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Phosphorus oxychloride

CAS No.
10025-87-3
Chemical Name:
Phosphorus oxychloride
Synonyms
POCl3;PHOSPHORYL CHLORIDE;PHOSPHOROUS OXYCHLORIDE;PHOSPHORYL TRICHLORIDE;oxychloride;PHOSPHORUS(V) OXYCHLORIDE;PHOSPHOROXYCHLORIDE;phosphoric trichloride;Phosphoryl oxychloride;OPCl3
CBNumber:
CB5218244
Molecular Formula:
Cl3OP
Lewis structure
pocl3_2 lewis structure
Molecular Weight:
153.33
MDL Number:
MFCD00011443
MOL File:
10025-87-3.mol
Last updated:2024-12-18 14:08:52

Phosphorus oxychloride Properties

Melting point 1.25 °C(lit.)
Boiling point 107 °C
Density 1.645 g/mL at 25 °C(lit.)
vapor density 5.3 (vs air)
vapor pressure 104 mm Hg ( 50 °C)
refractive index n20/D 1.461
Flash point 105.8°C
storage temp. Store below +30°C.
solubility Phosphorus(V) oxychloride is soluble in many organic solvents.
form Liquid
Specific Gravity 1.692 (15/15℃)
color Colorless
Odor Pungent odour
PH 1.0 (5g/l, H2O, 25℃)
Water Solubility reacts exothermically
Sensitive Moisture Sensitive
Merck 14,7349
Exposure limits TLV-TWA0.628 mg/m3 (0.1 ppm)(ACGIH).
Dielectric constant 14.0(22℃)
Stability Stable. Reacts violently with water. Incompatible with many metals, alcohols, amines, phenol, DMSO, strong bases.
InChIKey XHXFXVLFKHQFAL-UHFFFAOYSA-N
LogP 0.357 (est)
Substances Added to Food (formerly EAFUS) PHOSPHORUS OXYCHLORIDE
CAS DataBase Reference 10025-87-3(CAS DataBase Reference)
EWG's Food Scores 3
FDA UNII 9XM78OL22K
NIST Chemistry Reference Phosphoryl chloride(10025-87-3)
EPA Substance Registry System Phosphorus oxychloride (10025-87-3)

SAFETY

Risk and Safety Statements

Symbol(GHS)  GHS hazard pictogramsGHS hazard pictogramsGHS hazard pictograms
GHS05,GHS06,GHS08
Signal word  Danger
Hazard statements  H302-H314-H330-H372
Precautionary statements  P280-P301+P312-P303+P361+P353-P304+P340+P310-P305+P351+P338-P314
Hazard Codes  T+,C
Risk Statements  14-22-26-29-35-48/23-25
Safety Statements  26-45-7/8-36/37/39
RIDADR  UN 1810 8/PG 2
OEB C
OEL TWA: 0.1 ppm (0.6 mg/m3), STEL: 0.5 ppm (3 mg/m3)
WGK Germany  1
RTECS  TH4897000
19-21
TSCA  Yes
HazardClass  8
PackingGroup  II
HS Code  28121020
Hazardous Substances Data 10025-87-3(Hazardous Substances Data)
NFPA 704
0
4 2

Phosphorus oxychloride price More Price(23)

Manufacturer Product number Product description CAS number Packaging Price Updated Buy
Sigma-Aldrich 8.22339 Phosphoryl chloride for synthesis 10025-87-3 250ML $96.2 2024-03-01 Buy
Sigma-Aldrich 8.22339 Phosphoryl chloride for synthesis 10025-87-3 1L $171 2024-03-01 Buy
Sigma-Aldrich 8.22339 Phosphoryl chloride for synthesis 10025-87-3 300KG $11630 2024-03-01 Buy
Sigma-Aldrich 201170 Phosphorus(V) oxychloride 99% 10025-87-3 5g $45.9 2024-03-01 Buy
Sigma-Aldrich 201170 Phosphorus(V) oxychloride 99% 10025-87-3 1kg $105 2024-03-01 Buy
Product number Packaging Price Buy
8.22339 250ML $96.2 Buy
8.22339 1L $171 Buy
8.22339 300KG $11630 Buy
201170 5g $45.9 Buy
201170 1kg $105 Buy

Phosphorus oxychloride Chemical Properties,Uses,Production

Chemical Characteristics

Phosphorus oxychloride (chemical formula: POCl3), is a type of industrial raw material. It is a colorless and transparent liquid, and it has an unpleasant irritating odor. It will smoke intensely in humid air. Its relative density is 1.68, melting point is 1.25℃, boiling point is 105.1℃. It breaks down into phosphoric acid and hydrogen chloride in water and ethanol. When suddenly combined with a large amount of water, an intense reaction may occur. POCl3 reacts with water and alcohol to create phosphoric acid or phosphate. If alcohol replaces the water in the reaction, the end product will be trialkyl phosphate. This type of reaction often occurs in pyridine or ammonia, as it absorbs the produced HCl to stimulate the reaction. When catalyzed by a Lewis acid such as manganese chloride, POCl3 and a large amount of phenol (ArOH) heats to produce triaryl phosphate, such as in the reaction below: 3 C6H5OH + O=PCl3 → O=P(OC6H5)3 + 3 HCl. Phosphorus oxychloride is a Lewis base, and it produces compounds with many Lewis acids, such as in its reaction with titanium tetrachloride: Cl3P5+O− + TiCl4 → Cl3P5+O-−TiCl4. Its adduct with aluminum chloride (POCl3•AlCl3) is very stable, and thus POCl3 is used to remove the AlCl3 in the end products of Friedel-Crafts reactions. In the presence of AlCl3, POCl3 reacts with hydrogen bromide to create POBr3.

Usage

Phosphorus oxychloride can be used as a semiconductor dopant, and it is a raw material for light-conducting fibers. It is widely used in pesticides, pharmaceuticals, dyes, phosphates and flame retardant production. It is a raw material for producing organic phosphorus herbicide and chlordimeform, and it is a plasticizer in plastic production. Phosphorus oxychloride is also used in the chlorination of long-acting sulfa drugs, is an intermediate in dye production and a catalyst in organic synthesis of chlorinating agents, and it is an extracting agent in uranium mining. It is also used in producing pharmaceuticals.

Toxicology

Toxicity is similar to phosphorus trichloride, phosphorus pentachloride and phosgene. Large mice, oral, LD50: 380 mg/kg; inhaled, LC50: 32 ppm/4H. Acute poisoning in small mice results in restlessness, upper respiratory tract and conjunctival irritation, depression, convulsions, unsteady walking, lying on the side, and eventually, death. For large mice, in addition to the symptoms above, also exhibited tearing, cornea clouding, and pulmonary edema. Subacute and chronic toxicity: large mice, inhaled for 60 days at a concentration of 33.5mg/m3, exhibited slowed weight gain, skin ulcers, decreases survival rates in lung macrophages, no liver and kidney functions, and organ characteristic changes.

Hazards & Safety Information

Category Corrosive items
Toxicity grading highly toxic
Acute Toxicity Oral-Rat LD50: 380 mg/kg
Flammability and Hazardous characteristics being explosive upon coming across water with release of toxic chloride, phosphorus oxide gas
Storage and transportation characteristics Ventilated, low temperature and dry; and store it separately from alkali
Fire Extinguishing agent dry sand, dry stone powder; prohibit the usage of water
Occupational Standard TLV-TWA 0.1 PPM (0.6 mg/m3); STEL 0.5 PPM (3 mg/m3)

Chemical Properties

Phosphorus oxychloride is a clear, colorless to yellow, fuming, oily liquid with a pungent and musty odor.

Physical properties

Colorless fuming liquid with a pungent odor; density 1.645 g/mL; freezes at 1°C; boils at 105.5°C; reacts with water and ethanol.

Uses

Phosphorus oxychloride is used to produce hydraulic fluids, plasticizers, and fireretarding agents; as a chlorinating agent; and as a solvent in cryoscopy.

Uses

Phosphorus oxychloride is an important intermediate in the production of triarylphosphate esters (e.g., triphenyl phosphate and tricresyl phosphate), which have been used as flame retardants and plasticizers for PVC. It is acutely toxic to the eyes, throat, and respiratory tract. Phosphorus oxychloride is also used in nuclear reprocessing, as chlorinating agent, especially to replace oxygen in organic compounds, as solvent in cryoscopy and the semiconductor industry.

Preparation

Phosphorus oxychloride can be prepared from phosphorus trichloride or phosphorus pentachloride. It can be obtained from phosphorus trichloride by cautious addition of potassium chlorate:
3PCl3 + KClO3 → 3POCl3 + KCl
The oxychloride also is obtained by the action of boric acid or oxalic acid with phosphorus pentachloride:
3PCl5 + 2B(OH)3 → 3POCl3 + B2O3 + 6HCl
PCl5 + (COOH)2 → POCl3 + CO + CO2 + 2HCl
Phosphorus oxychloride also is made by heating calcium phosphate in a current of chlorine and carbon monoxide at 350°C:
2Ca3(PO42 + 9Cl2 + 6CO → 4POCl3 + 6CaCO3
Alternatively, heating a mixture of calcium phosphate and carbon in a current of chlorine at 750°C yields the oxychloride.

Definition

A white crystalline solid. It is a monobasic acid forming the anion H2PO2 – in water. The sodium salt, and hence the acid, can be prepared by heating yellow phosphorus with sodium hydroxide solution. The free acid and its salts are powerful reducing agents.

Reactivity Profile

Phosphorus oxychloride is water reactive. Incompatible with strong oxidizing agents, alcohols, bases (including amines). May react vigorously or explosively if mixed with diisopropyl ether or other ethers in the presence of trace amounts of metal salts [J. Haz. Mat., 1981, 4, 291]. Combining the chloride with zinc dust caused immediate ignition, due to the formation of phosphine gas which ignites, [Mellor, 1940, Vol. 8, 1025]. An exotherm starting with the mixing of Phosphorus oxychloride with acetone (a ketone) lead to an explosion, may behave similarly with other ketones, [Organic Process Research and Development, Vol.4, No. 6,200, "Phosphorus oxychloride and Acetone: An Incompatibility Investigation Using ARC."]

Hazard

The compound is highly irritating to skin, eyes and mucous membranes. Inhaling its vapors can cause pulmonary edema.

Health Hazard

Inhalation of vapors of phosphorus oxychloride produced acute and chronic toxicity in test subjects. In humans, exposure to its vapors may cause headache, dizziness, weakness, nausea, vomiting, coughing, chest pain, bronchitis, and pulmonary edema. Most of these symptoms are manifested from chronic exposure to its vapors.
LC50 value, inhalation (rats): 48 ppm (301 mg/m3)/4 h
Vapors of this compound are an irritant to the eyes and mucous membranes. The liquidis corrosive and can cause skin burns. An oral LD50 value for rats is documented to be 380 mg/kg (NIOSH 1986)..

Fire Hazard

Poisonous, corrosive, and irritating gases are generated when Phosphorus oxychloride is heated or is in contact with water. Phosphorus oxychloride may ignite other combustible materials (wood, paper, oil, etc.). Phosphorus oxychloride reacts violently with water. When heated to decomposition, Phosphorus oxychloride emits toxic fumes of chlorides and oxides of phosphorus; Phosphorus oxychloride will react with water or steam to produce heat and toxic and corrosive fumes. Incompatible with carbon disulfide; N,N-dimethylformamide; 2,5-dimethylpyrrole; 2,6-dimethyl- pyridine N-oxide; dimethylsulfoxide; Ferrocene-1,1-dicarboxylic acid; water; and zinc. Do not store with combustible materials, particularly fibrous organic materials, or with electrical or other equipment that can be corroded. Reacts violently with moisture.

Potential Exposure

Phosphorus oxychloride is used in the manufacture of pesticides, pharmaceuticals, plasticizers, gasoline additives; and hydraulic fluids.

Shipping

UN1810 Phosphorus oxychloride, Hazard class: 6.1; Labels: 6.1-Poisonous materials, 8-Corrosive material, Hazard Zone B.

Purification Methods

Distil the liquid under reduced pressure to separate it from the bulk of the HCl and the phosphoric acid (from hydrolysis); the middle fraction is re-distilled into ampoules containing a little purified mercury. These ampoules are sealed and stored in the dark for 4-6weeks with occasional shaking to facilitate reaction of any free chloride with the mercury. The POCl3 is then again fractionally distilled and stored in sealed ampoules in the dark until required [Herber J Am Chem Soc 82 792 1960]. Lewis and Sowerby [J Chem Soc 336 1957] refluxed their distilled POCl3 with Na wire for 4hours, then removed the Na and again distilled. Use Na only with almost pure POCl3 to avoid explosions. HARMFUL VAPOURS; work in an efficient fume cupboard.

Incompatibilities

A powerful oxidizer. Violently decomposes in water, forming heat and hydrochloric and phosphoric acids. Violent reaction with alcohols, phenols, amines, reducing agents; combustible materials; carbon disulfide; dimethylformamide, and many other many materials. Rapid corrosion of metals, except nickel and lead.

Waste Disposal

Pour onto sodium bicarbonate. Spray with aqueous ammonia and add crushed ice. Neutralize and pour into drain with running water. In accordance with 40CFR165, follow recommendations for the disposal of pesticides and pesticide containers. Must be disposed properly by following package label directions or by contacting your local or federal environmental control agency, or by contacting your regional EPA office.

Phosphorus oxychloride Preparation Products And Raw materials

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Supplier Tel Email Country ProdList Advantage
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