|Preferred IUPAC name
Chromium(VI) dichloride dioxide
|Systematic IUPAC name
Chromic acid chloride
Chromium chloride oxide
Chromium dioxide dichloride
3D model (JSmol)
|Molar mass||154.9008 g/mol|
|Appearance||deep red fuming liquid|
|Odor||musty, burning, acrid|
|Density||1.911 g/mL, liquid|
|Melting point||-96.5 °C|
|Boiling point||117 °C|
|Vapor pressure||20 mmHg (20 °C)|
|Main hazards||carcinogen, reacts violently with water|
|R-phrases (outdated)||R49 R46 R8 R35 R43 R50/53|
|S-phrases (outdated)||S53 S45 S60 S61|
|Flash point||noncombustible |
|US health exposure limits (NIOSH):|
|Ca TWA 0.001 mg Cr(VI)/m3|
IDLH (Immediate danger)
|SO2Cl2; VOCl3; MoO2Cl2; WO2Cl2; CrO2F2|
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
|what is ?)(|
Chromyl chloride is a chemical compound with the formula CrO2Cl2. This compound is a hygroscopic dark red liquid. The molecule is tetrahedral, like most commonly encountered chromium(VI) derivative chromate, [CrO4]2−. In terms of physical properties and structure, it resembles SO2Cl2.
It can also be prepared directly by exposing chromium trioxide to anhydrous hydrogen chloride gas.
CrO3(s) + 2HCl(g) <=> CrO2Cl2(l) + H2O(l)
CrO2Cl2 is highly electrophilic and an aggressive oxidizing agent, e.g. causing spontaneous combustion when dripped onto amorphous sulfur; can also oxidize toluene into benzaldehyde. Its electrophilicity is demonstrated by its reversible hydrolysis to chromic acid and hydrochloric acid:
- CrO2Cl2(aq) + 2H2O(l) <=> H2CrO4(aq) + 2HCl(aq)
Its high reactivity toward water is further indicated by the fact that CrO2Cl2 fumes in moist air.
Chromyl chloride test for chloride
The chromyl chloride test entails heating a sample suspected of containing chloride with potassium dichromate and concentrated sulfuric acid. If chloride is present, chromyl chloride is formed and red fumes of CrO2Cl2 are evident. If there is no chloride present, no red fumes are produced. No analogous compounds are formed with fluorides, bromides, iodides and cyanides, so this test is therefore specific for chlorides. The test is related to the synthesis shown above, exposure of CrO42− to HCl.
Reagent for oxidation of alkenes
Depending on solvent, CrO2Cl2 oxidizes terminal alkenes to aldehydes. Internal alkenes give alpha-chloroketones or related derivatives. It will also attack benzylic methyl groups to give aldehydes via the Étard reaction. Apart from this it can also be used for testing the absence of nitrate ions.
CrO2Cl2 is such an aggressive reagent that solvents must be chosen judiciously. In light of its high reactivity toward water, CrO2Cl2 can be expected to decompose upon exposure to alcohols, similar to the behavior of other highly electrophilic chlorides such as VOCl3, TiCl4, and SO2Cl2. Typical for other electrophilic chlorides, chlorocarbons are excellent solvents, especially dichloromethane
As a further practical complication, chromyl chloride attacks most greases.
Acute: HCl can be acutely lethal. Exposure to chromyl chloride vapour irritates the respiratory system and severely irritates the eyes, and the liquid burns the skin and eyes. Ingestion would cause severe internal damage.
Thus, CrO2Cl2 should be carefully handled in a well ventilated area. CrO2Cl2 is so aggressive that its storage can be problematic as it attacks rubber and most plastics as well as greases.
|Wikimedia Commons has media related to Chromyl chloride.|
- "NIOSH Pocket Guide to Chemical Hazards #0142". National Institute for Occupational Safety and Health (NIOSH).
- Moody, B.J. (1965). "22". Comparative Inorganic Chemistry (1 ed.). London: Edward Arnold. p. 381. ISBN 0-7131-3679-0.
- Pradyot Patnaik. Handbook of Inorganic Chemicals. McGraw-Hill, 2002, ISBN 0-07-049439-8
- F. Freeman, R. H. DuBois, T. G. McLaughlin. "Aldehydes by Oxidation of Terminal Olefins with Chromyl Chloride: 2,4,4-Trimethylpentanal". Organic Syntheses. ; Collective Volume, 6, p. 1028
- Prof CH Gray, ed. (1966). "IV". Laboratory Handbook of Toxic Agents (2 ed.). London: Royal Institute of Chemistry. p. 79.
- IARC (1999-11-05) . Volume 49: Chromium, Nickel, and Welding (PDF). pp. 21–23. ISBN 92-832-1249-5. Retrieved 2008-03-26.
- F. Freeman "Chromyl Chloride" in Encyclopedia of Reagents for Organic Synthesis (Ed: L. Paquette) 2004, J. Wiley & Sons, New York. doi:10.1002/047084289.