Chemical Properties
Melting point | 280 °C (white)(lit.) |
Boiling point | 280℃ |
Density | 2.34 g/mL at 25 °C(lit.) |
vapor density | 0.02 (vs air) |
vapor pressure | 0.03 mm Hg ( 21 °C) |
Flash point | 30°C |
storage temp. | 2-8°C |
solubility | insoluble |
form | powder (red) |
color | Red-brown |
Specific Gravity | 2.34 |
Odor | Acrid fumes when exposed to air |
PH | 3 at 37℃ and 500-10000mg/L |
Resistivity | 10 μΩ-cm, 20°C |
Water Solubility | insoluble |
Merck | 13,7433 |
Dielectric constant | 4.1(34℃) |
Exposure limits | ACGIH: TWA 2 ppm; STEL 4 ppm OSHA: TWA 2 ppm(5 mg/m3) NIOSH: IDLH 25 ppm; TWA 2 ppm(5 mg/m3); STEL 4 ppm(10 mg/m3) |
Stability | Stable. Highly flammable. Incompatible with strong oxidizing agents, strong bases. Light and heat sensitive. |
CAS DataBase Reference | 7723-14-0(CAS DataBase Reference) |
NIST Chemistry Reference | Phosphorus atom(7723-14-0) |
EPA Substance Registry System | Phosphorus (7723-14-0) |
Safety Information
Hazard Codes | F,N,C,T+ |
Risk Statements | 11-16-52/53-50-35-26/28-17 |
Safety Statements | 7-43-61-43C-45-38-26-5-27-6 |
RIDADR | UN 1338 4.1/PG 3 |
OEB | D |
OEL | TWA: 0.1 mg/m3 |
WGK Germany | 2 |
RTECS | TH3495000 |
F | 10-21 |
Autoignition Temperature | White phosphorus: 29 °C Red phosphorus: 260 °C |
TSCA | Yes |
HazardClass | 4.1 |
PackingGroup | III |
HS Code | 28047000 |
Hazardous Substances Data | 7723-14-0(Hazardous Substances Data) |
Toxicity | LD50 oral (rat) 3 mg/kg PEL (OSHA) 0.1 mg/m3 TLV-TWA (ACGIH) 0.02 ppm (0.1 mg/m3) |
IDLA | 5 mg/m3 |
MSDS
Provider | Language |
---|---|
Phosphorus | English |
SigmaAldrich | English |
ACROS | English |
ALFA | English |
Usage And Synthesis
Phosphorus is one of the most widely distributed elements on earth. It is found as phosphate salts in nearly all igneous rocks and in sedimentary deposits and sea beds. Phosphorus occurs in more than three hundred minerals, usually associated with Ca, Mg, Fe, Sr, Al, Na, and several other metals, and with anions such as silicates, sulfates, oxides, hydroxides, and halides. Phosphorus is an essential element present in all living matter and is vital in biological and ecological processes. It occurs in DNA and other nucleic acids, and in bones.
Phosphorus is used in pyrotechnics, smoke bombs, incendiary shells, and safety matches. It also is used in organic syntheses, manufacture of phosphoric acid, phosphorus trichloride, phosphine, and other compounds.
White phosphorus is a white, soft, wax-like transparent mass which often acquires a yellow appearance due to impurities, especially traces of red phosphorus. It has a garlic-like odor. It is made up of cubic crystals, has a density 1.82 g/cm3, and melts at 44.1°C to a colorless or yellowish liquid. X-ray diffraction studies and 31P-NMR analysis indicate tetrahedral P4 molecules with an interatomic distance of 2.21Å , and the molecules are able to rotate freely in the crystals. When cooled below –76.9°C, the cubic alpha form converts to a hexagonal beta modification with a density 1.88 g/cm3. The beta form, unlike the alpha form, does not rotate freely in the crystal but has a fixed orientation of P4 molecules in the lattice.
Red phosphorus is obtained from white phosphorus by heating at 230 to 240°C, allowing complete conversion to occur in about 48 hours. Conversion is catalyzed by sulfur, iodine, and selenium. The red allotrope also slowly deposits from liquid phosphorus or from a solution of white phosphorus, the rate and yield depending on catalysts, temperature, light, and other factors. Red phosphorus exhibits various modifications. Three important ones are an amorphous form at ordinary temperatures and two crystalline modifications which include a triclinic form and a hexagonal or a tetragonal form that may prevail at higher temperatures. There also are a few more modifications, all of which may coexist, accounting for variability in physical properties of red phosphorus. The triclinic variety of red phosphorus is the most stable of all allotropes of phosphorus at ordinary temperatures. Red phosphorus possesses a density of 2.0 to 2.31 g/cm3 and melts at 590°C.
Black phosphorus is the third major allotropic form of phosphorus. It occurs in two forms, one is an amorphous modification having a laminar structure similar to graphite and the other is an orthorhombic crystalline form. The density of black phosphorus may vary between 2.20 to 2.69 g/cm3. Black phosphorus is obtained from white phosphorus by heating the latter at 220°C under an extremely high pressure of about 10,000 atm.
When solid phosphorus of any form—white, red, or black—is melted, it forms the same liquid phosphorus. This liquid has a density of 1.74 g/cm3 and viscosity 1.69 centipoise at 50°C. Liquid phosphorus boils at 280.5°C. Upon cooling, liquid phosphorus solidifies to only white phosphorus. Liquid phosphorus and its vapors consist of tetrahedral P4 molecules. The vapors, on rapid condensation, convert to white phosphorus.
While white and red phosphorus have high electrical resistivity, the black variety has a low resistivity of 0.71 ohm-cm at 0°C. Solubility also varies widely. White phosphorus is soluble in a number of organic solvents. It is very highly soluble in carbon disulfide, about 400 g/100 g solvent at 0°C and moderately soluble in benzene (~3.59 g/100g at 25°C) and exhibits lower solubility in ether (~1.5g/100g at 25°C). Red and black phosphorus are insoluble in organic solvents. White phosphorus is a flammable solid, igniting spontaneously in air at 35°C. Red and black phosphorus are nonflammable. The latter is difficult to ignite.
Ca3(PO4)2 + 3SiO2 → 3CaSiO3 + P2O5
P2O5 + 5C → 2P + 5 CO
In commercial scale, white phosphorus is manufactured mostly from the mineral fluorapatite by heating with silica and coke in an electric-arc or blast furnace at a temperature of 1,200 to 1,500°C. An overall reaction may be represented in the following equation.
4Ca5F(PO4)3 + 18SiO2 + 30C → 18CaO • SiO2 • 2CaF2 + 30CO↑ + 3P4↑
(slag) White phosphorus also can be produced by a wet process using phosphoric acid, a process that was practiced historically in commercial production. In this method the starting material, phosphoric acid, usually is prepared in large vats by reacting phosphate rock with sulfuric acid:
Ca5F(PO4)3 + 5H2SO4 + 10H2O → 3H3PO4 + 5CaSO4 • 10H2O + HF
Phosphoric acid is filtered out of the mixture. It is then mixed with coke, charcoal or sawdust; dried; charred; and finally heated to white heat in a fireclay retort:
H3PO4 + 16C → P4 + 6H2 + 16CO
The vapor is condensed to obtain white phosphorus.
As stated earlier, all other forms of phosphorus can be made from white phosphorus. Thus, heating white phosphorus first at 260°C for a few hours and then at 350°C gives red phosphorus. The conversion is exothermic and can become explosive in the presence of iodine as a catalyst. When a solution of white phosphorus in carbon disulfide or phosphorus tribromide is irradiated the scarlet red variety is obtained.
Black phosphorus allotrope is produced by heating white phosphorus at 220°C under 12,000 atm pressure. The conversion is initially slow, but can became fast and explosive after an induction period.
White phosphorus is stored under water as it ignites in air. It may be cut into appropriate sizes only under water.
P4(g) + 5O2(g) → P4O10(s) + light
The mechanism involves a complicated oxidative process that occurs only at certain partial pressures of oxygen and not in pure oxygen at atmospheric pressure, nor in vacuum.
Red phosphorus ignites when struck with a hammer blow or when heated at 260°C. Black phosphorus ignites in contact with flame. White phosphorus reacts spontaneously with halogens at ordinary temperatures forming phosphorus trihalides. However, in excess halogen the product is phosphorus pentahalide:
P4(s) + 6Cl2(g) → 4PCl3 (l)
P4 (s) + 10Cl2 (g) → 4PCl5 (s)
White phosphorus reacts with sulfur on warming forming phosphorus trisulfide:
P4(s) + 6S(s) → 2P2S3 (s)
White phosphorus reacts with strong aqueous alkali solution forming hypophosphite with evolution of phosphine, PH3:
P4 + 3KOH + 3H2O → 3KH2PO2 + PH3 ↑
P4(s) + 6Cl2(g) → 4PCl3 (l)
P4 (s) + 10Cl2 (g) → 4PCl5 (s)
White phosphorus reacts with sulfur on warming forming phosphorus trisulfide:
P4(s) + 6S(s) → 2P2S3 (s)
White phosphorus reacts with strong aqueous alkali solution forming hypophosphite with evolution of phosphine, PH3:
P4 + 3KOH + 3H2O → 3KH2PO2 + PH3 ↑
P4 + 6Ca → 2Ca3P2
Reactions with alkali metals occur under warm conditions producing the corresponding metal phosphides:
P4 + 12Na → 4Na3P
White phosphorus has a white waxy appearance that turns slightly yellow with age andimpurities. There are two allotropic forms of white phosphorus. The alpha (α) form has acubic crystal structure, and the beta (β) form has a hexagonal crystalline structure. Whitephosphorus is extremely reactive and will spontaneously burst into flame when exposed to airat a temperature of about 35°C. It must be kept under water. But this property of spontaneouscombustion has made it useful for military applications.
White phosphorus is the most useful version of the three allotropes, and it is used inprocesses to manufacture the other two versions of phosphorus. White phosphorus’s meltingpoint 44.15°C, its boiling point is 280.5°C, and its density is 1.82 c/cm3.
Exposing white phosphorus to a process of heat produces red phosphorus. Red phosphorushas a density of 2.34 g/cm3.
Black phosphorus also starts with heating white phosphorus. The difference is that thewhite phosphorus is heated in the presence of a mercury catalyst and a small amount ofalready-formed black phosphorus. Its density is 2.4 g/cm3.
Red phosphorus is less reactive than the white variety. It is not poisonous, but largeamounts can explode. It is used in fireworks and matches.
Black phosphorus is the only one of the three that will conduct electricity; white and redare poor conductors. Black phosphorus has no significant commercial uses.
Discovered in 1669 by Brand, who prepared it from urine. Phosphorus exists in four or more allotropic forms: white (or yellow), red, and black (or violet). White phosphorus has two modifications: α and β with a transition temperature at –3.8°C. Never found free in nature, it is widely distributed in combination with minerals. Twenty-one isotopes of phosphorus are recognized. Phosphate rock, which contains the mineral apatite, an impure tricalcium phosphate, is an important source of the element. Large deposits are found in the Russia, China, Morocco, and in Florida, Tennessee, Utah, Idaho, and elsewhere. Phosphorus in an essential ingredient of all cell protoplasm, nervous tissue, and bones. Ordinary phosphorus is a waxy white solid; when pure it is colorless and transparent. It is insoluble in water, but soluble in carbon disulfide. It takes fire spontaneously in air, burning to the pentoxide. It is very poisonous, 50 mg constituting an approximate fatal dose. Exposure to white phosphorus should not exceed 0.1 mg/m3 (8-hour time-weighted average — 40- hour work week). White phosphorus should be kept under water, as it is dangerously reactive in air, and it should be handled with forceps, as contact with the skin may cause severe burns. When exposed to sunlight or when heated in its own vapor to 250°C, it is converted to the red variety, which does not phosphoresce in air as does the white variety. This form does not ignite spontaneously and it is not as dangerous as white phosphorus. It should, however, be handled with care as it does convert to the white form at some temperatures and it emits highly toxic fumes of the oxides of phosphorus when heated. The red modification is fairly stable, sublimes with a vapor pressure of 1 atm at 417°C, and is used in the manufacture of safety matches, pyrotechnics, pesticides, incendiary shells, smoke bombs, tracer bullets, etc. White phosphorus may be made by several methods. By one process, tricalcium phosphate, the essential ingredient of phosphate rock, is heated in the presence of carbon and silica in an electric furnace or fuel-fired furnace. Elementary phosphorus is liberated as vapor and may be collected under water.
Phosphorus is an essential constituent of plants and animals, being present in deoxyribonucleic acid (DNA), bones, teeth and other components of high biological importance. Phosphorus does not occur in its elemental state in nature, as it readily oxidises and therefore is deposited as phosphate rock. The remaining elements of group 15 are mostly obtained from minerals, but can also be found in their elemental form in the earth’s crust.
Red phosphors are formed either by heating white phosphorus or by exposing white phosphorusto sunlight. It is quite different from the explosive white phosphorus. For instance,when scratched on a surface, the heads of safety matches made of red phosphorus convert backto white phosphorus and ignite due to the heat of the slight friction of the match on a roughsurface. Red phosphorus is also used in fireworks, smoke bombs, and pesticides and to makephosphoric acid, electroluminescent paints, and fertilizers.
Most elemental phosphorus is used to manufacture phosphoric acid, a solid that is usedto produce triple-phosphate fertilizers. Some soils require large amounts of phosphorus toproduce a viable crop.
Sodium tripolyphosphate is the main phosphate found in detergents. It acts as a watersoftener and counteracts the elements that are responsible for “hard water” while at the sametime making the detergent a more effective cleaner.
Phosphorus exists in several allotropic forms: white (or yellow), red, and black (or violet). The last is of no industrial importance. Elemental yellow phosphorus extracted from bone was used to make “strike anywhere” matches. In 1845, the occupational disease “phossy jaw,” a jaw bone necrosis, was recognized in workers who manufactured such matches. A prohibitive tax imposed in 1912 on matches made from yellow phosphorus led to the use of less toxic materials, red phosphorus and phosphorus sesquisulfide. The United States appears to have lagged behind European countries in that signatories of the Berne Convention of 1906 agreed not to manufacture or import matches made with yellow phosphorus. Occasional injuries continued to result from using yellow phosphorus to manufacture fireworks until 1926, when an agreement was reached to discontinue using yellow phosphorus for this purpose.
The world production of elemental phosphorus exceeds 1,000,000 metric ton. It is manufactured either in electric or blast furnaces. Both depend on silica as a flux for the calcium present in the phosphate rock. Almost all of the phosphorus produced is converted into phosphoric acid or other phosphorus compounds.
Red phosphorus does not ignite spontaneously but may be ignited by friction, static electricity, heating, or oxidizing agents. Handling it in an aqueous solution helps prevent fires.
Some of the main types of poisonous gases used in warfare have a phosphorus base. Manycountries stockpile these gases, but, by agreement, the supplies are being reduced.
White phosphorus is a highly poisonous substance. The toxic routes are ingestion, skin contact, and inhalation.
Inhumansasingleoraldoseof70–100 mg can cause death. The toxic symptoms are nausea, vomiting, severe abdominal pain, diarrhea, coma, and convulsions. The other harmful effects from ingestion are liver damage and jaundice. An amount as small as 5–10 mg of white phosphorus can exhibit some of the foregoingtoxic effectsinhumans from an oral intake. The lethal doses and symptoms for other species varied with the species. The toxic symptoms were somnolence, convulsion, and lung injury. The lethal doses ranges from 3 mg/kg for rats to 50 mg/kg for dogs.
Inhalation of its vapors can cause irritation of respiratory tract. The chronic poisoning from inhalation (or ingestion) severely affected the lungs, kidney, and liver in test animals. The toxic symptoms were bronchopneumonia, bone changes, necrosis of the jaw (“phossy” jaw), anemia, and weight loss. Since the vapor pressure of white phosphorus is low [0.026 torr at 20°C (68°F)], the acute health hazard from a short exposure to its vapors under normal conditions of its handling and uses should be low..
Red phosphorus is much less toxic than the white allotrope; however, samples of red phosphorus may contain the white form as an impurity. Early signs of chronic systemic poisoning by phosphorus are reported to include anemia, loss of appetite, gastrointestinal distress, chronic cough, a garlic-like odor to the breath, and pallor. A common response to severe chronic poisoning is damage of the jaw (''phossy jaw") and other bones. Phosphorus has not been reported to show carcinogenic effects in humans.
Red phosphorus is a flammable solid but does not ignite spontaneously on exposure to air. At high temperatures (-300 °C), red phosphorus is converted to the white form.
Most plants contain phosphorus in concentrations varying from 0.1 to 0.4%, which are considerably lower than for potassium and nitrogen in plants. Phosphorus is an essential part of nucleoproteins in cell nuclei which control the cell division and the DNA molecules, the latter transmitting heredity to living organisms. Phosphorus also plays an important role in (a) stimulating early root growth, (b) hastening plant maturity, (c) transforming energy within the cells, and (d) developing and ripening the fruit and the seed. Phosphorus is rightly called the key to life, as it is directly involved in most life processes.
Relations between phosphorus and N, Cu, Fe, Mn and Zn are well known. Ratios of 3: 1 of N to P and 200: 1 of P to Zn are considered critical for addressing nutrient deficiency in plants. The ratio of nitrogen to phosphorus (N:P) serves as a Diagnosis and Recommendation Integrated System (DRIS) norm for interpreting results of plant analysis.
Soils have low total phosphate content and hence such soils provide low supplies of available phosphate (400 to 2000 kg/ha) to plants because mineral phosphate forms are not readily soluble. Plants absorb phosphorus as H2PO4-; and HPO42- ions. On average, a soil solution contains about 0.05 ppm phosphorus which varies from soil to soil. This amount of phosphorus is adequate for plants, as its concentration varies from 0.003 to 0.3 ppm depending on the crop. For instance, maximum corn yields are obtained at 0.01 ppm of the solutionphosphorus, while the incorporation of solution phosphorus in the case of wheat is only marginally more.
Soil phosphorus occurs in both organic and inorganic forms. Plants differ in their ability to compete for soil phosphorus at the growth stage when they need it most. Young plants rapidly absorb phosphorus and accumulate 75 % of their requirement when the crop produces 25 % of its dry weight. Winter wheat absorbs about 70% of phosphorus between tillering and flowering. For corn, the peak phosphorus demand is during the initial three weeks of the growing season.
Red phosphorus is much less reactive than the white allotrope but may ignite or react explosively with strong oxidizing agents.
Preparation Products And Raw materials
- IodomethaneHydrogen bromidePhosphoric acidPhosphorus tribromidePhosphorus pentoxidePhosphorus pentasulfideTHIOPHOSPHORYL CHLORIDE1-Bromobutane1-BromopropaneSodium tripolyphosphateIodoethane4-methylquinolineSodium Phosphate, DibasicPhenthoateHydroxytyrosol 4-Hydroxypyrimidinesodium hexametaphosphateIndazole2-BromoanthraceneBromoacetyl bromideSodium hypophosphiteO,O-Dimethyl phosphoramidothioate DL-IsoleucineCalcium hypophosphiteETHYL ALPHA-CHLOROPHENYLACETATEPropionyl bromideBromisovalAluminum phosphide1-FLUORENECARBOXYLIC ACIDperphosphoric acidZINC PHOSPHIDE2-Bromoisobutyryl Bromide
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Related Product Information
- Phosphorous sulfide (R)
- Phosphoric acid
- Phosphorus oxychloride
- White phosphorus
- Phosphorus pentoxide
- Phosphorus oxybromide
- Phosphorus pentachloride
- Phosphotungstic acid hydrate
- Phosphorus
- Ferrophosphorus
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