7723-14-0 Usage
Description
Phosphorus is a yellow waxy or colorless, transparent, volatile crystalline solid with a garlic-like odor. It is insoluble in water, slightly soluble in benzene, ethanol, and chloroform, and soluble in carbon disulfide. White phosphorus, a form of phosphorus, does not occur naturally but is manufactured from phosphate rocks. It reacts rapidly with oxygen and easily catches fire at temperatures 10°C-15°C above room temperature.
Uses
Used in Military Applications:
Phosphorus is used in various types of ammunition and to produce smoke for concealing troop movements and identifying targets.
Used in Chemical Production:
Phosphorus is used to produce phosphoric acid and other chemicals for use in fertilizers, food additives, and cleaning compounds.
Used in Pyrotechnics Industry:
Phosphorus is used to make safety matches, incendiary shells, and smoke bombs.
Used in Agricultural Industry:
Most elemental phosphorus is used to manufacture phosphoric acid, a solid that is used to produce triple-phosphate fertilizers, which are essential for crop growth.
Used in Detergent Industry:
Sodium tripolyphosphate, a phosphate, is used in detergents as a water softener and to enhance cleaning efficiency.
Used in Biological Systems:
Phosphorus is an essential constituent of plants and animals, being present in deoxyribonucleic acid (DNA), bones, teeth, and other components of high biological importance. It is the main element in adenosine triphosphate (ATP), the main energy source for living things.
Outline
Elemental phosphorus was discovered in 1669 by Hennig Brand. About two hundred years later James Readman developed a process for phosphorus recovery from phosphatic rocks using an electric furnace.
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.
Production
White phosphorus usually is obtained by heating some form of calcium phosphate with quartz and coke, usually in an electric furnace. The reactions may be written in two steps as follows:
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.
Reactions
Reactivity of white phosphorus is much greater than red or black phosphorus. Black phosphorus is the least reactive of all phosphorus allotropes. White phosphorus ignites in air spontaneously. When placed on a paper, the paper catches fire after a short delay. It catches fire at about 35°C. At room temperature white phosphorus glows in the dark on exposure to air emitting faint green light. Such chemiluminescence is attributed to the oxidation of P4 molecules in the vapor phase in contact with the surface of solid phosphorus:
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
Hazards
White phosphorus is a highly toxic substance, both an acute and chronic toxicant. Chronic exposure to it’s vapors can cause “phossy jaw;” necrosis of the jaw. Other symptoms are bronchopneumonia, bone changes, anemia and weight loss, Ingestion can cause nausea, vomiting, abdominal pain, diarrhea and coma. Skin contact can cause severe burns. In the eye it damages vision. Red phosphorus is much less toxic than its white allotrope. Its fumes, when burned, are highly irritating. White phosphorus is a flammable solid, igniting spontaneously when exposed to air.
Isotopes
There are a 23 isotopes of phosphorus, ranging from P-24 to P-46, with halflivesthat range from a few nanoseconds to about two and half minutes. The one stableisotope is phosphorus-31, which accounts for 100% of the natural phosphorus on Earth.
Origin of Name
Its name is derived from the Greek word phosphoros, which means
“bringer of light” or “light bearing.”
Characteristics
White phosphorus occurs in nature in phosphate rock. It is insoluble in water and alcoholand will ignite spontaneously in air. It exhibits what is known as phosphorescence; that is, itglows in the dark at room temperature. White phosphorus is poisonous and must be storedunder water.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.
History
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.
Production Methods
Elemental phosphorous is produced as a by-product or
intermediate in the production of phosphate fertilizer. Environmental
contamination with phosphorus results from its
manufacture into phosphorus compounds and during the
transport and use of these compounds. In the manufacturing
process, phosphate rock containing the mineral apatite (tricalcium
phosphate) is heated, and elementary phosphorus is
liberated as a vapor. Phosphorus is used to manufacture
explosives, incendiaries, smoke bombs, chemicals, rodenticides,
phosphor bronze, and fertilizer. The use of phosphate
fertilizers results in increased level of nutrients in fresh water and is a major source of environmental pollution
problem.
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.
Air & Water Reactions
When exposed to air emits a green light and gives off white fumes. Ignites at 30°C in moist air, higher temperatures are required for ignition in dry air [Merck 11th ed. 1989]. The reactivity of phosphorus with oxygen or air depends on the allotrope of phosphorus involved and the conditions of contact, white (yellow) phosphorus being by far more reactive. White phosphorus readily ignites in air if warmed, finely divided, or under conditions where the slow oxidative isotherm cannot be dissipated. Contact with finely divided charcoal or lampblack promotes ignition, probably by the absorbed oxygen. Contact with amalgamated aluminum also promotes ignition [Mellor 1940 and 1971].
Reactivity Profile
WHITE PHOSPHORUS reacts with air (fire, acidic solution); sulfur and oxidants (fire, explosion). Bromine trifluoride reacts similarly with arsenic, boron, bromine, iodine, phosphorus, and sulfur [Mellor 2:113. 1946-47]. Bromoazide explodes on contact with antimony, arsenic, phosphorus, silver foil, or sodium. Red phosphorus reacts in the cold with selenium oxychloride evolving light and heat; white phosphorus reacts explosively [Mellor 10:906. 1946-47]. When thorium is heated with phosphorus, they unite with incandescence [Svenska Akad. 1829. p. 1].
Hazard
Many of the compounds of phosphorus are extremely dangerous, both as fire hazardsand as deadly poisons to the nervous system of humans and animals. Some of the poisonouscompounds (PClx) can be absorbed by the skin as well as inhaled or ingested. Flushing withwater is the only way to stop the burning of white phosphorus on the skin, but water doesnot affect the combustion of some phosphorus compounds. Although red phosphorus is notas dangerous or poisonous as white phosphorus, merely applying some frictional heating willinduce the red allotrope to change back to the explosive white allotrope (the striking of a safetymatch is an example).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.
Health Hazard
Fire will produce irritating, corrosive and/or toxic gases. TOXIC; ingestion of substance or inhalation of decomposition products will cause severe injury or death. Contact with substance may cause severe burns to skin and eyes. Some effects may be experienced due to skin absorption. Runoff from fire control may be corrosive and/or toxic and cause pollution.
Health Hazard
White phosphorus is a highly toxic substance by all routes of exposure. Contact of the solid with the skin produces deep painful burns, and eye contact can cause severe damage. Ingestion of phosphorus leads (after a delay of a few hours) to symptoms including nausea, vomiting, belching, and severe abdominal pain. Apparent recovery may be followed by a recurrence of symptoms. Death may occur after ingestion of 50 to 100 mg due to circulatory, liver, and kidney effects. Phosphorus ignites and burns spontaneously when exposed to air, and the resulting vapors are highly irritating to the eyes and respiratory tract. 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.
Health Hazard
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..
Fire Hazard
White phosphorus ignites spontaneously upon contact with air, producing an irritating, dense white smoke of phosphorus oxides. Use water to extinguish phosphorus fires.
Fire Hazard
Extremely flammable; will ignite itself if exposed to air. Burns rapidly, releasing dense, white, irritating fumes. Substance may be transported in a molten form. May re-ignite after fire is extinguished. Corrosive substances in contact with metals may produce flammable hydrogen gas. Containers may explode when heated.
Flammability and Explosibility
White phosphorus ignites spontaneously upon contact with air, producing an
irritating, dense white smoke of phosphorus oxides. Use water to extinguish
phosphorus fires.
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.
Safety Profile
Human poison by ingestion. Experimental poison by ingestion and subcutaneous routes. Experimental reproductive effects. Human systemic effects by ingestion: cardiomyopathy, cyanosis, nausea or vomiting, sweating. Toxic quantities have an acute effect on the liver and can cause severe eye damage. Inhalation can cause photophobia with myosis, dilation of the pupils, retinal hemorrhage, congestion of the blood vessels, and, rarely, an optic neuritis. Chronic exposure by inhalation or ingestion can cause anemia, gastrointestinal effects, and brittleness of the long bones, leading to spontaneous fractures. The most common symptom, however, of chronic phosphorus poisoning is necrosis of the jaw (phossyjaw). More reactive than red phosphorus. Dangerous fire hazard when exposed to heat, flame, or by chemical reaction with oxidtzers. Igmtes spontaneously in air. Very reactive. If combustion occurs in a confined space, it will remove the oxygen and cause asphyxiation. Dangerous explosion hazard by chemical reaction with: alkaline hydroxides, NH4NO3, SbF5, Ba(BrO3)2, Be, Bl3, Ca(BrO3)2, Mg(BrO3)2, K(BrO3), NaBrO3, Zn(BrO3)2, Br2, halogens, BrF3, BrN3, (chlorates of Ba, Ca, Mg, K, Na, Zn), (iodates of Ba, Ca, Mg, K, Na, Zn), Ce, Cs,CsHC2, CS3N, (charcoal + air), ClO2, (Ch + heptane), Cl0, ClF3, ClO3, chlorosulfonic acid, Cr03, Cr(OCl)2, Cu, NCl, IBr, ICl, IFj, Fe, La, PbO2, Li, LizC2, Li6CS, Mg(ClO4)z, Mn, HgO, HgNO3, Nd, Ni, nitrates, NBr, N02, NBr3, NCh, NOF, FN02, O2, performic acid, Pt, K, KOH, K3N, I(Mn04, K2O2, Rb, RbHC2, Se2Cl2, SeOCl2, SeOF2, SeF4, AgNO3, Ag20, Na, Na2C2, NaClO2, NaOH, Na2O2, S, so3, H2SO4, Th, VOCl2, Zr, peroxyformic acid, chloro sulfuric acid, halogen azides, hexalithum dtshcide. Can react vigorously with oxidtzing materials. To fight fire, use water. Used in fertilizers, tracer bullets, incendiaries manufacturing, rat poison, and gas analysis. When heated to decomposition it emits highly toxic fumes of POx. See also PHOSPHORUS (red).
storage
Work with
white phosphorus should be conducted in a fume hood to prevent exposure by
inhalation, and splash goggles and impermeable gloves should be worn at all times
to prevent eye and skin contact. Phosphorus should be stored under water in
secondary containers in areas separate from oxidizing agents and other incompatible
substances.
Purification Methods
Purify white phosphorus by melting it under dilute H2SO4—dichromate (possible carcinogen) mixture and allow to stand for several days in the dark at room temperature. It remains liquid, and the initial milky appearance due to insoluble, oxidisable material gradually disappears. The phosphorus can then be distilled under vacuum in the dark [Holmes Trans Faraday Soc 58 1916 1962]. It sublimes in vacuo. Other methods of purification include extraction with dry CS2 followed by evaporation of the solvent, or washing with 6M HNO3, then H2O, and drying under vacuum. It ignites in air at ~50o, or by friction if dry. Store and cut it under H2O . POISONOUS.
Toxicity evaluation
Phosphorus is an oxidizing agent that, when exposed to air, may
burn spontaneously. Thus, direct contact may result in both
thermal and chemical burns. Second- and third-degree burns
can be seen at the point of contact. When absorbed, phosphorus
acts as a cellular poison by uncoupling oxidative phosphorylation.
Red phosphorus is not considered to be potentially toxic
as it is insoluble, nonvolatile, and unabsorbable.
Incompatibilities
White phosphorus reacts with a number of substances to form explosive mixtures.
For example, dangerous explosion hazards are produced upon reaction of
phosphorus with many oxidizing agents, including chlorates, bromates, and many
nitrates, with chlorine, bromine, peracids, organic peroxides, chromium trioxide, and
potassium permanganate, with alkaline metal hydroxides (phosphine gas is
liberated), and with sulfur, sulfuric acid, and many metals, including the alkali
metals, copper, and iron.
Red phosphorus is much less reactive than the white allotrope but may ignite or react
explosively with strong oxidizing agents.
Waste Disposal
Excess phosphorus and waste material containing this substance should be placed in
an appropriate container, clearly labeled, and handled according to your institution's
waste disposal guidelines.
Check Digit Verification of cas no
The CAS Registry Mumber 7723-14-0 includes 7 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 4 digits, 7,7,2 and 3 respectively; the second part has 2 digits, 1 and 4 respectively.
Calculate Digit Verification of CAS Registry Number 7723-14:
(6*7)+(5*7)+(4*2)+(3*3)+(2*1)+(1*4)=100
100 % 10 = 0
So 7723-14-0 is a valid CAS Registry Number.
InChI:InChI=1/P
This product is a nationally controlled contraband, and the Lookchem platform doesn't provide relevant sales information.
