Phosphorylchlorid

Avoid breathing vapors; keep upwind. Wear self-contained breathing apparatus. Avoid bodily contact with the material. Wear boots, protective gloves, and goggles. Do not handle broken packages without protective equipment. Wash away any material which may have contacted the body with copious amounts of water or soap and water. If contact with the material is anticipated, wear full protective clothing. Keep unnecessary people away; isolate hazard area and deny entry.

In case of fire in the surroundings, use appropriate extinguishing media. NO hydrous agents. NO water. In case of fire: keep drums, etc., cool by spraying with water. NO direct contact with water.

Fresh air, rest. Half-upright position. Artificial respiration may be needed. Refer for medical attention.

Remove contaminated clothes. Rinse skin with plenty of water or shower. Refer for medical attention .

First rinse with plenty of water for several minutes (remove contact lenses if easily possible), then refer for medical attention.

Rinse mouth. Do NOT induce vomiting. Refer for medical attention .

· CALL 911. Then call emergency response telephone number on shipping paper. If shipping paper not available or no answer, refer to appropriate telephone number listed on the inside back cover.

· Do not touch damaged containers or spilled material unless wearing appropriate protective clothing.

Warning: Phosphorus oxychloride is a corrosive agent. Contact with eyes may result in severe damage to the cornea, conjunctiva, and blood vessels. Caution is advised.

General First Aid:

(General first aid procedures)

Not combustible, but if involved in a fire may react to produce hydrogen chloride & phosphoric acid.

Fumes from fires are irritating to respiratory passages, eyes, skin, & may contain phosphine, phosphoric acid, hydrogen chloride.

· Wear positive pressure self-contained breathing apparatus (SCBA).

TIH (Toxic Inhalation Hazard) - Term used to describe gases and volatile liquids that are toxic when inhaled. Some are TIH materials themselves, e.g., chlorine, and some release TIH gases when spilled in water, e.g., chlorosilanes. [ERG 2016].

0.02 [ppm]

Use appropriate extinguishing agents on nearby combustible fires. Use water spray to knock down acid vapors.

This chemical reacts violently with moisture producing hydrochloric and phosphoric acids. Poisonous gases including chlorides and phosphorus oxides are produced in fire. Do not use water unless used in flooding quantities to control a large fire by wetting down combustibles burning in vicinity of this material. Use dry chemical, carbon dioxide, or dry sand; do not use water on material itself. Use water spray to absorb vapors and cool all affected containers with flooding quantities of water. Apply water from a s far a distance as possible. Avoid breathing vapors; keep upwind. Wear self-contained breathing apparatus. Avoid bodily contact wit the material. Wear boots, protective gloves, and goggles. Do not handle broken packages without protective equipment. Wash away any material which may have contacted the body with copious amounts of water or soap and water. If contact with the material is anticipated, wear full protective clothing. Keep unnecessary people away; isolate hazard area and deny entry. Vapors are heavier than air and will collect in low areas. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. ...From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position.

Keep in tightly closed containers.

Store in a cool, dry, well-ventilated location. Separate from acids, alkalies, alkali metals, alcohols.

Phosphorus oxychloride is stored and shipped in 3.8-L (1-gal) or smaller glass containers and DOT-specification wooden overpacking. Bulk POCl3 shipments are in nickel-clad tank cars of 15,000-30,000 L (4000-8000 gal) each. Glass and glass-lined steel equipment frequently is used for storage, as well as for reaction vessels.

Where possible, automatically pump liquid from drums or other storage containers to process containers. Sources of ignition such as smoking and open flames are prohibited where this chemical is handled, used, or stored. Metal containers involving the transfer of 5 gallons or more of this chemical should be grounded and bonded. Drums must be equipped with self-closing valves, pressure vacuum bungs, and flame arresters. Use only non-sparking tools and equipment, especially when opening and closing containers of this chemical. Wherever this chemical is used, handled , manufactured, or stored, use explosion-proof electrical equipment and fittings.

Releases may require isolation or evacuation. Use water spray to cool & disperse vapors & protect personnel.

Keep material out of water sources and sewers; build dikes to contain flow as necessary; use water spray to knock down vapors; do not use water on material itself; and neutralize spilled material with crushed limestone, soda ash, or lime. For a land spell, dig a pit, pond, lagoon, or holding area to contain liquid or solid material; dike surface flow using soil. sand bags, foamed polyurethane, or foamed concrete; absorb bulk liquid with fly ash or cement powder; neutralize with agricultural lime (slaked lime), crushed limestone, or sodium bicarbonate. For a water spill, neutralize with agricultural lime (slaked lime), crushed limestone, or sodium bicarbonate; use mechanical dredges or lifts to remove immobilized masses of pollutants and precipitates; adjust pH to neutral (pH 7). For air spills apply water spray or mist to knock down vapors; vapor knock down water is corrosive or toxic and should be diked for containment. Stop leak if you can do so without risk. Do not touch spilled material. Keep combustibles (wood, paper, oil, etc.) away from spilled material. Clean up only under supervision of an expert. Keep this chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the build-up of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters water ways, notify downstream users of potentially contaminated waters.

Principles and methods for destruction of chemical weapons: ... "Destruction of chemical weapons" means a process by which chemicals are converted in an essentially irreversible way to a form unsuitable for production of chemical weapons, and which in an irreversible manner renders munitions and other devices unusable as such. ... Each ... /nation/ shall determine how it shall destroy chemical weapons, except that the following processes may not be used: dumping in any body of water, land burial or open-pit burning. It shall destroy chemical weapons only at specifically designated and appropriately designed and equipped facilities. ... Each ... /nation/ shall ensure that its chemical weapons destruction facilities are constructed and operated in a manner to ensure the destruction of the chemical weapons; and that the destruction process can be verified under the provisions of this Convention.

TERRESTRIAL FATE: Hydrolysis is expected to be the most important fate process for phosphorus oxychloride in the environment(1). Phosphorus oxychloride is expected to volatilize from dry soil surfaces(SRC) based upon a vapor pressure of 40 mm Hg(1).

AQUATIC FATE: Phosphorus oxychloride hydrolyzes rapidly in water at room temperature(1).

ATMOSPHERIC FATE: According to a model of gas/particle partitioning of semivolatile organic compounds in the atmosphere(1), phosphorus oxychloride, which has a vapor pressure of 40 mm Hg at 27.3 °C(2), is expected to exist solely as a vapor in the ambient atmosphere. Vapor-phase phosphorus oxychloride is degraded in the atmosphere by reaction with photochemically-produced hydroxyl radicals(SRC); the half-life for this reaction in air is reported to be >290 days, calculated from its rate constant of <4X10-14 cu cm/molecule-sec at 25 deg(3). Phosphorus oxychloride does not contain chromophores that absorb at wavelengths >290 nm(4) and therefore is not expected to be susceptible to direct photolysis by sunlight(SRC).

The substance can be absorbed into the body by inhalation of its vapour and by ingestion.

inhalation, ingestion, skin and/or eye contact

Phosphorus oxychloride. No toxicokinetic studies were located. Phosphorus oxychloride is acutely very toxic when inhaled by rats and guinea pigs, causing extensive irritation of the respiratory tract. It is also acutely toxic to rats via the oral route. The substance is corrosive to rabbit skin and causes severe eye damage. Little reliable information is available on the effects of repeated inhalation in animals. Irritation of the respiratory tract would be expected and has been claimed in one poorly reported rat study, although no reliance can be placed on these data, particularly as it is not clear if continuous or repeated exposure was used. No reliable genotoxicity or animal reproductive toxicity data are available. No animal carcinogenicity study was located. Single exposure of humans to airborne material has been reported to cause conjunctivitis, pharyngitis and respiratory tract irritation, including pulmonary edema. No reliable threshold concentration for these effects is available. Similar effects were seen following repeated exposure including asthmatic bronchitis and, in severe cases, emphysema. Exposure levels were 10-20 mg/cu m, rising to 70 mg/cu m, and sometimes to higher levels. Workers who suffered respiratory effects were reported to show increased respiratory tract sensitivity to phosphorus oxychloride and to other irritant substances, particularly phosphorus bichloride and pentachloride. No human data are available on the genotoxic or carcinogenic potential of phosphorus oxychloride or on its potential to cause reproductive toxicity.

Sore throat. Cough. Burning sensation. Dizziness. Laboured breathing. Nausea. Headache. Unconsciousness. Vomiting. Weakness. Shortness of breath. Symptoms may be delayed.

Pain. Redness. Blisters. Skin burns.

Pain. Redness. Severe deep burns. Loss of vision.

Burning sensation. Abdominal pain. Shock or collapse. Further see Inhalation.

irritation eyes, skin, respiratory system; eye, skin burns; dyspnea (breathing difficulty), cough, pulmonary edema; dizziness, headache, lassitude (weakness, exhaustion); abdominal pain, nausea, vomiting; nephritis

/SIGNS AND SYMPTOMS/ Potential symptoms of overexposure are irritation of eyes, skin, respiratory system; eye, skin burns; dyspnea, cough, lung edema; dizziness, headache, weakness; abdominal pain, nausea, vomiting; nephritis.

/SIGNS AND SYMPTOMS/ Acute poisoning is characterized by burns and extensive reddening of eyes, pains in throat and bronchi, and cough. Those constantly or frequently exposed to very small doses ... suffer from chronic poisoning which manifests itself in form of pulmonary irritation, cough, and when ingested, asthmatical respiration. /it/ ... causes actual burns of mucous membranes of mouth and the digestive tract.

/SIGNS AND SYMPTOMS/ Burns of ... cornea ... have been noted in 2 cases to be slow in healing ... .

/SIGNS AND SYMPTOMS/ Exposure to the vapor of phosphorus oxychloride may cause irritation of the eyes, dizziness, headache, weakness, anorexia, nausea, vomiting, chest pain, cough, dyspnea, bronchitis, bronchopneumonia, pulmonary edema and nephritis. Both chronic and acute cases of occupational intoxication have been recorded.

For more Human Toxicity Excerpts (Complete) data for PHOSPHORUS OXYCHLORIDE (14 total), please visit the HSDB record page.

Phosphorus oxychloride's production and use to manufacture alkyl and aryl orthophosphate triesters(1), manufacture of insecticides, dye intermediates, pharmaceuticals, synthesis of various nerve agents(2), solvent in cryoscopy(3), manufacture of gasoline additives and hydraulic fluid, chlorinating agent and catalyst, dopant for semiconductor grade silicon, tricresyl phosphate, and fire retarding agent(4) may result in its release to the environment through various waste streams(SRC).

Phosphorus oxychloride hydrolyzes rapidly in water at room temperature(1), and therefore will not volatilize from water or moist soil surfaces(SRC). Phosphorus oxychloride is expected to volatilize from dry soil surfaces(SRC) based upon a vapor pressure of 40 mm Hg(1).

/LABORATORY ANIMALS: Acute Exposure/ 6 male Sprague-Dawley rats were exposed for 18 minutes to a concentration of 159.7 g/cu m. This exposure caused laboured breathing within less than 2 minutes, weakness, convulsions, collapse and death in 10 minutes. All animal died within 18 minutes.

/LABORATORY ANIMALS: Acute Exposure/ In a Russian study ..., acute inhalation exposure of rats to lethal or near lethal concentrations of phosphorus oxychloride resulted in immediate signs of irritation (rubbing of faces and restlessness). At 5-15 minutes of exposure, the rats exhibited inactivity and decreased respiration, followed by convulsions. Rats that survived showed continued lacrimation and corneal opacities, and ulcers around the mouth several days after cessation of exposure. The report provided a "threshold concentration" of 0.006 mg/L (0.96 ppm) based upon "integrated characteristics". It is unclear as to what effect this threshold pertains or the precise nature of the "integrated characteristics". Although no further details were provided, information in this report affirms the irritation and lethal capacity of phosphorus oxychloride following acute inhalation exposure.

/LABORATORY ANIMALS: Acute Exposure/ The results of an inhalation study in rats were /reported/. Groups of male Sprague-Dawley rats (number not provided) were exposed for 18 minutes to 159.7 mg phosphorus oxychloride/L (25,462 ppm). Conditions in the 35-L chamber were: 25 °C, 85% humidity, and 4.0 L/minute airflow. The concentration of the test material was such that there was a fog in the chamber. Within two minutes the rats /were/ having difficulty breathing and their eye/s/ were closed. At 10 minutes, weakness, convulsions, and collapse were observed, and one rat died. At 18 minutes all rats were dead. Necropsy revealed lung congestion. No further details were provided.

/LABORATORY ANIMALS: Acute Exposure/ Experiments using groups of 10 male guinea pigs /were also conducted/. The experimental protocol was the same as that described for the experiments with rats. Like the rats, the response of the guinea pigs was consistent with exposure to an irritating chemical (restlessness, lacrimation, pawing at nose and head). The 4-hr LC50 was 52.5 umole/mole of air (numerically equivalent to 52.5 ppm). Deaths occurred within 48 hours after exposure; no further details were provided. Neutralization of the phosphorus oxychloride with ammonia resulted in a lowering of the LC50 to 41.3 umole/mole of air (numerically equivalent to 41.3 ppm). Similar to the results observed for rats, the simultaneous exposure of the guinea pigs to ammonia was thought to decrease the irritation responses to the phosphorus oxychloride exposure but to increase the overall toxicity. The series of exposures and the respective responses used to obtain the median lethal concentration were not provided and, therefore, no other exposure-response data are available.

For more Non-Human Toxicity Excerpts (Complete) data for PHOSPHORUS OXYCHLORIDE (11 total), please visit the HSDB record page.

Persons in charge of vessels or facilities are required to notify the National Response Center (NRC) immediately, when there is a release of this designated hazardous substance, in an amount equal to or greater than its reportable quantity of 1000 lb or 454 kg. The toll free number of the NRC is (800) 424-8802. The rule for determining when notification is required is stated in 40 CFR 302.4 (section IV. D.3.b).

Releases of CERCLA hazardous substances are subject to the release reporting requirement of CERCLA section 103, codified at 40 CFR part 302, in addition to the requirements of 40 CFR part 355. Phosphorus oxychloride is an extremely hazardous substance (EHS) subject to reporting requirements when stored in amounts in excess of its threshold planning quantity (TPQ) of 500 lbs.

Phosphorus oxychloride is designated as a hazardous substance under section 311(b)(2)(A) of the Federal Water Pollution Control Act and further regulated by the Clean Water Act Amendments of 1977 and 1978. These regulations apply to discharges of this substance. This designation includes any isomers and hydrates, as well as any solutions and mixtures containing this substance.

Phosphorus oxychloride

1

5000

80

220

A Commercial Grade