Chlorodifluoromethane

Chlorodifluoromethane
Names
Preferred IUPAC name
Chloro(difluoro)methane
Other names
Chlorodifluoromethane
Difluoromonochloromethane
Monochlorodifluoromethane
HCFC-22
R-22
Genetron 22
Freon 22
Arcton 4
Arcton 22
UN 1018
Difluorochloromethane
Fluorocarbon-22
Refrigerant 22
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.000.793
EC Number 200-871-9
KEGG
RTECS number PA6390000
Properties
CHClF2
Molar mass 86.47 g/mol
Appearance Colorless gas
Odor sweetish[1]
Density 3.66 kg/m3 at 15 °C, gas
Melting point −175.42 °C (−283.76 °F; 97.73 K)
Boiling point −40.7 °C (−41.3 °F; 232.5 K)
0.7799 vol/vol at 25 °C; 3.628 g/L
log P 1.08
Vapor pressure 908 kPa at 20 °C
0.033 mol.kg−1.bar−1
-38.6·10−6 cm3/mol
Structure
Tetrahedral
Hazards
Main hazards Dangerous for the environment (N), Central nervous system depressant, Carc. Cat. 3
R-phrases (outdated) R59
S-phrases (outdated) S23 S24 S25 S59
NFPA 704
Flammability (red): no hazard code Health code 1: Exposure would cause irritation but only minor residual injury. E.g., turpentine Reactivity code 1: Normally stable, but can become unstable at elevated temperatures and pressures. E.g., calcium Special hazards (white): no codeNFPA 704 four-colored diamond
1
1
Flash point nonflammable [1]
632 °C (1,170 °F; 905 K)
US health exposure limits (NIOSH):
PEL (Permissible)
none[1]
REL (Recommended)
TWA 1000 ppm (3500 mg/m3) ST 1250 ppm (4375 mg/m3)[1]
IDLH (Immediate danger)
N.D.[1]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
N verify (what is YesYN ?)
Infobox references

Chlorodifluoromethane or difluoromonochloromethane is a hydrochlorofluorocarbon (HCFC). This colorless gas is better known as HCFC-22, or R-22. It is commonly used as a propellant and refrigerant. These applications are being phased out in developed countries due to the compound's ozone depletion potential (ODP) and high global warming potential (GWP), although global use of R-22 continues to increase because of high demand in developing countries.[2] R-22 is a versatile intermediate in industrial organofluorine chemistry, e.g. as a precursor to tetrafluoroethylene. R-22 cylinders are colored light green.[3]

Production and current applications

Worldwide production of R-22 in 2008 was about 800 Gg per year, up from about 450 Gg per year in 1998, with most production in developing countries.[2] R-22 use is increasing in developing countries, largely for air conditioning applications. Air conditioning sales are growing 20% annually in India and China.

R-22 is prepared from chloroform:

HCCl3 + 2 HF → HCF2Cl + 2 HCl

An important application of R-22 is as a precursor to tetrafluoroethylene. This conversion involves pyrolysis to give difluorocarbene, which dimerizes:[4]

2 CHClF2 → C2F4 + 2 HCl

The compound also yields difluorocarbene upon treatment with strong base and is used in the laboratory as a source of this reactive intermediate.

The pyrolysis of R-22 in the presence of chlorofluoromethane gives hexafluorobenzene.

Environmental effects

R-22 is often used as an alternative to the highly ozone-depleting CFC-11 and CFC-12, because of its relatively low ozone depletion potential of 0.055,[5] among the lowest for chlorine-containing haloalkanes. However, even this lower ozone depletion potential is no longer considered acceptable.

As an additional environmental concern, R-22 is a powerful greenhouse gas with a global warming potential equal to 1810 (which indicates 1810 times as powerful as carbon dioxide).[4] Hydrofluorocarbons (HFCs) are often substituted for R-22 because of their lower Ozone Depleting Potential, but these refrigerants also have high global warming potential. R-410A, for example, is often substituted, but has a Global Warming Potential of 1725. Another substitute is R404A with a Global Warming Potential of 3900. Other substitute refrigerants are available with low Global Warming Potential. Ammonia (R717), for example, has a Global Warming Potential of <1 and is a popular substitute on fishing vessels. Propane (R-290), is another example, and has a Global Warming Potential of 3, although it is rarely used in refrigeration systems because of its flammability and potential for explosion.

Phaseout in the European Union

Since January 1, 2010, it has been illegal to use newly manufactured HCFCs to service refrigeration and air-conditioning equipment - only reclaimed and recycled HCFCs may be used. In practice this means that the gas has to be removed from the equipment before servicing and replaced afterwards, rather than refilling with new gas.

Since January 1, 2015, it has been illegal to use any HCFCs to service refrigeration and air-conditioning equipment; broken equipment that used HCFC refrigerants must be replaced with equipment that does not use them.[6]

Phaseout in the United States

R-22 has been mostly phased out in new equipment in the United States under the Montreal Protocol, and has been replaced by other refrigerants with lower ozone depletion potential such as propane (R-290), pentafluoroethane, R-134a (1,1,1,2-tetrafluoroethane), and blended mixtures of HFCs such as R-409A, R-410A, R-438A, and R-507A.[7][8] See refrigerant for specific components of the R-400 and R-500 HFC blends used to replace R-22.

R-22, retrofit using substitute refrigerants

R-407A is for use in for low- and medium-temp refrigeration. Uses a POE oil.

R-407C is for use in air conditioning. Uses a minimum of 20 percent POE oil.

R-407F is for use in medium- and low-temperature refrigeration applications (supermarkets, cold storage, and process refrigeration); direct expansion system design only. Uses a POE oil.

R-421A is for use in “air conditioning split systems, heat pumps, supermarket pak systems, dairy chillers, reach-in storage, bakery applications, refrigerated transport, self-contained display cabinets, and walk-in coolers.” Uses MO to POE.

R-422B is for use in low-, medium-, and high-temperature applications. It is not recommended for use in flooded applications.

R-422C is for use in medium- and low-temperature applications. The TXV power element will need to be changed to a 404A/507A element and critical seals (elastomers) may need to be replaced.

R-422D is for use in low-temp applications, and is mineral oil compatible.

R-424A is for use in air conditioning as well as medium-temp refrigeration temperature ranges of 20 to 50˚F. It works with MO, AB, and POE oils.

R-427A is for use in air conditioning and refrigeration applications. It does not require all the mineral oil to be removed. It works with MO, AB, and POE oils.

R-434A is for use in water cooled and process chillers for air conditioning and medium- and low-temperature applications. It works with MO, AB, and POE oils.

R-438A is for use in low-, medium-, and high-temperature applications. It is compatible with all lubricants. [9]

Physical properties

Property Value
Density (ρ) at -69 °C (liquid) 1.49 g.cm−3
Density (ρ) at -41 °C (liquid) 1.413 g.cm−3
Density (ρ) at -41 °C (gas) 4.706 kg.m−3
Density (ρ) at 15 °C (gas) 3.66 kg.m−3
Specific gravity at 21 °C (gas) 3.08 (air = 1)
Specific volume (ν) at 21 °C (gas) 0.275 m3.kg−1
Density (ρ) at 15 °C (gas) 3.66 kg.m−3
Triple point temperature (Tt) -157.39 °C (115.76 K)
Critical temperature (Tc) 96.2 °C (369.3 K)
Critical pressure (pc) 4.936 MPa (49.36 bar)
Vapor pressure at 21.1 °C (pc) 0.9384 MPa (9.384 bar)[10]
Critical density (ρc) 6.1 mol.l−1
Latent heat of vaporization (lv) at boiling point (-40.7 °C) 233.95 kJ.kg−1
Heat capacity at constant pressure (Cp) at 30 °C (86 °F) 0.057 kJ.mol−1.K−1
Heat capacity at constant volume (Cv) at 30 °C (86 °F) 0.048 kJ.mol−1.K−1
Heat capacity ratio (γ) at 30 °C (86 °F) 1.178253
Compressibility factor (Z) at 15 °C 0.9831
Acentric factor (ω) 0.22082
Molecular dipole moment 1.458 D
Viscosity (η) at 0 °C 12.56 µPa.s (0.1256 cP)
Ozone depletion potential (ODP) 0.055 (CCl3F = 1)
Global warming potential (GWP) 1810 (CO2 = 1)

It has two allotropes: crystalline II below 59 K and crystalline I above 59 K to 115.73 K.

Price history and availability

EPA's analysis indicated the amount of existing inventory was between 22,700 MT (metric tons) and 45,400 MT.[11][12]

YEAR 2010 2011 2012 2013 2014 2015-2019 2020
R-22 (Pounds in millions) Virgin 110 100 55.4 56.5 44.5 TBD 0
R-22 (Pounds in millions) Recoupment -- -- -- 6.5 6.5 -- --
R-22 (Pounds in millions) TOTAL 110 100 55.4 63.0 51.0 -- --

TBD = To be determined [13]

In 2012 the EPA reduced the amount of R-22 by 45%, causing the price to rise by more than 300%. For 2013, the EPA has reduced the amount of R-22 by 29%.[14]

Refrigerants Price History

References

  1. 1 2 3 4 5 "NIOSH Pocket Guide to Chemical Hazards #0124". National Institute for Occupational Safety and Health (NIOSH).
  2. 1 2 Rosenthal, Elisabeth; Lehren, Andrew W. (June 20, 2012). "Relief in Every Window, but Global Worry Too". New York Times. Retrieved June 21, 2012.
  3. Günter Siegemund, Werner Schwertfeger, Andrew Feiring, Bruce Sart, Fred Behr, Herward Vogel, Blaine McKusick "Fluorine Compounds, Organic" Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2002. doi:10.1002/14356007.a11_349
  4. The Montreal Protocol on Substances that Deplete the Ozone Layer. UNEP, 2000. ISBN 92-807-1888-6
  5. EPA Phase-out
  6. R-438A
  7. Retrofit Refrigerants Archived 2013-06-24 at Archive.is
  8. http://frogen.co.uk/product/frogen-r22/
  9. EPA, A Rule by the Environmental Protection Agency on 04/03/2013
  10. EPA Consumption Allowance, § 82.16 Phaseout schedule of class II controlled substances.
  11. Virgin R-22 Allocations Final Rule (April 3, 2013)
  12. Specialty Cooling and Heating (Blog) January 22, 2013 Archived October 6, 2013, at the Wayback Machine.
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