fact the first elementary substance to be discovered that was not known since ancient times. [2] It glows greenish in the dark (when exposed to oxygen) and is highly flammable and pyrophoric (self-igniting) upon contact with air. It is toxic, causing severe liver damage on ingestion and phossy jaw from chronic ingestion or inhalation. The odour of combustion of this form has a characteristic garlic odor, and samples are commonly coated with white "diphosphorus pentoxide", which consists of P4O10 tetrahedral with oxygen inserted between the phosphorus atoms and at their vertices. White phosphorus is only slightly soluble in water and can be stored under water. P4 is soluble in benzene, oils, carbon disulfide, and disulfur dichloride.

Contents

Structure

White phosphorus crystal structure White phosphorus.png
White phosphorus crystal structure

White phosphorus exists as molecules of four phosphorus atoms in a tetrahedral structure, joined by six phosphorus—phosphorus single bonds. The tetrahedral arrangement results in ring strain and instability. [3] Although both are called "white phosphorus", in fact two different crystal allotropes are known, interchanging reversibly at 195.2 K. [4] The element's standard state is the body-centered cubic α form, which is actually metastable under standard conditions. [3] The β form is believed to have a hexagonal crystal structure. [4]

Molten and gaseous white phosphorus also retains the tetrahedral molecules, until 800 °C (1,500 °F; 1,100 K) when it starts decomposing to P
2 molecules. [5] 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. [6] 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. The average P-P bond length is 2.183(5) Å. [5]

Chemical properties

Despite white phosphorus not being the most stable allotropes of phosphorus, its molecular nature allows it to be easily purified. Thus, it's defined to have a zero enthalpy of formation.

In base, white phosphorus spontaneously disproportionates to phosphine and various phosphorus oxyacid salts. [7]

Many reactions of white phosphorus involve insertion into the P-P bonds, such as the reaction with oxygen, sulfur, phosphorus tribromide and the NO+ ion.

It ignites spontaneously in air at about 50 °C (122 °F), and at much lower temperatures if finely divided (due to melting-point depression). Phosphorus reacts with oxygen, usually forming two oxides depending on the amount of available oxygen: P4O6 (phosphorus trioxide) when reacted with a limited supply of oxygen, and P4O10 when reacted with excess oxygen. On rare occasions, P4O7, P4O8, and P4O9 are also formed, but in small amounts. This combustion gives phosphorus(V) oxide:

P4 + 5 O2 → P4O10

Production and applications

The white allotrope can be produced using several methods. In the industrial process, phosphate rock is heated in an electric or fuel-fired furnace in the presence of carbon and silica. [8] Elemental phosphorus is then liberated as a vapour and can be collected under phosphoric acid. An idealized equation for this carbothermal reaction is shown for calcium phosphate (although phosphate rock contains substantial amounts of fluoroapatite, which would also form silicon tetrafluoride):

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

In this way, an estimated 750,000 tons were produced in 1988. [9]

Most (83% in 1988) white phosphorus is used as a precursor to phosphoric acid, half of which is used for food or medical products where purity is important. The other half is used for detergents. Much of the remaining 17% is mainlu used for the production of chlorinated compounds phosphorus trichloride, phosphorus oxychloride, and phosphorus pentachloride: [10]

P4 + 10Cl2 → 4PCl5

Other products derived from white phosphorus include phosphorus pentasulfide and various metal phosphides. [9]

Other polyhedrane analogues

Although white phosphorus forms the tetrahedron, the simplest possible Platonic hydrocarbon, no other polyhedral phosphorus clusters are known. [11] White phosphorus converts to the thermodynamically-stabler red allotrope, but that allotrope is not isolated polyhedra.

Cubane, in particular, is unlikely to form, [11] and the closest approach is the half-phosphorus compound P4(CH)4, produced from phosphaalkynes. [12] Other clusters are more thermodynamically favorable, and some have been partially formed as components of larger polyelemental compounds. [11]

Safety

White phosphorus is rather acutely toxic, with a lethal dose of 50-100 mg (1 mg/kg body weight). Its mode of action is thought to involve its reducing properties. It is metabolized to phosphate, which is not toxic. [9]

White phosphorus is used as a weapon because it is pyrophoric. For the same reasons, it is dangerous to handle. Measures are taken to protect samples from air. Anecdotal report of problems for beachcombers who may collect washed-up samples while unaware of their true nature. [13] [14]

See also

Related Research Articles

<span class="mw-page-title-main">Chalcogen</span> Group of chemical elements

The chalcogens are the chemical elements in group 16 of the periodic table. This group is also known as the oxygen family. Group 16 consists of the elements oxygen (O), sulfur (S), selenium (Se), tellurium (Te), and the radioactive elements polonium (Po) and livermorium (Lv). Often, oxygen is treated separately from the other chalcogens, sometimes even excluded from the scope of the term "chalcogen" altogether, due to its very different chemical behavior from sulfur, selenium, tellurium, and polonium. The word "chalcogen" is derived from a combination of the Greek word khalkόs (χαλκός) principally meaning copper, and the Latinized Greek word genēs, meaning born or produced.

<span class="mw-page-title-main">Phosphorus</span> Chemical element with atomic number 15 (P)

Phosphorus is a chemical element; it has symbol P and atomic number 15. Elemental phosphorus exists in two major forms, white phosphorus and red phosphorus, but because it is highly reactive, phosphorus is never found as a free element on Earth. It has a concentration in the Earth's crust of about one gram per kilogram. In minerals, phosphorus generally occurs as phosphate.

A polyphosphate is a salt or ester of polymeric oxyanions formed from tetrahedral PO4 (phosphate) structural units linked together by sharing oxygen atoms. Polyphosphates can adopt linear or a cyclic (also called, ring) structures. In biology, the polyphosphate esters ADP and ATP are involved in energy storage. A variety of polyphosphates find application in mineral sequestration in municipal waters, generally being present at 1 to 5 ppm. GTP, CTP, and UTP are also nucleotides important in the protein synthesis, lipid synthesis, and carbohydrate metabolism, respectively. Polyphosphates are also used as food additives, marked E452.

<span class="mw-page-title-main">Diborane</span> Chemical compound

Diborane(6), commonly known as diborane, is the chemical compound with the formula B2H6. It is a highly toxic, colorless, and pyrophoric gas with a repulsively sweet odor. Given its simple formula, borane is a fundamental boron compound. It has attracted wide attention for its electronic structure. Several of its derivatives are useful reagents.

<span class="mw-page-title-main">Phosphine</span> Chemical compound hydrogen phosphide

Phosphine (IUPAC name: phosphane) is a colorless, flammable, highly toxic compound with the chemical formula PH3, classed as a pnictogen hydride. Pure phosphine is odorless, but technical grade samples have a highly unpleasant odor like rotting fish, due to the presence of substituted phosphine and diphosphane (P2H4). With traces of P2H4 present, PH3 is spontaneously flammable in air (pyrophoric), burning with a luminous flame. Phosphine is a highly toxic respiratory poison, and is immediately dangerous to life or health at 50 ppm. Phosphine has a trigonal pyramidal structure.

A tetrahedral intermediate is a reaction intermediate in which the bond arrangement around an initially double-bonded carbon atom has been transformed from trigonal to tetrahedral. Tetrahedral intermediates result from nucleophilic addition to a carbonyl group. The stability of tetrahedral intermediate depends on the ability of the groups attached to the new tetrahedral carbon atom to leave with the negative charge. Tetrahedral intermediates are very significant in organic syntheses and biological systems as a key intermediate in esterification, transesterification, ester hydrolysis, formation and hydrolysis of amides and peptides, hydride reductions, and other chemical reactions.

<span class="mw-page-title-main">Phosphoric acids and phosphates</span> Class of chemical species; phosphorus oxoacids and their deprotonated derivatives

In chemistry, a phosphoric acid, in the general sense, is a phosphorus oxoacid in which each phosphorus (P) atom is in the oxidation state +5, and is bonded to four oxygen (O) atoms, one of them through a double bond, arranged as the corners of a tetrahedron. Two or more of these PO4 tetrahedra may be connected by shared single-bonded oxygens, forming linear or branched chains, cycles, or more complex structures. The single-bonded oxygen atoms that are not shared are completed with acidic hydrogen atoms. The general formula of a phosphoric acid is Hn+2−2xPnO3n+1−x, where n is the number of phosphorus atoms and x is the number of fundamental cycles in the molecule's structure, between 0 and ⁠n + 2/2⁠.

<span class="mw-page-title-main">Phosphaalkyne</span>

In chemistry, a phosphaalkyne is an organophosphorus compound containing a triple bond between phosphorus and carbon with the general formula R-C≡P. Phosphaalkynes are the heavier congeners of nitriles, though, due to the similar electronegativities of phosphorus and carbon, possess reactivity patterns reminiscent of alkynes. Due to their high reactivity, phosphaalkynes are not found naturally on earth, but the simplest phosphaalkyne, phosphaethyne (H-C≡P) has been observed in the interstellar medium.

<span class="mw-page-title-main">Phosphorus pentoxide</span> Chemical compound

Phosphorus pentoxide is a chemical compound with molecular formula P4O10 (with its common name derived from its empirical formula, P2O5). This white crystalline solid is the anhydride of phosphoric acid. It is a powerful desiccant and dehydrating agent.

<span class="mw-page-title-main">Phosphoryl chloride</span> Chemical compound

Phosphoryl chloride is a colourless liquid with the formula POCl3. It hydrolyses in moist air releasing phosphoric acid and fumes of hydrogen chloride. It is manufactured industrially on a large scale from phosphorus trichloride and oxygen or phosphorus pentoxide. It is mainly used to make phosphate esters.

<span class="mw-page-title-main">Phosphorus pentasulfide</span> Chemical compound

Phosphorus pentasulfide is the inorganic compound with the formula P2S5 (empirical) or P4S10 (molecular). This yellow solid is the one of two phosphorus sulfides of commercial value. Samples often appear greenish-gray due to impurities. It is soluble in carbon disulfide but reacts with many other solvents such as alcohols, DMSO, and DMF.

<span class="mw-page-title-main">Tetrahedral molecular geometry</span> Central atom with four substituents located at the corners of a tetrahedron

In a tetrahedral molecular geometry, a central atom is located at the center with four substituents that are located at the corners of a tetrahedron. The bond angles are cos−1(−1⁄3) = 109.4712206...° ≈ 109.5° when all four substituents are the same, as in methane as well as its heavier analogues. Methane and other perfectly symmetrical tetrahedral molecules belong to point group Td, but most tetrahedral molecules have lower symmetry. Tetrahedral molecules can be chiral.

Diphosphorus is an inorganic chemical with the chemical formula P
2. Unlike nitrogen, its lighter pnictogen neighbor which forms a stable N2 molecule with a nitrogen to nitrogen triple bond, phosphorus prefers a tetrahedral form P4 because P-P pi-bonds are high in energy. Diphosphorus is, therefore, very reactive with a bond-dissociation energy (117 kcal/mol or 490 kJ/mol) half that of dinitrogen. The bond distance has been measured at 1.8934 Å.

<span class="mw-page-title-main">Molecular solid</span> Solid consisting of discrete molecules

A molecular solid is a solid consisting of discrete molecules. The cohesive forces that bind the molecules together are van der Waals forces, dipole–dipole interactions, quadrupole interactions, π–π interactions, hydrogen bonding, halogen bonding, London dispersion forces, and in some molecular solids, coulombic interactions. Van der Waals, dipole interactions, quadrupole interactions, π–π interactions, hydrogen bonding, and halogen bonding are typically much weaker than the forces holding together other solids: metallic, ionic, and network solids. Intermolecular interactions typically do not involve delocalized electrons, unlike metallic and certain covalent bonds. Exceptions are charge-transfer complexes such as the tetrathiafulvane-tetracyanoquinodimethane (TTF-TCNQ), a radical ion salt. These differences in the strength of force and electronic characteristics from other types of solids give rise to the unique mechanical, electronic, and thermal properties of molecular solids.

<span class="mw-page-title-main">Allotropes of phosphorus</span> Solid forms of the element phosphorus

Elemental phosphorus can exist in several allotropes, the most common of which are white and red solids. Solid violet and black allotropes are also known. Gaseous phosphorus exists as diphosphorus and atomic phosphorus.

Thiophosphates (or phosphorothioates, PS) are chemical compounds and anions with the general chemical formula PS
4−xO3−
x (x = 0, 1, 2, or 3) and related derivatives where organic groups are attached to one or more O or S. Thiophosphates feature tetrahedral phosphorus(V) centers.

<span class="mw-page-title-main">Tetranitrogen</span> Chemical compound

Tetranitrogen is a neutrally charged polynitrogen allotrope of the chemical formula N
4 and consists of four nitrogen atoms. The tetranitrogen cation is the positively charged ion, N+
4, which is more stable than the neutral tetranitrogen molecule and is thus more studied.

The phosphaethynolate anion, also referred to as PCO, is the phosphorus-containing analogue of the cyanate anion with the chemical formula [PCO]− or [OCP]−. The anion has a linear geometry and is commonly isolated as a salt. When used as a ligand, the phosphaethynolate anion is ambidentate in nature meaning it forms complexes by coordinating via either the phosphorus or oxygen atoms. This versatile character of the anion has allowed it to be incorporated into many transition metal and actinide complexes but now the focus of the research around phosphaethynolate has turned to utilising the anion as a synthetic building block to organophosphanes.

<span class="mw-page-title-main">Allotropes of arsenic</span>

Arsenic in the solid state can be found as gray, black, or yellow allotropes. These various forms feature diverse structural motifs, with yellow arsenic enabling the widest range of reactivity. In particular, reaction of yellow arsenic with main group and transition metal elements results in compounds with wide-ranging structural motifs, with butterfly, sandwich and realgar-type moieties featuring most prominently.

Pnictogen-substituted tetrahedranes are pnictogen-containing analogues of tetrahedranes with the formula RxCxPn4-x. Computational work has indicated that the incorporation of pnictogens to the tetrahedral core alleviates the ring strain of tetrahedrane. Although theoretical work on pnictogen-substituted tetrahedranes has existed for decades, only the phosphorus-containing species have been synthesized. These species exhibit novel reactivities, most often through ring-opening and polymerization pathways. Phosphatetrahedranes are of interest as new retrons for organophosphorus chemistry. Their strain also make them of interest in the development of energy-dense compounds.

References

  1. ↑ "White phosphorus". American Chemical Society. Retrieved 2024-08-10.
  2. ↑ Weeks, Mary Elvira (1932). "The discovery of the elements. II. Elements known to the alchemists". Journal of Chemical Education. 9 (1): 11. Bibcode:1932JChEd...9...11W. doi:10.1021/ed009p11.
  3. 1 2 Housecroft, C. E.; Sharpe, A. G. (2004). Inorganic Chemistry (2nd ed.). Prentice Hall. p. 392. ISBN   978-0-13-039913-7.
  4. 1 2 Durif, A.; Averbuch-Pouchot, M.T. (1996). Topics in phosphate chemistry. Singapore [u.a.]: World Scientific. p. 3. ISBN   978-981-02-2634-3.
  5. 1 2 Simon, Arndt; Borrmann, Horst; Horakh, Jörg (1997). "On the Polymorphism of White Phosphorus". Chemische Berichte. 130 (9): 1235–1240. doi:10.1002/cber.19971300911.
  6. ↑ 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.
  7. ↑ Engel, Robert; Cohen, JaimeLee Iolani (2004). Synthesis of Carbon-Phosphorus Bonds (2nd ed.). Boca Raton: CRC Press. §2.3. ISBN   0-8493-1617-0. LCCN   2003060796.
  8. ↑ Threlfall, R.E., (1951). 100 years of Phosphorus Making: 1851–1951. Oldbury: Albright and Wilson Ltd
  9. 1 2 3 Diskowski, Herbert; Hofmann, Thomas (2000). "Phosphorus". Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.a19_505. ISBN   978-3-527-30385-4.
  10. ↑ Chemistry Part I Class XII (PDF) (Reprinted ed.). India: NCERT. January 2019. p. 177. ISBN   978-81-7450-648-1.
  11. 1 2 3 Corbridge, D. E. C. (1995) "Phosphorus: An Outline of its Chemistry, Biochemistry, and Technology" 5th Edition Elsevier: Amsterdam. § 4.1.12. ISBN   0-444-89307-5.
  12. ↑ Streubel, Rainer (1995). "Phosphaalkyne Cyclooligomers: From Dimers to Hexamers—First Steps on the Way to Phosphorus–Carbon Cage Compounds". Angewandte Chemie International Edition in English. 34 (4): 436–438. doi:10.1002/anie.199504361.
  13. ↑ "A dangerous guide to beachcombing".
  14. ↑ "Woman mistakes WWII-era munition for precious stone on German beach | DW | 05.08.2017". Deutsche Welle .
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