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Phosphine

Phosphine
Phosphine structure
CAS No.
7803-51-2
Chemical Name:
Phosphine
Synonyms
PH3;Fosfina;Fosfano;Gas-ex-B;PHOSPHINE;phosphane;Phosphene;Chebi:30278;phosphine00;Fosforowodor
CBNumber:
CB8716837
Molecular Formula:
H3P
Formula Weight:
34
MOL File:
7803-51-2.mol

Phosphine Properties

Melting point:
-133°
Boiling point:
−87.5 °C(lit.)
Density 
0.491 (estimate)
vapor density 
1.15 (vs air)
form 
colorless gas
Water Solubility 
0.26 volumes in H2O (20°C); insoluble hot H2O; slightly soluble alcohol, ether, cuprous chloride solutions [HAW93] [MER06]
Merck 
13,7424
Exposure limits
TLV-TWA 0.42 mg/m3 (0.3 ppm) (ACGIH and OSHA); STEL 1.4 mg/m3 (1 ppm) (ACGIH); IDLH 200 ppm (NIOSH).
Stability:
Stable, but pyrophoric - spontaneously flammable in air. Note the very wide explosion limits. Incompatible with oxidizing agents, halogens, nitric acid.
CAS DataBase Reference
7803-51-2(CAS DataBase Reference)
NIST Chemistry Reference
Phosphine(7803-51-2)
SAFETY
  • Risk and Safety Statements
  • Hazard and Precautionary Statements (GHS)
  • NFPA
Hazard Codes  F+,T+,N
Risk Statements  12-17-26-34-50
Safety Statements  28-36/37-45-61-63
RIDADR  UN 2199 2.3
WGK Germany  2
RTECS  SY7525000
HazardClass  2.3
Hazardous Substances Data 7803-51-2(Hazardous Substances Data)
Symbol(GHS):
Signal word: Danger
Hazard statements:
Code Hazard statements Hazard class Category Signal word Pictogram P-Codes
H220 Extremely flammable gas Flammable gases Category 1 Danger P210, P377, P381, P403
H280 Contains gas under pressure; may explode if heated Gases under pressure Compressed gas
Liquefied gas
Dissolved gas
Warning P410+P403
H314 Causes severe skin burns and eye damage Skin corrosion/irritation Category 1A, B, C Danger P260,P264, P280, P301+P330+ P331,P303+P361+P353, P363, P304+P340,P310, P321, P305+ P351+P338, P405,P501
H330 Fatal if inhaled Acute toxicity,inhalation Category 1, 2 Danger P260, P271, P284, P304+P340, P310,P320, P403+P233, P405, P501
H400 Very toxic to aquatic life Hazardous to the aquatic environment, acute hazard Category 1 Warning P273, P391, P501
Precautionary statements:
P210 Keep away from heat/sparks/open flames/hot surfaces. — No smoking.
P260 Do not breathe dust/fume/gas/mist/vapours/spray.
P273 Avoid release to the environment.
P280 Wear protective gloves/protective clothing/eye protection/face protection.
P284 Wear respiratory protection.
P305+P351+P338 IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continuerinsing.

NFPA 704

Diamond Hazard Value Description
4
4 2
Health   4 Very short exposure could cause death or major residual injury (e.g. hydrogen cyanide, phosgene, methyl isocyanate, hydrofluoric acid)
Flammability   4 Will rapidly or completely vaporize at normal atmospheric pressure and temperature, or is readily dispersed in air and will burn readily. Includes pyrophoric substances. Flash point below room temperature at 22.8 °C (73 °F). (e.g. acetylene, propane, hydrogen gas)
Instability   2 Undergoes violent chemical change at elevated temperatures and pressures, reacts violently with water, or may form explosive mixtures with water (e.g. white phosphorus, potassium, sodium)
Special  

(NFPA, 2010)

Phosphine price More Price(2)

Manufacturer Product number Product description CAS number Packaging Price Updated Buy
Sigma-Aldrich 295647 Phosphine electronic grade, ≥99.9995% 7803-51-2 10g $1650 2018-11-20 Buy
Sigma-Aldrich 295647 Phosphine electronic grade, ≥99.9995% 7803-51-2 50g $5160 2018-11-20 Buy

Phosphine Chemical Properties,Uses,Production

Chemical Properties

Phosphine is a pyrophoric chemical and spontaneously flammable in air. It is incompatible with strong oxidising agents, halogens, nitric acid. It has the odour of garlic or decaying fish. It is slightly soluble in water. It is flammable and is an explosive gas at ambient temperature. Phosphine decomposes on heating or on burning producing toxic fumes including phosphorus oxides. It reacts violently with air, oxygen, oxidants such as chlorine and nitrogen oxides, metal nitrates, halogens, and other toxic substances, and causes fire and explosion hazard.

Chemical Properties

Phosphine is a colorless gas that is shipped as liquefied compressed gas. Odorless when pure. It has the odor of garlic or the foul odor of decaying fish. The level at which humans detect the odor of phosphine (odor threshold) does not provide sufficient warning of dangerous concentrations. Phosphine presents an additional hazard in that it ignites at very low temperatures. Shipped as a liquefied compressed gas. The pure compound is odorless. The Odor Threshold is 0.14 ppm.

Uses

Phosphine is the most widely used fumigant for insect con-trol in the durable commodities throughout the world. It is increasingly used as a treatment to re-place methyl bromide especially because of its low cost, fast dispersion in the air and low residues. Versatility of use is a major advantage for phosphine, as it can be used in a variety of storage buildings, during transit (e.g. in ship holds) or in plastic sheet enclosures. It is close to an ideal fumigant except for few drawbacks: slow activity, the rapid increase in insect resistance, flammability at higher concentrations (>900 ppm) and corrosion of copper, silver and gold. The phosphine resistance among the insect populations was found to be the result of selection pressure caused by inadequate fumigations in the storage units; storage facilities not adequately sealed before fumigation; and fumigant concentrations not being monitored. The understanding of phosphine resistance mechanism, improved monitoring tactics and management of resistance are the priorities in tackling the problem (Rajendran, 2001). The other problems like corrosion and flammability were found to be limited by using the combination of heat (30–36℃), carbon dioxide (3–7%) and phosphine at 80–100 ppm, while achieving a complete insect control.

Uses

Phosphine is used as a fumigant, in the synthesis of many organophosphorus compounds, and as a doping agent for electronic components. It occurs in the waste gases from plants manufacturing semiconductors and thin-film photovoltaic cells. The presence of bound residues of phosphine in fumigated commodities has been reported (Rangaswamy and Sasikala 1986).

Definition

A colorless gas that is slightly soluble in water. It has a characteristic fishy smell. It can be made by reacting water and calcium phosphide or by the action of yellow phosphorus on a concentrated alkali. Phosphine usually ignites spontaneously in air because of contamination with diphosphine. It decomposes into its elements if heated to 450°C in the absence of oxygen and it burns in oxygen or air to yield phosphorus oxides. It reacts with solutions of metal salts to precipitate phosphides. Like its nitrogen analog ammonia it forms salts, called phosphonium salts. It also forms complex addition compounds with metal ions. As in ammonia, one or more of the hydrogen atoms can be replaced by alkyl groups.

Definition

phosphine: A colourless highlytoxic gas, PH3; m.p.-133°C; b.p.–87.7°C; slightly soluble in water.Phosphine may be prepared by reactingwater or dilute acids with calciumphosphide or by reactionbetween yellow phosphorus and concentratedalkali. Solutions of phosphineare neutral but phosphinedoes react with some acids to givephosphonium salts containing PH4+ions, analogous to the ammoniumions. Phosphine prepared in the laboratoryis usually contaminated withdiphosphine and is spontaneouslyflammable but the pure compound isnot so. Phosphine can function as aligand in binding to transition-metalions. Dilute gas mixtures of very purephosphine and the rare gases areused for doping semiconductors.

Definition

ChEBI: The simplest phosphine, consisting of a single phosphorus atom with three hydrogens attached.

Air & Water Reactions

Highly flammable. Usually ignites spontaneously in air. Burns with a luminous flame [Merck 11th ed. 1989]. Insoluble in water.

Reactivity Profile

Phosphine is a reducing agent. Ignites spontaneously in air when pure [Sidgwick, 1950, p. 729]. Liquefied Phosphine can be detonated [Rust, 1948, p. 301]. Ignites or reacts violently with boron trichloride, dichlorine oxide, halogens (bromine, chlorine, iodine), metal nitrates, nitrogen oxides, nitric acid, nitrous acid, nitrogen trichloride [Bretherick, 5th ed., 1995, p. 1562]. Forms explosive mixtures with even small amounts of oxygen. Autoignites at low pressures [Fisher, E. O. et al., Angew. Chem., 1968, 7, p. 136].

Health Hazard

Phosphine is a super- toxic gas with a probable oral lethal dose of 5 mg/kg or 7 drops for a 150 pound person. An air concentration of 3 ppm is safe for long term exposure, 500 ppm is lethal in 30 minutes, and a concentration of 1,000 ppm is lethal after a few breaths.

Health Hazard

Phosphine is a highly poisonous gas. The symptoms of its acute toxic effectsin humans can be respiratory passage irritation, cough, tightness of chest, painful breathing, a feeling of coldness, and stupor. Inhalation of high concentrations of phosphine in air can cause lung damage, convulsion, coma, and death. In addition to damaging the respiratory system, exposure to this compound can cause nausea, vomiting, diarrhea, and depression of the central nervous system. Exposure to a concentration of 1000 ppm in air for 5 minutes can be fatal to humans (NIOSH 1986).
LC50 value, inhalation (rats): 11 ppm (15.3 mg/m3)/4 h
Chronic exposure is likely to cause phosphorus poisoning. Nutritional and toxicological studies indicated that ingestion of a phosphine-fumigated diet by rats for 2 years did not cause marked modification of growth, feed intake, functional behavior, or the incidence or type of tumors (Cabrol Telle et al. 1985).

Fire Hazard

Phosphine can explode with powerful oxidizers. The gas is heavier than air and may travel along the ground to an ignition source. Container may explode in heat of fire. When heated to decomposition, Phosphine emits highly toxic fumes of phosphorus oxides. Reacts violently with: air; boron trichloride; bromine; chlorine; chlorine monoxide; nitric acid; nitric oxide; nitrous oxide; nitrogen trioxide; silver nitrate; nitrous acid; mercuric nitrate; nitrogen trichloride; oxygen; and (potassium plus ammonia). Stable up to 131F. May become unstable at high temperatures.

Agricultural Uses

Fumigant, Insecticide: Phosphine gas is used indoors to control a broad spectrum of insects for non-food/non-feed commodities in sealed containers or structures. There are no homeowner or agricultural row crop uses for this product. The end-use product is a poisonous liquefied gas under pressure, and is A U.S. EPA restricted Use Pesticide (RUP) due to the acute inhalation toxicity of phosphine gas. Phosphine is only occasionally used in industry, and exposure usually results accidentally as a byproduct of various processes. Exposures may occur when acid or water comes in contact with metallic phosphides (aluminum phosphide, calcium phosphide). These two phosphides are used as insecticides or rodenticides for grain, and phosphine is generated during grain fumigation. Phosphine may also evolve during the generation of acetylene from impure calcium carbide, as well as during metal shaving, sulfuric acid tank cleaning, rustproofing, and ferrosilicon, phosphoric acid and yellow phosphorus explosive handling. U.S. EPA restricted Use Pesticide (RUP). Currently listed as “pending” in the EU.

Trade name

ECO2 FUME TM®; VAPORPH3OS®

Safety Profile

A poison by inhalation. A very toxic gas whose effects are not completely understood. The chef effects are central nervous system depression and lung irritation. There may be pulmonary edema, dilation of the heart, and hyperemia of the visceral organs. Inhalation can cause coma and convulsions leading to death within 48 hours. However, most cases recover without after-effects. Chronic poisoning, characterized by anemia, bronchitis, gastrointestinal disturbances, and visual, speech, and motor disturbances, may result from continued exposure to very low concentrations.Very dangerous fire hazard by spontaneous chemical reaction. Moderately explosive when exposed to flame. Explosive reaction with dichlorine oxide, silver nitrate, concentrated nitric acid, nitrogen trichloride, oxygen. Reacts with mercury(Ⅱ) nitrate to form an explosive product. Ignition or violent reaction with air, boron trichloride, Br2, Cl2, aqueous halogen solutions, iodine, metal nitrates, NOx NCh, NO3, N20, HN02, K + NH3, oxidants. The organic derivatives of phosphine (phosphines) react vigorously with halogens. To fight fire, use CO2, dry chemical, or water spray. Dangerous; when heated to decomposition it emits highly toxic fumes of POx. Used as a fumigant, doping agent for electronic components, and in chemical synthesis

Potential Exposure

Phosphine is used as a fumigant; in the semiconductor industry, as a doping agent for electronic components to introduce phosphorus into silicon crystals; in chemical synthesis; used as a polymerization initiator; as an intermediate for some flame retardants. Also, exposures may occur when acid or water comes in contact with metallic phosphides (aluminum phosphide, calcium phosphide). These two phosphides are used as insecticides or rodenticides for grain, and phosphine is generated during grain fumigation. When phosphine toxicity is suspected, but phosphine exposure is not obvious, one should suspect transdermal contamination and/or ingestion of phosphides. Phosphine may also evolve during the generation of acetylene from impure calcium carbide, as well as during metal shaving; sulfuric acid tank cleaning; rustproofing, ferrosilicon, phosphoric acid; and yellow phosphorus explosive handling.

First aid

If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 minutes, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, If phosphides have been ingested, do not induce emesis. Phosphides will release phosphine in the stomach; therefore, watch for signs similar to those produced by phosphine inhalation. Administer a slurry of activated charcoal at 1 gm/kg (usual adult dose: 6090 g; child dose: 2550 g). A soda can and a straw may be of assistance when offering charcoal to a child. Do not make an unconscious person vomit. Medical observation is recommended for 2448 hours after breathing overexposure, as pulmonary edema may be delayed. As first aid for pulmonary edema, a doctor or authorized paramedic may consider administering a drug or other inhalation therapy.

Shipping

UN2199 Phosphine, Hazard Class: 2.3; Labels: 2.3-Poisonous gas, 2.1-Flammable gas, Inhalation Hazard Zone A. Cylinders must be transported in a secure upright position, in a well -ventilated truck. Protect cylinder and labels from physical damage. The owner of the compressed gas cylinder is the only entity allowed by federal law (49CFR) to transport and refill them. It is a violation of transportation regulations to refill compressed gas cylinders without the express written permission of the owner.

Purification Methods

PH3 is best purified in a gas line (in a vacuum) in an efficient fume cupboard. It is spontaneously flammable, has a strong odour of decayed fish and is POISONOUS. The gas is distilled through solid KOH towers (two), through a Dry ice-acetone trap (-78o, to remove H2O, and P2H4 which spontaneously ignites with O2), then through two liquid N2 traps (-196o), followed by distillation into a -126o trap (Dry ice-methylcyclohexane slush), allowed to warm in the gas line and then sealed in ampoules preferably under N2. IR: max 2327 (m), 1121 (m) and 900 (m) cm-1 . [Klement in Handbook of Preparative Inorganic Chemistry (Ed. Brauer) Academic Press Vol I pp 525-530 1963, Gokhale & Jolly Inorg Synth IX 56 1967.] PH3 has also been absorbed into a solution of cuprous chloride in hydrochloric acid (when CuCl.PH3 is formed). PH3 gas is released when the solution is heated, and the gas is purified by passage through KOH pellets and then over P2O5. Its solubility is 0.26mL/1 mL of H2O at 20o, and a crystalline hydrate is formed on releasing the pressure on an aqueous solution.

Incompatibilities

Phosphine reacts with acids, air, copper, moisture, oxidizers, oxygen, chlorine, nitrogen oxides; metal nitrates; halogens, halogenated hydrocarbons; copper and many other substances, causing fire and explosion hazard. Extremely explosive; may ignite spontaneously on contact with air at (or about) 100C. Attacks many metals. Incompatible with oxidizers (chlorates, nitrates, peroxides, permanganates, perchlorates, chlorine, bromine,fluorine, etc.); contact may cause fires or explosions. Keep away from alkaline materials, strong acids, amines, ammonia, ethylene oxide, metal nitrates, nitrous acid, phosgene, strong bases.

Waste Disposal

Return refillable compressed gas cylinders to supplier. Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant (≥100 kg/mo) must conform with EPA regulations governing storage, transportation, treatment, and waste disposal. 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. Controlled discharges of Phosphine may be passed through 10% NAOH solution in a scrubbing tower. The product may be discharged to a sewer.

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Raw materials

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