Chlorofluorocarbon

A chlorofluorocarbon (CFC) is an organic compound that contains carbon, chlorine, and fluorine, produced as a volatile derivative of methane and ethane. A common subclass is the hydrochlorofluorocarbons (HCFCs), which contain hydrogen, as well. They are also commonly known by the DuPont trade name Freon. The most common representative is dichlorodifluoromethane (R-12 or Freon-12). Many CFCs have been widely used as refrigerants, propellants (in aerosol applications), and solvents. The manufacture of such compounds is being phased out by the Montreal Protocol because they contribute to ozone depletion.

Structure, properties, production

As in simpler alkanes, carbon in the CFCs and the HCFCs is tetrahedral. Since the fluorine and chlorine atoms differ greatly in size from hydrogen and from each other, the methane derived CFCs deviate from perfect tetrahedral symmetry.^[1]

The physical properties of the CFCs and HCFCs are tunable by changes in the number and identity of the halogen atoms. In general they are volatile, but less so than parent alkane. The decreased volatility is attributed to the molecular polarity induced by the halides and the polarizability of halides, which induces intermolecular interactions. Thus, methane boils at -161 °C whereas the fluoromethanes boil between -51.7 (CF₂H₂) and -128 °C (CF₄). The CFCs have still higher boiling points because the chloride is even more polarizable than fluoride. Because of their polarity, the CFCs are useful solvents. The CFCs are far less flammable than methane, in part because they contain fewer C-H bonds and in part because, in the case of the chlorides and bromides, the released halides quench the free radicals that sustain flames.

The densities of CFCs are invariably higher than the corresponding alkanes. In general the density of these compounds correlates with the number of chlorides.

CFCs and HCFCs are usually produced by halogen exchange starting from chlorinated methanes and ethanes. Illustrative is the synthesis of chlorodifluoromethane from chloroform:

HCCl₃ + 2 HF → HCF₂Cl + 2 HCl

The brominated derivatives are generated by free-radical reactions of the chlorofluorocarbons, replacing C-H bonds with C-Br bonds. The production of the anesthetic 2-bromo-2-chloro-1,1,1-trifluoroethane ("halothane") is illustrative:

CF₃CH₂Cl + Br₂ → CF₃CHBrCl + HBr

Reactions

The most important reaction of the CFCs is the photo-induced scission of a C-Cl bond:

CCl₃F → CCl₂F^. + Cl^.

The chlorine atom, written often as Cl^., behaves very differently from the chlorine molecule (Cl₂). The radical Cl^. is long-lived in the upper atmosphere, where it catalyzes the conversion of ozone into O₂. Ozone absorbs UV-radiation better than does O₂, so its depletion allows more of this high energy radiation to reach the Earth's surface. Bromine atoms are even more efficient catalysts, hence brominated CFCs are also regulated.

Applications

Applications exploit the low toxicity, low reactivity, and low flammability of the CFCs and HCFCs. Every permutation of fluorine, chlorine, and hydrogen based on methane and ethane has been examined and most have been commercialized. Furthermore, many examples are known for higher numbers of carbon as well as related compounds containing bromine. Uses include refrigerants, blowing agents, propellants in medicinal applications, and degreasing solvents.

Billions of kilograms of chlorodifluoromethane are produced annually as a precursor to tetrafluoroethylene, the monomer that is converted into Teflon.^[2]

Classes of compounds, nomenclature

• Chlorofluorocarbons (CFCs): when derived from methane and ethane these compounds have the formulae CCl_mF_4-m and C₂Cl_mF_6-m, where m is nonzero.
• Hydrochlorofluorocarbons (HCFCs): when derived from methane and ethane these compounds have the formulae CCl_mF_nH_4-m-n and C₂Cl_xF_yH_6-x-y, where m, n, x, and y are nonzero.
• Bromochlorofluorocarbons and bromofluorocarbons have formulae similar to the CFCs and HCFCs but also bromine.
• Hydrofluorocarbons (HFC's): when derived from methane, ethane, propane, and butane, these compounds have the respective formulae CF_mH_4-m, C₂F_mH_6-m, C₃F_mH_8-m, and C₄F_mH_10-m, where m is nonzero.

Commercial names

Freon is DuPont's brand name for CFCs, HCFCs and related compounds. Other commercial names from around the world are Algofrene, Arcton, Asahiflon, Daiflon, Eskimon, FCC, Flon, Flugene, Forane, Fridohna, Frigen, Frigedohn, Genetron, Isceon, Isotron, Kaiser, Kaltron, Khladon, Ledon, Racon, and Ucon.

Numbering system

A numbering system is used for fluorinated alkanes, prefixed with Freon-, R-, CFC-, and HCFC-. The rightmost value indicates the number of fluorine atoms, the next value to the left is the number of hydrogen atoms plus 1, and the next value to the left is the number of carbon atoms less one (zeroes are not stated). Remaining atoms are chlorine. Thus, Freon-12 indicates a methane derivative (only two numbers) containing two fluorine atoms (the second 2) and no hydrogen (1-1). It is therefore CCl₂F₂.

Freons containing bromine is signified by four numbers. Isomers, which are common for ethane and propane derivatives, are indicated by letters following the numbers.

History

Carbon tetrachloride was used in fire extinguishers and glass "anti-fire grenades" from the late nineteenth century until around the end of World War II. Experimentation with chloroalkanes for fire suppression on military aircraft began at least as early as the 1920s. Freon is a trade name for a group of CFCs which are used primarily as refrigerants, but also have uses in fire-fighting and as propellants in aerosol cans. Bromomethane is widely used as a fumigant. Dichloromethane is a versatile industrial solvent.

The Belgian scientist Frédéric Swarts pioneered the synthesis of CFCs in the 1890s. He developed an effective exchange agent to replace chloride in carbon tetrachloride with fluoride to synthesize CFC-11 (CCl₃F) and CFC-12 (CCl₂F₂).

In the late 1920s, Thomas Midgley, Jr. improved the process of synthesis and led the effort to use CFC as refrigerant to replace ammonia (NH₃), chloromethane (CH₃Cl), and sulfur dioxide (SO₂), which are toxic but were in common use. In searching for a new refrigerant, requirements for the compound were: low boiling point, low toxicity, and to be generally non-reactive. In a demonstration for the American Chemical Society, Midgley flamboyantly demonstrated all these properties by inhaling a breath of the gas and using it to blow out a candle^[3] in 1930.^[4][5]

Commercial development and use of CFCs and related compounds

During World War II, various chloroalkanes were in standard use in military aircraft, although these early halons suffered from excessive toxicity. Nevertheless, after the war they slowly became more common in civil aviation as well. In the 1960s, fluoroalkanes and bromofluoroalkanes became available and were quickly recognized as being highly effective fire-fighting materials. Much early research with Halon 1301 was conducted under the auspices of the US Armed Forces, while Halon 1211 was, initially, mainly developed in the UK. By the late 1960s they were standard in many applications where water and dry-powder extinguishers posed a threat of damage to the protected property, including computer rooms, telecommunications switches, laboratories, museums and art collections. Beginning with warships, in the 1970s, bromofluoroalkanes also progressively came to be associated with rapid knockdown of severe fires in confined spaces with minimal risk to personnel.

By the early 1980s, bromofluoroalkanes were in common use on aircraft, ships, and large vehicles as well as in computer facilities and galleries. However, concern was beginning to be expressed about the impact of chloroalkanes and bromoalkanes on the ozone layer. The Vienna Convention on Ozone Layer Protection did not cover bromofluoroalkanes as it was thought, at the time, that emergency discharge of extinguishing systems was too small in volume to produce a significant impact, and too important to human safety for restriction.

Regulation

Since the late 1970s, the use of CFCs has been heavily regulated because of their destructive effects on the ozone layer. After the development of his electron capture detector, James Lovelock was the first to detect the widespread presence of CFCs in the air, finding a concentration of 60 parts per trillion of CFC-11 over Ireland. In a self-funded research expedition ending in 1973, Lovelock went on to measure the concentration of CFC-11 in both the Arctic and Antarctic, finding the presence of the gas in each of 50 air samples collected, but incorrectly concluding that CFCs are not hazardous to the environment. The experiment did however provide the first useful data on the presence of CFCs in the atmosphere. The damage caused by CFCs was discovered by Sherry Rowland and Mario Molina who, after hearing a lecture on the subject of Lovelock's work, embarked on research resulting in the first publication suggesting the connection in 1974. It turns out that one of CFCs' most attractive features—their low reactivity— is key to their most destructive effects. CFCs' lack of reactivity gives them a lifespan that can exceed 100 years, giving them time to diffuse into the upper stratosphere. Once in the stratosphere, the sun's ultraviolet radiation is strong enough to cause the homolytic cleavage of the C-Cl bond.

By 1987, in response to a dramatic seasonal depletion of the ozone layer over Antarctica, diplomats in Montreal forged a treaty, the Montreal Protocol, which called for drastic reductions in the production of CFCs. On March 2, 1989, 12 European Community nations agreed to ban the production of all CFCs by the end of the century. In 1990, diplomats met in London and voted to significantly strengthen the Montreal Protocol by calling for a complete elimination of CFCs by the year 2000. By the year 2010 CFCs should be completely eliminated from developing countries as well.

Ozone-depleting gas trends

Because the only CFCs available to countries adhering to the treaty is from recycling, their prices have increased considerably. A worldwide end to production should also terminate the smuggling of this material.

By the time of the Montreal Protocol it was realised that deliberate and accidental discharges during system tests and maintenance accounted for substantially larger volumes than emergency discharges, and consequently halons were brought into the treaty, albeit with many exceptions.

Regulatory Gap

While the production and consumption of CFCs are regulated under the Montreal Protocol, emissions from pre-existing banks of CFCs are not regulated under the agreement. As of 2002, there were 5,791 kilotons of CFCs in existing products such as refrigerators, air conditioners, aerosol cans and others.^[6] Approximately one-third of these CFCs are projected to be emitted over the next decade if action is not taken, posing a threat to both the ozone layer and the climate.^[7] A proportion of these CFCs can be safely captured and destroyed.

Regulation and DuPont

In 1978 the United States banned the use of CFCs such as Freon in aerosol cans, the beginning of a long series of regulatory actions against their use. The critical DuPont manufacturing patent for Freon ("Process for Fluorinating Halohydrocarbons", U.S. Patent #3258500) was set to expire in 1979. In conjunction with other industrial peers DuPont sponsored efforts such as the "Alliance for Responsible CFC Policy" to question anti-CFC science, but in a turnabout in 1986 DuPont, with new patents in hand, publicly condemned CFCs.^[8] DuPont representatives appeared before the Montreal Protocol urging that CFCs be banned worldwide and stated that their new HCFCs would meet the worldwide demand for refrigerants.^[8]

Phase out of CFCs

Use of certain chloroalkanes as solvents for large scale application, such as dry cleaning, have been phased out, for example, by the IPPC directive on greenhouse gases in 1994 and by the Volatile Organic Compounds (VOC) directive of the EU in 1997. Permitted chlorofluoroalkane uses are medicinal only.

Bromofluoroalkanes have been largely phased out and the possession of equipment for their use is prohibited in some countries like the Netherlands and Belgium, from 1 January 2004, based on the Montreal Protocol and guidelines of the European Union.

Production of new stocks ceased in most (probably all) countries as of 1994. However many countries still require aircraft to be fitted with halon fire suppression systems because no safe and completely satisfactory alternative has been discovered for this application. There are also a few other, highly specialized uses. These programs recycle halon through "halon banks" coordinated by the Halon Recycling Corporation^[9] to ensure that discharge to the atmosphere occurs only in a genuine emergency and to conserve remaining stocks.

The interim replacements for CFCs are hydrochlorofluorocarbons (HCFCs), which deplete stratospheric ozone, but to a much lesser extent than CFCs.^[10] Ultimately, hydrofluorocarbons (HFCs) will replace HCFCs with essentially no ozone destruction (although all three groups of halocarbons are powerful greenhouse gases). DuPont began producing hydrofluorocarbons as alternatives to Freon in the 1980s. These included Suva refrigerants and Dymel propellants.^[11] Natural refrigerants are climate friendly solutions that are enjoying increasing support from large companies ^[12] and governments interested in reducing global warming emissions from refrigeration and air conditioning. Hydrofluorocarbons are included in the Kyoto Protocol because of their very high Global Warming Potential and are facing calls to be regulated under the Montreal Protocol due to the recognition of halocarbon contributions to climate change ^[13].

On September 21, 2007, approximately 200 countries agreed to accelerate the elimination of hydrochlorofluorocarbons entirely by 2020 in a United Nations-sponsored Montreal summit. Developing nations were given until 2030. Many nations, such as the United States and China, who had previously resisted such efforts, agreed with the accelerated phase out schedule.^[14]

Development of alternatives for CFCs

Work on alternatives for chlorofluorocarbons in refrigerants began in the late 1970s after the first warnings of damage to stratospheric ozone were published. The hydrochlorofluorocarbons (HCFCs) are less stable in the lower atmosphere, enabling them to break down before reaching the ozone layer. Nevertheless, a significant fraction of the HCFCs do break down in the stratosphere and they have contributed to more chlorine buildup there than originally predicted. Later alternatives lacking the chlorine, the hydrofluorocarbons (HFCs) have an even shorter lifetimes in the lower atmosphere. One of these compounds, HFC-134a, is now used in place of CFC-12 in automobile air conditioners. Hydrocarbon refrigerants (a propane/isobutane blend) are also used extensively in mobile air conditioning systems in Australia, the USA and many other countries, as they have excellent thermodynamic properties and perform particularly well in high ambient temperatures. One of the natural refrigerants (along with Ammonia and Carbon Dioxide), hydrocarbons have negligible environmental impacts and are also used worldwide in domestic and commercial refrigeration applications, and are becoming available in new split system air conditioners.^[15] Various other solvents and methods have replaced the use of CFCs in laboratory analytics.^[16]

Safety

According to their Material Safety Data Sheets, CFCs and HCFCs are colourless, volatile, relatively non-toxic liquids and gases with a faintly sweet ethereal odour. Overexposure may cause dizziness, loss of concentration, Central Nervous System depression and/or cardiac arrhythmia. Vapors displace air and can cause asphyxiation in confined spaces. Although non-flammable, their combustion products include hydrofluoric acid, and related species.^[17]

References

1. ↑ Günter Siegemund, Werner Schwertfeger, Andrew Feiring, Bruce Smart, 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
2. ↑ M. Rossberg et al. “Chlorinated Hydrocarbons” in Ullmann’s Encyclopedia of Industrial Chemistry 2006, Wiley-VCH, Weinheim. doi:10.1002/14356007.a06_233.pub2
3. ↑ Inventors accessed December 21, 2007
4. ↑ Carlisle, Rodney (2004). Scientific American Inventions and Discoveries, p.351. John Wiley & Songs, Inc., New Jersey. ISBN 0-471-24410-4.
5. ↑ McNeill, J.R. Something New Under the Sun: An Environmental History of the Twentieth-Century World (2001) New York: Norton, xxvi, 421 pp. (as reviewed in the Journal of Political Ecology)
6. ↑ IPCC/TEAP Special Report on Ozone and Climate
7. ↑ Chlorofluorocarbons: An Overlooked Climate Threat, EESI Congressional Briefing
8. ↑ ^{8.0 8.1} "Ethics of Du Pont's CFC Strategy 1975–1995", Smith B. Journal of Business Ethics, Volume 17, Number 5, April 1998, pp. 557-568(12)
9. ↑ Welcome to the Halon Corporation
10. ↑ "Ozone Layer Depletion", U.S. Environmental Protection Agency accessed June 25, 2008
11. ↑ "1930: Freon", DuPont Heritage accessed June 25, 2008
12. ↑ [1] "Refrigerants Naturally"
13. ↑ Velders et.al., PNAS March 20, 2007 vol. 104 no. 12 4814-4819 [2] "The importance of the Montreal Protocol in protecting climate"
14. ↑ HCFC Phaseout Schedule
15. ↑ "Greenpeace, Cool Technologies"
16. ↑ Use of Ozone Depleting Substances in Laboratories. TemaNord 516/2003
17. ↑ "MSDS R12"

External links

• Gas conversion table
• Nomenclature FAQ
• Numbering Scheme for Ozone-Depleting Substances and their Substitutes
• Class I Ozone-Depleting Substances
• CFC Illegal Trade
• Numbering Scheme for Ozone-Depleting Substances and their Substitutes
• Class I Ozone-Depleting Substances
• Class II Ozone-Depleting Substances (HCFCs)
• History of Halon use by the US Navy
• Ozone Loss: The Chemical Culprits
• Process using pyrolysis in an ultra high temperature plasma arc for the elimination of CFCs
• [3] Environmental Investigation Agency
• [4] Environmental Investigation Agency in the USA
• Freon in Car A/C