14977-61-8 Usage
Description
Chromyl chloride, also known as chromium(VI) oxide dichloride, is a dark red covalent liquid with a musty, burning odor. It is a highly reactive compound that is corrosive to tissue and is 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 reacts with solutions of alkalis to produce chromate ions. It is used as an oxidizing agent in organic chemistry and is known for its ability to oxidize methyl groups at the ends of aromatic side chains to aldehyde groupings (étard’s reaction).
Uses
1. Used in Organic Chemistry:
Chromyl chloride is used as an oxidizing agent for organic oxidations and chlorinations. It is particularly effective in the oxidation of hydrocarbons and in the preparation of various coordination complexes of chromium.
2. Used in the Production of Chromium Dioxide (CrO2) Thin Films:
Chromyl chloride is used as a precursor in the chemical vapor deposition process to deposit highly spin-polarized chromium dioxide (CrO2) thin films on 100 TiO2 substrates.
3. Used as a Solvent for Chromium Oxide:
Chromyl chloride serves as a solvent for chromium oxide, which is useful in various chemical reactions and processes.
4. Used in the Polymerization of Olefins:
Chromyl chloride acts as a catalyst for the polymerization of olefins, a process that is essential in the production of various plastics and synthetic materials.
5. Used in the Etard Reaction:
Chromyl chloride is used in the Etard reaction for the production of aldehydes and ketones, which are important intermediates in the synthesis of various organic compounds.
6. Used in the Preparation of Various Coordination Complexes of Chromium:
Chromyl chloride is utilized in the preparation of different chromium coordination complexes, which have applications in various fields, including catalysis and materials science.
Physical Properties:
Chromyl chloride is a dark red, fuming liquid with reddish-yellow vapors. It has a density of 1.91 g/mL and freezes at -96.5°C. It boils at 117°C and reacts with water. The compound is soluble in chloroform, carbon tetrachloride, benzene, carbon disulfide, and nitrobenzene.
Preparation
Chromyl chloride is prepared by reacting chromium(III) chloride with hydrochloric acid: CrO3 + 2HCl → CrO2Cl2 + H2O Also, it may be prepared by warming potassium dichromate with potassium chloride in concentrated sulfuric acid: K2Cr2O7 + 4KCl + 3H2SO4 → 2Cr2O2Cl2 + 3K2SO4 + 3H2O.
Reactivity Profile
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].
Hazard
Corrosive to tissue. Strong oxidizing agent.
Skin and upper respiratory tract irritant. Probable
carcinogen.
Health Hazard
Inhalation causes severe irritation of upper respiratory system. Contact with eyes or skin causes irritation and burning. Ingestion causes burning of mouth and stomach.
Fire Hazard
Behavior in Fire: Vapors are very irritating to eyes and mucous membranes. May increase severity of fire.
Safety Profile
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.
Potential Exposure
Chromium oxychloride is used in making chromium complexes and dyes; and used in various organic oxidation and chlorination reactions
Shipping
UN1758 Chromium oxychloride, Hazard class: 8; Labels: 8-Corrosive material.
Purification Methods
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.
Incompatibilities
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
Check Digit Verification of cas no
The CAS Registry Mumber 14977-61-8 includes 8 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 5 digits, 1,4,9,7 and 7 respectively; the second part has 2 digits, 6 and 1 respectively.
Calculate Digit Verification of CAS Registry Number 14977-61:
(7*1)+(6*4)+(5*9)+(4*7)+(3*7)+(2*6)+(1*1)=138
138 % 10 = 8
So 14977-61-8 is a valid CAS Registry Number.
InChI:InChI=1/2ClH.2Cr.5O/h2*1H;;;;;;;/q;;2*+1;;;;;/p-2/rCl2Cr2O5/c1-3(5,6)9-4(2,7)8
14977-61-8Relevant articles and documents
Thorpe, T. E.
, p. 514 - 515 (1868)
Seddon, Kenneth R.,Thomas, Valerie H.
, (1977)
Chromyl complexes with aryloxy and siloxy ligands
Stavropoulos, Pericles,Bryson, Nathan,Youinou, Marie-Thérèse,Osborn, John A.
, p. 1807 - 1811 (2008/10/08)
Interaction of CrO3 and 1 equiv of Ph3CCl in dichloromethane yields a mixture of CrO2Cl2, CrO2Cl(OCPh3) (1), and CrO2-(OCPh3)2 (2). Fractional crystallization gives pure samples of red 1 and orange 2, which have been characterized by X-ray diffraction. Crystal data for 1: space group P1; a = 9.913 (3), b = 10.173 (3), c = 9.019 (3) ?; α = 92.93 (2), β = 92.74 (2), γ = 110.84 (3)°; Z = 2; R1 = 0.044, R2 = 0.059. Crystal data for 2: space group C2/c; a = 23.857 (6), b = 8.759 (3), c = 15.105 (5) ?; β = 110.48 (3)°; Z = 4; R1 = 0.036, R2 = 0.057. A similar result was obtained on reaction of CrO3 and 1 equiv of Ph3SiCl, giving CrO2Cl2, CrO2Cl(OSiPh3) (3), and CrO2(OSiPh3)2 (4). These results are compared with the in situ systems CrO3/Me3SiCl and CrO3/Me3SiOSiMe3, which have been studied by 1H NMR spectroscopy and EI mass spectrometry.
Characterisation of Chromium(VI) Oxide Tetrafluoride, CrOF4, and Caesium Pentafluoro-oxochromate(VI) Cs
Hope, Eric G.,Jones, Peter J.,Levason, William,Ogden, J. Steven,Tajik, Mahmoud,Turff, Jeremy W.
, p. 529 - 534 (2007/10/02)
The title compounds have been characterised by elemental analyses, i.r. and u.v. - visible spectroscopy, and some of their reactions are described.Matrix isolation studies on CrOF4 show characteristic i.r. absorptions at 1027.7 and 746.3, 741.6 cm-1 in nitrogen matrices, which are assigned as the A1 (Cr=O) and E(Cr-F) modes respectively of the C4v monomer.Chromium isotope fine structure and relative intensity estimates suggest a bond angle of ca. 106 deg for OCrF.The electronic spectrum of matrix-isolated CrOF4 shows prominent charge-transfer bands at 40000 and 27000 cm-1.