ホスフィン 化学特性,用途語,生産方法
性質
ホスフィンは、同じ15族元素である窒素を含むアンモニアと非常に類似した構造を持っていますが、アンモニアと比較するとリン原子の非共有電子対がプロトンを受け取る力はかなり弱いです。塩基性は持ちますが、かなり弱塩基です。
ホスフィンの生成方法としては、二リン化三カルシウムに水を加えるという方法などがありますが、他にも黄リンに水酸化ナトリウムを加えた時に生じる粗ホスフィンガス (ホスフィンと水素ガスの混合物) を生成することによって製造する方法などがあります。
解説
ホスフィン，リンの水素化物とそのアルキル，アリール置換体の総称であるが，普通には水素化リンPH3をさす．PH3(34.00)は黄リンをKOH水溶液と煮沸するか，リン化カルシウムCa3P2を加水分解すると得られる．天然にも含リン有機物(魚など)の腐敗の際に少量生じる．無色，悪臭(魚などの腐敗臭)のある気体．気体分子は三方すい型．密度0.746 g cm－3(－90 ℃)．P-H約1.42 Å．∠H-P-H約93°．融点－133 ℃，沸点－87.7 ℃．水に微溶．氷酢酸，CS2に易溶．普通は微量のジホスファンP2H4を含むため，空気に触れると自然発火する(純粋なら150 ℃ で発火)．酸素，ハロゲン単体とはげしく反応する．金属と反応してリン化物をつくる．還元性が大きい．有機反応原料，ホスフィン錯体の製造原料，穀物の燻(くん)蒸などに用いられる．猛毒．
用途
N型エピタキシャル成長シリコン、ドープした酸化シリコンのデポジッション、イオン注入用などのドーパントガス
危険性
ホスフィンは常温の空気中で酸素と反応して自然発火し、爆発を引き起こしてしまう恐れがあります。また、極めて毒性が強いため、体内に摂取してしまうと、肺水腫などを引き起こしてしまい、死に至る可能性があります。
保管する際にはボンベ中に厳重に保管、管理を行い、使用する際には絶対に人の肌、口、目に触れないよう注意が必要です。毒物および劇物取締法では、「毒物 (リン化水素およびこれを含有する製剤) 」に該当します。GHS分類においては、可燃性ガスが区分1、急性毒性が区分1、特定標的臓器毒性が区分1に指定されています。
参考文献
説明
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.
化学的特性
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.
物理的性質
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.
天然物の起源
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, P
2H
4) 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.
使用
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.
定義
ChEBI: The simplest phosphine, consisting of a single phosphorus atom with three hydrogens attached.
調製方法
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 85C. 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.
空気と水の反応
Highly flammable. Usually ignites spontaneously in air. Burns with a luminous flame [Merck 11th ed. 1989]. Insoluble in water.
反応プロフィール
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].
危険性
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.
健康ハザード
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.
火災危険
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.
大気中のホスフィン
ホスフィンは、地球の大気中にわずかに存在しています。これは部分的な還元と不均化による有機物の分解により、生物学的に生成されたと考えられてきました。
また、木星の乱気流中にもホスフィンは存在しており、これは木星の内部で生成されているとされています。木星での大気中のホスフィンは別の物質と絶えず反応をしています。
使用用途
1. 半導体の原料
ホスフィンは、半導体製造における原料物質として使用されています。非共有電子対を持っており電子豊富なため、ドーピング剤としてケイ素をn形半導体にする場合に用いられています。また、InGaP (インジウムガリウムリン) など、半導体を製造する際の不純物を添加する目的でも有用です。
これらの半導体は、DVD 等の光ディスク向けレーザーダイオード、光ファイバー通信向けレーザーダイオード、受光ダイオードや高輝度発光ダイオード、携帯電話向けの電子デバイスなどに使用されてきました。
2. リンを含む化合物の製造
高純度のホスフィンガスを熱分解することによって黄リンを、さらに熱を加えることで赤リンを合成可能です。また、ホスフィンはさまざまなリンを含む化合物の原料です。ホスフィンはラジカル付加やマイケル付加、酸触媒や置換反応などのさまざまな反応を起こすことができるため、多種多様なリン原子を含む有機化合物の原料として使用されています。
3. 殺虫剤
穀物類の貯蔵庫において、主に害虫駆除や防カビ・殺菌を目的とした燻蒸作業にホスフィンが使用されます。ホスフィンは、大気中に均一に広まりやすく、「対象物の隙間に深く浸透する」「堅い種子の殻も透過する」という利点があるためです。
农业用途
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.
製品名
ECO2 FUME TM®; VAPORPH3OS®
材料の用途
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.
安全性プロファイル
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
職業ばく露
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.
環境運命予測
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.
貯蔵
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.
輸送方法
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.
純化方法
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.
不和合性
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.
廃棄物の処理
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.
ホスフィン 上流と下流の製品情報
原材料
準備製品