ジクロロジオキソクロム(VI) 化学特性,用途語,生産方法
解説
CrO2Cl2(154.90)．二塩化二酸化クロム(Ⅵ)ともいう．アルカリ金属(ナトリウム，カリウムなど)の二クロム酸塩と塩化物とを混合し，これに濃硫酸を加えて蒸留するか，酸化クロム(Ⅵ)と乾燥した塩化水素の作用で得られる．融点－96.5 ℃，沸点117 ℃．臭素に似た血赤色の液体で，湿った空気中で発煙する．水には溶けにくいが，すみやかに加水分解を受けてクロム酸を生じる．二硫化炭素，クロロホルム，四塩化炭素に可溶．熱や光によって分解される．強い酸化剤で，有機物とは爆発的に反応することもある．オレフィン類の重合触媒，炭化水素の酸化剤に用いられる．そのほか，染料やクロムの錯体の製造，塩化クロミル反応にも用いられる．塩化クロミル反応：Cl－ を含む試料に二クロム酸カリウムと硫酸を加えて加熱すると血赤色の塩化クロミルの蒸気を発生する．これを水中に導き水酸化アルカリを加えると黄色のクロム酸アルカリの溶液となる．この溶液を酸性にしたのち，エチルエーテルと過酸化水素を加えて振ると青色の過クロム酸がエーテル層に移る．ヨウ素や臭素では揮発性のクロム化合物を生成しないので，この反応は Cl－ の検出反応として利用される．有毒．[CAS 14977-61-8]
森北出版「化学辞典（第2版）
化学的特性
Chromyl chloride is a dark red fuming liquid with a musty, burning odor.
物理的性質
Dark red, fuming liquid; reddish yellow vapors; musty buring odor; density 1.91 g/mL; freezes at -96.5°C; boils at 117°C; reacts with water; soluble in chloroform, carbon tetrachloride, benzene, carbon disulfide and nitrobenzene.
使用
Highly spin-polarized chromium dioxide (CrO2) thin films were deposited on 100 TiO2 substrates by chemical vapor deposition using chromyl chloride as a precursor. Chromyl chloride (Cr02C12) reacts with cyclohexane solvent at 75 OC to give a dark precipitate along with chlorocyclohexane and a small amount of cyclohexene (in 10.0 and ca. 0.3% yields based on chromium). Chromyl chloride, CrO2C12, oxidizes cyclooctane, isobutane, and toluene under mild conditions (25-60" C). The reactions give chlorinated products (chlorocyclooctane, tert- butyl chloride, and benzyl chloride) and a dark chromium-containing precipitate. Used for Organic oxidations and chlorination, chromium coordination complexes, catalyst for polymerization of olefins. Chromyl chloride in carbon tetrachloride solution reacts in the cold with cyclohexene, cyclopentene, and 1-hexene to give the various isomeric chlorohydrins as the major products.
製造方法
Chromyl chloride is prepared by reacting chromium(III) chloride with hydrochloric acid:
CrO
3 + 2HCl → CrO
2Cl
2 + H
2O
Also, it may be prepared by warming potassium dichromate with potassium chloride in concentrated sulfuric acid:
K
2Cr
2O
7 + 4KCl + 3H
2SO
4 → 2Cr
2O
2Cl
2 + 3K
2SO
4 + 3H
2O.
定義
A dark red covalent liquid
prepared either by distilling a dry mixture
of potassium dichromate and sodium chloride
with concentrated sulfuric acid or by
the action of concentrated sulfuric acid on
chromium(VI) oxide dissolved in concentrated
hydrochloric acid. Chromyl chloride
is hydrolyzed by water, and with solutions
of alkalis it undergoes immediate hydrolysis
to produce chromate ions. It is used as
an oxidizing agent in organic chemistry.
Chromyl chloride oxidizes methyl groups
at the ends of aromatic side chains to aldehyde
groupings (étard’s reaction).
一般的な説明
A dark red fuming liquid with a pungent odor. Corrosive to tissue.
反応プロフィール
Chromyl chloride is a powerful and often violent oxidizing agent. Reacts readily with many inorganic and organic materials in the absence of a dilutent. Contact with hydrogen sulfide or phosphine can cause ignition. Contact with phosphorus tribromide, acetone, ethanol, ether, and turpentine causes ignition. Contact with moist phosphorus or with phosphorus trichloride leads to explosive reaction. Contact with ammonia causes incandescence. Reacts with sodium azide to form chromyl azide, which is explosive in the absence of a dilutent. Causes ignition of flowers of sulfur and of urea on contact. [Bretherick, 1979, p. 822-823].
危険性
Corrosive to tissue. Strong oxidizing agent.
Skin and upper respiratory tract irritant. Probable
carcinogen.
健康ハザード
Inhalation causes severe irritation of upper respiratory system. Contact with eyes or skin causes irritation and burning. Ingestion causes burning of mouth and stomach.
火災危険
Behavior in Fire: Vapors are very irritating to eyes and mucous membranes. May increase severity of fire.
安全性プロファイル
Suspected carcinogen.
Probably a poison by various routes.
Mutation data reported. Corrosive. A strong
irritant. Hydrolyzes to form chromic and
hydrochloric acids. A strong oxidner and
chlorinating agent. Violent reaction with
water. Reacts violently with alcohol, ether,
acetone, turpentine. Ignites or explodes on
contact with nonmetal halides (e.g., disulfur
dichloride, phosphorus trichloride, and
phosphorus tribromide), nonmetal hydrides
(e.g., hydrogen sulfide and hydrogen
phosphide), flowers of sulfur, moist
phosphorus, sodium azide, and urea. During
preparation can violently explode.
Incompatible with ammonia, disulfur
dichloride, organic solvents, phosphorus,
phosphorus trichloride, sodium azide, and
sulfur. When heated to decomposition it
emits toxic fumes of Cl-. See also
CHROMIUM COMPOUNDS.
職業ばく露
Chromium oxychloride is used in making chromium complexes and dyes; and used in various organic oxidation and chlorination reactions
輸送方法
UN1758 Chromium oxychloride, Hazard class: 8; Labels: 8-Corrosive material.
純化方法
Purify it by distillation under reduced pressure. It hydrolyses violently with H2O and is a powerful oxidant which explodes with P, and ignites in contact with S, NH3, EtOH and many organic compounds. TOXIC.
不和合性
Contact with water is violent and forms hydrochloric and chromic acids, and chlorine gas. A powerful oxidizer. Reacts violently with acetone, alcohol, ammonia, ether, fuels, organic solvents, moist phosphorus, phosphorus trichloride; sodium azide; sulfur, reducing agents; turpentine. Contact with nonmetal halides, such as disulfur dichloride, phosphorus trichloride; and phosphorus tribromide; nonmetal hydrides, such as hydrogen sulfide; hydrogen phosphide, and urea, causes a danger fire and explosion hazard
ジクロロジオキソクロム(VI) 上流と下流の製品情報
原材料
準備製品