1H-トリアジリン 化學(xué)特性,用途語,生産方法
解説
HN3(43.03)．窒化水素酸，ヒドラゾ酸ともいう．アジ化ナトリウムに酸を作用させると得られる．室溫では無色，揮発性の液體．密度1.13 g cm－3．融點(diǎn)－80 ℃，沸點(diǎn)35.7 ℃．気體分子は，N-N-Nは直線狀で，∠H-N-Nは114°の折れ線形構(gòu)造である．不安定で，加熱，光などにより分解する．アジ化水素の水溶液はアジ化水素酸といい，弱酸性を示す．HN3 ＋ H2O ? H3O＋ ＋ N3－(pKa 4.77(298 K))水溶液はかなり安定であるが，光照射で分解する．皮膚，粘膜をおかす．血圧降下を起こす．有毒．森北出版「化學(xué)辭典（第2版）
用途
工業(yè)用の砲弾起爆裝置に重金屬アジドとして使われる。
毒性
無色のフッ化水素に似た刺激臭のある流動性の液體。融點(diǎn)－80℃，沸點(diǎn) 37℃，比重 1.126。水に溶け酸性を示すので，水溶液をアジ化水素酸 (トリアゾ水素酸) という。電離定數(shù) 2.8×10-5 (25℃) 。有毒で蒸気を吸入すると粘膜をおかし，めまいを起す。爆発性。水溶液はやや安定であるが，濃溶液は不安定で白金黒の存在で爆発する。アジ化ナトリウムに硫酸を作用させてつくられる。
説明
Hydrazoic acid or hydrogen azide is a dangerous explosion risk when shocked or heated. It is the gas-forming agent in many air bag systems in automobiles and escape chutes in airplanes.
化學(xué)的特性
Colorless, volatile liquid; obnoxious
odor.Soluble in water.
物理的性質(zhì)
Colorless, volatile liquid; pungent disagreeable odor; density 1.09 g/mL;solidifies at -80°C; boils at 37°C; highly soluble in water; soluble in alkalies,alcohol and ether; pKa4.6 at 25°C.
使用
Hydrazoic acid is used in making heavymetal azides for detonators. It forms readilywhen sodium azide reacts with acid orhydrazine is mixed with nitrous acid.
定義
A colorless liquid
with a nauseating smell. It is highly poisonous
and explodes in the presence of oxygen
and oxidizing agents. It can be made by
distilling a mixture of sodium azide
(NaN
3) and a dilute acid. It is usually used
as an aqueous solution. The salts of hydrazoic
acid (azides), especially lead azide
(Pb(N
3)
2), are used in detonators because
of their ability to explode when given a mechanical
shock.
製造方法
Hydrazoic acid is prepared by reacting sulfuric acid with sodium azide:
H
2SO
4 + NaN
3 → HN
3 + Na
2SO
4
or by treating hydrazine with nitrous acid:
N
2H
4 + HNO
2 → HN
3 + 2H
2O
or by heating sodium amide with nitrous oxide:
NaNH
2 + N
2O → HN
3 + NaOH
調(diào)製方法
Hydrazoic acid is formed (1) by reaction of sodium nitrate with molten sodamide, (2) by reaction of nitrous oxide with molten sodamide, (3) by reaction of nitrous acid and hydrazinium ion (N2H5 + ), (4) by oxidation of hydrazinium salts, (5) by reaction of ethyl nitrite with NaOH solution and acidifying.
反応性
Hydrazoic acid reacts (1) with metals, e.g., magnesium, aluminum, zinc, iron, to form azides or hydrazoates (or trinitrides), (2) with heavy metal salt solutions to form insoluble azides, e.g., silver azide AgN3, mercury(I) azide HgN3, lead azide PbN6. Silver, mercury(I), and copper(I) azides decompose in the light to form nitrogen plus the metal. (3) It reacts with NH4OH to form ammonium azide NH4·N3, (4) with hydrazine to form hydrazine azide N2H4·HN3, (5) with sodium hypochlorite plus acetic acid to form chlorazide ClN3, explosive, (6) with sodium amalgam to form NH3 with some hydrazine, (7) with potassium permanganate to form nitrogen and H2O.
危険性
Dangerous explosion risk when shocked or
heated. Strong irritant to eyes and mucous membranes.
健康ハザード
The acute toxicity of hydrazoic acidthrough inhalation and other routes of exposurehas been found to be high to very high.The symptoms and the intensity of poisoningare similar to sodium azide. It is, however,less toxic than hydrogen cyanide. Inhumans, inhalation of its vapors can produceirritation of eyes and respiratory tract, bronchitis,headache, dizziness, weakness, anddecreased blood pressure (Matheson 1983).Prolonged exposure to high concentrationscan result in collapse, convulsion, and death.An exposure to 1100 ppm for 1 hour waslethal to rats. Chronic exposure to a lowlevel of this compound in air may producehypotension.
Animals given intraperitoneal dosages ofhydrazoic acid showed the symptoms ofheavy breathing, convulsions, depression,and fall in blood pressure. It affected thecentral nervous system, but no damage wasobserved in the liver or kidney.
LD50 value, intraperitoneal (mice): 22 mg/kg.
火災(zāi)危険
In pure form or highly concentrated solution,
hydrazoic acid is a dangerous explosive compound.
It is unstable and sensitive to heat
and shock. The explosion hazard decreases
significantly with more dilute solutions.
It forms shock-sensitive metal azides
when react with metal salts, and fluorine
azide with fluorine (Lawless and Smith 1968)
and susceptible to form chlorine azide and
bromine azide with chlorine gas and bromine
vapor. All these products can explode violently
on impact. With carbon disulfide it
forms a violently explosive salt (Mellor
1946; NFPA 1997).
廃棄物の処理
Hydrazoic acid may be destroyed by convertingit to sodium azide. The latter isdecomposed with nitrous acid in a hood(National Research Council 1995). The followingmethod is used. It is diluted in waterto a strength below 5%; or its solution inorganic solvents that is immiscible in wateris shaken vigorously with water in a separatoryfunnel. The aqueous solution containinghydrazoic acid is neutralized with sodiumhydroxide and separated from any organiclayer. Sodium azide, so formed, is destroyedby reacting the aqueous solution with anexcess of sodium nitrite followed by 20%sulfuric acid until the solution is acidic. Thereaction is carried out in a three-necked flaskequipped with a stirrer, a dropping funnel,and a gas outlet line to vent out nitric oxide.The reaction mixture is flushed down thedrain.
參考文獻(xiàn)
S. Musso, et al., Inorg. Chem., 34, 3329 (1995), DOI: 10.1021/ic00116a027.
1H-トリアジリン 上流と下流の製品情報
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