포스핀(기체)

포스핀(기체) 속성

포스핀(기체) C화학적 특성, 용도, 생산

개요

Phosphine is a colorless, flammable gas that is heavier than air and has a characteristic odor described as being similar to decaying fish. Pure phosphine is claimed to be odorless, even at a level of 200 ppm. The odor threshold for commercially available phosphine ranges from 0.02 ppm to 3 ppm. It has an autoignition temperature of 100°F (37.8°C) and ignites spontaneously when traces of other phosphorous hydrides such as diphosphine are present. For all practical purposes, phosphine should be handled both as a pyrophoric and highly toxic gas.
Phosphine is stable at room temperature and begins to decompose at about 707°F (375°C), with complete decomposition at about 1100°F (593°C). Phosphine is readily oxidized by common oxidizers such as potassium permanganate and sodium hypochlorite. Unlike arsine, it will have some reaction with the alkalis. Phosphine is a strong reducing agent and can precipitate a number of heavy metals from solutions of their salts. It will react violently with oxidizers such as oxygen, chlorine, fluorine, and nitric oxide.
Phosphine is shipped in the pure form as a liquefied gas, and is also commonly available as a mixture when blended with hydrogen or inert gases.

화학적 성질

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.

물리적 성질

Colorless gas with an odor of decaying fish; flammable; burns with a luminous flame; density 1.492 g/L; liquefies at -87.7°C; solidifies at -133°C; critical temperature 51.35°C; critical pressure 64.55 atm; slightly soluble in water; the solution is weakly basic.

출처

Phosphine is produced naturally in small amounts in marshy lands, especially in damp graveyards, resulting from bacterial decay of animal and vegetable matter containing phosphorus. The atmospheric oxidation of impure phosphine (containing trace amounts of diphosphine, P₂H₄) emits pale flickering lights, the so-called “Will o’ the wisps” or “corpse candles” seen on dark nights. The compound has very little commercial application. It is used to prepare phosphonium salts, which also can be made by other processes.

용도

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.

생산 방법

Phosphine, also known as phosphorated hydrogen or hydrogen phosphide (PH3), has no direct commercial use. However, it may be generated from aluminum or zinc phosphide and water for grain fumigation. It may be present in phosphorus as a polymer or generated at low rates under alkaline conditions and at a temperature of 85
C. The generation of acetylene from calcium carbide containing calcium phosphide as an impurity and metal processing procedures in which phosphides are formed are the most frequent sources of industrial hygiene problems with phosphine.

정의

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

공기와 물의 반응

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

반응 프로필

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].

위험도

Phosphine is a highly toxic and flammable gas. Acute effects are irritation, tightness of chest, painful breathing, and lung damage. High concentration can be fatal. A fire hazard.

건강위험

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.

화재위험

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.

농업용

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.

상품명

ECO2 FUME TM®; VAPORPH3OS®

Materials Uses

Phosphine is noncorrosive and, therefore, may be used with most ofthe commercially available metals. However, since phosphine is mainly used for the electronics industry, type 316 and 316L stainless steel is recommended for the gas delivery systems. Stainless steel regulators should be used for all high purity applications with phosphine and phosphine mixtures. In all cases, systems should be adequately designed to withstand the pressures to be encountered.

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

잠재적 노출

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.

환경귀착

Because of its very high vapor pressure, phosphine exists in air as a gas and volatilizes from water and surface soil. At high concentrations, the vapors may spontaneously combust in air. Atmospheric phosphine may be degraded by photochemically produced hydroxyl radicals with an expected half-life of less than 1 day. Phosphine can bind to subsurface soils and is degraded quickly. The chemical does not accumulate in the food chain.

저장

Since phosphine is an extremely toxic and flammable gas, appropriate precautions must be taken in its storage and handling. Store and use phosphine and phosphine mixtures only in ventilated gas cabinets, exhaust hoods, or highly ventilated rooms that supply a large volume of forced air ventilation. Explosion-proof forced draft gas cabinets or fume hoods are recommended. Use piping and equipment adequately designed to withstand the pressures to be encountered.
Since phosphine may form explosive mixtures with air, keep it away from heat and all ignition sources such as flames and sparks. All lines, connections, equipment, etc. must be thoroughly checked for leaks and grounded prior to use. Only use spark-proof tools and explosion-proof equipment. The compatibility with plastics and elastomers should be confirmed.
For basic safety information on the handling of compressed gas cylinders, refer to CGA P-I, Safe Handling of Compressed Gases in Containers.

운송 방법

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.

비 호환성

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.

폐기물 처리

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.

포스핀(기체) 준비 용품 및 원자재

원자재

아인산 3-Amino-4-chlorobenzenesulfonic acid

준비 용품

포노포스 1,4-Bis(4-cyanostyryl)benzene U-47319 프로피온알데히드 n-뷰탈알데히드 Pazinaclone 산화 란탄 THIOPHEN-2-YLMETHYL-PHOSPHONIC ACID DIETHYL ESTER fluorescent whitening agent ATS-X Beraprost 칼슘 하이포인산염 Ferric pyrophosphate

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