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Chromyl chloride

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Chromyl chloride
Wireframe model of chromyl chloride
Wireframe model of chromyl chloride
Ball and stick model of chromyl chloride
Ball and stick model of chromyl chloride
Chromyl chloride in vial
Names
Preferred IUPAC name
Chromium(VI) dichloride dioxide
Systematic IUPAC name
Dichloridodioxidochromium
Other names
Chromic acid chloride

Chromium oxychloride

Etard Reagent
Chlorochromic anhydride
Chromic oxychloride
Chromium chloride oxide
Chromium dioxide dichloride
Chromium dioxychloride
Chromium oxychloride
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.035.491 Edit this at Wikidata
EC Number
  • 239-056-8
2231
RTECS number
  • GB5775000
UNII
UN number 1758
  • InChI=1S/2ClH.Cr.2O/h2*1H;;;/q;;+2;;/p-2 checkY
    Key: AHXGRMIPHCAXFP-UHFFFAOYSA-L checkY
  • InChI=1S/2ClH.Cr.2O/h2*1H;;;/q;;+2;;/p-2
    Key: AHXGRMIPHCAXFP-UHFFFAOYSA-L
  • InChI=1/2ClH.Cr.2O/h2*1H;;;/q;;+2;;/p-2/rCl2CrO2/c1-3(2,4)5
    Key: AHXGRMIPHCAXFP-GRYJOLFGAD
  • Cl[Cr](Cl)(=O)=O
Properties
CrO2Cl2
Molar mass 154.9008 g/mol
Appearance Blood-red fuming liquid, similar to bromine
Odor Musty, burning, acrid[1]
Density 1.911 g/mL, liquid
Melting point −96.5 °C (−141.7 °F; 176.7 K)
Boiling point 118.5 °C (245.3 °F; 391.6 K)
Reacts with water
Vapor pressure 20 mmHg (20 °C)[1]
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
 Toxic, oxidizer, carcinogenic, mutagenic, reacts violently with water[1]
GHS labelling:
GHS03: OxidizingGHS05: CorrosiveGHS07: Exclamation markGHS08: Health hazardGHS09: Environmental hazard
Danger
H271, H314, H317, H340, H350, H410
P201, P210, P280, P303+P361+P353, P305+P351+P338+P310, P308+P313[2]
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 0: Will not burn. E.g. waterInstability 2: Undergoes violent chemical change at elevated temperatures and pressures, reacts violently with water, or may form explosive mixtures with water. E.g. white phosphorusSpecial hazard W+OX: Reacts with water in an unusual or dangerous manner AND is oxidizer
3
0
2
W
OX
Flash point noncombustible[1]
NIOSH (US health exposure limits):
PEL (Permissible)
 none[1]
REL (Recommended)
 Ca TWA 0.001 mg Cr(VI)/m3[1]
IDLH (Immediate danger)
 N.D.[1]
Safety data sheet (SDS) Sigma Aldrich - Chromyl Chloride
Related compounds
Related compounds
 Sulfuryl chloride
Vanadium oxytrichloride
MoO2Cl2
Tungsten dichloride dioxide
Chromyl fluoride
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Chromyl chloride is an inorganic compound with the formula CrO2Cl2. It is a reddish brown compound that is a volatile liquid at room temperature, which is unusual for transition metal compounds.

Preparation

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Chromyl chloride can be prepared by the reaction of potassium chromate or potassium dichromate with hydrogen chloride in the presence of sulfuric acid, followed by distillation.[3][4]

K2Cr2O7 + 6 HCl → 2 CrO2Cl2 + 2 KCl + 3 H2O

The sulfuric acid serves as the dehydration agent. It can also be prepared directly by exposing chromium trioxide to anhydrous hydrogen chloride gas.

CrO3 + 2 HCl ⇌ CrO2Cl2 + H2O

The method used to prepare chromyl chloride is the basis for a qualitative test for chloride: a sample suspected of containing chloride is heated with a mixture of potassium dichromate and concentrated sulfuric acid. If chloride is present, chromyl chloride forms as evidenced by red fumes of CrO2Cl2. Analogous compounds are not formed with fluorides, bromides, iodides and cyanides.

Usage

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Test for the presence of chlorides

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The chromyl chloride test involves heating a sample suspected to contain chlorides with potassium dichromate and concentrated sulfuric acid. If a chloride is present, chromyl chloride forms, its presence being indicated by the formation of red smoke. Otherwise, no red smoke will obviously appear. No similar compound is formed in the presence of fluoride, bromide, iodide, or cyanide, making this test specific to chlorides.

Reagent for oxidation of alkenes

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Chromyl chloride oxidizes internal alkenes to alpha-chloroketones or related derivatives.[5] It will also attack benzylic methyl groups to give aldehydes via the Étard reaction. Dichloromethane is a suitable solvent for these reactions.[6]

Others

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CrO2Cl2 can also be used to test for the absence of nitrate ions.

Safety considerations

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Main article: Hexavalent chromium
Chromyl chloride is often stored in sealed glass ampoules to prevent vapours leaking out of the container

Chromyl chloride is severely corrosive and easily burns the skin and eyes.[7]

References

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Wikimedia Commons has media related to Chromyl chloride.
  1. ^ a b c d e f g NIOSH Pocket Guide to Chemical Hazards. "#0142". National Institute for Occupational Safety and Health (NIOSH).
  2. ^ "Chromyl chloride 200042" (PDF). Sigma-Aldrich. Archived from the original on 2020-09-01.
  3. ^ Moody, B.J. (1965). "22". Comparative Inorganic Chemistry (1 ed.). London: Edward Arnold. p. 381. ISBN 0-7131-3679-0.
  4. ^ Sisler, Harry H. (1946). Chromyl Chloride [Chromium(VI) Dioxychloride]. Inorganic Syntheses. Vol. 2. pp. 205–207. doi:10.1002/9780470132333.ch63. ISBN 9780470132333.
  5. ^ Freeman, Fillmore; DuBois, Richard H.; McLaughlin, Thomas G. (1971). "Aldehydes by Oxidation of Terminal Olefins with Chromyl Chloride: 2,4,4-Trimethylpentanal". Org. Synth. 51: 4. doi:10.15227/orgsyn.051.0004.
  6. ^ F. Freeman (2004). "Chromyl Chloride". Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rc177. ISBN 0471936235.
  7. ^ Prof CH Gray, ed. (1966). "IV". Laboratory Handbook of Toxic Agents (2 ed.). London: Royal Institute of Chemistry. p. 79.
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