Phosphate
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, phosphoric acid.
The phosphate or orthophosphate ion is derived from phosphoric acid by the removal of three protons. Removal of one proton gives the dihydrogen phosphate ion while removal of two protons gives the hydrogen phosphate ion. 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 where one or more hydrogen atoms are replaced by organic groups. An example is trimethyl phosphate,. The term also refers to the trivalent functional group in such esters. Phosphates may contain sulfur in place of one or more oxygen atoms.
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. The addition and removal of phosphate groups 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, which in turn is the conjugate base of the dihydrogen phosphate ion, which in turn is the conjugate base of orthophosphoric acid,.Many phosphates are 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
In water solution, orthophosphoric acid and its three derived anions coexist according to the dissociation and recombination equilibria below| Equilibrium | Dissociation constant Ka | pKa |
| pKa1 = 2.14 | ||
| pKa2 = 7.20 | ||
| 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 the dihydrogen phosphate ion,, is practically the only species present. Around pH 9.8 the monohydrogen phosphate ion,, is the only species present. At pH 13 or higher, the acid is completely dissociated as the phosphate ion,.
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,, and behave as separate weak acids because the successive pKa differ by more than 4.
Phosphate can form many polymeric ions such as pyrophosphate,, and triphosphate,. The various metaphosphate ions have an empirical formula of and are found in many compounds.
Biochemistry of phosphates
In biological systems, phosphorus can be found as free phosphate anions in solution or bound to organic molecules as various organophosphates.Inorganic phosphate is generally denoted Pi and at physiological pH primarily consists of a mixture of and ions. At a neutral pH, as in the cytosol, the concentrations of the orthophosphoric acid and its three anions have the ratios
Thus, only the and ions are present in significant amounts in the cytosol. In extracellular fluid, this proportion is inverted.
Inorganic phosphate can also be present as pyrophosphate anions, which give orthophosphate by hydrolysis:
Organic phosphates are commonly found in the form of esters as nucleotides 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.
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 may contain fluoroapatite, a hydroxy calcium phosphate where some of the hydroxyl groups have been replaced by fluoride ions.Medical and biological research uses
Phosphates are medicinal salts of phosphorus. Some phosphates, which help cure many urinary tract infections, are used to make urine more acidic. To avoid the development of calcium stones in the urinary tract, some phosphates are used. For patients who are unable to get enough phosphorus in their daily diet, phosphates are used as dietary supplements, usually because of certain disorders or diseases. Injectable phosphates can only be handled by qualified health care providers.Plant metabolism
Plants take up phosphorus through several pathways: the arbuscular mycorrhizal pathway and the direct uptake pathway.Adverse health effects
, or a high blood level of phosphates, is associated with elevated mortality in the general population. The most common cause of hyperphosphatemia in people, dogs, and cats is kidney failure. In cases of hyperphosphatemia, limiting consumption of phosphate-rich foods, such as some meats and dairy items and foods with a high phosphate-to-protein ratio, such as soft drinks, fast food, processed foods, condiments, and other products containing phosphate-salt additives is advised.Phosphates induce vascular calcification, and a high concentration of phosphates in blood was found to be a predictor of cardiovascular events.
Production
Geological occurrence
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.The largest global producer and exporter of phosphates is China, with Morocco possessing the greatest known reserves. 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, Palestine, Western Sahara, Navassa Island, Tunisia, Togo, and Jordan, countries that have large phosphate-mining industries.
Phosphorite mines are primarily found in:
- North America: United States, especially Florida, with lesser deposits in North Carolina, Idaho, and Tennessee
- Africa: Morocco, Algeria, Egypt, Niger, Senegal, Togo, Tunisia, Mauritania
- Middle East: Saudi Arabia, Jordan, Israel, Syria, Iran and Iraq, at the town of Akashat, near the Jordanian border.
- Central Asia: Kazakhstan
- Oceania: Australia, Makatea, Nauru, and Banaba Island
Some phosphate rock deposits, such as Mulberry in Florida, are notable for their inclusion of significant quantities of radioactive uranium isotopes. This is a concern because radioactivity can be released into surface waters from application of the resulting phosphate fertilizer.
In December 2012, Cominco Resources announced an updated JORC compliant resource of their Hinda project in Congo-Brazzaville of 531 million tons, making it the largest measured and indicated phosphate deposit in the world.
Around 2018, Norway discovered phosphate deposits almost equal to those in the rest of Earth combined.
In July 2022 China announced quotas on phosphate exportation.
Saudi Arabia has significant phosphate reserves and mining operations.
The largest importers in millions of metric tons of phosphate are Brazil 3.2, India 2.9 and the USA 1.6.
Mining
The three principal phosphate producer countries account for about 70% of world production.| Country | Production | Share of global production | Reserves |
| Algeria | 0.54 | ||
| Australia | 1.17 | ||
| Brazil | 3.00 | ||
| China | 44.83 | ||
| Egypt | 2.47 | ||
| Finland | - | ||
| India | 0.49 | ||
| Iraq | 0.09 | ||
| Israel | 1.48 | ||
| Jordan | 3.36 | ||
| Kazakhstan | 0.72 | ||
| Mexico | 0.76 | ||
| Morocco | 13.45 | ||
| Peru | 1.79 | ||
| Russia | 5.60 | ||
| Saudi Arabia | 1.48 | ||
| Senegal | 0.45 | ||
| South Africa | 0.99 | ||
| Syria | 0.34 | ||
| Togo | 0.45 | ||
| Tunisia | 1.79 | ||
| Uzbekistan | - | ||
| United States | 12.37 | ||
| Vietnam | 1.21 | ||
| Other countries | 1.17 | ||
| Total | ' | 100 | ' |