Phosphorus

Phosphorus is a chemical element with the 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 (compare copper at about 0.06 grams). In minerals, phosphorus generally occurs as phosphate.

Elemental phosphorus was first isolated as white phosphorus in 1669. White phosphorus emits a faint glow when exposed to oxygen – hence the name, taken from Greek mythology, meaning 'light-bearer' (Latin ), referring to the " Morning Star", the planet Venus. The term '' phosphorescence'', meaning glow after illumination, derives from this property of phosphorus, although the word has since been used for a different physical process that produces a glow. The glow of phosphorus is caused by oxidation of the white (but not red) phosphorus — a process now called chemiluminescence. Together with nitrogen, arsenic, antimony, and bismuth, phosphorus is classified as a pnictogen.

Phosphorus is an element essential to sustaining life largely through phosphates, compounds containing the phosphate ion, PO₄³⁻. Phosphates are a component of DNA, RNA, ATP, and phospholipids, complex compounds fundamental to cells. Elemental phosphorus was first isolated from human urine, and bone ash was an important early phosphate source. Phosphate mines contain fossils because phosphate is present in the fossilized deposits of animal remains and excreta. Low phosphate levels are an important limit to growth in some aquatic systems. The vast majority of phosphorus compounds mined are consumed as fertilisers. Phosphate is needed to replace the phosphorus that plants remove from the soil, and its annual demand is rising nearly twice as fast as the growth of the human population. Other applications include organophosphorus compounds in detergents, pesticides, and nerve agents.

Characteristics

Allotropes

Phosphorus has several allotropes that exhibit strikingly diverse properties. The two most common allotropes are white phosphorus and red phosphorus.Abundance
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From the perspective of applications and chemical literature, the most important form of elemental phosphorus is white phosphorus, often abbreviated as WP. It is a soft, waxy solid which consists of tetrahedral molecules, in which each atom is bound to the other three atoms by a formal single bond. This tetrahedron is also present in liquid and gaseous phosphorus up to the temperature of when it starts decomposing to molecules. The molecule in the gas phase has a P-P bond length of ''r''_g = 2.1994(3) Å as was determined by gas electron diffraction. The nature of bonding in this tetrahedron can be described by spherical aromaticity or cluster bonding, that is the electrons are highly delocalized. This has been illustrated by calculations of the magnetically induced currents, which sum up to 29 nA/T, much more than in the archetypical aromatic molecule benzene (11 nA/T).

White phosphorus exists in two crystalline forms: α (alpha) and β (beta). At room temperature, the α-form is stable. It is more common, has cubic crystal structure and at , it transforms into β-form, which has hexagonal crystal structure. These forms differ in terms of the relative orientations of the constituent P₄ tetrahedra. The β form of white phosphorus contains three slightly different 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.

White phosphorus is the least stable, the most reactive, the most volatile, the least dense and the most toxic of the allotropes. White phosphorus gradually changes to red phosphorus. This transformation is accelerated by light and heat, and samples of white phosphorus almost always contain some red phosphorus and accordingly appear yellow. For this reason, white phosphorus that is aged or otherwise impure (e.g., weapons-grade, not lab-grade WP) is also called yellow phosphorus. When exposed to oxygen, white phosphorus glows in the dark with a very faint tinge of green and blue. It is highly flammable and pyrophoric (self-igniting) upon contact with air. Owing to its pyrophoricity, white phosphorus is used as an additive in napalm. The odour of combustion of this form has a characteristic garlic smell, and samples are commonly coated with white phosphorus pentoxide, which consists of tetrahedra with oxygen inserted between the phosphorus atoms and at their vertices. White phosphorus is insoluble in water but soluble in carbon disulfide.

Thermal decomposition of P₄ at 1100 K gives diphosphorus, P₂. This species is not stable as a solid or liquid. The dimeric unit contains a triple bond and is analogous to N₂. It can also be generated as a transient intermediate in solution by thermolysis of organophosphorus precursor reagents. At still higher temperatures, P₂ dissociates into atomic P.

Red phosphorus is polymeric in structure. It can be viewed as a derivative of P₄ wherein one P-P bond is broken, and one additional bond is formed with the neighbouring tetrahedron resulting in chains of P₂₁ molecules linked by van der Waals forces. Red phosphorus may be formed by heating white phosphorus to or by exposing white phosphorus to sunlight. Phosphorus after this treatment is amorphous. Upon further heating, this material crystallises. In this sense, red phosphorus is not an allotrope, but rather an intermediate phase between the white and violet phosphorus, and most of its properties have a range of values. For example, freshly prepared, bright red phosphorus is highly reactive and ignites at about , though it is more stable than white phosphorus, which ignites at about . After prolonged heating or storage, the color darkens (see infobox images); the resulting product is more stable and does not spontaneously ignite in air.

Violet phosphorus is a form of phosphorus that can be produced by day-long annealing of red phosphorus above 550 °C. In 1865, Hittorf discovered that when phosphorus was recrystallised from molten lead, a red/purple form is obtained. Therefore, this form is sometimes known as "Hittorf's phosphorus" (or violet or α-metallic phosphorus).

Black phosphorus is the least reactive allotrope and the thermodynamically stable form below . It is also known as β-metallic phosphorus and has a structure somewhat resembling that of graphite. It is obtained by heating white phosphorus under high pressures (about ). It can also be produced at ambient conditions using metal salts, e.g. mercury, as catalysts. In appearance, properties, and structure, it resembles graphite, being black and flaky, a conductor of electricity, and has puckered sheets of linked atoms.

Another form, scarlet phosphorus, is obtained by allowing a solution of white phosphorus in carbon disulfide to evaporate in sunlight.

Chemiluminescence

When first isolated, it was observed that the green glow emanating from white phosphorus would persist for a time in a stoppered jar, but then cease. Robert Boyle in the 1680s ascribed it to "debilitation" of the air. Actually, it is oxygen being consumed. By the 18th century, it was known that in pure oxygen, phosphorus does not glow at all; there is only a range of partial pressures at which it does. Heat can be applied to drive the reaction at higher pressures.

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

Since its discovery, '' phosphors'' and '' phosphorescence'' were used loosely to describe substances that shine in the dark without burning. Although the term phosphorescence is derived from phosphorus, the reaction that gives phosphorus its glow is properly called chemiluminescence (glowing due to a cold chemical reaction), not phosphorescence (re-emitting light that previously fell onto a substance and excited it).

Isotopes

There are 23 known isotopes of phosphorus, ranging from to . Only is stable and is therefore present at 100% abundance. The half-integer nuclear spin and high abundance of ³¹P make phosphorus-31 NMR spectroscopy a very useful analytical tool in studies of phosphorus-containing samples.

Two radioactive isotopes of phosphorus have half-lives suitable for biological scientific experiments. These are:
* , 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.
* , 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.
The high energy beta particles from penetrate skin and corneas and any ingested, inhaled, or absorbed is readily incorporated into bone and nucleic acids. For these reasons, Occupational Safety and Health Administration in the United States, and similar institutions in other developed countries require personnel working with to wear lab coats, disposable gloves, and safety glasses or goggles to protect the eyes, and avoid working directly over open containers. Monitoring personal, clothing, and surface contamination is also required. Shielding requires special consideration. The high energy of the beta particles gives rise to secondary emission of X-rays via Bremsstrahlung (braking radiation) in dense shielding materials such as lead. Therefore, the radiation must be shielded with low density materials such as acrylic or other plastic, water, or (when transparency is not required), even wood.

Occurrence

Universe

In 2013, astronomers detected phosphorus in Cassiopeia A, which confirmed that this element is produced in supernovae as a byproduct of supernova nucleosynthesis. The phosphorus-to-iron ratio in material from the supernova remnant could be up to 100 times higher than in the Milky Way in general.

In 2020, astronomers analysed ALMA and ROSINA data from the massive star-forming region AFGL 5142, to detect phosphorus-bearing molecules and how they are carried in comets to the early Earth.

Crust and organic sources

Phosphorus has a concentration in the Earth's crust of about one gram per kilogram (compare copper at about 0.06 grams). It is not found free in nature, but is widely distributed in many minerals, usually as phosphates. Inorganic phosphate rock, which is partially made of apatite (a group of minerals being, generally, pentacalcium triorthophosphate fluoride (hydroxide)), is today the chief commercial source of this element. According to the US Geological Survey (USGS), about 50 percent of the global phosphorus reserves are in the Arab nations. 85% of Earth's known reserves are in Morocco with smaller deposits in China, Russia, Florida, Idaho, Tennessee, Utah, and elsewhere. Albright and Wilson in the UK and their Niagara Falls plant, for instance, were using phosphate rock in the 1890s and 1900s from Tennessee, Florida, and the Îles du Connétable ( guano island sources of phosphate); by 1950, they were using phosphate rock mainly from Tennessee and North Africa.

Organic sources, namely urine, bone ash and (in the latter 19th century) guano, were historically of importance but had only limited commercial success. As urine contains phosphorus, it has fertilising qualities which are still harnessed today in some countries, including Sweden, using methods for reuse of excreta. To this end, urine can be used as a fertiliser in its pure form or part of being mixed with water in the form of sewage or sewage sludge.

Compounds

Phosphorus(V)

The most prevalent compounds of phosphorus are derivatives of phosphate (PO₄³⁻), a tetrahedral anion. Phosphate is the conjugate base of phosphoric acid, which is produced on a massive scale for use in fertilisers. Being triprotic, phosphoric acid converts stepwise to three conjugate bases:
:H₃PO₄ + H₂O H₃O⁺ + H₂PO₄⁻       ''K''_a1 = 7.25×10⁻³

:H₂PO₄⁻ + H₂O H₃O⁺ + HPO₄²⁻       ''K''_a2 = 6.31×10⁻⁸

:HPO₄²⁻ + H₂O H₃O⁺ +  PO₄³⁻        ''K''_a3 = 3.98×10⁻¹³

Phosphate exhibits a tendency to form chains and rings containing P-O-P bonds. Many polyphosphates are known, including ATP. Polyphosphates arise by dehydration of hydrogen phosphates such as HPO₄²⁻ and H₂PO₄⁻. For example, the industrially important pentasodium triphosphate (also known as sodium tripolyphosphate, STPP) is produced industrially on by the megatonne by this condensation reaction:
: 2 Na₂ HO)PO₃+ Na HO)₂PO₂→ Na_{5 3}P-O-P(O)₂-O-PO₃+ 2 H₂O
Phosphorus pentoxide (P₄O₁₀) is the acid anhydride of phosphoric acid, but several intermediates between the two are known. This waxy white solid reacts vigorously with water.

With metal cations, phosphate forms a variety of salts. These solids are polymeric, featuring P-O-M linkages. When the metal cation has a charge of 2+ or 3+, the salts are generally insoluble, hence they exist as common minerals. Many phosphate salts are derived from hydrogen phosphate (HPO₄²⁻).

PCl₅ and PF₅ are common compounds. PF₅ is a colourless gas and the molecules have trigonal bipyramidal geometry. PCl₅ is a colourless solid which has an ionic formulation of PCl₄⁺ PCl₆⁻, but adopts the trigonal bipyramidal geometry when molten or in the vapour phase. PBr₅ is an unstable solid formulated as PBr₄⁺Br⁻and PI₅ is not known. The pentachloride and pentafluoride are Lewis acids. With fluoride, PF₅ forms PF₆⁻, an anion that is isoelectronic with SF₆. The most important oxyhalide is phosphorus oxychloride, (POCl₃), which is approximately tetrahedral.

Before extensive computer calculations were feasible, it was thought that bonding in phosphorus(V) compounds involved ''d'' orbitals. Computer modeling of molecular orbital theory indicates that this bonding involves only s- and p-orbitals.

Phosphorus(III)

All four symmetrical trihalides are well known: gaseous PF₃, the yellowish liquids PCl₃ and PBr₃, and the solid PI₃. These materials are moisture sensitive, hydrolysing to give phosphorous acid. The trichloride, a common reagent, is produced by chlorination of white phosphorus:
:P₄ + 6 Cl₂ → 4 PCl₃
The trifluoride is produced from the trichloride by halide exchange. PF₃ is toxic because it binds to haemoglobin.

Phosphorus(III) oxide, P₄O₆ (also called tetraphosphorus hexoxide) is the anhydride of P(OH)₃, the minor tautomer of phosphorous acid. The structure of P₄O₆ is like that of P₄O₁₀ without the terminal oxide groups.

Phosphorus(I) and phosphorus(II)

These compounds generally feature P–P bonds.Greenwood, N. N.; & Earnshaw, A. (1997). Chemistry of the Elements (2nd Edn.), Oxford:Butterworth-Heinemann. . Examples include catenated derivatives of phosphine and organophosphines. Compounds containing P=P double bonds have also been observed, although they are rare.

Phosphides and phosphines

Phosphides arise by reaction of metals with red phosphorus. The alkali metals (group 1) and alkaline earth metals can form ionic compounds containing the phosphide ion, P³⁻. These compounds react with water to form phosphine. Other phosphides, for example Na₃P₇, are known for these reactive metals. With the transition metals as well as the monophosphides there are metal-rich phosphides, which are generally hard refractory compounds with a metallic lustre, and phosphorus-rich phosphides which are less stable and include semiconductors. Schreibersite is a naturally occurring metal-rich phosphide found in meteorites. The structures of the metal-rich and phosphorus-rich phosphides can be complex.

Phosphine (PH₃) and its organic derivatives (PR₃) are structural analogues of ammonia (NH₃), but the bond angles at phosphorus are closer to 90° for phosphine and its organic derivatives. It is an ill-smelling, toxic compound. Phosphorus has an oxidation number of −3 in phosphine. Phosphine is produced by hydrolysis of calcium phosphide, Ca₃P₂. Unlike ammonia, phosphine is oxidised by air. Phosphine is also far less basic than ammonia. Other phosphines are known which contain chains of up to nine phosphorus atoms and have the formula P_''n''H_''n''+2. The highly flammable gas diphosphine (P₂H₄) is an analogue of hydrazine.

Oxoacids

Phosphorous oxoacids are extensive, often commercially important, and sometimes structurally complicated. They all have acidic protons bound to oxygen atoms, some have nonacidic protons that are bonded directly to phosphorus and some contain phosphorus - phosphorus bonds. Although many oxoacids of phosphorus are formed, only nine are commercially important, and three of them, hypophosphorous acid, phosphorous acid, and phosphoric acid, are particularly important.

Nitrides

The PN molecule is considered unstable, but is a product of crystalline phosphorus nitride decomposition at 1100 K. Similarly, H₂PN is considered unstable, and phosphorus nitride halogens like F₂PN, Cl₂PN, Br₂PN, and I₂PN oligomerise into cyclic Polyphosphazenes. For example, compounds of the formula (PNCl₂)_''n'' exist mainly as rings such as the trimer hexachlorophosphazene. The phosphazenes arise by treatment of phosphorus pentachloride with ammonium chloride:

PCl₅ + NH₄Cl → 1/''n'' (NPCl₂)_''n'' + 4 HCl

When the chloride groups are replaced by alkoxide (RO⁻), a family of polymers is produced with potentially useful properties.

Sulfides

Phosphorus forms a wide range of sulfides, where the phosphorus can be in P(V), P(III) or other oxidation states. The three-fold symmetric P₄S₃ is used in strike-anywhere matches. P₄S₁₀ and P₄O₁₀ have analogous structures. Mixed oxyhalides and oxyhydrides of phosphorus(III) are almost unknown.

Organophosphorus compounds

Compounds with P-C and P-O-C bonds are often classified as organophosphorus compounds. They are widely used commercially. The PCl₃ serves as a source of P³⁺ in routes to organophosphorus(III) compounds. For example, it is the precursor to triphenylphosphine:
:PCl₃ + 6 Na + 3 C₆H₅Cl → P(C₆H₅)₃ + 6 NaCl
Treatment of phosphorus trihalides with alcohols and phenols gives phosphites, e.g. triphenylphosphite:
:PCl₃ + 3 C₆H₅OH → P(OC₆H₅)₃ + 3 HCl
Similar reactions occur for phosphorus oxychloride, affording triphenylphosphate:
:OPCl₃ + 3 C₆H₅OH → OP(OC₆H₅)₃ + 3 HCl

History

Etymology

The name ''Phosphorus'' in Ancient Greece was the name for the planet Venus and is derived from the Greek words (φῶς = light, φέρω = carry), which roughly translates as light-bringer or light carrier. (In Greek mythology and tradition, Augerinus (Αυγερινός = morning star, still in use today), Hesperus or Hesperinus (΄Εσπερος or Εσπερινός or Αποσπερίτης = evening star, still in use today) and Eosphorus (Εωσφόρος = dawnbearer, not in use for the planet after Christianity) are close homologues, and also associated with Phosphorus-the-morning-star).

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

Discovery

The discovery of phosphorus, the first element to be discovered that was not known since ancient times, is credited to the German alchemist Hennig Brand in 1669, although others might have discovered phosphorus around the same time. Brand experimented with urine, which contains considerable quantities of dissolved phosphates from normal metabolism. Working in Hamburg, Brand attempted to create the fabled 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. It was named ''phosphorus mirabilis'' ("miraculous bearer of light").Schmundt, Hilmar (21 April 2010)
"Experts Warn of Impending Phosphorus Crisis"
'' Der Spiegel''.

Brand's process originally involved letting urine stand for days until it gave off a terrible smell. Then he boiled it down to a paste, heated this paste to a high temperature, and led the vapours through water, where he hoped they would condense to gold. Instead, he obtained a white, waxy substance that glowed in the dark. Brand had discovered phosphorus. Specifically, Brand produced ammonium sodium hydrogen phosphate, . While the quantities were essentially correct (it took about of urine to make about 60 g of phosphorus), it was unnecessary to allow the urine to rot first. Later scientists discovered that fresh urine yielded the same amount of phosphorus.

Brand at first tried to keep the method secret, but later sold the recipe for 200 thalers to D. Krafft from Dresden. Krafft toured much of Europe with it, including England, where he met with Robert Boyle. The secret—that the substance was made from urine—leaked out, and Johann Kunckel (1630–1703) was able to reproduce it in Sweden (1678). Later, Boyle in London (1680) also managed to make phosphorus, possibly with the aid of his assistant, Ambrose Godfrey-Hanckwitz. Godfrey later made a business of the manufacture of phosphorus.

Boyle states that Krafft gave him no information as to the preparation of phosphorus other than that it was derived from "somewhat that belonged to the body of man". This gave Boyle a valuable clue, so that he, too, managed to make phosphorus, and published the method of its manufacture. Later he improved Brand's process by using sand in the reaction (still using urine as base material),

: 4 + 2 + 10 C → 2 + 10 CO +

Robert Boyle was the first to use phosphorus to ignite sulfur-tipped wooden splints, forerunners of our modern matches, in 1680.

Phosphorus was the 13th element to be discovered. Because of its tendency to spontaneously combust when left alone in air, it is sometimes referred to as "the Devil's element".

Bone ash and guano

Antoine Lavoisier