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Chromium(VI) oxide(CAS No. 1333-82-0)

Chromium(VI) oxide CrO3 (cas 1333-82-0) Molecular Structure

1333-82-0 Structure

Identification and Related Records

【Name】
Chromium(VI) oxide
【CAS Registry number】
1333-82-0
【Synonyms】
Chromic acid, polymer-supported
Chromic anhydride
Chromium trioxide
Chromiumoxide
Chromic acid
Chromium Oxide
【EINECS(EC#)】
215-607-8
【Molecular Formula】
CrO3 (Products with the same molecular formula)
【Molecular Weight】
99.99
【Inchi】
InChI=1/Cr.3O/rCrO3/c2-1(3)4
【InChIKey】
WGLPBDUCMAPZCE-UHFFFAOYSA-N
【Canonical SMILES】
O=[Cr](=O)=O
【MOL File】
1333-82-0.mol

Chemical and Physical Properties

【Appearance】
dark red crystals or powder
【Density】
2.7g/cm3
【Melting Point】
196℃
【Boiling Point】
330℃
【Flash Point】
250℃
【Water】
1660 g/L (20℃)
【Solubilities】
Highly soluble
【Color/Form】
Dark red, bipyramidal prismatic crystals, flakes or granular powder
Brown solid
Flake, ground powder form
Dark-red flakes or powder [Note: Often used in an aqueous solution (H2CrO4)].
【Stability】
Stable. Strong oxidizer. Reacts with most organic material in a violent and often explosive fashion. Moisture sensitive.
【HS Code】
28191000
【Storage temp】
Do not store near combustible materials. Store in a tightly closed container. Store in a cool, dry, well-ventilated area away from incompatible substances. Corrosives area.
【Computed Properties】
Molecular Weight:99.9943 [g/mol]
Molecular Formula:CrO3
H-Bond Donor:0
H-Bond Acceptor:3
Rotatable Bond Count:0
Exact Mass:99.925256
MonoIsotopic Mass:99.925256
Topological Polar Surface Area:51.2
Heavy Atom Count:4
Formal Charge:0
Complexity:61.8
Isotope Atom Count:0
Defined Atom Stereocenter Count:0
Undefined Atom Stereocenter Count:0
Defined Bond Stereocenter Count:0
Undefined Bond Stereocenter Count:0
Covalently-Bonded Unit Count:1

Safety and Handling

【Hazard Codes】
O:Oxidizingagent;T+:Verytoxic;N:Dangerousfortheenvironment;
【Risk Statements】
R24/25;R26;R35;R42/43;R45;R46;R48/23;R50/53;R62;R9
【Safety Statements 】
S45;S53;S60;S61
【HazardClass】
5.1
【Safety】
Hazard Codes: OxidizingO,Very toxicT+,Dangerous for the environmentN,ToxicT
Risk Statements: 45-46-9-24/25-26-35-42/43-48/23-50/53-62-8
R45:May cause cancer.
R46:May cause heritable genetic damage.
R9:Explosive when mixed with combustible material.
R24:Toxic in contact with skin.
R25 :Toxic if swallowed.
R26:Very toxic by inhalation.
R35:Causes severe burns.
R42/43:May cause sensitization by inhalation and skin contact.
R50/53:Very toxic to aquatic organisms, may cause long-term adverse effects in the aquatic environment.
R8 :Contact with combustible material may cause fire.
R62:Risk of impaired fertility.
Safety Statements: 53-45-60-61-36/37/39-28-26-22
S53:Avoid exposure - obtain special instructions before use.
S45:In case of accident or if you feel unwell, seek medical advice immediately (show the label whenever possible.)
S60:This material and its container must be disposed of as hazardous waste.
S61:Avoid release to the environment. Refer to special instructions / safety data sheets.
S36/37/39:Wear suitable protective clothing, gloves and eye/face protection.
S28:After contact with skin, wash immediately with plenty of soap-suds.
S26: In case of contact with eyes, rinse immediately with plenty of water and seek medical advice.
S22:Do not breathe dust.
RIDADR: UN 1463 5.1/PG 2
WGK Germany: 3
RTECS: GB6650000
HazardClass: 5.1
PackingGroup: II
HS Code: 28191000
【PackingGroup 】
II
【Sensitive】
Hygroscopic
【Skin, Eye, and Respiratory Irritations】
Very irritating to eyes and respiratory tract.
Probably a severe eye, skin, & mucous membrane irritant.
【Transport】
UN 1463
【Fire Fighting Procedures】
Use water; however, the decomposing material will form a hot viscous foam & caution should be exercised against possibility of steam explosion.
Personal protection: wear full protective clothing.
【Fire Potential】
Powerful oxidizer contact with combustible material may cause fire.
Ignites on contact with alcohls, acetic anhydride + tetrahydronaphthalene, acetone, butanol, chromium(II) sulfide, cyclohexanol, dimethyl formamide, ethanol, ethylene glycol, methanol, 2-propanol, pyridine.
【Formulations/Preparations】
Technical: technical flake 99.75%
Crystal grade, high purity, less dust
【DOT Emergency Guidelines】
/GUIDE 141: OXIDIZERS - TOXIC/ Fire or Explosion: These substances will accelerate burning when involved in a fire. May explode from heat or contamination. Some may burn rapidly. Some will react explosively with hydrocarbons (fuels). May ignite combustibles (wood, paper, oil, clothing, etc.). Containers may explode when heated. Runoff may create fire or explosion hazard. /Chromium trioxide, anhydrous/
/GUIDE 141: OXIDIZERS - TOXIC/ Health: Toxic by ingestion. Inhalation of dust is toxic. Fire may produce irritating, corrosive and/or toxic gases. Contact with substance may cause severe burns to skin and eyes. Runoff from fire control or dilution water may cause pollution. /Chromium trioxide, anhydrous/
/GUIDE 141: OXIDIZERS - TOXIC/ Public Safety: CALL Emergency Response Telephone Number . As an immediate precautionary measure, isolate spill or leak in all directions for at least 50 meters (150 feet) for liquids and at least 25 meters (75 feet) for solids. Keep unauthorized personnel away. Stay upwind. Keep out of low areas. Ventilate closed spaces before entering. /Chromium trioxide, anhydrous/
/GUIDE 141: OXIDIZERS - TOXIC/ Protective Clothing: Wear positive pressure self-contained breathing apparatus (SCBA). Wear chemical protective clothing that is specifically recommended by the manufacturer. It may provide little or no thermal protection. Structural firefighters' protective clothing will only provide limited protection. /Chromium trioxide, anhydrous/
/GUIDE 141: OXIDIZERS - TOXIC/ Evacuation: Large spill: Consider initial downwind evacuation for at least 100 meters (330 feet). Fire: If tank, rail car or tank truck is involved in a fire, ISOLATE for 800 meters (1/2 mile) in all directions; also, consider initial evacuation for 800 meters (1/2 mile) in all directions. /Chromium trioxide, anhydrous/
/GUIDE 141: OXIDIZERS - TOXIC/ Fire: Small fires: Use water. Do not use dry chemicals or foams. CO2 or Halon may provide limited control. Large fires: Flood fire area with water from a distance. Move containers from fire area if you can do it without risk. Do not move cargo or vehicle if cargo has been exposed to heat. Fight fire from maximum distance or use unmanned hose holders or monitor nozzles. Cool containers with flooding quantities of water until well after fire is out. ALWAYS stay away from tanks engulfed in fire. For massive fire, use unmanned hose holders or monitor nozzles; if this is impossible, withdraw from area and let fire burn. /Chromium trioxide, anhydrous/
/GUIDE 141: OXIDIZERS - TOXIC/ Spill or Leak: Keep combustibles (wood, paper, oil, etc.) away from spilled material. Do not touch damaged containers or spilled material unless wearing appropriate protective clothing. Stop leak if you can do it without risk. Small dry spills: With clean shovel place material into clean, dry container and cover loosely; move containers from spill area. Large spills: Dike far ahead of spill for later disposal. /Chromium trioxide, anhydrous/
/GUIDE 141: OXIDIZERS - TOXIC/ First Aid: Move victim to fresh air. Call 911 or emergency medical service. Give artificial respiration if victim is not breathing. Administer oxygen if breathing is difficult. Remove and isolate contaminated clothing and shoes. Contaminated clothing may be a fire risk when dry. In case of contact with substance, immediately flush skin or eyes with running water for at least 20 minutes. Keep victim warm and quiet. Ensure that medical personnel are aware of the material(s) involved and take precautions to protect themselves. /Chromium trioxide, anhydrous/
【Reactivities and Incompatibilities】
Acetylene is oxidized violently.
Stirring chromium trioxide (added in small portions) with unheated /hexamethylphosphoramide/ leads to the formation of a complex useful for oxidizing alcohols to carbonyl derivatives. The trioxide must not be crushed before being added to the solvent, because violent decomposition may then occur.
Arsenic reacts with chromium trioxide with incandescence.
Ignition occurs when chromium trioxide comes in contact with a small portion of chromium sulfide.
Reacts violently with diethyl ether at room temperature.
Sodium or potassium reacts with chromium trioxide with incandescence.
Mixed with potassium ferricyanide an explosion occurred when the dust was ignited by a spark.
During the preparation of a chromium trioxide-pyridine complex, the proportion of the trioxide was increased. Since the trioxide dissolves in the pyridine by swelling, then rapidly dissolving with the evolution of heat, the excessive amount of chromium trioxide produced overheating, which resulted in an explosion and fire.
Selenium reacts violently with chromium trioxide.
Incompatibilities: pharmaceutical incompatibility: alcohol, ether, glycerol, spirit nitrous ether, & almost every organic substance; bromides, chlorides, iodides, hypophosphites, sulfites, & sulfides.
An attempt to prepare a 10% wt soln of chromic trioxide in n,n-dimethylformamide produced an almost instantaneous inflammation, followed by an eruption which forcibly ejected the contents of the flask onto the inner walls of the fume hood.
In the report of an explosion of mixtures of potassium permanganate & chromic trioxide by ch heathcock (chem eng news 59 (8): 9 (1981)). dauben et al (j org chem (34): 3587 (1969)), & ratcliffe & rodehurst (j org chem (35): 4000 (1970)) state that cooling & stirring are required & that chromic trioxide is added to the pyridine in chloroform soln. the pyridine is never added to chromic trioxide. an acetone-ice bath, proper stirring, & proper mixing of reagents are needed for safe handling of these oxidation systems.
Can react explosively with acetic anhydride, acetic acid, ethyl acetate, isoamyl alcohol, & benzaldehyde. less hazardous with ethylene glycol, furfural, glycerol, & methanol.
Can react violently with most metal powders, ammonia & ammonium salts, phosphorus, many finely divided organic cmpd, flammable liquids, acids, & sulfur.
Benzene may react vigorously with oxidizing agents such as chromic acid.
Bromine pentafluoride contact with chromium trioxide at ambient or slightly elevated temp is violent, ignition often occurring.
Violence of reaction depends on concn of peroxyformic acid and scale and proportion of reactants. The following observation was made with additions to 2-3 drops of ca 90% acid. Impure chromium trioxide cause violent decomp, sometimes accelerating to explosion.
In a study of hypergolic ignition of ethylene glycol by oxidants, chromium trioxide caused ignition on contact at ambient temp.
Interaction of the two oxidants chromium trioxide & chlorine trifluoride/ is incandescent.
Presence of nitric acid or nitrates in chromium trioxide may cause oxidation reactions to accelerate out of control.
A mixture of chromium trioxide and butyric acid became incandescent on heating to 100 deg C.
During oxidation of a sec-alcohol to ketone in cold dimethylformamide soln, addition of solid trioxide caused ignition. Addition of lumps of trioxide was later found to cause local ignition on addition to ice-cooled dimethylformamide under nitrogen. Addition of 2 g of chromium trioxide to 18 ml of solvent to form a 10 wt % soln caused immediate ignition and ejection of the flask contents.
Contact of the trioxide with the aprotic amide solvent /1,3-dimethylhexahydropyrimidone/ (dimethylpropyleneurea) is always explosive, with fire.
Hydrogen sulfide contact with the heated chromium trioxide causes incandescence.
Combustible materials may ignite or explode on contact with chromium trioxide. A few drops of oil which fell into a container of the oxide led to an explosion which produced fatal burns. If a few drops of 2-butanone contact solid chromium trioxide, a few seconds' delay ensues while some of the oxidant attains the critical temp of 330 deg C. Then combustion occurs with enough vigor to raise a fire-ball several feet, and spattering also occurs.
Butanol, isobutanol, acetaldehyde, propionaldehyde, butylaldehyde, benzaldehyde, acetic acid, pelargonic acid, ethyl acetate, isopropyl acetate, pentyl acetate, diethylether, methyldioxane, dimethyldioxane, acetone and benzylethlyaniline /cause possible ignition hazards/.
Phosphorus and the molten /chromium/ trioxide react explosively.
Mixtures of potassium hexacyanoferrate and chromium trioxide explode and inflame when heated above 196 deg C. Friction alone is sufficient to ignite violently the mixture when ground with silver sand.
A mixture sulfur & chromium trioxide ignites on warming.
Powerful oxidizer; oxidizes alcohol and most other organic substances, sometimes with dangerous violence.
【Other Preventative Measures】
Apply petrolatum or paraffin oils to nose before exposure.
The worker should immediately wash the skin when it becomes contaminated.
SRP: Local exhaust ventilation should be applied wherever there is an incidence of point source emissions or dispersion of regulated contaminants in the work area. Ventilation control of the contaminant as close to its point of generation is both the most economical and safest method to minimize personnel exposure to airborne contaminants.
SRP: Contaminated protective clothing should be segregated in such a manner so that there is no direct personal contact by personnel who handle, dispose, or clean the clothing. Quality assurance to ascertain the completeness of the cleaning procedures should be implemented before the decontaminated protective clothing is returned for reuse by the workers. Contaminated clothing should not be taken home at end of shift, but should remain at employee's place of work for cleaning.
SRP: The scientific literature for the use of contact lenses in industry is conflicting. The benefit or detrimental effects of wearing contact lenses depend not only upon the substance, but also on factors including the form of the substance, characteristics and duration of the exposure, the uses of other eye protection equipment, and the hygiene of the lenses. However, there may be individual substances whose irritating or corrosive properties are such that the wearing of contact lenses would be harmful to the eye. In those specific cases, contact lenses should not be worn. In any event, the usual eye protection equipment should be worn even when contact lenses are in place.
Work clothing that becomes wet or significantly contaminated should be removed and replaced.
Workers whose clothing may have become contaminated should change into uncontaminated clothing before leaving the work premises.
【Protective Equipment and Clothing】
Wear appropriate personal protective clothing to prevent skin contact.
Wear appropriate eye protection to prevent eye contact.
Eyewash fountains should be provided in areas where there is any possibility that workers could be exposed to the substance; this is irrespective of the recommendation involving the wearing of eye protection.
Facilities for quickly drenching the body should be provided within the immediate work area for emergency use where there is a possibility of exposure. [Note: It is intended that these facilities provide a sufficient quantity or flow of water to quickly remove the substance from any body areas likely to be exposed. The actual determination of what constitutes an adequate quick drench facility depends on the specific circumstances. In certain instances, a deluge shower should be readily available, whereas in others, the availability of water from a sink or hose could be considered adequate.]
Recommendations for respirator selection. Condition: At concentrations above the NIOSH REL, or where there is no REL, at any detectable concentration. Respirator Class(es): Any self-contained breathing apparatus that has a full facepiece and is operated in a pressure-demand or other positive pressure mode. Any supplied-air respirator that has a full facepiece and is operated in pressure-demand or other positive pressure mode in combination with an auxiliary self-contained breathing apparatus operated in pressure-demand or other positive pressure mode.
Recommendations for respirator selection. Condition: Escape from suddenly occurring respiratory hazards: Respirator Class(es): Any air-purifying, full-facepiece respirator with a high-efficiency particulate filter. Any appropriate escape-type, self-contained breathing apparatus.
【Specification】
Chromium trioxide (CAS NO.10043-01-3) is highly toxic, corrosive and carcinogenic. It is the main example of the environmental hazard known as "hexavalent chromium". The related chromium (III) derivatives are not particularly dangerous, thus reductants are used to destroy chromium(VI) samples. Chromium trioxide, being a powerful oxidizer, will ignite some organic materials (such as ethanol) on contact.
【Disposal Methods】

SRP: At the time of review, criteria for land treatment or burial (sanitary landfill) disposal practices are subject to significant revision. Prior to implementing land disposal of waste residue (including waste sludge), consult with environmental regulatory agencies for guidance on acceptable disposal practices.
Chemical reduction of concentrated materials to Cr (III) and precipitation by pH adjustment. Precipitates are normally disposed in a chemical waste landfill. Recovery and recycle is a viable alternative to disposal for chromium in plating wastes, tannery wastes, cooling tower blowdown and chemical plant wastes. Recommendable methods: Reduction & precipitation. Not recommendable method: Landfill. Peer-review: Cr (VI) can be removed from soln of low acidity by ion exchange. This can allow recovery of Cr (VI), or the resin can be solidified and disposed of to a landfill. Do not landfill chromium trioxide. Contact with combustible material may cause fire. (Peer-review conclusions of an IRPTC expert consultation (May 1985))
Wastewater treatment sludge from the production of chrome green pigments is a poor candidate for incineration. /Chrome green pigments/

Use and Manufacturing

【Use and Manufacturing】
Methods of Manufacturing
Produced commercially by the action of concentrated sulfuric acid on a solution of chromate or dichromate: Faith et al, Industrial Chemicals (John Wiley, NY, 4th ed, 1975) pp. 270-4.

U.S. Exports
(1977) 4.1X10+9 G
(1981) 2.4X10+9 G

U.S. Imports
(1977) 2.0X10+8 G
(1981) 9.0X10+8 G

U.S. Production
(1977) 3.3X10+10 G
(1981) 2.9X10+10 G

Consumption Patterns
metal finishing, 73%; wood preservatives, 24%; other (eg, chem intermed for chromium dioxide), 3% (1981)
Chemical profile: Chromic acid. Wood preserving, 63%; metal finishing, 22%; other, including water treatment, magnetic particles and catalysts, 7%; exports, 8%.
Chemical profile: Chromic acid. Demand: 1987: 57,500 tons; 1988: 62,500 tons; 1992 /projected/: 78,800 tons (Includes exports but not imports, which totaled 2,870 tons in 1987.)
【Usage】
Medication (vet).

Biomedical Effects and Toxicity

【Pharmacological Action】
- Substances used for the detection, identification, analysis, etc. of chemical, biological, or pathologic processes or conditions. Indicators are substances that change in physical appearance, e.g., color, at or approaching the endpoint of a chemical titration, e.g., on the passage between acidity and alkalinity. Reagents are substances used for the detection or determination of another substance by chemical or microscopical means, especially analysis. Types of reagents are precipitants, solvents, oxidizers, reducers, fluxes, and colorimetric reagents. (From Grant & Hackh's Chemical Dictionary, 5th ed, p301, p499)
【Therapeutic Uses】
Indicators and Reagents
Formerly treatment for warts & cauterization of hemorrhoids
Medication (VET): formerly in soln as a topical antiseptic & astringent
A 25 to 100% soln has been applied on a glass rod for the destruction of warts and indolent ulcers, the surrounding tissure being protected with soft paraffin. A 2 to 5% soln was formerly used in the treatment of Vincent's angina, with the warning that stronger soln were destructive and should not be used.
Chromium(VI) oxide has been used as a cauterizing agent, esp to stop nose bleeds.
【Biomedical Effects and Toxicity】
Rats that were exposed for a single inhalation of chromium(VI) trioxide mist from electroplating at a concn of 3.18 mg chromium(VI)/m3 for 30 min rapidly absorbed chromium from the lungs. The content of chromium in the lungs declined from 13.0 mg immediately after exposure to 1.1 mg at 4 wk in a triphasic pattern with an overall half-life of 5 days.

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