Phosphate

Last updated
Phosphate
Phosphat-Ion.svg
Aromatic ball and stick model of phosphate Phosphate-3D-balls.png
Aromatic ball and stick model of phosphate
Space-filling model of phosphate Phosphate-3D-vdW.png
Space-filling model of phosphate
Names
Systematic IUPAC name
Phosphate [1]
Identifiers
3D model (JSmol)
3903772
ChEBI
ChemSpider
1997
MeSH Phosphates
PubChem CID
UNII
Properties
PO3−
4
Molar mass 94.9714 g mol−1
Conjugate acid Monohydrogen phosphate
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

In chemistry, a phosphate is an anion, salt, functional group or ester derived from a phosphoric acid. It most commonly means orthophosphate, a derivative of orthophosphoric acid H
3
PO
4
.

Contents

The phosphate or orthophosphate ion [PO
4
]3−
is derived from phosphoric acid by the removal of three protons H+
. Removal of one or two protons gives the dihydrogen phosphate ion [H
2
PO
4
]
and the hydrogen phosphate ion [HPO
4
]2−
ion, respectively. These names are also used for salts of those anions, such as ammonium dihydrogen phosphate and trisodium phosphate.

In organic chemistry, phosphate or orthophosphate is an organophosphate, an ester of orthophosphoric acid of the form PO
4
RR′R″
where one or more hydrogen atoms are replaced by organic groups. An example is trimethyl phosphate, (CH
3
)
3
PO
4
. The term also refers to the trivalent functional group OP(O-)
3
in such esters.

Orthophosphates are especially important among the various phosphates because of their key roles in biochemistry, biogeochemistry, and ecology, and their economic importance for agriculture and industry. [2] The addition and removal of phosphate groups (phosphorylation and dephosphorylation) are key steps in cell metabolism.

Orthophosphates can condense to form pyrophosphates.

Chemical properties

The phosphate ion has a molar mass of 94.97 g/mol, and consists of a central phosphorus atom surrounded by four oxygen atoms in a tetrahedral arrangement. It is the conjugate base of the hydrogen phosphate ion H(PO
4
)2−
, which in turn is the conjugate base of the dihydrogen phosphate ion H
2
(PO
4
)
, which in turn is the conjugate base of orthophosphoric acid, H
3
PO
4
.

Many phosphates are not soluble in water at standard temperature and pressure. The sodium, potassium, rubidium, caesium, and ammonium phosphates are all water-soluble. Most other phosphates are only slightly soluble or are insoluble in water. As a rule, the hydrogen and dihydrogen phosphates are slightly more soluble than the corresponding phosphates.

Equilibria in solution

Phosphoric acid speciation Phosphoric acid speciation.png
Phosphoric acid speciation

In water solution, orthophosphoric acid and its three derived anions coexist according to the dissociation and recombination equilibria below [3]

EquilibriumDissociation constant Ka [4] pKa
H3PO4H
2
PO
4
+ H+
Ka1 = [ H+
] [ H
2
PO
4
] / [ H
3
PO
4
] ≈ 7.5 × 10−3
pKa1 = 2.14
H
2
PO
4
HPO2−
4
+ H+
Ka2 = [ H+
] [ HPO2−
4
] / [ H
2
PO
4
] ≈ 6.2 × 10−8
pKa2 = 7.20
HPO2−
4
PO3−
4
+ H+
Ka3 = [ H+
] [ PO3−
4
] / [ HPO2−
4
] ≈ 2.14 × 10−13
pKa3 = 12.37

Values are at 25 °C and 0 ionic strength.

The pKa values are the pH values where the concentration of each species is equal to that of its conjugate bases. At pH 1 or lower, the phosphoric acid is practically undissociated. Around pH 4.7 (mid-way between the first two pKa values) the dihydrogen phosphate ion, [H
2
PO
4
]
, is practically the only species present. Around pH 9.8 (mid-way between the second and third pKa values) the monohydrogen phosphate ion, [HPO
4
]2−
, is the only species present. At pH 13 or higher, the acid is completely dissociated as the phosphate ion, (PO
4
)3−
.

This means that salts of the mono- and di-phosphate ions can be selectively crystallised from aqueous solution by setting the pH value to either 4.7 or 9.8.

In effect, H
3
PO
4
, H
2
(PO
4
)
and H(PO
4
)2−
behave as separate weak acids because the successive pKa differ by more than 4.

Phosphate can form many polymeric ions such as pyrophosphate), (P
2
O
7
)4−
, and triphosphate, (P
3
O
10
)5−
. The various metaphosphate ions (which are usually long linear polymers) have an empirical formula of (PO
3
)
and are found in many compounds.

Biochemistry of phosphates

In biological systems, phosphorus can be found as free phosphate anions in solution (inorganic phosphate) or bound to organic molecules as various organophosphates.

Inorganic phosphate is generally denoted Pi and at physiological (homeostatic) pH primarily consists of a mixture of [HPO
4
]2−
and [H
2
PO
4
]
ions. At a neutral pH, as in the cytosol (pH = 7.0), the concentrations of the orthophoshoric acid and its three anions have the ratios

[ H
2
PO
4
] / [ H
3
PO
4
] ≈ 7.5 × 104
[ HPO2−
4
] / [ H
2
PO
4
] ≈ 0.62
[ PO3−
4
] / [ HPO2−
4
] ≈ 2.14 × 10−6

Thus, only [H
2
PO
4
]
and [HPO
4
]2−
ions are present in significant amounts in the cytosol (62% [H
2
PO
4
]
, 38% [HPO
4
]2−
). In extracellular fluid (pH = 7.4), this proportion is inverted (61% [HPO
4
]2−
, 39% [H
2
PO
4
]
).

Inorganic phosphate can be present also as of pyrophosphate anions [P
2
O
7
]4−
, which can give orthophosphate by hydrolysis:

[P
2
O
7
]4−
+ H2O 2 [HPO
4
]2−

Organic phosphates are commonly found in the form of esters as nucleotides (e.g. AMP, ADP, and ATP) and in DNA and RNA. Free orthophosphate anions can be released by the hydrolysis of the phosphoanhydride bonds in ATP or ADP. These phosphorylation and dephosphorylation reactions are the immediate storage and source of energy for many metabolic processes. ATP and ADP are often referred to as high-energy phosphates, as are the phosphagens in muscle tissue. Similar reactions exist for the other nucleoside diphosphates and triphosphates.

Blood values sorted by mass and molar concentration.png
Reference ranges for blood tests, showing 'inorganic phosphorus' in purple at right, being almost identical to the molar concentration of phosphate

Bones and teeth

An important occurrence of phosphates in biological systems is as the structural material of bone and teeth. These structures are made of crystalline calcium phosphate in the form of hydroxyapatite. The hard dense enamel of mammalian teeth consists of fluoroapatite, a hydroxy calcium phosphate where some of the hydroxyl groups have been replaced by fluoride ions.

Medical and biological research uses

Orthophosphate salts of sodium and potassium are common agents for the preparation of buffer solutions for animal cells.

Plant metabolism

Plants take up phosphorus through several pathways: the arbuscular mycorrhizal pathway and the direct uptake pathway.

Production

Geological occurrence

Phosphate mine near Flaming Gorge, Utah, 2008 Phosphate Mine Panorama.jpg
Phosphate mine near Flaming Gorge, Utah, 2008
Train loaded with phosphate rock, Metlaoui, Tunisia, 2012 Train loaded with phosphate rock, Metlaoui Tunisia-4298B.jpg
Train loaded with phosphate rock, Métlaoui, Tunisia, 2012

Phosphates are the naturally occurring form of the element phosphorus, found in many phosphate minerals. In mineralogy and geology, phosphate refers to a rock or ore containing phosphate ions. Inorganic phosphates are mined to obtain phosphorus for use in agriculture and industry. [2]

The largest global producer and exporter of phosphates is Morocco. Within North America, the largest deposits lie in the Bone Valley region of central Florida, the Soda Springs region of southeastern Idaho, and the coast of North Carolina. Smaller deposits are located in Montana, Tennessee, Georgia, and South Carolina. The small island nation of Nauru and its neighbor Banaba Island, which used to have massive phosphate deposits of the best quality, have been mined excessively. Rock phosphate can also be found in Egypt, Israel, Western Sahara, Navassa Island, Tunisia, Togo, and Jordan, countries that have large phosphate-mining industries.

Phosphorite mines are primarily found in:

In 2007, at the current rate of consumption, the supply of phosphorus was estimated to run out in 345 years. [5] However, some scientists thought that a "peak phosphorus" will occur in 30 years and Dana Cordell from Institute for Sustainable Futures said that at "current rates, reserves will be depleted in the next 50 to 100 years". [6] Reserves refer to the amount assumed recoverable at current market prices, and, in 2012, the USGS estimated 71 billion tons of world reserves, while 0.19 billion tons were mined globally in 2011. [7] Phosphorus comprises 0.1% by mass of the average rock [8] (while, for perspective, its typical concentration in vegetation is 0.03% to 0.2%), [9] and consequently there are quadrillions of tons of phosphorus in Earth's 3 * 1019 ton crust, [10] albeit at predominantly lower concentration than the deposits counted as reserves from being inventoried and cheaper to extract; if it is assumed that the phosphate minerals in phosphate rock are hydroxyapatite and fluoroapatite, phosphate minerals contain roughly 18.5% phosphorus by weight and if phosphate rock contains around 20% of these minerals, the average phosphate rock has roughly 3.7% phosphorus by weight.

Some phosphate rock deposits, such as Mulberry in Florida, [11] are notable for their inclusion of significant quantities of radioactive uranium isotopes. This syndrome is noteworthy because radioactivity can be released into surface waters [12] in the process of application of the resultant phosphate fertilizer (e.g. in many tobacco farming operations in the southeast US).

In December 2012, Cominco Resources announced an updated JORC compliant resource of their Hinda project in Congo-Brazzaville of 531 Mt, making it the largest measured and indicated phosphate deposit in the world. [13]

Mining

The three principal phosphate producer countries (China, Morocco and the United States) account for about 70% of world production.

Production and global reserves of natural phosphate by country in 2015
(USGS, 2016) [14]
CountryProduction
(millions kg)
Share of
global
production (%)
Reserves
(millions kg)
Algeria 1,2000.542,200,000
Australia 2,6001.171,030,000
Brazil 6,7003.00315,000
China 100,00044.833,700,000
Egypt 5,5002.471,250,000
India 1,1000.4965,000
Iraq 2000.09430,000
Israel 3,3001.48130,000
Jordan 7,5003.361,300,000
Kazakhstan 1,6000.72260,000
Mexico 1,7000.7630,000
Morocco (incl. Western Sahara)30,00013.4550,000,000
Peru 4,0001.79820,000
Russia 12,5005.601,300,000
Saudi Arabia 3,3001.48956,000
Senegal 1,0000.4550,000
South Africa 2,2000.991,500,000
Syria 7500.341,800,000
Togo 1,0000.4530,000
Tunisia 4,0001.79100,000
United States 27,60012.371,100,000
Vietnam 2,7001.2130,000
Other countries2,6001.17380,000
Total223,00010069,000,000

Ecology

Sea surface phosphate from the World Ocean Atlas WOA09 sea-surf PO4 AYool.png
Sea surface phosphate from the World Ocean Atlas
Relationship of phosphate to nitrate uptake for photosynthesis in various regions of the ocean. Note that nitrate is more often limiting than phosphate. See the Redfield ratio. PhosphatetoNitrate.png
Relationship of phosphate to nitrate uptake for photosynthesis in various regions of the ocean. Note that nitrate is more often limiting than phosphate. See the Redfield ratio.

In ecological terms, because of its important role in biological systems, phosphate is a highly sought after resource. Once used, it is often a limiting nutrient in environments, and its availability may govern the rate of growth of organisms. This is generally true of freshwater environments, whereas nitrogen is more often the limiting nutrient in marine (seawater) environments. Addition of high levels of phosphate to environments and to micro-environments in which it is typically rare can have significant ecological consequences. For example, blooms in the populations of some organisms at the expense of others, and the collapse of populations deprived of resources such as oxygen (see eutrophication) can occur. In the context of pollution, phosphates are one component of total dissolved solids, a major indicator of water quality, but not all phosphorus is in a molecular form that algae can break down and consume. [15]

Calcium hydroxyapatite and calcite precipitates can be found around bacteria in alluvial topsoil. [16] As clay minerals promote biomineralization, the presence of bacteria and clay minerals resulted in calcium hydroxyapatite and calcite precipitates. [16]

Phosphate deposits can contain significant amounts of naturally occurring heavy metals. Mining operations processing phosphate rock can leave tailings piles containing elevated levels of cadmium, lead, nickel, copper, chromium, and uranium. Unless carefully managed, these waste products can leach heavy metals into groundwater or nearby estuaries. Uptake of these substances by plants and marine life can lead to concentration of toxic heavy metals in food products. [17]

See also

Related Research Articles

Phosphorus Chemical element with atomic number 15

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. In minerals, phosphorus generally occurs as phosphate.

Pyrophosphate salt or ester of diphosphoric acid

In chemistry, pyrophosphates are phosphorus oxyanions that contain two phosphorus atoms in a P-O-P linkage. A number of pyrophosphate salts exist, such as Na2H2P2O7. Often pyrophosphates are called diphosphates. The parent pyrophosphates are derived from partial or complete neutralization of pyrophosphoric acid. Important salts include disodium pyrophosphate and tetrasodium pyrophosphate. The pyrophosphate bond, as found in ATP, is very important in biochemistry.

Phosphoric acid chemical compound

Phosphoric acid, also known as orthophosphoric acid or phosphoric(V) acid, is a weak acid with the chemical formula H
3
PO
4
. It is normally encountered as a colorless, syrup of 85% concentration in water. The pure compound is a colorless solid.

Phosphite anion anion

A phosphite anion or phosphite in inorganic chemistry usually refers to [HPO3]2− but includes [H2PO3] ([HPO2(OH)]). These anions are the conjugate bases of phosphorous acid (H3PO3). The corresponding salts, e.g. sodium phosphite (Na2HPO3) are reducing in character.

Calcium phosphate is a family of materials and minerals containing calcium ions (Ca2+) together with inorganic phosphate anions. Some so-called calcium phosphates contain oxide and hydroxide as well. They are white solids of nutritious value. Calcium phosphates are found in many living organisms, e.g., bone mineral and tooth enamel. In milk, it exists in a colloidal form in micelles bound to casein protein with magnesium, zinc, and citrate - collectively referred to as colloidal calcium phosphate (CCP). Various calcium phosphate minerals are used in the production of phosphoric acid and fertilizers. Overuse of certain forms of calcium phosphate can lead to nutrient-containing surface runoff and subsequent adverse effects upon receiving waters such as algal blooms and eutrophication.

Pyrophosphoric acid chemical compound

Pyrophosphoric acid, also known as diphosphoric acid, is the inorganic compound with the formula H4P2O7 or, more descriptively, [(HO)2P(O)]2O. Colorless and odorless, it is soluble in water, diethyl ether, and ethyl alcohol. The anhydrous acid crystallizes in two polymorphs, which melt at 54.3 °C and 71.5 °C. The compound is not particular useful, except that it is a component of polyphosphoric acid and the conjugate acid of the pyrophosphate anion. Anions, salts, and esters of pyrophosphoric acid are called pyrophosphates.

Phosphorous acid, is the compound described by the formula H3PO3. This acid is diprotic (readily ionizes two protons), not triprotic as might be suggested by this formula. Phosphorous acid is an intermediate in the preparation of other phosphorus compounds. Organic derivatives of phosphorous acid, compounds with the formula RPO3H2, are called phosphonic acids.

Phosphoric acids and phosphates

A phosphoric acid, in the general sense, is a phosphorus oxoacid in which each phosphorus atom is in the oxidation state +5, and is bonded to four oxygen atoms, one of them through a double bond, arranged as the corners of a tetrahedron. Two or more of these PO
4
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.

Ammonium phosphate chemical compound

Ammonium phosphate is an ammonium salt of orthophosphoric acid. It is a highly unstable compound with the formula (NH4)3PO4. Because of its instability, it is elusive and of no commercial value. A related "double salt", (NH4)3PO4.(NH4)2HPO4 is also recognized but is too unstable for practical use. Both triammonium salts evolve ammonia. In contrast to the unstable nature of the triammonium salts, the diammonium phosphate (NH4)2HPO4 monoammonium salt (NH4)H2PO4, are stable materials that are commonly used as fertilizers to provide plants with fixed nitrogen and phosphorus.

Phosphorus oxoacid is a generic name for any acid whose molecule consists of atoms of phosphorus, oxygen, and hydrogen. There is a potentially infinite number of such compounds. Some of them are unstable and have not been isolated, but the derived anions and organic groups are present in stable salts and esters. The most important ones — in biology, geology, industry, and chemical research — are the phosphoric acids, whose esters and salts are the phosphates.

Tricalcium phosphate chemical compound Ca₃O₈P₂

Tricalcium phosphate (sometimes abbreviated TCP) is a calcium salt of phosphoric acid with the chemical formula Ca3(PO4)2. It is also known as tribasic calcium phosphate and bone phosphate of lime (BPL). It is a white solid of low solubility. Most commercial samples of "tricalcium phosphate" are in fact hydroxyapatite.

Sodium monofluorophosphate chemical compound

Sodium monofluorophosphate, commonly abbreviated MFP, is an inorganic compound with the chemical formula Na2PO3F. Typical for a salt, MFP is odourless, colourless, and water-soluble. This salt is an ingredient in some toothpastes.

In chemical nomenclature, the IUPAC nomenclature of inorganic chemistry is a systematic method of naming inorganic chemical compounds, as recommended by the International Union of Pure and Applied Chemistry (IUPAC). It is published in Nomenclature of Inorganic Chemistry. Ideally, every inorganic compound should have a name from which an unambiguous formula can be determined. There is also an IUPAC nomenclature of organic chemistry.

An oxyacid, oxoacid, or ternary acid is an acid that contains oxygen. Specifically, it is a compound that contains hydrogen, oxygen, and at least one other element, with at least one hydrogen atom bond to oxygen that can dissociate to produce the H+ cation and the anion of the acid.

Dicalcium phosphate chemical compound CaHPO₄

Dicalcium phosphate is the calcium phosphate with the formula CaHPO4 and its dihydrate. The "di" prefix in the common name arises because the formation of the HPO42– anion involves the removal of two protons from phosphoric acid, H3PO4. It is also known as dibasic calcium phosphate or calcium monohydrogen phosphate. Dicalcium phosphate is used as a food additive, it is found in some toothpastes as a polishing agent and is a biomaterial.

Dihydrogen phosphate Inorganic ion

Dihydrogen phosphate or dihydrogenphosphate ion is an inorganic ion with the formula [H2PO4]-. Its formula can also be written as [PO2(OH)2]-, which shows the presence of two O-H bonds. Together with hydrogen phosphate, dihydrogen phosphate occurs widely in natural systems. Their salts are used in fertilizers and in cooking. Most dihydrogen phosphate salts are colorless, water soluble, and nontoxic.

Dipotassium phosphate chemical compound

Dipotassium phosphate (K2HPO4) (also dipotassium hydrogen orthophosphate; potassium phosphate dibasic) is the inorganic compound with the formula K2HPO4.(H2O)x (x = 0, 3, 6). Together with monopotassium phosphate (KH2PO4.(H2O)x) it is often used as a fertilizer, food additive, and buffering agent.

Monosodium phosphate chemical compound

Monosodium phosphate (MSP), also known as monobasic sodium phosphate and sodium dihydrogen phosphate, is an inorganic compound of sodium with a dihydrogen phosphate (H2PO4) anion. One of many sodium phosphates, it is a common industrial chemical. The salt exists in an anhydrous form, as well as mono- and dihydrates.

Hypophosphoric acid chemical compound

Hypophosphoric acid is a mineral acid with the formula H4P2O6, with phosphorus in a formal oxidation state of +4. In the solid state it is present as the dihydrate, H4P2O6·2H2O. In hypophosphoric acid the phosphorus atoms are identical and joined directly with a P−P bond. There is an isomeric form isohypophosphoric acid which has a different structure with non-identical phosphorus atoms, one of which has a directly bonded H atom and an oxidation state of +3, which is joined by a P−O−P bridge to the second phosphorus atom which has an oxidation state of +5.

Vanadium phosphates are inorganic compounds with the formula VOxPO4 as well related hydrates with the formula VOxPO4(H2O)n. Some of these compounds are used commercially as catalysts for oxidation reactions.

References

  1. "Phosphates – PubChem Public Chemical Database". The PubChem Project. USA: National Center of Biotechnology Information.
  2. 1 2 "Phosphate Primer". Florida Industrial and Phosphate Research Institute. Florida Polytechnic University. Archived from the original on 29 August 2017.
  3. Campbell, Neil A.; Reece, Jane B. (2005). Biology (Seventh ed.). San Francisco, California: Benjamin Cummings. p. 65. ISBN   0-8053-7171-0.
  4. Kipton J. Powell, Paul L. Brown, Robert H. Byrne, Tamás Gajda, Glenn Hefter, Staffan Sjöberg, Hans Wanner (2005): "Chemical speciation of environmentally significant heavy metals with inorganic ligands. Part 1: The Hg2+
    , Cl, OH, CO2−
    3
    , SO2−
    4
    , and PO3−
    4
    aqueous systems". Pure and Applied Chemistry, volume 77, issue 4, pages 739–800. doi:10.1351/pac200577040739
  5. Reilly, Michael (May 26, 2007). "How Long Will it Last?". New Scientist . 194 (2605): 38–9. Bibcode:2007NewSc.194...38R. doi:10.1016/S0262-4079(07)61508-5.
  6. Leo Lewis (2008-06-23). "Scientists warn of lack of vital phosphorus as biofuels raise demand". The Times.
  7. U.S. Geological Survey Phosphate Rock
  8. U.S. Geological Survey Phosphorus Soil Samples
  9. Floor Anthoni. "Abundance of Elements". Seafriends.org.nz. Retrieved 2013-01-10.
  10. American Geophysical Union, Fall Meeting 2007, abstract #V33A-1161. Mass and Composition of the Continental Crust
  11. Central Florida Phosphate Industry: Environmental Impact Statement. 2. United States. Environmental Protection Agency. 1979.
  12. C. Michael Hogan (2010). Mark McGinley and C. Cleveland (Washington, DC.: National Council for Science and the Environment) (ed.). "Water pollution". Encyclopedia of Earth . Archived from the original on 2010-09-16.
  13. "Updated Hinda Resource Announcement: Now world's largest phosphate deposit (04/12/2012)". Cominco Resources.
  14. USGS Minerals Year Book - Phosphate Rock
  15. Hochanadel, Dave (December 10, 2010). "Limited amount of total phosphorus actually feeds algae, study finds". Lake Scientist. Retrieved June 10, 2012. [B]ioavailable phosphorus – phosphorus that can be utilized by plants and bacteria – is only a fraction of the total, according to Michael Brett, a UW engineering professor ...
  16. 1 2 Schmittner KE, Giresse P (1999). "Micro-environmental controls on biomineralization: superficial processes of apatite and calcite precipitation in Quaternary soils, Roussillon, France". Sedimentology. 46 (3): 463–76. Bibcode:1999Sedim..46..463S. doi:10.1046/j.1365-3091.1999.00224.x.
  17. Gnandi, K.; Tchangbedjil, G.; Killil, K.; Babal, G.; Abbel, E. (March 2006). "The Impact of Phosphate Mine Tailings on the Bioaccumulation of Heavy Metals in Marine Fish and Crustaceans from the Coastal Zone of Togo". Mine Water and the Environment. 25 (1): 56–62. doi:10.1007/s10230-006-0108-4.