PHOSPHATES, INORGANIC AND ORGANIC

 

 

Occurrence and Uses

Phosphorus does not occur in a free state in nature, but it is found in combination in many plant and animal compounds. In addition, it is found in phosphate rock formations such as apatite (a form of calcium phosphate). Large deposits of phosphate rocks are located in the United States (Tennessee and Florida), in parts of North Africa, and on some Pacific Islands.

 

Inorganic and organic phosphates are widely used in industry as lubricant additives, fire retardants, plasticizers and chemical intermediates. They are found in the rubber, plastics, paper, varnish and metal industries, and as ingredients in pesticides and cleaning compounds.

 

Dibutyl phenyl phosphate and tributyl phosphate are components of hydraulic fluid in aircraft engines, and hexamethylphosphoramide is a de-icing additive for jet fuels. Dibutyl phosphate is used in metal separation and extraction, and as a catalyst in the manufacture of phenol and urea resins. Trimethyl phosphate is found in the automobile industry as an antifoulant for spark plugs and as a gasoline additive for the control of surface ignition and rumbling.

 

Phosphoric acid is found in dental cement, rubber latex, fire-control agents and drilling muds for oil-well operations. It is used for flavouring non-alcoholic beverages, dyeing cotton, water treatment, refractory bricks, in the manufacture of superphosphate fertilizer, cleaning of metals before painting, and as an additive in gasoline and a binder in ceramics.

 

Tricresyl phosphate (TCP) is used as a solvent for nitrocellulose esters and numerous natural resins. It is a plasticizer for chlorinated rubber, vinyl plastics, polystyrene and polyacrylic and polymethacrylic esters. Tricresyl phosphate also acts as a binder for resins and nitrocellulose to improve toughness, elasticity and polishing properties of coatings. Alone or associated with hydrocarbons, it is used as an antiwear and antifriction additive in numerous synthetic lubricants, incorrectly termed “oils” by reason of their appearance. It is also employed as a hydraulic fluid. When incorporated in gasoline, tricresyl phosphate counteracts the harmful effects of lead deposits. In addition, it is an excellent fire retardant in many industries.

 

Tetrasodium pyrophosphate has a wide range of applications in the paper, food, textile and rubber industries. It is also used in oil-well drilling, water treatment, cheese emulsification, laundry detergents, and in the electrodeposition of metals. Tetrasodium pyrophosphate is useful for textile dyeing, scouring of wool, and clay and paper processing. Tributyl phosphate functions as a plasticizer for cellulose esters, lacquers, plastics and vinyl resins. It is also a complexing agent in the extraction of heavy metals and an antifoam agent in ore separation processes. Triphenyl phosphate is a flame-retardant plasticizer for cellulosics and a plasticizer for hot-melt adhesives. It is useful in the upholstery and roofing paper industries.

 

Several of the organic phosphates are used for the production of pyrotechnics, explosives and pesticides. Calcium phosphide is used for signal fires, torpedoes, pyrotechnics, and as a rodenticide. Phosphorus sulphide finds use in the manufacture of safety matches, ignition compounds, lube oil additives and pesticides. Phosphine is used for rodent control and as an insecticide applied for the fumigation of animal feed, leaf-stored tobacco and box cars.

 

White phosphorus is utilized for the manufacture of rat poisons; red phosphorus is used in pyrotechnics, safety matches, chemical synthesis, pesticides, incendiary shells, tracer bullets and smoke bombs. Tetraphosphorus trisulphide is used for making match heads and friction strips for boxes of “safety” matches.

 

Phosphorus pentoxide is added to asphalt in the air blowing process to increase the melting point and is used in the development of specialty glasses for vacuum tubes. Phosphorus trichloride is a component of textile finishing agents and an intermediate or reagent in the manufacture of many industrial chemicals, including insecticides, synthetic surfactants and ingredients for silver polish. Phosphorus oxychloride and phosphorus pentachloride serve as chlorinating agents for organic compounds.

 

Phosphorus

Phosphorus (P) exists in three allotropic forms: white (or yellow), red and black, the last being of no industrial importance. White phosphorus is a colourless or waxlike solid that darkens when exposed to light and glows in the dark (phosphoresces). It ignites spontaneously in the presence of air and burns with a blue flame, producing a characteristically disagreeable odour that is somewhat reminiscent of garlic. The red form is more stable.

 

Historical importance

Elemental phosphorus was first extracted from animal matter, especially from bone, in the early part of the nineteenth century. Its usefulness in “strike-anywhere” matches was quickly seen and much demand for this element developed as a result. Shortly thereafter, a serious disease appeared in people handling it; the first cases were recognized in 1845, when jaw-bone necrosis occurred in phosphorus-processing workers. This severe and face-disfiguring malady, which terminated fatally in about 20% of the cases during the nineteenth century, was soon recognized and measures sought for its alleviation. This became possible with the development of effective substitutes in the form of red phosphorus and the relatively safe phosphorus sesquisulphide. The European countries also entered into an agreement (the Berne Convention of 1906) in which it was stipulated that the signatories would not manufacture or import matches that were made with white phosphorus.

 

A major phosphorus hazard in some countries, however, continued to exist from the use of white phosphorus in the pyrotechnics industry until agreement for its exclusion was reached with these manufacturers. At the present, health hazards from white phosphorus still endanger people who are involved with the various stages of production and in the manufacture of its compounds.

 

The mechanism involved in this jaw-bone damage has not been fully explained. It is believed by some that the action is due to the local effect of the phosphorus in the oral cavity, and that the infection occurs in the constant presence of infective organisms in the mouth and about the teeth. In fact, it is found that exposed persons with carious teeth are more likely to be affected by the condition, although it is difficult to explain the disease in workers with no teeth at all.

 

A second, possibly more plausible, explanation is that phosphorus necrosis of the jaw is a manifestation of a systemic disease, one that involves many organs and tissues and, principally, the bones. Supporting this concept are the following significant facts:

 

· As mentioned previously, edentulous individuals have been known to develop jaw necrosis when exposed to phosphorus in their work, even though their “dental hygiene” may be said to be good.

· Young, growing, experimental animals, given appropriate doses of white phosphorus, develop bone changes in the “growing” areas of their bones, the metaphyses.

· On occasion, injured bones in adults exposed to phosphorus have been found to heal exceedingly slowly.

 

Hazards

Health hazards. Acute exposure to yellow phosphorus vapour released by spontaneous combustion causes severe irritation of the eye, with photophobia, lacrimation and blepharospasm; severe respiratory tract irritation; and deep, penetrating burns of the skin. Direct skin contact with phosphorus, which occurs both in production and during wartime, leads to deeply penetrating second- and third-degree burns, similar to hydrogen fluoride burns. Massive haemolysis with subsequent haematuria, oliguria and renal failure have been described, although this constellation of events is most likely due to previously advocated treatment with copper sulphate.

 

Upon ingestion, phosphorus induces burns of the mouth and gastrointestinal (GI) tract, with oral sensations of burning, vomiting, diarrhoea and severe abdominal pain. Burns progress to second and third degree. Oliguria may occur secondary to fluid loss and poor perfusion of the kidney; in less severe cases, the proximal renal tubule is transiently damaged. Absence of sugar in otherwise normal cerebrospinal fluid (CSF) is reportedly pathognomonic.

 

Following absorption from the GI tract, yellow phosphorus has direct effects on the myocardium, circulatory system in the limbs (peripheral vasculature), liver, kidneys and brain. Hypotension and dilated cardiomyopathy have been reported; interstitial myocardial oedema without cellular infiltration has been observed on autopsy. Intracellular protein synthesis appears to be depressed in heart and liver.

 

Three clinical stages have been described following ingestion. In Stage I, immediately after ingestion, there is nausea and vomiting, abdominal pain, jaundice and garlic odour of the breath. Phosphorescent vomitus may be hazardous to attending medical staff. Stage II is characterized by a 2- to 3-day latent period where the patient is asymptomatic. During this time, cardiac dilatation as well as fatty infiltration of the liver and kidney may occur. Severe, bloody vomiting, bleeding into many tissues, uremia and marked anaemia precede death, defined as Stage III.

 

Prolonged intake (10 months to 18 years) may cause necrosis of the mandible and maxilla with sequestration of bone; release of sequestra leads to facial deformity (“phossy jaw”). Toothache and excessive salivation may be the first symptoms. Additionally, anaemia, cachexia and liver toxicity may occur. With chronic exposure, necrosis of the mandible with facial deformity was frequently described in the literature until the early 1900s. There are rare reports of this phenomenon among production workers and rodenticide manufacturers.

 

Reproductive and carcinogenic effects have not been reported.

 

Phosphine  gas is generated by the reaction of phosphoric acid heated with metals which are being treated for cleaning (similar to phosgene), from heating of phosphorus trichloride, from wetting of aluminium phosphate, from flare manufacture using calcium phosphide, and from acetylene gas production. Inhalation causes severe mucous membrane irritation, leading to coughing, shortness of breath, and pulmonary oedema up to 3 days following exposure. The pathophysiologic effect involves inhibition of mitochondrial respiration as well as direct cytotoxicity.

 

Phosphine is also liberated from accidentally or intentionally ingested aluminium phosphide by chemical interaction with hydrochloric acid in the stomach. There is a large body of literature from India describing cases of suicidal ingestion of this rodenticide. Phosphine is also used as a fumigant, and there are many case reports which describe accidental death from inhalation when in proximity to grain fumigated during storage. Toxic systemic effects which have been described include nausea, vomiting, abdominal pain, central nervous system excitation (restlessness), pulmonary oedema, cardiogenic shock, acute pericarditis, atrial infarction, renal damage, hepatic failure and hypoglycemia. A silver nitrate test was positive in gastric aspirate and in the breath (the latter with a lower sensitivity). Measurement of blood aluminium may serve as a surrogate for toxin identification. Treatment includes gastric lavage, vasopressive agents, respiratory support, administration of anti-arrhythmics, and high-dose magnesium sulphate infusion.

 

Zinc phosphide, a commonly used rodenticide, has been associated with severe intoxication of animals that ingest treated bait or the carcasses of poisoned animals. Phosphine gas is liberated in the stomach by stomach acid.

 

Organophosphorus Compounds

The tricresyl phosphates (TCPs) are part of a series of organophosphorus compounds which have been shown to cause delayed neurotoxicity. The 1930 outbreak of “ginger jake” paralysis was caused by the contamination of ginger extract by cresyl phosphates, used in the processing of the spice. Since that time, there have been several incidents reported of accidental poisoning of food by tri-o-cresyl phosphate (TOCP). There are few case series reports of occupational exposure in the literature. Acute occupational exposures have been described as causing gastrointestinal symptoms followed by a latent period of days to 4 weeks, after which extremity pain and tingling progress to motor paralysis of the lower extremities up to the thighs, and of the upper extremities to the elbow. There is rarely sensory loss. Partial to total recovery may take years. Fatalities have occurred in high-dose ingestion. The anterior horn cells and pyramidal tracts are affected, with autopsy finding of demyelination and anterior horn cell damage. In humans the oral lethal dose is 1.0 g/kg; 6 to 7 mg/kg produces severe paralysis. There is no reported skin or eye irritation, though TOCP is absorbed through the skin. Inhibition of cholinesterase activities does not appear to correlate with symptoms or quantity of exposure. Exposed cats and hens developed damage in the spinal cord and sciatic nerves, with damage to the Schwann cells and myelin sheath resulting from dying back of the longer axons. There was no evidence of teratogenicity in rats dosed up to 350 mg/kg/day.

 

Three molecules of o-, m- or p-cresol esterify one molecule of phosphoric acid, and, since commercial cresol is normally a mixture of the three isomers with an ortho isomer content varying between 25 and 40% according to the source, the resultant TCP is a mixture of the three symmetrical isomers, which are very difficult to separate. However, since the toxicity of commercial TCP derives from the presence of the ortho isomer, many countries stipulate that the esterified phenolic fraction should contain no more than 3% o-cresol. Consequently, the difficulty lies in the selection of a cresol free of the ortho isomer. A TCP prepared from m- or p-cresol has the same properties as the technical product, but the cost of separating and purifying these isomers is prohibitive.

 

Two related phosphate-containing esters, cresyldiphenyl phosphate and o-isopropylphenyldiphenyl phosphate, are also neurotoxic to several species, including humans, chickens and cats. Adult animals are generally more susceptible than the young. After a single, large exposure to these neurotoxic organophosphorus compounds, axonal damage becomes apparent after 8 to 10 days. Chronic low-level exposures can also lead to neurotoxicity. Axons of the peripheral nerves and the ascending and descending tracts of the spinal cord are affected through a mechanism other than cholinesterase inhibition. While a few of the organophosphate anticholinesterase insecticides cause this effect (diisopropyl fluorophosphate, leptofos and mipafox), the delayed neuropathy apparently occurs through a mechanism other than cholinesterase inhibition. There is a poor correlation between the inhibition of pseudo- or true cholinesterase and the neurotoxic effect.

 

Triphenyl phosphate may cause a slight reduction in cholinesterase activity, but is otherwise of low toxicity in humans. This compound sometimes occurs in combination with tri-o-cresyl phosphate (TOCP). No teratogenicity was found in rats fed up to 1% in their diet. Intraperitoneal injection of 0.1 to 0.5 g/kg in cats caused paralysis after 16 to 18 days. Skin irritation has not been demonstrated, and eye effects have not been reported.

 

Triphenyl phosphite (TPP) has been shown to cause neurotoxicity in laboratory animals which is similar to that described for TOCP. Studies of rats showed early hyperexcitability and tremors followed by flaccid paralysis, with the lower extremities more affected than the upper extremities. The pathologic lesion showed spinal cord damage with mild cholinesterase inhibition. A study of cats receiving injections showed virtually the same clinical findings. TPP has also been demonstrated to be a skin irritant and sensitizer.

 

Tributyl phosphate causes eye, skin and mucous membrane irritation, as well as pulmonary oedema in laboratory animals. Rats exposed to a commercial formulation (bapros) of 123 ppm for 6 hours developed respiratory irritation. When ingested, the  was 3 g/kg, with weakness, dyspnea, pulmonary oedema and muscle twitching observed. It weakly inhibits plasma and red blood cell cholinesterase.

 

Hexamethyl phosphoramide has been shown to cause cancer of the nasal cavity when administered to rats at levels between 50 and 4,000 ppb over 6 to 24 months. Squamous metaplasia was seen in the nasal cavity and trachea, the latter at the highest dose. Other findings included dose-dependent increases in tracheal inflammation and desquamation, bone marrow erythropoietic hyperplasia, testicular atrophy, and degeneration of the convoluted tubules of the kidney.

 

Other Inorganic Phosphorus Compounds

Phosphorus pentoxide (phosphorus anhydride), phosphorus pentachloride, phosphorus oxychloride, and phosphorus trichloride have irritant properties, causing a spectrum of mild effects such as eye corrosion, skin and mucous membrane burns, and pulmonary oedema. Chronic or systemic exposure generally is not as important because of the low tolerance to direct contact with these chemicals.

 

The mist of phosphoric acid is mildly irritating to the skin, the eyes, and the upper respiratory tract. In groups of workers, phosphorus pentoxide (the anhydride of phosphoric acid) fumes were shown to be perceptible but not uncomfortable at concentrations of 0.8 to 5.4 , to produce cough at concentrations between 3.6 and 11.3 , and to be intolerable to unacclimated workers at a concentration of 100 . There is a small risk of pulmonary oedema with inhalation of the mist. Skin contact with the mist leads to mild irritation, but no systemic toxicity. A 75% solution of phosphoric acid dropped on the skin causes severe burns. A study of a cohort of phosphate workers who were occupationally exposed to phosphoric acid showed no increase in cause-specific mortality.

 

The median lethal concentration for phosphorus oxychloride and its ammonia neutralization products were found to be 48.4 and 44.4 micromoles per mole of air for rats, and 52.5 and 41.3 for guinea-pigs. Fifteen per cent of phosphorus oxychloride was hydrolyzed. Most case series reports of health effects from phosphorus oxychloride also include exposure to other phosphorus-containing compounds. Alone, it is described as causing stomach necrosis when ingested, necrosis of the respiratory tract on inhalation, skin ulceration from direct application, and eye ulceration with loss of vision in rabbits. Chronic exposure of animals showed abnormalities in mineral metabolism, and osteoporosis with elimination of excessive amounts of inorganic phosphorus, calcium salts and chlorides from the body. In combination with other phosphorus compounds, phosphorus oxychloride has been shown to cause asthma and bronchitis in case series reports.

 

Phosphorus pentasulphide is hydrolyzed to hydrogen sulphide gas and phosphoric acid, exerting effects of these substances on contact with mucus membranes (see phosphoric acid, above, and also hydrogen sulphide elsewhere in this Encyclopaedia). The oral  was 389 mg/kg in rats. Twenty milligrams instilled in rabbit eyes was severely irritating after 24 hours. After 24 hours, 500 mg applied to rabbit skin was found to be moderately irritating.

 

The vapour of phosphorus trichloride is a severe irritant of the mucous membranes, eyes and skin. Similar to phosphorus pentasulphide, hydrolysis to hydrochloric acid and phosphoric acid on contact with mucous membranes accounts for much of this effect. Inhalation of the vapour can cause throat irritation, bronchospasm and/or pulmonary oedema for up to 24 hours after exposure, depending on the dose. Reactive airways disease syndrome (RADS), with prolonged symptoms of wheezing and cough, can occur from acute or repeated exposure to the vapour. On contact, phosphorus trichloride causes severe burns of the eyes, skin and mucous membranes. Ingestion, inadvertent or suicidal, causes burns of the gastrointestinal tract. Seventeen people who were exposed to phosphorus trichloride and its hydrolysis products following a tanker accident were medically evaluated. Dyspnea, cough, nausea, vomiting, eye burning and lacrimation were experienced by those closest to the spill. Lactate dehydrogenase was transiently elevated in six. While chest radiographs were normal, pulmonary function tests showed a significant drop in forced vital capacity and . Improvement in these parameters was seen in the 17 patients re-tested after 1 month. The  was 104 ppm for 4 hours in rats. Nephrosis was the chief finding at autopsy, with negligible pulmonary damage.

 

Phosphorus pentachloride fume inhalation causes severe irritation of the respiratory tract, leading to documented bronchitis. Delayed onset of pulmonary oedema could occur, although it has not been reported. Exposure of the eyes to fumes also leads to severe irritation, and skin contact would be expected to cause contact dermatitis. The  for 4 hours of inhalation is 205 .

 

Phosphates and superphosphates. The principal problem with phosphates in the environment is the causation of eutrophication of lakes and ponds. Phosphates enter bodies of water from run-off of agriculture (sources include phosphorus-containing compounds used as fertilizer and pesticides, and plant and animal decay) and from detergents used in homes and industry. Excessive growth of blue-green algae occurs because phosphorus is generally the limiting nutrient essential for growth. Rapid algae growth affects use of lakes for fishing and recreational activities. It also complicates purification of drinking water.

 

Toxicity of Phosphates

Phosphate mining has been associated with physical trauma. Pneumoconiosis is not of concern in this setting because of the small amount of dust that is generated. Phosphate dust is created in the drying process, and is of concern in causation of pneumoconiosis in the handling and transport of the material. Fluorides may be present in the dust and lead to toxicity.

 

In addition, phosphate dust is created in the creation of superphosphates, which are used for fertilization. A study of women employed in the manufacture of superphosphates found abnormalities of menstrual function. Severe eye damage and blindness have been described in humans and animals from direct contact with superphosphates.

 

Safety and Health Measures

Fire hazard. Phosphorus can ignite spontaneously when exposed to air and start fires and cause explosions. Severe burns can be caused when chips and bits of white phosphorus contact the skin and ignite after drying.

 

Owing to its flammability in air, white phosphorus should be kept covered with water at all times. In addition, scattered pieces should be doused with water, even before they dry and begin to burn; phosphorus fires may be controlled with water (fog or spray), by covering with sand or earth, or with carbon dioxide extinguishers. The substance should be stored in a cool, ventilated, isolated area and away from powerful oxidizing agents, acute fire hazards, and the direct rays of the sun.

 

In case of skin contact by burning phosphorus slivers, dousing them with a 1 to 5% solution of aqueous copper sulphate will put out the fire and at the same time form a non-flammable compound on the surface of the phosphorus. Following this treatment, the slivers may be removed with more large quantities of water. A soft-soap solution containing a similar concentration of copper sulphate may be more effective than the simple aqueous solution.

 

Inorganic and organic phosphates tables

Table 104.141 - Chemical information.

Table 104.142 - Health hazards.

Table 104.143 - Physical and chemical hazards.

Table 104.144 - Physical and chemical properties.

 

___________________________________________________________________________

 

Table 104.141       Phosphates, Inorganic & Organic: Chemical identification

 

CHEMICAL

SYNONYMS/ UN CODE

CAS-NUMBER

CHEMICAL FORMULA

CALCIUM PHOSPHIDE

Calcium photophor;

Photophor

UN1360

1305-99-3

 

 

DIBUTYL PHOSPHATE

Dibutyl acid phosphate;

Dibutyl hydrogen phosphate;

Dibutyl phosphate;

Dinbutyl phosphate;

Phosphoric acid, dibutyl ester

107-66-4

 

 

DIBUTYL PHENYL PHOSPHATE

Dibutyl phenyl phosphate;

Phosphoric acid, dibutyl phenyl ester

2528-36-1

 

 

DIETHYLTHIOPHOSPHORYL CHLORIDE

o,o-Diethylphosphorochloridothioate;

Diethylchlorothiophosphate;

Phosphonothioic acid, chloro, o,o-diethyl ester

UN2751

2524-04-1

 

 

DIMETHYL HYDROGEN PHOSPHITE

Bis(hydroxymethyl)phosphine oxide;

Dimethoxyphosphine oxide;

Dimethyl acid phosphite;

Dimethyl phosphite;

Dimethyl phosphonate;

Dimethyl phosphorus acid;

Hydrogen dimethyl phosphite;

Phosphonic acid, dimethyl ester

868-85-9

 

 

HEXAMETHYL PHOSPHORAMIDE

Hexametapol;

Hexamethyl phosphoramide;

Hexamethylphosphoric acid triamide;

Hexamethylphosphoric triamide;

Tris(dimethylamino)phosphine oxide;

Tris(dimethylamino)phosphorus oxide

680-31-9

 

 

PHENYLPHOSPHINE

Phenylphosphine

638-21-1

 

 

PHOSPHINE

Gas-ex-B;

Hydrogen phosphide;

Phosphorus trihydride

UN2199

7803-51-2

 

 

PHOSPHORUS (red)

Phosphorus, amorphous

UN1338

7723-14-0

 

 

PHOSPHORUS-CHLORIDE

Phosphorus chloride;

Phosphorus trichloride;

Trichlorophosphine

UN1809

7719-12-2

 

 

PHOSPHORUS-OXIDE

Diphosphorus pentoxide;

Phosphorus(V) oxide;

Phosphorus pentaoxide;

Phosphorus pentoxide;

Phosphorus pentoxide

UN1807

1314-56-3

 

 

PHOSPHORUS OXYCHLORIDE

Phosphorus oxytrichloride;

Phosphoryl chloride

UN1810

10025-87-3

 

 

PHOSPHORUS PENTACHLORIDE

Phosphoric chloride;

Phosphorus perchloride

UN1806

10026-13-8

 

 

PHOSPHORUS PENTASULFIDE

Phosphoric sulfide;

Phosphorus persulfide;

Sulphur phosphide;

Thiophosphoric anhydride

UN1340

1314-80-3

 

 

TETRAPHOSPHORUS TRISULPHIDE

 

1314-85-8

 

 

THIOPHOSPHORYL CHLORIDE

Phosphorothioic trichloride;

Phosphorothionic trichloride;

Phosphorus sulfochloride;

Phosphorus thiochloride;

Thiophosphoric trichloride;

Thiophosphoryl trichloride

UN1837

3982-91-0

 

 

TRICRESYL PHOSPHATE

Flexol plasticizer TCP;

Phosphoric acid, tritolyl ester;

Tris(tolyloxy)phosphine oxide;

Tritolyl phosphate

UN2574

1330-78-5

 

 

TRI-o-CRESYL PHOSPHATE

o-Cresyl phosphate;

Phosphoric acid, tri-o-tolyl ester;

TOCP;

TOFK;

o-Tolyl phosphate;

TOTP;

Tricresyl phosphate;

Triocresyl phosphate;

Tri-2-methylphenyl phosphate;

Tris(o-cresyl)phosphate;

Tris(o-methylphenyl)phosphate;

Tris(o-tolyl)phosphate;

Tri-o-tolyl phosphate;

Tri-2-tolyl phosphate

78-30-8

 

 

TRIETHYL PHOSPHATE

Ethyl phosphate;

Phosphoric acid, triethyl ester;

TEP

78-40-0

 

 

TETRAPOTASSIUM PYROPHOSPHATE

Diphosphoric acid, tetrapotassium salt;

Potassium pyrophosphate;

Tetrapotassium diphosphorate;

TKPP

7320-34-5

 

 

TETRASODIUM PYROPHOSPHATE

Anhydrous tetrasodium pyrophosphate;

Phosphotex;

Pyrophosphate;

Sodium pyrophosphate;

Tetrasodium diphosphate;

Tetrasodium pyrophosphate, anhydrous;

TSPP

7722-88-5

 

 

TRIS(2,3-DIBROMOPROPYL) PHOSPHATE

2,3-Dibromo1propanol phosphate;

(2,3-Dibromopropyl) phosphate;

Fyrol HB32;

NCI-C03270;

Phosphoric acid, tris(2,3-dibromopropyl) ester;

1-Propanol, 2,3-dibromo, phosphate (3:1);

RCRA Waste number U235;

TDBPP;

T 23P;

Tris;

TrisBP;

Tris(dibromopropyl)phosphate;

Tris(2,3-dibromopropyl) phosphoric acid ester;

Tris (flame retardant);

USAF DO41;

Zetifex ZN

126-72-7

 

 

TRIS(2-ETHYLHEXYL) PHOSPHATE

2-Ethyl-1-hexanol phosphate;

1-Hexanol, 2-ethyl-, phosphate;

Phosphoric acid, tris(2-ethylhexyl) ester;

TOF;

Triethylhexyl phosphate;

Trioctyl phosphate

78-42-2

 

 

TRIMETHYL PHOSPHATE

Methyl phosphate;

NCI-C03781;

Phosphoric acid, trimethyl ester;

TMP;

o,o,o-Trimethyl phosphate

512-56-1

 

 

TRIBUTYL PHOSPHATE

Butyl phosphate, tri;

Tbp;

Tributyl phosphate;

Trinbutyl phosphate

126-73-8

 

 

TRIETHYL PHOSPHITE

Phosphorus acid, triethyl ester

UN2323

122-52-1

 

 

TRIMETHYL PHOSPHITE

Methyl phosphite;

Trimethoxyphosphine;

Phosphorus acid, trimethyl ester

UN2329

121-45-9

 

 

TRIPHENYL PHOSPHATE

Celluflex TPP;

TPP

115-86-6

 

 

TRIPHENYL PHOSPHITE

 

101-02-0

 

 

TRIPHENYL PHOSPHINE

 

603-35-0

 

 

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Table 104.142      Phosphates, Inorganic & Organic: Health hazards

 

CHEMICAL NAME

CAS-NUMBER

ICSC SHORT-TERM EXPOSURE

ICSC LONG-TERM EXPOSURE

ICSC ROUTES OF EXPOSURE AND SYMPTOMS

US NIOSH TARGET ORGANS & ROUTES OF ENTRY

US NIOSH SYMPTOMS

DIBUTYL PHOSPHATE

107-66-4

 

 

 

Resp sys; skin; eyes

Inh; ing; con

Irrit eyes, skin, resp sys; head

DIETHYLTHIOPHOSPHORYL CHLORIDE

2524-04-1

eyes; skin; resp tract; lungs

 

Inhalation: burning sensation, confusion, cough, dizziness, headache, nausea, shortness of breath, sore throat, unconsciousness, vomiting, weakness, symptoms may be delayed

Skin: may be absorbed, redness, burning sensation, pain

Eyes: vapour will be absorbed, redness, pain, blurred vision, loss of vision, severe deep burns

Ingestion: confusion, diarrhoea, headache, nausea, vomiting

 

 

PHOSPHINE

7803-51-2

eyes; skin; resp tract; lungs; CNS; blood; liver; kidneys; heart

 

Inhalation: burning sensation, diarrhoea, dizziness, dullness, headache, tremors, laboured breathing, nausea, sore throat

Skin: redness, pain, on contact with liquid: frostbite

Eyes: in case of frostbite: redness, pain

Resp sys

Inh; con (liq)

Nau, vomit, abdom pain, diarr; thirst; chest tight, dysp; musc pain, chills; stupor or syncope; pulm edema; liq: frostbite

PHOSPHORUS

7723-14-0

eyes; skin; resp tract; lungs; liver; kidneys

bone

Inhalation: burning sensation, unconsciousness, symptoms may be delayed

Skin: skin burns, pain

Eyes: pain, loss of vision, severe deep burns

Ingestion: abdominal cramps, unconsciousness

Resp sys; liver; kidneys; jaw; teeth; blood; eyes; skin

Inh; ing; con

Irrit eyes, resp tract; eye, skin burns; abdom pain, nau, jaun; anemia; cachexia; dental pain, salv, jaw pain, swell

PHOSPHORUS PENTACHLORIDE

10026-13-8

 

 

Inhalation: burning sensation, cough, shortness of breath, vomiting, symptoms may be delayed

Skin: may be absorbed, roughness, serious skin burns

Eyes: pain, severe deep burns

Ingestion: abdominal cramps, abdominal pain, burning sensation, weakness

Resp sys; eyes; skin

Inh; ing; con

Irrit eyes, skin, resp sys; bron; derm

PHOSPHORUS PENTASULFIDE

1314-80-3

 

 

 

Resp sys; CNS; eyes; skin

Inh; ing; con

Irrit eyes, skin, resp sys; apnea, coma, convuls; conj pain, lac, photo, kerato-conj, corn vesic; dizz; head; ftg; irrity, insom; GI dist

PHOSPHORUS PENTOXIDE

1314-56-3

eyes; skin; resp tract; lungs

 

Inhalation: burning sensation, cough, shortness of breath

Skin: redness, skin burns, pain

Eyes: redness, pain, severe deep burns

Ingestion: abdominal pain, diarrhoea, nausea, vomiting

 

 

PHOSPHORUS TRICHLORIDE

7719-12-2

 

 

Inhalation: burning sensation, cough, diarrhoea, dizziness, headache, shortness of breath, sore throat, vomiting

Skin: serious skin burns, pain, blisters

Eyes: redness, blurred vision, severe deep burns

Ingestion: burning sensation, sore throat ,

Resp sys; eyes; skin

Inh; ing; con

Irrit eyes, skin, nose, throat; pulm edema; eye, skin burns

TETRAPOTASSIUM PYROPHOSPHATE

7320-34-5

eyes; skin; resp tract; lungs

 

Inhalation: burning sensation, cough, laboured breathing

Skin: redness, pain, blisters

Eyes: redness, pain, severe deep burns

Ingestion: burning sensation, sore throat, abdominal cramps, weakness

 

 

TETRASODIUM PYROPHOSPHATE

7722-88-5

eyes; skin; resp tract

 

Inhalation: burning sensation, cough

Skin: redness, pain

Eyes: redness, pain

Ingestion: nausea, vomiting, diarrhoea

Eyes; skin; resp sys

Inh; ing; con

Irrit eyes, skin, nose, throat; derm

THIOPHOSPHORYL CHLORIDE

3982-91-0

eyes; skin; resp tract; lungs

lungs

Inhalation: burning sensation, confusion, cough, headache, wheezing, laboured breathing, shortness of breath, sore throat, unconsciousness, vomiting, weakness, symptoms may be delayed

Skin: may be absorbed, skin burns, pain

Eyes: pain, loss of vision, severe deep burns

Ingestion: abdominal cramps, abdominal pain, burning sensation, confusion, cough, headache, nausea, shortness of breath, sore throat, unconsciousness, vomiting

 

 

TRIBUTYL PHOSPHATE

126-73-8

eyes; skin; resp tract; lungs; CNS

skin; blood

Inhalation: dizziness, headache, convulsions, laboured breathing, nausea, sore throat

Skin: may be absorbed, redness, roughness, burning sensation

Eyes: redness, pain

Ingestion: abdominal cramps, diarrhoea, laboured breathing, nausea, unconsciousness, vomiting, weakness, hypersalivation

Resp sys; skin; eyes

Inh; ing; con

Irrit eyes, skin, resp sys; head; nau

TRI-o-CRESYL PHOSPHATE

78-30-8

 

 

Inhalation: headache, nausea, vomiting, muscular pain, symptoms may be delayed

Skin: may be absorbed, redness, pain

Ingestion: abdominal pain, nausea, vomiting

PNS; CNS

Inh; abs; ing; con

GI dist; peri neur; cramps in calves; pares in feet or hands; weak feet, wrist drop, para

TRIETHYL PHOSPHITE

122-52-1

eyes; skin; resp tract; lungs; CNS

 

Inhalation: burning sensation, headache, nausea, sore throat, symptoms may be delayed

Skin: may be absorbed, redness

Eyes: redness, pain

Ingestion: abdominal pain

 

 

TRIMETHYL PHOSPHATE

512-56-1

CNS

CNS; genes

 

 

 

TRIPHENYL PHOSPHATE

115-86-6

 

 

 

Blood; PNS

Inh; ing

Minor changes in blood enzymes; in animals: musc weak, para

TRIPHENYLPHOSPHINE

603-35-0

eyes; skin; resp tract

 

Inhalation: cough, sore throat

Skin: redness

Eyes: redness, pain

Ingestion: cough

 

 

TRIPHENYL PHOSPHITE

101-02-0

eyes; skin; resp tract; CNS

 

Inhalation: burning sensation, cough, irritant unconsciousness

Skin: redness, pain

Eyes: redness, pain

 

 

TRIS(2-ETHYLHEXYL PHOSPHATE)

78-42-2

skin

 

Skin: redness

Eyes: redness

 

 

 

___________________________________________________________________________

 

Table 104.143     Phosphates, Inorganic & Organic: Physical & chemical hazards

 

For UN Class: 1.5 = very insensitive substances which have a mass explosion hazard; 2.1 = flammable gas; 2.3 = toxic gas; 3 = flammable liquid; 4.1 = flammable solid; 4.2 = substance liable to spontaneous combustion; 4.3 = substance which in contact with water emits flammable gases; 5.1 = oxidizing substance; 6.1 = toxic; 7 = radioactive; 8 = corrosive substance

 

CHEMICAL NAME

CAS-NUMBER

PHYSICAL

CHEMICAL

UN CLASS OR DIVISION / SUBSIDIARY RISKS

CALCIUM PHOSPHIDE

1305-99-3

 

 

4.3/ 6.1

DIETHYLTHIOPHOSPHORYL CHLORIDE

2524-04-1

 

The substance decomposes on heating producing toxic fumes Upon heating, toxic fumes are formed

8

PHOSPHINE

7803-51-2

The gas is heavier than air

The substance may spontaneously ignite on contact with air On combustion, forms toxic fumes of phosphorus oxides Reacts with water, halogens, nitric acid, nitrous oxides, oxygen, copper, causing fire and explosion hazard On contact with air it emits toxic fumes of phosphorus oxides

6.1 / 2.1

PHOSPHORUS

7723-14-0

 

The substance may spontaneously ignite on contact with air producing toxic fumes (phosphorus oxides) Reacts violently with oxidants, halogens and sulphur, with fire and explosion hazard Reacts with strong alkalies, giving off toxic gas (phosphine)

4.2/ 6.1

PHOSPHORUS OXYCHLORIDE

10025-87-3

 

 

8

PHOSPHORUS PENTACHLORIDE

10026-13-8

 

On burning toxic gases are formed The solution in water is a strong acid, it reacts violently with bases and is corrosive Reacts with water, producing hydrogen chloride fume and phosphoric acid mist On contact with air it emits corrosive fumes Attacks plastics and rubber

8

PHOSPHORUS PENTASULFIDE

1314-80-3

 

 

4.3/ 4.1

PHOSPHORUS PENTOXIDE

1314-56-3

 

The solution in water is a strong acid, it reacts violently with bases and is corrosive Reacts violently with perchloric acid causing fire and explosion hazard Reacts violently with water forming phosphoric acid with heat generation In the presence of water reacts with metals forming flammable or poisonous gases (hydrogen or phosphine)

8

PHOSPHORUS TRICHLORIDE

7719-12-2

The vapour is heavier than air

On combustion, forms toxic, corrosive, flammable fumes of phosphorus oxides, hydrogen chloride, phosphorus The substance decomposes on heating and on contact with water producing toxic acid fumes and gases (phosphine), and is corrosive to many metals The substance is a strong oxidant and reacts with combustible and reducing materials The solution in water is a strong acid, it reacts violently with bases and is corrosive to many metals Reacts violently with bases causing fire and explosion hazard Reacts with alcohols and phenols On contact with air it emits corrosive fumes Attacks many metals forming combustible gas (Hydrogen)  Attacks many materials

3/ 6.1

TETRAPHOSPHORUS TRISULPHIDE

1314-85-8

 

 

4.1

TETRAPOTASSIUM PYROPHOSPHATE

7320-34-5

 

The solution in water is a medium strong base Reacts with strong acids

 

TETRASODIUM PYROPHOSPHATE

7722-88-5

 

On combustion, forms toxic gases The solution in water is a weak base Reacts with acids

 

THIOPHOSPHORYL CHLORIDE

3982-91-0

The vapour is heavier than air

The substance decomposes on contact with water or humidity producing phosphoric acid, hydrogen chloride, hydrogen sulfide, which are toxic and flammable Upon heating, toxic fumes are formed Reacts with strong oxidants and alcohols Attacks many metals in presence of water

8

TRIBUTYL PHOSPHATE

126-73-8

 

The substance decomposes on heating and on burning producing toxic vapours and gases (carbon and phosphorus oxides, and phosphine) Attacks some forms of plastics, rubber and coatings

 

TRICRESYL PHOSPHATE

1330-78-5

 

 

6.1

TRI-o-CRESYL PHOSPHATE

78-30-8

 

The substance decomposes on heating and on burning producing toxic fumes (including phosphorus oxides) Reacts with oxidants

6.1

TRIETHYL PHOSPHITE

122-52-1

 

The substance decomposes on burning producing toxic fumes Reacts with oxidants and strong bases

3

TRIMETHYL PHOSPHATE

512-56-1

 

The substance decomposes on heating producing toxic fumes of  

 

TRIMETHYL PHOSPHITE

121-45-9

 

 

3

TRIPHENYL PHOSPHITE

101-02-0

 

On combustion, forms toxic fumes () The substance decomposes on heating or on burning producing toxic fumes (phosphorus oxides) Reacts with strong oxidants

 

TRIPHENYLPHOSPHINE

603-35-0

Dust explosion possible if in powder or granular form, mixed with air

The substance decomposes on heating producing highly toxic fumes of phosphorus oxides and phosphine Reacts with strong acids and strong oxidants

 

TRIS(2-ETHYLHEXYL) PHOSPHATE

78-42-2

 

The substance decomposes on heating producing phosphine, phosphorus oxides Reacts with strong oxidants

 

 

___________________________________________________________________________

 

Table 104.144       Phosphates, Inorganic & Organic: Physical & chemical properties

 

CHEMICAL NAME

CAS-NUMBER

COLOUR/FORM

BOILING POINT

(°C)

MELTING POINT

(°C)

MOLECULAR WEIGHT

SOLUBILITY IN WATER

RELATIVE DENSITY (WATER=1)

RELATIVE VAPOUR DENSITY (AIR=1)

VAPOUR PRESSURE/ (KPA)

INFLAM.

LIMITS

FLASH POINT

(°C)

AUTO IGNITION POINT

(°C)

CALCIUM PHOSPHIDE

1305-99-3

red-brown crystalline powder or gray lumps

 

1600

182.20

 

2.51

 

 

 

 

 

DIBUTYL PHENYL PHOSPHATE

2528-36-1

clear slightly yellow liquid

131-132

 

286.34

sl sol

1.0691

@ 25 °C/ 25 °C

 

0.007 torr

@ 25 °C

 

129 cc; 177 oc

 

DIBUTYL PHOSPHATE

107-66-4

pale amber liquid

 

 

210.21

insol

1.06

 

1 mm Hg

 

 

 

DIETHYLTHIOPHOSPHORYL CHLORIDE

2524-04-1

colourless to light amber liquid

>110

<-75

188.62

insol

1.196

@ 25 °C/ 25 °C

 

0.25

@ 50 °C

 

110

 

DIMETHYL HYDROGEN PHOSPHITE

868-85-9

mobile, colourless liquid

72-73

@ 25 mm Hg

 

110.05

sol

1.200

 

 

 

 

 

HEXAMETHYL PHOSPHORAMIDE

680-31-9

colourless, mobile liquid

233

5-7

179.24

misc

1.03

6.18

0.03 mm Hg

 

 

 

PHENYLPHOSPHINE

638-21-1

 

160.5

 

110.09

 

1001

@ 15 °C

 

 

 

 

 

PHOSPHINE

7803-51-2

colourless gas

-87.7

-133

34.00

sl sol

0.75

1.17

3530

1.79 ll

? ul

flammable gas

100-150

PHOSPHORUS

7723-14-0

white: colourless 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

Yellow: 280; Red: 280 (ignites

@ 200)

Yellow: 44.1; Violet: 590; Red: 590

@ 43 atm

30.9737

insol

Red: 2.34; Violet: 2.36; Black: 2.70; Yellow: 1.82

Red: 4.77; White: 4.42

3.5 Pa

 

 

Red: 260; white: 30

PHOSPHORUS PENTACHLORIDE

10026-13-8

white to pale yellow crystalline mass; tetragonal crystals

160

148

208.27

 

4.65 g/l

@ 296 °C (GAS)

 

133 Pa

@ 55.5 °C

 

 

 

PHOSPHORUS PENTASULPHIDE

1314-80-3

gray-yellow crystals; light yellow, triclinic crystals; solid flakes or powder; greenish gray color

513-515

286-290

222.29

insol

 

 

1 mm Hg

@ 300 °C

 

 

260-290 dust; 275 liquid

PHOSPHORUS PENTOXIDE

1314-56-3

white monoclinic or powdery crystals; /there are/ several crystalline & amorphous modifications; commercial form, hexagonal

300 sublimes

580-5

141.96

v sol

2.39

 

1

@ 384 °C

 

 

 

PHOSPHORUS TRICHLORIDE

7719-12-2

colourless, clear, liquid

76

-112

137.35

reacts

1.574

@ 21 °C

4.75

12.7

 

 

 

PHOSPHORYL-OXYCHLORIDE

10025-87-3

colourless to light yellow, oily liquid

105.8

1.25

153.33

 

1.645

@ 25 °C/4 °C

5.3

40 mm Hg

@ 27.3 °C

 

 

 

TETRAPHOSPHORUS TRISULPHIDE

1314-85-8

yellowish-green, long, rhombic needles from benzene

407.5

172.5

220.08

insol

2.03 @ 20°C/

4°C

 

 

 

 

100

TETRAPOTASSIUM PYROPHOSPHATE

7320-34-5

white granules or powder

 

1090

 

v sol

 

 

 

 

 

 

TETRASODIUM PYROPHOSPHATE

7722-88-5

crystals; colourless, transparent crystals or white powder

 

988

265.94

2.61 g/100 ml

@ 0 °C; 6.7 g/100 ml

@ 25 °C

2.534

 

 

 

 

 

THIOPHOSPHORYL CHLORIDE

3982-91-0

colourless liquid; crystallizes as alpha-form at -40.8 °C or as beta-form at -36.2 °C

125

-35

169.41

decomposes

1.635

5.86

2.9

@ 25 °C

 

 

 

TRIBUTYL PHOSPHATE

126-73-8

colourless liq

289

<80

266.32

sol

0.976

@ 25 °C/ 25 °C

9.20

17

@ 177 °C

 

146

410

TRICRESYL PHOSPHATE

1330-78-5

practically colourless liquid

420

 

 

0.36 mg/l

@ 25 °C

1.162

@ 25/25 °C

 

 

 

 

410

TRI-o-CRESYL PHOSPHATE

78-30-8

colourless or pale yellow liq

410

11

368.37

insol

1.1955

12.7

10 mm Hg

@ 265 °C

 

225

385

TRIETHYL PHOSPHATE

78-40-0

liquid; colourless

215.5

-56.4

182.16

sol

1.0695

6.28

1 mm Hg

@ 39.6 °C

 

 

 

TRIETHYL PHOSPHITE

122-52-1

colourless liquid

157.9

-112

166.16

insol

0.9629

 

0.6

 

52

250

TRIMETHYL PHOSPHATE

512-56-1

colourless liquid

197.2

-46

140.08

v sol

1.2144

 

 

 

 

 

TRIMETHYL PHOSPHITE

121-45-9

colourless liquid

111.5

 

124.08

 

1.0520

4.3

 

 

 

 

TRIPHENYL PHOSPHATE

115-86-6

crystals from absolute alcohol-ligroin, prisms from alcohol, needles from ether-ligroin; colourless crystalline powder; white platelets

245

@ 11 mm Hg

50

326.28

insol

1.2055

@ 50 °C/4 °C

1.19

1 mm Hg

@ 193.5 °C

 

 

 

TRIPHENYL PHOSPHINE

603-35-0

monoclinic platelets or prisms from ether; white crystalline solid

>360

80.5

262.28

insol

1.075

@80 °C/4 °C

9.0

 

 

180 oc

 

TRIPHENYL PHOSPHITE

101-02-0

water-white to pale yellow solid or oily liquid

360

25

310.29

insol

1.1844

 

 

 

218 oc

 

TRIS-2,3-DIBROMOPROPYL PHOSPHATE

126-72-7

viscous, pale yellow liquid; dense, nearly colourless liquid

 

FP 5.5

697.93

8.0 mg/l

2.27

@ 25 °C

 

0.00019 mm Hg

@ 25 °C

 

 

 

TRIS(2-ETHYLHEXYL) PHOSPHATE

78-42-2

viscous liquid

220

@ 5 mm Hg

-74

434.72

insol

0.926

14.95

0.25

@ 200 °C

 

207

 

 

___________________________________________________________________________