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Phosphorus trichloride

Basic information Chemical Properties Uses Preparation Safety Related Supplier

Phosphorus trichloride Basic information

Product Name:
Phosphorus trichloride
CAS:
7719-12-2
MF:
Cl3P
MW:
137.33
EINECS:
231-749-3
Mol File:
7719-12-2.mol
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Phosphorus trichloride Chemical Properties

Melting point:
-112 °C
Boiling point:
74-78 °C(lit.)
Density 
1.574 g/mL at 25 °C
vapor density 
4.75 (vs air)
vapor pressure 
23.32 psi ( 55 °C)
refractive index 
n20/D 1.5148(lit.)
Flash point:
76°C
storage temp. 
Store at RT.
solubility 
Soluble in benzene, carbon sulfide, ether, chloroform, carbon tetrachloride.
form 
Liquid
color 
Yellow
Specific Gravity
approximate 1.6
Odor
Pungent, irritating odor
PH Range
1
Water Solubility 
reacts
Sensitive 
Moisture Sensitive
Merck 
14,7358
BRN 
969177
Exposure limits
TLV-TWA 1.12 mg/m3 (0.2 ppm) (ACGIH), 2.8 mg/m3 (0.5 ppm) (OSHA).
Stability:
Stable, but light sensitive. Incompatible with water, many metals, fluorine, acids, variety of organic materials including acids, alcohols and reducing agents. Reaction with water is violent and yields toxic gas.
CAS DataBase Reference
7719-12-2(CAS DataBase Reference)
NIST Chemistry Reference
Phosphorus trichloride(7719-12-2)
EPA Substance Registry System
Phosphorus trichloride (7719-12-2)
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Safety Information

Hazard Codes 
T+,C
Risk Statements 
14-26/28-29-35-48/20-40-37
Safety Statements 
26-36/37/39-45-7/8-43-28
RIDADR 
UN 3390 6.1/PG 1
WGK Germany 
2
RTECS 
TH3675000
21
TSCA 
Yes
HazardClass 
6.1
PackingGroup 
I
HS Code 
28121043
Hazardous Substances Data
7719-12-2(Hazardous Substances Data)

MSDS

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Phosphorus trichloride Usage And Synthesis

Chemical Properties

A colorless or slightly yellow fuming liquid with a pungent and irritating odor resembling that of hydrochloric acid. Causes severe burns to skin, eyes and mucous membranes. Very toxic by inhalation, ingestion and skin absorption. Reacts with water to evolve hydrochloric acid, an irritating and corrosive gas apparent as white fumes.

Uses

Phosphorus trichloride is used to prepare phosphine and other phosphorus compounds; used during electrodeposition of metal on rubber and for making pesticides, surfactants, gasoline additives, plasticizers, dyestuffs, textile finishing agents, germicides, medicinal products, and other chemicals.

Preparation

Phosphorus trichloride is prepared by reacting white phosphorus with dry chlorine present in limited quantity. Excess chlorine will yield phosphorus pentachloride, PCl5.
P4 + 6Cl2 → 4PCl3
P4 + 10Cl2 → 4PCl5
The compound is prepared in a retort attached to inlet tubes for dry chlorine and dry carbon dioxide and a distillation flask. White phosphorus is placed on sand in the retort. All air, moisture, and any phosphorus oxide vapors present in the apparatus are expelled by passing dry carbon dioxide.
Dry chlorine is then introduced into the apparatus. If a flame appears on phosphorus it indicates presence of excess chlorine. In that event, the rate of chlorine introduction should be decreased. For obtaining phosphorus trichloride, flame should appear at the end of the chlorine-entry tube. The trichloride formed is collected by condensation in the distillation flask. A soda lime tube is attached to the apparatus to prevent moisture entering the flask.
Phosphorus trichloride also can be prepared by reducing phosphorus oxychloride vapors with carbon at red heat:
POCl3 + C → PCl3 + CO

Chemical Properties

Phosphorus trichloride is a colorless to yellow, fuming liquid. Odor like hydrochloric acid.

Physical properties

Colorless fuming liquid; pungent odor; refractive index 1.516 at 14°C; density 1.574g/mL at 21°C; boils at 76°C; freezes at -112°C; decomposes in water; soluble in benzene, carbon disulfide, ether and chloroform and other halogenated organic solvents.

Uses

Phosphorus trichloride is an important intermediate in the production of insecticides, herbicides, and organophosphorus pesticides as well as other chemicals such as phosphoryl chloride, phosphorus pentachloride, thiophosphoryl chloride, and phosphonic acid. It is also used in the production of synthetic surfactants, phosphites, gasoline additives, flame retardants, silver polish, and producing iridescent metallic deposits.

Uses

Phosphorus trichloride is used as a chlorinating agent; as an intermediate in making gasoline additives, dyes, surfactants, and pesticides; in the manufacture of phosphorus pentachloride and phosphorus oxychloride; and as a catalyst.

Uses

Phosphorus trichloride (PCl3) is used in the manufacture of other phosphorus compounds. It is also an insecticide, a gasoline additive, an ingredient in dyes, and a “finisher” for the surface of textiles.

Production Methods

Phosphorus trichloride (PCl3) is made by reacting yellow phosphorus with chlorine and is used in chemical manufacturing. It hydrolyzes to phosphoric acid and hydrochloric acid.

Reactivity Profile

Phosphorus trichloride is a strong reducing agent that may ignite combustible organic materials upon contact. May generate flammable and potentially explosive gaseous hydrogen upon contact with many common metals (except nickel and lead). Reactions with water are violent and produce heat and flashes of fire [AAR, 1999]. Gives intensely exothermic reactions with iodine monochloride [Mellor 2, Supp. 1:502. 1956]. Several laboratory explosions have been reported arising from mixtures with acetic acid, along with other acids, sulfuric acid and derivatives, carboxylic acids, etc. These have been ascribed to poor heat control allowing the formation of phosphine [J. Am. Chem. Soc. 60:488. 1938]. Ignites when mixed with hydroxylamine [Mellor 8:290. 1946-47]. Causes an explosion on contact with nitric acid [Comp. Rend. 28:86]. Phosphorus trichloride is incompatible with many common oxidants such as: sodium peroxide, fluorine, chromyl chloride, iodine chloride, to name a few. Isopropanol can react with PCl3, forming toxic HCl gas. (Logsdon, John E., Richard A. Loke., "Isopropyl Alcohol." Kirk-Othmer Encyclopedia of Chemical Technology. John Wiley & Sons, Inc. 1996.)

Hazard

Phosphorus trichloride is highly corrosive. Its vapors are an irritant to mucous membranes. Chronic exposure to its vapors can cause bronchitis. It reacts violently with water and explodes in contact with acetic and nitric acids, and several other substances (Patnaik. P. 1999. A Comprehensive Guide to the Hazardous Properties of Chemical Substances, 2nd. Ed. New York: John Wiley & Sons).

Health Hazard

Phosphorus trichloride is a highly corrosive substance. Its vapors are an irritant to the upper and lower respiratory tracts. Chronic exposure to its vapors can produce coughing, bronchitis, and pneumonia.
LC50 value, inhalation (guinea pigs): 50 ppm (280 mg/m3)/4 h
The liquid is corrosive to the skin and can cause acid burns..

Health Hazard

Phosphorus trichloride is highly toxic; it may cause death or permanent injury. Contact is highly irritating to the skin, eyes, and mucous membranes, and the material is an irritant through oral and inhalation exposure.

Fire Hazard

Phosphorus trichloride will react violently with water, producing heat and toxic and corrosive fumes. When heated to decomposition, Phosphorus trichloride emits highly toxic fumes of chlorides and phosphorus oxides. Phosphorus trichloride may ignite other combustible materials. Reacts violently with water. Reacts explosively with acetic acid, aluminum, chromyl chloride, diallylphosphite and allyl alcohol, dimethyl sulfoxide, fluorine, hydroxylamine, iodine monochloride, lead dioxide, nitric acid, nitrous acid, organic matter, potassium, and sodium. Avoid contact with water, steam, or acids. Hazardous polymerization may not occur.

Safety Profile

Poison by ingestion and inhalation. A corrosive irritant to skin, eyes (at 2 ppm), and mucous membranes. Potentially explosive reaction with chlorobenzene + sodtum, hethyl sulfoxide, molten sodmm, chromyl chloride, nitric acid, sodium peroxide, oxygen (above 100℃), tetravinyl lead. Reacts with carboxylic acids (e.g., acetic acid) to form violently unstable products. Violent reaction or ignition with Al, chromium pentafluoride, dtallyl phosphite + allyl alcohol, F2, hexa fluoroisoprop ylideneaminolithium, hydroxylamine, iodine chloride, PbO2, HNO2, organic matter, potassium, selenium dioxide, sulfur acids (e.g., sulfuric acid, fluorosulfuric acid, oleum). Violent reaction with water evolves hydrogen chloride and diphosphane gas, that then ignite. Incompatible with metals or oxidants. Wdl react with water, steam, or acids to produce heat and toxic and corrosive fumes; can react with oxidzing materials. To fight fire, use CO2, dry chemical. Used as a chlorinating agent, catalyst, and chemical intermedtate. Dangerous; when heated to decomposition it emits highly toxic fumes of Cland POx.

Potential Exposure

Phosphorus trichloride is used as an intermediate and as a chlorinating agent and catalyst; in the manufacture of agricultural chemicals; pharmaceuticals, chlorinated compounds; dyes, gasoline additives; acetyl cellulose; phosphorus oxychloride; plasticizers, saccharin, and surfactants.

Shipping

UN1809 Phosphorous trichloride, Hazard class: 6.1; Labels: 6.1-Poisonous materials, 8-Corrosive material, Inhalation Zone B.

Purification Methods

Heat it under reflux to expel dissolved HCl, then distil it. It has been further purified by vacuum fractionation several times through a -45o trap into a receiver at -78o. [Forbes Inorg Synth II 145 1946.] HARMFUL VAPOURS.

Incompatibilities

Phosphorus trichloride is a strong reducing Violent reaction with water, producing heat and hydrochloric and phosphorous acids. Violent reaction with hydrides, alcohols, phenols and bases; water, when in contact with combustible organics; chemically active metals: sodium, potassium, aluminum; strong sulfuric or nitric acid. Attacks most metals except nickel and lead; may generate flammable hydrogen gas on contact with metals. Attacks plastics, rubber, and coatings.

Waste Disposal

Decompose with water, forming phosphoric and hydrochloric acids. The acids may then be neutralized and diluted slowly to solution of soda ash and slaked lime with stirring, then flush to sewer with large volumes of water.

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Basic information Chemical Properties Uses Preparation Safety Related Supplier