ホスフィン
三水素化りん · りん化水素 · ホスフィン · ホスフィンガス · ホスファン · 水素化リン · 燐化水素 · PH3
識別子と物理属性
| CAS No. | 13967-14-1 |
|---|---|
| 分子式 | H3P |
| 平均分子量 | 33.998 g/mol |
| 単同位体質量 | 33.99723673 g/mol |
| SMILES | P |
| InChIKey | XYFCBTPGUUZFHI-UHFFFAOYSA-N |
| PubChem CID | 24404 |
| ChEMBL | CHEMBL2227836 |
| ChEBI | CHEBI:30278 |
| EC No. | 232-260-8 |
| DTXSID | DTXSID2021157 |
| 現地名 | ホスフィン |
化学・物理的性質
| XLogP | -0.1 |
|---|---|
| 極性表面積 | 0 |
| 水素結合供与体数 | 0 |
| 水素結合受容体数 | 0 |
| 回転可能結合数 | 0 |
| 重原子数 | 1 |
| 形式電荷 | 0 |
| 複雑度 | 0 |
| 物質分類 | Hazardous Air Pollutants (HAPs)Toxic Gases & Vapors -> HydridesFlammable agents - 4th degree-> NIOSH Emergency Response Categories |
| pH | SOLN ARE NEUTRAL |
| SpringerMaterials Properties | Coriolis coupling |
| 農薬 | Pesticide -> EPA IRISInsecticidesActive substance -> EU Pesticides database: Approved |
| 臭い | Disagreeable, garlic-like odor.Almost odorless in purest form, but odor of decaying fish when occurring industrially.Foul odor of decaying fishFish- or garlic-like odor [Note: Pure compound is odorless]. |
| 密度 | 0.746 at -130 °F (EPA, 1998) - Less dense than waterwill float1.390 g/L at 25 °CDensity: 1.529 g/L at 0 °CDensity (gas): 1.53 kg/m³Relative density (water = 1): 0.80.491 (estimate) |
| Color/Form | Colorless gasflammableColorless gas [Note: Shipped as a liquefied compressed gas]. |
| 溶解度 | Slight (NIOSH, 2024)Slightly soluble in water (0.26 volume at 20 °C)Insoluble in waterSlightly soluble in cold water. Insoluble in hot water.Soluble in alcohol, ether, and cuprous chloride solutionSlightly soluble in ethanol, etherinsoluble in H2Oslightly soluble in ethanol, ethyl etherH2O (20℃) に 0.26 容、熱水に不溶、エタノール、エーテル、塩化第一銅溶液に難溶 [HAW93][MER06] |
| 引火点 | Flammable gasNA (Gas) |
| 沸点 | -126 °F at 760 mmHg (EPA, 1998)-87.75 °C-87.7 °C-87.75 °C @760 [mm Hg]−87.5 °C(lit.) |
| Decomposition | Hazardous decomposition products formed under fire conditions - Oxides of phosphorus.When heated to decomposition it emits toxic fumes of /phosphorus oxides/. |
| 融点 | -207 °F (EPA, 1998)-133.8 °C-132.5 °C-133 °C-209 °F-133° |
| 蒸気密度 | 1.15 (vs air) |
| 蒸気圧 | 3905kPa at 25℃ |
| 外観・状態 | 無色のガス |
| 色 | colorless gasflammable |
| 比熱容量 | Cp(gas): 1.09 J/(g·K), at 25℃ |
| Merck | 13,7424 |
| ヘンリー定数 | 8.1×10-5 mol/(m3Pa) at 25℃, Wilhelm et al. (1977) |
| 誘電率 | 2.5(-60℃) |
| 安定性 | 安定しているが、空気中で自然発火しやすい。非常に広い爆発限界に注意してください。酸化剤、ハロゲン、硝酸とは相容れない。 |
| CAS データベース | 7803-51-2(CAS DataBase Reference) |
| NISTの化学物質情報 | Phosphine(7803-51-2) |
| EPAの化学物質情報 | Phosphine (7803-51-2) |
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.
安全性と法規制
| GHS 分類 | DangerH220: Extremely flammable gas [Danger Flammable gases]P203, P210, P222, P260, P264, P271, P273, P280, P284, P301+P330+P331, P302+P361+P354, P304+P340, P305+P354+P338, P316, P320, P321, P363, P377, P381, P391, P403, P403+P233, P405, and P501 (click each P-code to see the statement)H220 (100%): Extremely flammable gas [Danger Flammable gases]P203, P210, P222, P260, P264, P271, P273, P280, P284, P301+P330+P331, P302+P361+P354, P304+P340, P305+P354+P338, P316, P320, P321, P363, P377, P381, P391, P403, P403+P233, P405, P410+P403, and P501 (click each P-code to see the statement) |
|---|---|
| Hazards Identification | Toxic/poison by inhalation (TIH/PIH) |
| 規制情報 | Chemical: PhosphineHazard Traits - HematotoxicityHepatotoxicity and Digestive System ToxicityNephrotoxicity and Other Toxicity to the Urinary SystemNeurotoxicityRespiratory ToxicityCouncil Directive (EEC) No 414/1991 (Repealed by Reg. EC No 1107/2009 (amended))Phosphine is listed on the EPA's Chemical Data Reporting (CDR) system. Manufacturers and importers of Phosphine are required to report information about their production and use of this chemical to the EPA under the Toxic Substances Control Act (TSCA). (40 eCFR Part 711)Dossier complete 08/566/EC, Reg. (EU) 2018/155, Reg. (EU) 2024/324, Reg. (EU) No 1043/2012, Reg. (EU) No 2023/114Status: Active Update: 20-04-2023 https://echa.europa.eu/registration-dossier/-/registered-dossier/18616 |
| その他の安全情報 | IMAP assessments - Phosphine: Environment tier I assessment- Indoor Air: Phosphine can be released into indoor air as a gas. |
| 輸送ラベル（DOT） | Poison Gas Flammable Gas |
| 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, it emits highly toxic fumes of phosphorus oxides. Reacts violently with: airboron trichloridebrominechlorinechlorine monoxidenitric acid |
用途
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
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.
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, 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.
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.
製法・合成法
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.
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.