Phosphorus tribromide

270.69

270.69

3903060

232-178-2

58R3866PUA

1808

DTXSID7064869

Fuming colorless liquid|PALE YELLOW LIQUID

2827590000

0

4.34

Clear to slightly hazy colorless to yellow or light brown Liquid

2.85 g/cm³ @ Temp: 15 °C

-41.5 °C

173.2 °C

172.9°C

n20/D 1.697(lit.)

Solubility in water: reaction.;soluble in acetone, alcohol, carbon disulfide, hydrogen sulfide, water (decomposes)

-20°C

0.27 psi ( 54 °C)

Decomposes hydrogen bromide gas in contact with water; flammable, burning produces toxic phosphorus oxides and bromide fumes

Penetrating odor

Heat of formation: -184.5 kJ/mol; heat of evaporation: 31 kJ/mol|HEAT OF SOLUTION: -446 BTU/LB= -248 CAL/G= -10.4X10+5 J/KG|HEAT OF VAPORIZATION: 64.4 BTU/LB= 35.8 CAL/G= 1.50X10+5 J/KG

Fumes in air. Decomposed by water to form phosphorous acid and hydrobromic acid. Reaction with warm water is very rapid and may be violent [Mellor v.8. 1032 1940]. Based on a scenario where the chemical is spilled into an excess of water (at least 5 fold excess of water), half of the maximum theoretical yield of Hydrogen Bromide gas will be created in 11 minutes. Experimental details are in the following: "Development of the Table of Initial Isolation and Protective Distances for the 2008 Emergency Response Guidebook", ANL/DIS-09-2, D.F. Brown, H.M. Hartmann, W.A. Freeman, and W.D. Haney, Argonne National Laboratory, Argonne, Illinois, June 2009.

Acids, Strong Non-oxidizing

Water-Reactive

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].

IN PRESENCE OF MOISTURE, HIGHLY CORROSIVE TO MOST METALS EXCEPT LEAD & NICKEL

38.9 kJ/mol

II

8

UN 3264 8/PG 2

2

34-37-40-14-67

26-45-36/37-36/37/39

TH4460000

C

The warehouse is ventilated, low temperature and dry; stored separately from alkalis, oxidants, organic matter and flammable substances

Reacts with water or acid to generate heat or even explode

Stable, but reacts violently with water. Incompatible with moisture, strong bases, strong oxidizing agents, reactive metals, acids, alcohols.

P261-P280-P305 + P351 + P338-P310

H314-H335

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.

Will react with water, steam or acids to produce heat, toxic and corrosive fumes.|Reacts violently with water, evolving hydrogen bromide, an irritating & corrosive gas apparent as white fumes.|Interaction with warm water is very rapid and may be violent with limited quantities.|During disposal of the tribromide by a recommended procedure involving slow addition of a mixture of soda ask (sodium carbonate) and dry slaked lime (calcium hydroxide), a violent reaction, accompanied by flame, occurred a few sec after the first drop. Cautious addition of the bromide to a large volume of ice water is suggested for disposal.|For more Hazardous Reactivities and Incompatibilities (Complete) data for PHOSPHORUS TRIBROMIDE (13 total), please visit the HSDB record page.

Special Hazards of Combustion Products: Irritating hydrogen bromide and phosphoric acid vapors may form in fire. Behavior in Fire: Acids formed by reaction with water will attack metals and generate flammable hydrogen gas, which may form explosive mixtures in enclosed spaces. (USCG, 1999)|Corrosives, Reactive - 2nd degree

|Danger|H314: Causes severe skin burns and eye damage [Danger Skin corrosion/irritation]|P260, P261, P264, P271, P280, P301+P330+P331, P303+P361+P353, P304+P340, P305+P351+P338, P310, P312, P321, P363, P403+P233, P405, and P501|H314 (100%): Causes severe skin burns and eye damage [Danger Skin corrosion/irritation]|Aggregated GHS information provided by 105 companies from 13 notifications to the ECHA C&L Inventory. Each notification may be associated with multiple companies.

Excerpt from ERG Guide 137 [Substances - Water-Reactive - Corrosive]: As an immediate precautionary measure, isolate spill or leak area in all directions for at least 50 meters (150 feet) for liquids and at least 25 meters (75 feet) for solids. SPILL: See ERG Table 1 - Initial Isolation and Protective Action Distances on the UN/NA 1808 datasheet. FIRE: If tank, rail car or tank truck is involved in a fire, ISOLATE for 800 meters (1/2 mile) in all directions; also, consider initial evacuation for 800 meters (1/2 mile) in all directions. (ERG, 2016)

Excerpt from ERG Guide 137 [Substances - Water-Reactive - Corrosive]: Fully encapsulating, vapor-protective clothing should be worn for spills and leaks with no fire. Do not touch damaged containers or spilled material unless wearing appropriate protective clothing. Stop leak if you can do it without risk. Use water spray to reduce vapors; do not put water directly on leak, spill area or inside container. Keep combustibles (wood, paper, oil, etc.) away from spilled material. SMALL SPILL: Cover with DRY earth, DRY sand or other non-combustible material followed with plastic sheet to minimize spreading or contact with rain. Use clean, non-sparking tools to collect material and place it into loosely covered plastic containers for later disposal. Prevent entry into waterways, sewers, basements or confined areas. (ERG, 2016)

Acid-gas canister-type mask (full face type for emergencies); chemical safety goggles; apron, gloves, clothing, and safety shoes all made from rubber (USCG, 1999)|... Self-contained breathing apparatus.|ACID-GAS CANISTER-TYPE MASK (FULL FACE TYPE FOR EMERGENCIES); CHEMICAL SAFETY GOGGLES; APRON, GLOVES, CLOTHING, & SAFETY SHOES ALL MADE FROM RUBBER.

Not combustible, but if involved in a fire decomposes to produce hydrogen bromide, phosphoric acid, phosphine.

... 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.

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.

Isolate the area until the release is under full control. Use water spray to cool and disperse vapors and protect personnel.

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.

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.

No person may /transport,/ offer or accept a hazardous material for transportation in commerce unless that person is registered in conformance ... and the hazardous material is properly classed, described, packaged, marked, labeled, and in condition for shipment as required or authorized by ... /the hazardous materials regulations (49 CFR 171-177)./|The International Air Transport Association (IATA) Dangerous Goods Regulations are published by the IATA Dangerous Goods Board pursuant to IATA Resolutions 618 and 619 and constitute a manual of industry carrier regulations to be followed by all IATA Member airlines when transporting hazardous materials.|The International Maritime Dangerous Goods Code lays down basic principles for transporting hazardous chemicals. Detailed recommendations for individual substances and a number of recommendations for good practice are included in the classes dealing with such substances. A general index of technical names has also been compiled. This index should always be consulted when attempting to locate the appropriate procedures to be used when shipping any substance or article.

... Irritating eyes, skin, and respiratory system. Corrosive, Causes severe eye and skin burns. Fumes from fires are irritating to respiratory passages, eyes, skin, and may contain phosphine, phosphoric acid, hydrogen bromide.|Inhalation causes severe irritation of nose, throat, and lungs. Contact with eyes or skin causes severe burns.

LC50 fathead minnows at 71 mg/L (25 mg/L NOEC) for 96 hr.

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.

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.

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)

INHALATION: remove victim to clear air; if necessary, apply artificial respiration and/or administer oxygen. INGESTION: dilute by drinking water, then neutralize with milk of magnesia, egg white, etc,; do not use sodium bicarbonate. EYES: immediately flush with large amounts of water for at least 15 min. SKIN: immediately flush with large amounts of water; remove contaminated clothing. (USCG, 1999)

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/

/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]

Phosphorous tribromide: ACTIVE|PURITY: PURIFIED, 88.55%.

Fire Hazards -> Corrosives, Reactive - 2nd degree