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Phosgene

From Wikipedia, the free encyclopedia

"COCl2" redirects here. For the compound CoCl2, see Cobalt(II) chloride.
Not to be confused with phosphine, phosphene, oxalyl chloride, or phosgene oxime.

Phosgene[1]

Names
IUPAC name : Carbonyl dichloride
Other names
CG; carbon dichloride oxide; carbon oxychloride; Chloroformyl chloride; dichloroformaldehyde;
dichloromethanone; dichloromethanal
Identifiers
CAS Registry Number

75-44-5

ChEBI

CHEBI:29365

ChemSpider

6131

EC number

200-870-3

InChI[show]
Jmol-3D images

Image

PubChem

6371

RTECS number

SY5600000

SMILES[show]
UNII

117K140075

UN number

1076
Properties

Chemical formula

COCl2

Molar mass

98.92 g mol1

Appearance

colorless gas

Odor

suffocating, like musty hay[2]

Density

4.248 g/L (15 C, gas)

-----

1.432 g/cm3 (0 C, liquid)

Melting point

118 C (180 F; 155 K)

Boiling point

8.3 C (46.9 F; 281.4 K)

Solubility in water

decomposes in water[3]

Solubility

soluble in benzene, toluene,acetic acid ------ decomposes in alcohol andacid

Vapor pressure

1.6 atm (20C)[2]


Structure

Molecular shape

Planar, trigonal

Dipole moment

1.17 D
Hazards

SDS

ICSC 0007

EU Index

006-002-00-8

EU classification
T+

R-phrases

R26 R34

S-phrases

(S1/2) S9 S26 S36/37/39S45

NFPA 704

4 blue - 0 red - 1 yellow


Flash point

Non-flammable

Threshold Limit Value

0.1 ppm

LC50 (Median lethal

500 ppm (human, 1 min)

concentration)

340 ppm (rat, 30 min)


438 ppm (mouse, 30 min)
243 ppm (rabbit, 30 min)
316 ppm (guinea pig, 30 min)
1022 ppm (dog, 20 min)
145 ppm (monkey, 1 min)[4]

US health exposure limits (NIOSH):


PEL (Permissible)

TWA 0.1 ppm (0.4 mg/m3)[2]

REL (Recommended)

TWA 0.1 ppm (0.4 mg/m3) C 0.2 ppm (0.8 mg/m3) [15-minute][2]

IDLH (Immediate danger) 2 ppm[2]


Related compounds
Related compounds

Thiophosgene
Formaldehyde
Carbonic acid
Urea
Carbon monoxide
Chloroformic acid

Except where otherwise noted, data are given for materials in their standard state (at 25 C [77 F], 100 kPa).
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Infobox references

Phosgene is the chemical compound with the formula COCl2. This colorless gas gained infamy as
a chemical weapon during World War I where it was responsible for about 85% of the 100,000
deaths caused by chemical weapons. It is also a valued industrial reagent and building block
in synthesis of pharmaceuticals and other organic compounds. In low concentrations, its odor
resembles freshly cut hay or grass.[5] In addition to its industrial production, small amounts occur
naturally from the breakdown and thecombustion of organochlorine compounds, such as those used
in refrigeration systems.[6] The chemical was named by combining the Greek words 'phos' (meaning
light) and genesis (birth); it does not mean it contains any phosphorus (cf. phosphine).
Contents

1 Structure and basic properties

2 Production
2.1 Adventitious occurrence

3 Uses

3.1 Synthesis of carbonates

3.2 Synthesis of isocyanates

3.3 Laboratory uses

4 Other chemistry

5 History

5.1 Chemical warfare

6 Safety

7 See also

8 References

9 External links

Structure and basic properties[edit]


Phosgene is a planar molecule as predicted by VSEPR theory. The C=O distance is 1.18 , the C
Cl distance is 1.74 and the ClCCl angle is 111.8.[7] It is one of the simplest acid chlorides,
being formally derived from carbonic acid.

Production[edit]
Industrially, phosgene is produced by passing purified carbon monoxide and chlorine gas through a
bed of porous activated carbon, which serves as a catalyst:[6]
CO + Cl2 COCl2 (Hrxn = 107.6kJ/mol)
The reaction is exothermic, therefore the reactor must be cooled. Typically, the reaction is conducted
between 50 and 150 C. Above 200 C, phosgene reverts to carbon monoxide and chlorine,
Keq (300K) = 0.05. World production of this compound was estimated to be 2.74 million tonnes in
1989.[6]
Because of safety issues, phosgene is often produced and consumed within the same plant, and
extraordinary measures are made to contain this toxic gas. It is listed on schedule 3 of the Chemical
Weapons Convention: All production sites manufacturing more than 30 tonnes per year must be
declared to the OPCW.[8] Although less dangerous than many other chemical weapons, such
as sarin, phosgene is still regarded as a viable chemical warfare agent because it is so easy to
manufacture when compared to the production requirements of more technically advanced chemical
weapons such as the first-generation nerve agent tabun.[9]

Adventitious occurrence[edit]
Upon ultraviolet (UV) radiation in the presence of oxygen, chloroform slowly converts into phosgene
by a radical reaction. To suppress this photodegradation, chloroform is often stored in brown-tinted
glass containers. Chlorinated compounds used to remove oil from metals, such as automotive brake
cleaners, are converted to phosgene by the UV rays of arc welding processes.[10]
Phosgene may also be produced during testing for leaks of older-style refrigerant
gases. Chloromethanes (R12, R22 and others) were formerly leak-tested in situ by employing a
small gas torch (propane, butane or propylene gas) with a sniffer tube and a copper reaction plate in
the flame nozzle of the torch. If any refrigerant gas was leaking from a pipe or joint, the gas would be
sucked into the flame via the sniffer tube and would cause a colour change of the gas flame to a
bright greenish blue. In the process, phosgene gas would be created due to the thermal reaction. No
valid statistics are available, but anecdotal reports suggest that numerous refrigeration technicians
suffered the effects of phosgene poisoning due to their ignorance of the toxicity of phosgene,
produced during such leak testing.[citation needed] Electronic sensing of refrigerant gases phased out the
use of flame testing for leaks in the 1980s. Similarly, phosgene poisoning is a consideration for
people fighting fires that are occurring in the vicinity of freon refrigeration equipment, smoking in the
vicinity of a freon leak, or fighting fires using halon or halotron.[citation needed]

Uses[edit]
The great majority of phosgene is used in the production of isocyanates, the most important
being toluene diisocyanate (TDI) andmethylene diphenyl diisocyanate (MDI). These two isocyanates
are precursors to polyurethanes.

Synthesis of carbonates[edit]
Significant amounts are also used in the production of polycarbonates by its reaction with bisphenol
A.[6] Polycarbonates are an important class of engineering thermoplastic found, for example, in
lenses in eyeglasses. Diols react with phosgene to give either linear or cyclic carbonates (R = H,
alkyl, aryl):
HOCR2-X-CR2OH + COCl2 1/n [OCR2-X-CR2OC(O)-]n + 2 HCl

Synthesis of isocyanates[edit]

The synthesis of isocyanates from amines illustrates the electrophilic character of this reagent and
its use in introducing the equivalent of "CO2+":[11]
RNH2 + COCl2 RN=C=O + 2 HCl (R = alkyl, aryl)
Such reactions are conducted in the presence of a base such as pyridine that absorbs the hydrogen
chloride.

Laboratory uses[edit]
In the research laboratory phosgene still finds limited use in organic synthesis. A variety of
substitutes have been developed, notably trichloromethyl chloroformate ("diphosgene"), a liquid at
room temperature, and bis(trichloromethyl) carbonate ("triphosgene"), a crystalline substance.
[12]
Aside from the above reactions that are widely practiced industrially, phosgene is also used to
produce acid chlorides and carbon dioxide from carboxylic acids:
RCO2H + COCl2 RC(O)Cl + HCl + CO2
Such acid chlorides react with amines and alcohols to give, respectively, amides and esters, which
are commonly used intermediates. Thionyl chloride is more commonly and more safely employed for
this application. A specific application for phosgene is the production of chloroformic esters:
ROH + COCl2 ROC(O)Cl + HCl
Phosgene is stored in metal cylinders. The outlet is always standared, a tapered thread that is
known as CGA 160

Other chemistry[edit]
Although it is somewhat hydrophobic, phosgene reacts with water to release hydrogen
chloride and carbon dioxide:
COCl2 + H2O CO2 + 2 HCl
Analogously, with ammonia, one obtains urea:
COCl2 + 4 NH3 CO(NH2)2 + 2 NH4Cl
Halide exchange with nitrogen trifluoride and aluminium tribromide gives COF2 and COBr2,
respectively.[6]

History[edit]
Phosgene was synthesized by the British chemist John Davy (17901868) in 1812 by exposing a
mixture of carbon monoxide and chlorine to sunlight. He named it "phosgene" in reference of the use
of light to promote the reaction; from Greek, phos (light) and gene (born).[13] It gradually became
important in the chemical industry as the 19th century progressed, particularly in dye manufacturing.

Chemical warfare[edit]
Further information: Use of poison gas in World War I and Second Italo-Abyssinian War
Following the extensive use of phosgene gas in combat during World War I, it was stockpiled by
various countries as part of their secret chemical weapons programs.[14][15][16]
In May 1928, eleven tons of phosgene escaped from a war surplus store in central Hamburg. [17] 300
people were poisoned of whom 10 died.[17]

US Army phosgene identification poster from World War II

Phosgene was then only frequently used by the Imperial Japanese Army against the Chinese during
the Second Sino-Japanese War.[18]Gas weapons, such as phosgene, were produced by Unit 731 and
authorized by specific orders given by Hirohito (Emperor Showa) himself, transmitted by the chief of
staff of the army. For example, the Emperor authorized the use of toxic gas on 375 separate
occasions during the Battle of Wuhan from August to October 1938.[19]

Safety[edit]
Phosgene is an insidious poison as the odor may not be noticed and symptoms may be slow to
appear.[20] The odor detection threshold for phosgene is 0.4 ppm, four times the threshold limit value.
Its high toxicity arises from the action of the phosgene on the proteins in the pulmonary alveoli, the
site of gas exchange: their damage disrupts the blood-air barrier, causing suffocation. It reacts with
the amines of the proteins, causing crosslinking by formation of urea-like linkages, in accord with the
reactions discussed above. Phosgene detection badges are worn by those at risk of exposure. [6]
Sodium bicarbonate may be used to neutralise liquid spills of phosgene. Gaseous spills may be
mitigated with ammonia.[21]

See also[edit]

Diphosgene

Triphosgene

Bhopal disaster

Carbonyl fluoride

Carbonyl bromide

Formaldehyde

References[edit]
1.
2.

3.

Jump up^ Merck Index, 11th Edition, 7310.


^ Jump up to:a b c d e "NIOSH Pocket Guide to Chemical Hazards #0504". National Institute for
Occupational Safety and Health (NIOSH).
Jump up^ http://www.inchem.org/documents/icsc/icsc/eics0007.htm

4.

Jump up^ "Phosgene". Immediately Dangerous to Life and Health. National Institute for
Occupational Safety and Health (NIOSH).

5.

Jump up^ CBRNE - Lung-Damaging Agents, Phosgene May 27, 2009

6.

^ Jump up to:a b c d e f Wolfgang Schneider; Werner Diller (2005), "Phosgene", Ullmann's


Encyclopedia of Industrial Chemistry, Weinheim: Wiley-VCH, doi:10.1002/14356007.a19_411

7.

Jump up^ Nakata, M.; Kohata, K.; Fukuyama, T.; Kuchitsu, K. (1980). "Molecular Structure of
Phosgene as Studied by Gas Electron Diffraction and Microwave Spectroscopy. The r z Structure and Isotope
Effect". Journal of Molecular Spectroscopy 83: 105117. doi:10.1016/0022-2852(80)90314-8.

8.

Jump up^ Annex on Implementation and Verification ("Verification Annex")

9.

Jump up^ https://itportal.decc.gov.uk/cwc_files/S2AAD_guidance.pdf

10.

Jump up^ "Common Cleaners Can Turn Into Poison Gas". American Iron Magazine. TAM
Communications. Retrieved 14 October 2011.

11.

Jump up^ R. L. Shriner, W. H. Horne, and R. F. B. Cox (1943). "p-Nitrophenyl


Isocyanate". Org. Synth.; Coll. Vol. 2, p. 453

12.

Jump up^ Hamley, P. "Phosgene" Encyclopedia of Reagents for Organic Synthesis, 2001
John Wiley, New York. doi: 10.1002/047084289X.rp149

13.

Jump up^ John Davy (1812). "On a Gaseous Compound of Carbonic Oxide and
Chlorine". Philosophical Transactions of the Royal Society of London 102: 144
151. doi:10.1098/rstl.1812.0008.JSTOR 107310.

14.

Jump up^ Base's phantom war reveals its secrets, Lithgow Mercury, 7/08/2008

15.

Jump up^ Chemical warfare left its legacy, Lithgow Mercury, 9/09/2008

16.

Jump up^ Chemical bombs sit metres from Lithgow families for 60 years, The Daily
Telegraph, September 22, 2008

17.

^ Jump up to:a b Ryan, T.Anthony (1996). Phosgene and Related Carbonyl Halides. Elsevier.
pp. 154155. ISBN 0444824456.

18.

Jump up^ Yuki Tanaka, "Poison Gas, the Story Japan Would Like to Forget", Bulletin of the
Atomic Scientists, October 1988, p. 1617

19.

Jump up^ Y. Yoshimi and S. Matsuno, Dokugasusen Kankei Shiry II, Kaisetsu, Jugonen
Sens Gokuhi Shiryoshu, 1997, p. 2729

20.

Jump up^ Borak J., Diller W. F. (2001). "Phosgene exposure: mechanisms of injury and
treatment strategies". Journal of Occupational and Environmental Medicine 43 (2): 110
9.doi:10.1097/00043764-200102000-00008. PMID 11227628.

21.

Jump up^ "Phosgene: Health and Safety Guide". International Programme on Chemical
Safety. 1998.

External links[edit]

Davy's account of his discovery of phosgene

International Chemical Safety Card 0007

CDC - Phosgene - NIOSH Workplace Safety and Health Topic

NIOSH Pocket Guide to Chemical Hazards

U.S. CDC Emergency Preparedness & Response

U.S. EPA Acute Exposure Guideline Levels

Regime For Schedule 3 Chemicals And Facilities Related To Such Chemicals, OPCW
website

CBWInfo website

Use of Phosgene in WWII and in modern-day warfare (Refer to Section 4.C of the article)

An experience with accidental poisoning by heated tetrachlorethylene solvent

http://en.wikipedia.org/wiki/Phosgene