Chemical Fact Sheet
Phosphorus
| Chemical Abstract Number (CAS #) | 7723-14-0 |
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| Synonyms | BLACK-PHOSPHORUS; BONIDE-BLUE-DEATH-RAT-KILLER; Exolit-LPKN; Exolit VPK-n 361; FOSFORO-BIANCO-(ITALIAN); GELBER-PHOSPHOR-(GERMAN); PHOSPHORE-BLANC-(FRENCH); Phosphorous- (white); Phosphorus-(red); Phosphorus,-white,-molten-(dry); PHOSPHORUS-31; RAT-NIP; RED-PHOSPHORUS; TETRAFOSFOR-(DUTCH); TETRAPHOSPHOR-(GERMAN); VIOLET-PHOSPHORUS; WEISS-PHOSPHOR(GERMAN); WHITE-PHOSPHORUS; YELLOW-PHOSPHORUS |
| Analytical Methods | SM4500P |
| Molecular Formula | P |
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Synopsis
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Phosphorus- (Gr. phosphoros, light bearing; ancient name for the planet Venus when appearing before sunrise), P; at. wt. 30.973762(4); at. no. 15; m.p. (white) 44.15 deg C; b.p. 280.5 deg C; sp. gr. (white) 1.82 (red) 2.20, (black) 2.25 to 2.69; valence 3 or 5. 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: alpha and beta with a transition temperature at -3.8 deg C. Never found free in nature, it is widely distributed in combination with minerals. Seventeen isotopes of phosphorus are recognized. Phosphate rock, which contains the mineral apatite, an impure tri-calcium phosphate, is an important source of the element. Large deposits are found in the U.S.S.R., in 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/cu. m (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 deg 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 4l7 deg 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, tri-calcium 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. If desired, the phosphorus vapor and carbon monoxide produced by the reaction can be oxidized at once in the presence of moisture to produce phosphoric acid, an important compound in making super-phosphate fertilizers. In recent years, concentrated phosphoric acids, which may contain as much as 70 to 75% P2O5 content, have become of great importance to agriculture and farm production. World-wide demand for fertilizers has caused record phosphate production. Phosphates are used in the production of special glasses, such as those used for sodium lamps. Bone-ash, calcium phosphate, is also used to produce fine chinaware and to produce mono-calcium phosphate used in baking powder. Phosphorus is also important in the production of steels, phosphor bronze, and many other products. Trisodium phosphate is important as a cleaning agent, as a water softener, and for preventing boiler scale and corrosion of pipes and boiler tubes. Organic compounds of phosphorus are important. Amorphous (red) phosphorus costs about $60/kg (99.5%). |
| Use | WHITE PHOSPHORUS MFR RAT POISONS; FOR SMOKE SCREENS, GAS ANALYSIS. RED PHOSPHORUS: PYROTECHNICS; MFR SAFETY MATCHES; IN ORG SYNTHESIS; MFR PHOSPHORIC ACID, PHOSPHINE, PHOSPHORIC ANHYDRIDE, PHOSPHORUS PENTACHLORIDE, PHOSPHORUS TRICHLORIDE; MFR FERTILIZERS, PESTICIDES, INCENDIARY SHELLS, SMOKE BOMBS, TRACER BULLETS. CHEM INT FOR PHOSPHORIC ACID, CALCIUM METAPHOSPHATE, PHOSPHORUS TRICHLORIDE, PHOSPHORUS PENTOXIDE, PHOSPHORUS PENTASULFIDE, MISC APPLICATIONS. WHITE PHOSPHORUS HAS BEEN USED AS INSECTICIDE IN PASTES MADE BY GRINDING YELLOW PHOSPHORUS IN PRESENCE OF WATER & MIXING WITH FLOUR. PHOSPHORUS PASTE WAS USED TO CONTROL AMERICAN COCKROACH, ALSO AS RAT POISON. |
| Consumption Patterns | 77% IS USED IN THE PRODUCTION OF PHOSPHORIC ACID; 2% IS USED TO PRODUCE PHOSPHORUS TRICHLORIDE (FOR ORGANIC PHOSPHATES, PLASTICIZERS, GASOLINE & OIL ADDITIVES, FLOTATION AGENTS, FLAME RETARDANTS, & INSECTICIDES); 2% TO PRODUCE PHOSPHORUS PENTASULFIDE (FOR PHOSPHATE PESTICIDES, LUBRICATING OIL ADDITIVES, & FLOTATION AGENTS); 19% IN MISC APPLICATIONS (1968). END USE PATTERN DERIVATIVE: PHOSPHORIC ACID, 85%; PHOSPHORUS PENTASULFIDE, 5%; PHOSPHORUS TRICHLORIDE, 5%; MISC, 5% (1984-ESTIMATE). CHEMICAL PROFILE: Phosphorus. Thermal phosphoric acid, 82%; (sodium phosphates, 70%; direct phosphoric acid sales, 20%; calcium ammonium and potassium phosphates, 10%); direct reaction chemical production, including phosphorus trichloride, pentasulfide and pentoxide, 12%; exports, 6%. CHEMICAL PROFILE: Phosphorus. Demand: 1987: 340,000 tons; 1988: 330,000 tons; 1992 /projected/: 310,000 tons (Includes exports; in addition, between 4,000 and 5,000 tons were imported in 1987, mostly from Canada). |
| Apparent Color | WHITE: COLORLESS OR WHITE, TRANSPARENT, CRYSTALLINE SOLID; WAXY APPEARANCE; Yellow: White to yellow, soft, waxy solid; BLACK: POLYMORPHIC, ORTHORHOMBIC CRYSTALLINE FORM, AMORPHOUS FORM; RED: RED TO VIOLET POWDER; POLYMORPHISM; VIOLET: VIOLET MONOCLINIC; VIOLET |
| Odor | White: garlic-like |
| Boiling Point | Yellow: 280 deg C; Red: 280 deg C (ignites at 200 deg C). |
| Melting Point | Yellow: 44.1 deg C; Violet: 590 deg C; Red: 590 deg C at 43 atm. |
| Molecular Weight | 30.97376 |
| Density | SP GR: RED: 2.34; VIOLET: 2.36; BLACK: 2.70; YELLOW: 1.82 @ 20 DEG C/4 DEG C. |
| Sensitivity Data | Yellow: Fumes are irritating to the respiratory tract and cause severe ocular irritation. Red: Irritates eyes. |
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Chemical and Physical Properties |
DENSITY: 1.83 /ALPHA-WHITE/; DENSITY: 1.88; MP: 44.1 DEG C; VP: 0.181 MM HG; BP: 280 DEG C /BETA WHITE/; WHITE: SOMETIMES CALLED YELLOW PHOSPHORUS; COLOR DUE TO IMPURITIES; SUBLIMES IN VACUO @ ORDINARY TEMP WHEN EXPOSED TO LIGHT; WHEN EXPOSED TO AIR IN DARK, EMITS GREENISH LIGHT & GIVES OFF WHITE FUMES. SAME LIQ IS OBTAINED ON MELTING /THE ALLOTROPIC FORMS/; PHOSPHORUS ATOMS EXIST AS SYMMETRICAL, TETRAHEDRAL PHOSPHORUS(4) MOL IN LIQUID PHASE & IN VAPOR PHASE BELOW 800 DEG C; MOL DISSOCIATE TO PHOSPHORUS(2) ABOVE 800 DEG C; ATOMIC NUMBER: 15; VALENCES 3, 5; ONE NATURALLY OCCURRING ISOTOPE: (31)PHOSPHORUS. RED: PROPERTIES OF RED PHOSPHORUS ARE INTERMEDIATE BETWEEN THOSE OF WHITE & BLACK FORMS; SUBLIMES @ 416 DEG C, TRIPLE POINT 589.5 DEG C UNDER 43.1 ATM; LESS ACTIVE THAN WHITE FORM; REACTS ONLY @ HIGH TEMP; YIELDS WHITE MODIFICATION WHEN DISTILLED @ 290 DEG C. BLACK: RESEMBLES GRAPHITE IN TEXTURE; DENSITY: RHOMBOHEDRAL 3.56; CUBIC 3.83. WHITE: COMBINES DIRECTLY WITH HALOGENS TO FORM TRI- OR PENTAHALIDES; COMBINES WITH SULFUR TO FORM SULFIDES; REACTS WITH SEVERAL METALS TO FORM PHOSPHIDES; YIELDS ORTHOPHOSPHORIC ACID WHEN TREATED WITH NITRIC ACID; REACTS WITH ALKALI HYDROXIDES WITH FORMATION OF PHOSPHINE & SODIUM HYPOPHOSPHITE. WHITE PHOSPHORUS: INCOMPATIBILITIES: SULFUR, IODINE, OIL OF TURPENTINE, POTASSIUM CHLORATE. EXISTS IN THREE MAIN ALLOTROPIC FORMS: WHITE, BLACK, & RED. WHITE /ALLOTROPIC FORM/: COLORLESS OR WHITE, TRANSPARENT, CRYSTALLINE SOLID; WAXY APPEARANCE. Yellow /allotropic form/: White to yellow, soft, waxy solid. BLACK /ALLOTROPIC FORM/: POLYMORPHIC, ORTHORHOMBIC CRYSTALLINE FORM, AMORPHOUS FORM. VIOLET /ALLOTROPIC FORM/: VIOLET MONOCLINIC. RED /ALLOTROPIC FORM/: RED TO VIOLET POWDER; POLYMORPHISM. White phosphorus burns rapidly in air to form phosphoric oxide. White: garlic-like odor |
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Environmental Impact |
Occupational exposure involves acetyl cellulose makers, bronze alloy makers, munitions workers, smoke bomb and incendiary makers, pesticide rat poison worker, fertilizer makers, electroluminescent-coating makers, and semiconductor workers. From 23 American cities phosphorus concn in sewage sludge, determined by emission spectrometry, ranged from 0.27 to 3.2% dry wt. |
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Environmental Fate |
ABUNDANCE IN EARTH'S CRUST: APPROX 0.12%. DOES NOT OCCUR FREE IN NATURE; FOUND IN FORM OF PHOSPHATES IN MINERALS CHLORAPATITE, FLUORAPATITE, VIVIANITE, WAVELLITE & "PHOSPHATE ROCK" OR PHOSPHORITE; OCCURS IN SMALL QUANTITIES IN GRANITE ROCKS; OCCURS IN ALL FERTILE SOIL; AN ESSENTIAL CONSTITUENT OF PROTOPLASM, NERVOUS TISSUE & BONES. ELEMENTAL PHOSPHORUS HAS BEEN REPORTED AS SUCH IN A METEORITE. A comprehensive examination of metal levels at various trophic levels within an undisturbed Precambrian Shield lake ecosystem was made. Concn of 21 naturally occurring elements including phosphorus were measured in sediments, clams, fish, birds, and mammals. Mercury was the only element to exhibit biomagnification. Macronutrient and trace metal content was determined in reindeer lichens (Cladonia cladina) from 23 bogs; C arbuscula was sampled from 20 localities, C stellaris (C alpestris) from 12 and C mitis from 2. Calculated on the basis of the total atmospheric fallout in the region, the annual retention percentages in the Cladonis carpets were 124% for phosphorus. Apparently there is a significant active uptake of phosphorus; it is chiefly accumulated in the living top part. The elemental composition of a group of airborne and settled grain dusts is reported. Concn of phosphorus were less than 1% in barley, corn, Durum wheat, flax, and spring wheat dusts, while oats and selected other grain dusts contained approximately 4000 and 2800 ppm, respectively. |
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Disposal |
Generators of waste (equal to or greater than 100 kg/mo) containing this contaminant, EPA hazardous waste number D003, must conform with USEPA regulations in storage, transportation, treatment and disposal of waste. Phosphorus (white or yellow) is a waste chemical stream constituent which may be subjected to ultimate disposal by controlled incineration. Yellow: After solidification & covering with sand or dirt, may be disposed of in a secured sanitary landfill. Cover with wet sand, shovel into bucket and remove to safe, open, isolated area where the phosphorus can be burnt off under supervision after drying out. Small spillages of phosphorus can be burnt off in a fume cupboard. Recommendable methods: Incineration & open burning. Not recommendable method: Landfill. Peer-review: Spontaneously flammable if dry. Mix with wet earth, allow to dry, ignite at a remote place. (Peer-review conclusions of an IRPTC expert consultation (May 1985)). White and yellow phosphorus is a waste chemical stream constituent which may be subjected to ultimate disposal by controlled incineration. Controlled incineration followed by alkaline scrubbing and particulate removal equipment. |
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