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Other Classes -> Phosphorus Compounds

Corrosives

2.862 at 86 °F (USCG, 1999) - Denser than water; will sink

2.852 at 15 °C

Fuming colorless liquid

PALE YELLOW LIQUID

Reacts with water, ethanol; soluble in acetone, carbon disulfide

Soluble in acetone, alcohol, carbon disulfide, hydrogen sulfide, water (decomposes)

343 °F at 760 mmHg (USCG, 1999)

173.2 °C

... If involved in a fire, /phosphorus tribromide/ decomposes to produce hydrogen bromide, phosphoric acid, phosphine.

When heated to decomposition it emits toxic fumes of /hydrogen bromide and phosphorous oxides/.

-42.9 °F (USCG, 1999)

-41.5 °C

Danger

H314: Causes severe skin burns and eye damage [Danger Skin corrosion/irritation]

P260, P261, P264, P271, P280, P301+P330+P331, P302+P361+P354, P304+P340, P305+P354+P338, P316, P319, P321, P363, P403+P233, P405, and P501 (click each P-code to see the statement)

This chemical does not meet GHS hazard criteria for 10.4% (11 of 106) of reports.

Danger

H314 (89.6%): Causes severe skin burns and eye damage [Danger Skin corrosion/irritation]

Chemical: Phosphorous tribromide

Status: Cease Manufacture Update: 03-10-2018 https://echa.europa.eu/registration-dossier/-/registered-dossier/19307

Phosphorus tribromide: Does not have an individual approval but may be used under an appropriate group standard

The New Jersey Worker and Community Right to Know Act requires public and private employers to provide information about hazardous substances at their workplaces. (N.J.S.A. 34:5A-1 et. seq.)

Special Hazards of Combustion Products: Irritating hydrogen bromide and phosphoric acid vapors may form in fire.

· EXCEPT FOR ACETIC ANHYDRIDE (UN1715), THAT IS FLAMMABLE, some of these materials may burn, but none ignite readily.

Inhalation causes severe irritation of nose, throat, and lungs. Ingestion causes burns of mouth and stomach. Contact with eyes or skin causes severe burns. (USCG, 1999)

· CORROSIVE and/or TOXIC; inhalation, ingestion or contact (skin, eyes) with vapors, dusts or substance may cause severe injury, burns or death.

Corrosive to skin; [Quick CPC] Inhalation can cause severe irritation of lungs; [CAMEO] Reacts with moisture in the air forming phosphonic acid and hydrogen bromide gas; Causes severe burns; Inhalation may cause chemical pneumonitis and pulmonary edema; [HSDB] Reacts violently with water producing white fumes of hydrogen bromide; Causes burns; Inhalation causes severe irritation of nose, throat, and lungs; [CHRIS] Causes somnolence, muscle weakness, and dyspnea in oral lethal-dose studies of rats; [RTECS]

PHOSPHORUS TRIBROMIDE reacts with oxidizing agents to generate heat and products that may be flammable, combustible, or otherwise reactive; the reactions may be violent. Forms complexes with potassium or sodium metal that explode when shocked. Dropwise addition to 3-phenylpropanol caused an explosion when stirring of the mixture was discontinued [Chem. Brit., 1974, 10, 101-102].

If ... THERE IS NO FIRE, go directly to the Table of Initial Isolation and Protective Action Distances /(see table below)/ ... to obtain initial isolation and protective action distances. IF THERE IS A FIRE, or IF A FIRE IS INVOLVED, go directly to the appropriate guide /(see guide(s) below)/ and use the evacuation information shown under PUBLIC SAFETY.

Table of Water-Reactive Materials Which Produce Toxic Gases. Phosphorus tribromide

/GUIDE 137: SUBSTANCES - WATER-REACTIVE - CORROSIVE/ Fire or Explosion: EXCEPT FOR ACETIC ANHYDRIDE (UN1715), THAT IS FLAMMABLE, some of these materials may burn, but none ignite readily. May ignite combustibles (wood, paper, oil, clothing, etc.). Substance will react with water (some violently), releasing corrosive and/or toxic gases and runoff. Flammable/toxic gases may accumulate in confined areas (basement, tanks, hopper/tank cars, etc.). Contact with metals may evolve flammable hydrogen gas. Containers may explode when heated or if contaminated with water. Substance may be transported in a molten form.

/GUIDE 137: SUBSTANCES - WATER-REACTIVE - CORROSIVE/ Health: CORROSIVE and/or TOXIC; inhalation, ingestion or contact (skin, eyes) with vapors, dusts or substance may cause severe injury, burns or death. Fire will produce irritating, corrosive and/or toxic gases. Reaction with water may generate much heat that will increase the concentration of fumes in the air. Contact with molten substance may cause severe burns to skin and eyes. Runoff from fire control or dilution water may cause pollution.

For more DOT Emergency Guidelines (Complete) data for PHOSPHORUS TRIBROMIDE (10 total), please visit the HSDB record page.

· 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.

INHALATION: remove victim to clear air; if necessary, apply artificial respiration and/or administer oxygen.

General First Aid:

Serious health hazard. May be harmful if inhaled ... Corrosive ...

Do not use water on adjacent fires. Acids formed by reaction with water will attack metals and generate flammable hydrogen gas, which may form explosive mixtures in enclosed spaces.

· 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].

... Use water spray to knock down acid vapors.

If material involved in fire: Use dry chemical, dry sand, or carbon dioxide. Do not use water on material itself. If large quantities of combustibles are involved, use water in flooding quantities as spray and fog. Use water spray to knock-down vapors. Cool all affected containers with flooding quantities of water. Apply water from as far a distance as possible.

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

KEEP TIGHTLY CLOSED.

SRP: The most favorable course of action is to use an alternative chemical product with less inherent propensity for occupational exposure or environmental contamination. Recycle any unused portion of the material for its approved use or return it to the manufacturer or supplier. Ultimate disposal of the chemical must consider: the material's impact on air quality; potential migration in soil or water; effects on animal, aquatic, and plant life; and conformance with environmental and public health regulations.

In case of contact with eyes, rinse immediately with plenty of water and seek medical advice. In case of accident or if you feel unwell, seek medical advice immediately (show label where possible).

SRP: The scientific literature for the use of contact lenses in industry is conflicting. The benefit or detrimental effects of wearing contact lenses depend not only upon the substance, but also on factors including the form of the substance, characteristics and duration of the exposure, the uses of other eye protection equipment, and the hygiene of the lenses. However, there may be individual substances whose irritating or corrosive properties are such that the wearing of contact lenses would be harmful to the eye. In those specific cases, contact lenses should not be worn. In any event, the usual eye protection equipment should be worn even when contact lenses are in place.

Personnel protection: Avoid breathing vapors. Keep upwind. ... Avoid bodily contact with the material. ... Do not handle broken packages unless earing appropriate personal 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 anticipated, wear appropriate chemical protect clothing.

If material not involved in fire: Keep material out of water sources and sewers. Build dikes to contain flow an necessary. Use water spray to knock-down vapors. Do not use water on material itself. Neutralize spilled material with crushed limestone, soda ash, or lime.

Excerpt from ERG Guide 137 [Substances - Water-Reactive - Corrosive]:

Immediate precautionary measure

When spilled in water

When spilled in water

EYES: irrigate opened eyes for several minutes under running water. INGESTION: do not induce vomiting. Rinse mouth with water (never give anything by mouth to an unconscious person). Seek immediate medical advice. SKIN: should be treated immediately by rinsing the affected parts in cold running water for at least 15 minutes, followed by thorough washing with soap and water. If necessary, the person should shower and change contaminated clothing and shoes, and then must seek medical attention. INHALATION: supply fresh air. If required provide artificial respiration.

Bromine vapour causes irritation and direct damage to the mucous membranes. Elemental bromine also burns the skin. The bromide ion is a central nervous system depressant and chronic exposure produces neuronal effects. This is called bromism and can result in central reactions reaching from somnolence to coma, cachexia, exicosis, loss of reflexes or pathologic reflexes, clonic seizures, tremor, ataxia, loss of neural sensitivity, paresis, papillar edema of the eyes, abnormal speech, cerebral edema, delirium, aggressiveness, and psychoses. (L625, L626, L627)

Bromine is a powerful oxidizing agent and is able to release oxygen free radicals from the water in mucous membranes. These free radicals are also potent oxidizers and produce tissue damage. In additon, the formation of hydrobromic and bromic acids will result in secondary irritation. The bromide ion is also known to affect the central nervous system, causing bromism. This is believed to be a result of bromide ions substituting for chloride ions in the in actions of neurotransmitters and transport systems, thus affecting numerous synaptic processes. (L626, L627, A543)

Bromine vapour causes irritation and direct damage to the mucous membranes. Symptoms include lacrimation, rhinorrhoea, eye irritation with mucous secretions from the oropharyngeal and upper airways, coughing, dyspnoea, choking, wheezing, epistaxis, and headache. The bromide ion is a central nervous system depressant producing ataxia, slurred speech, tremor, nausea, vomiting, lethargy, dizziness, visual disturbances, unsteadiness, headaches, impaired memory and concentration, disorientation and hallucinations. This is called bromism. (L626, L627)

/SIGNS AND SYMPTOMS/ Symptomatology (...ingestion or skin contact): 1. Corrosion of mucous membranes of mouth, throat and esophagus, with immediate pain and dysphagia. Necrotic areas...grayish white but soon acquire a blackish discoloration (yellow in case of nitric acid) & sometimes shrunken or wrinkled texture... 2. Epigastric pain...may be assoc with nausea & vomiting... at times, gastric hemorrhage may be intense, and vomitus then contains fresh blood. Profound thirst. 3. Ulceration of all membranes and tissues with which the acid comes in contact. After the ingestion of concn mineral acid, this corrosion may lead within a few hr or a few days to gastric perforation and peritonitis. 4. Circulatory collapse with clammy skin, weak & rapid pulse, shallow resp, and scanty urine. Circulatory shock is often immediate cause of death. ... symptomatology.../ingestion/: 6. Late esophageal, gastric & pyloric strictures & stenoses, which may require major surgical repair, should be anticipated. Signs of obstruction commonly appear within a few wk but may be delayed for months and even years. Permanent scars may also appear in the cornea, skin and oropharynx. 7. Uncorrected circulatory collapse of several hr...may lead to renal failure & ischemic lesions in liver & heart. /Acids/[Gosselin, R.E., R.P. Smith, H.C. Hodge. Clinical Toxicology of Commercial Products. 5th ed. Baltimore: Williams and Wilkins, 1984., p. III-10]

/CASE REPORTS/ A 60-year-old laboratory technician developed pulmonary infiltrates consistent with chemical pneumonitis following accidental exposure to a mixture of hydrogen bromide and phosphorus tribromide. A protracted clinical course ensued consistent with bronchiolitis obliterans. These problems may have been avoided if the potential for subsequent damage had been realized at the time of the initial exposure. Health personnel must be aware of the potentially delayed effects of accidental exposures to respiratory irritants.[Kraut A, Lilis R; Chest 94 (1): 208-10 (1988)]

/OTHER TOXICITY INFORMATION/ Corrosive to skin & tissue.[Lewis, R.J. Sr.; Hawley's Condensed Chemical Dictionary 14th Edition. John Wiley & Sons, Inc. New York, NY 2001., p. 873]

/OTHER TOXICITY INFORMATION/ Extremely destructive to tissue of the mucous membranes and upper respiratory tract. Inhalation may be fatal as a result of spasm, inflammation and edema of the larynx and bronchi, chemical pneumonitis and pulmonary edema.[Gangolli, S. (2005). Dictionary of Substances and Their Effects (DOSE, 3rd Electronic Edition). Royal Society of Chemistry . Online version Available from, as of NOvember 17, 2006: http://www.knovel.com/knovel2/Toc.jsp?BookID=527&VerticalID=0]

/LABORATORY ANIMALS: Acute Exposure/ Application of 10 or 50 uL neat PBr3 to intact skin of an anesthetized NZW rabbit caused edema and necrosis of the treated skin within 10 minutes of dosing. Microscopic examination confirmed necrosis of the skin and underlying areas, including the skeletal muscle of the subcutis.[Wolfe RE et al; Acute and Subchronic Toxicity Evaluations of the Halon Replacement Candidate Phosphorus Tribromide MAN TECH/GEO-CENTERS JOINT VENTURE TOXIC HAZARDS RESEARCH. DOD Report No A683923. (1997) Available from, as of November 17, 2006: http://www.stormingmedia.us/83/8308/A830823.html]

/LABORATORY ANIMALS: Acute Exposure/ Toxicity was not observed in rats exposed for 4 hr to 0.4 mg/L in an inhalation exposure. Male rats (5/group) were exposed to PBr3 vapor, 4 hr/d for 5 d, at 0, 0.06, 0.16 and 0.51 mg/L PBr3; 0.06 mg/L was the NOAEL.[Mattle DR et al; Risk Assessment for Phosphorus Tribromide. MANTECH-GEOCENTERS JOINT VENTURE DAYTON OH. Report number A296483 (1998) Available from, as of November 17, 2006: http://www.stormingmedia.us/29/2964/A296483.html]

/LABORATORY ANIMALS: Subchronic or Prechronic Exposure/ Rats (10/sex/group) were exposed to PBr3 vapor, 4 hr/d, 5 d/ wk, for 4 wk at 0, 0.03, 0.01 and 0.3 mg/L; the NOAEL was 0.1 mg/L.[Mattle DR et al; Risk Assessment for Phosphorus Tribromide. MANTECH-GEOCENTERS JOINT VENTURE DAYTON OH. Report number A296483 (1998) Available from, as of November 17, 2006: http://www.stormingmedia.us/29/2964/A296483.html]

/GENOTOXICITY/ Results of genotoxicity testing using bacterial Salmonella strains indicated PBr3 is not a mutagen for either frame shift or base-pair substitution tester strains in both buffered and unbuffered solutions.[Mattle DR et al; Risk Assessment for Phosphorus Tribromide. MANTECH-GEOCENTERS JOINT VENTURE DAYTON OH. Report number A296483 (1998) Available from, as of November 17, 2006: http://www.stormingmedia.us/29/2964/A296483.html]

Phosphorus tribromide reacts with moisture in the air to produce phosphonic acid and hydrogen bromide gas (HBr). A 10 cc cartridge of PBr3, tested as fire suppressant, would react to form an estimate 25 g of HBr. If uniformly distributed in a room 10X10X5 m in size, the maximum HBr concentration would be 0.05 mg/L (50 mg/cu inch); if in a 61.5X46.2X14.8 m /airplane/ hanger, it would be 5.9X10-4 mg/ L (0.59 mg/cu inch). Since the exposure limit for HBr is 10 mg/cu m, the maximal hanger concentration would be below the action level, indicating that an acceptable exposure level during usage on aircraft is possible based on the physical characteristics of PBr3 and the small amount necessary for fire suppression.

Basic treatment: Establish a patent airway (oropharyngeal or nasopharyngeal airway, if needed). Suction if necessary. Watch for signs of respiratory insufficiency and assist ventilations if necessary. Administer oxygen by nonrebreather mask at 10 to 15 L/min. Monitor for pulmonary edema and treat if necessary ... . Monitor for shock and treat if necessary ... . Anticipate seizures and treat if necessary ... . For eye contamination, flush eyes immediately with water. Irrigate each eye continuously with 0.9% saline (NS) during transport ... . Do not use emetics. For ingestion, rinse mouth and administer 5 ml/kg up to 200 ml of water for dilution if the patient can swallow, has a strong gag reflex, and does not drool. Administer activated charcoal ... . Cover skin burns with dry sterile dressings after decontamination ... . /Bromine, methyl bromide, and related compounds/

Advanced treatment: Consider orotracheal or nasotracheal intubation for airway control in the patient who is unconscious, has severe pulmonary edema, or is in severe respiratory distress. Positive-pressure ventilation techniques with a bag valve mask device may be beneficial. Consider drug therapy for pulmonary edema ... . Consider administering a beta agonist such as albuterol for severe bronchospasm ... . Monitor cardiac rhythm and treat arrhythmias if necessary ... . Start IV administration of D5W /SRP: "To keep open", minimal flow rate/. Use 0.9% saline (NS) or lactated Ringer's (LR) if signs of hypovolemia are present. For hypotension with signs of hypovolemia, administer fluid cautiously. Consider vasopressors if patient is hypotensive with a normal fluid volume. Watch for signs of fluid overload ... . Treat seizures with diazepam or lorazepam ... . Use proparacaine hydrochloride to assist eye irrigation ... . /Bromine, methyl bromide, and related compounds/

Basic treatment: Establish a patent airway (oropharyngeal or nasopharyngeal airway, if needed). Suction if necessary. Watch for signs of respiratory insufficiency and assist ventilations if necessary. Administer oxygen by nonrebreather mask at 10 to 15 L/min. Monitor for pulmonary edema and treat if necessary ... . Monitor for shock and treat if necessary ... . Anticipate seizures and treat if necessary ... . For eye contamination, flush eyes immediately with water. Irrigate each eye continuously with 0.9% saline (NS) during transport ... . Do not use emetics. For ingestion, rinse mouth and administer 5 ml/kg up to 200 ml of water for dilution if the patient can swallow, has a strong gag reflex, and does not drool ... . Administer activated charcoal ... . If product was ingested, protect yourself from contact with vomitus as it may cause burns. /Phosphorus and related compounds/

Advanced treatment: Consider orotracheal or nasotracheal intubation for airway control in the patient who is unconscious, has severe pulmonary edema, or is in severe respiratory distress. Positive-pressure ventilation techniques with a bag valve mask device may be beneficial. Consider drug therapy for pulmonary edema ... . Monitor cardiac rhythm and treat arrhythmias if necessary ... . Start IV administration of D5W /SRP: "To keep open", minimal flow rate/. Use 0.9% saline (NS) or lactated Ringer's (LR) if signs of hypovolemia are present. For hypotension with signs of hypovolemia, administer fluid cautiously. Watch for signs of fluid overload ... . Treat seizures with diazepam or lorazepam ... . Monitor for signs of hypoglycemia (decreased LOC, tachycardia, pallor, dilated pupils, diaphoresis, and/or dextrose stick or glucometer readings below 50 mg/dl) and administer 50% dextrose if necessary. Draw blood sample before administration ... . Use proparacaine hydrochloride to assist eye irrigation ... . /Phosphorus and related compounds/

Compounds containing direct phosphorus to halogen bonds hydrolyze readily, forming injurious phosphorus-containing acids and halogen halides. For example, phosphorus tribromide will hydrolyze to give H2PO3 and HBr.

Bromine is mainly absorbed via inhalation, but may also enter the body through dermal contact. Bromine salts can be ingested. Due to its reactivity, bromine quickly forms bromide and may be deposited in the tissues, displacing other halogens. (L626)

Used as a catalyst and in chemical analysis and synthesis; [HSDB]

Semiconductor Manufacturing [Category: Industry]

Phosphorus tribromide is mainly used as a brominating agent in organic chemistry.

Analysis (testing for sugar & oxygen); catalyst; synthesis

Phosphorus halides including phosphorus trichloride and phosphorus tribromide have been considered as potential replacements for Halon 1301 as fire suppressants. There has been one report of PBr3 effectiveness on real-scale flames, indicating an effectiveness two orders of magnitude better than Halon 1301.

Phosphorous tribromide: ACTIVE

PURITY: PURIFIED, 88.55%.