Chlorofluorocarbon

Chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) are fully or partly halogenated hydrocarbons that contain carbon (C), hydrogen (H), chlorine (Cl), and fluorine (F). They are produced as volatile derivatives of methane, ethane, and propane. The most common example of a CFC is dichlorodifluoromethane (R-12). R-12, also commonly called Freon, is used as a refrigerant. Many CFCs have been widely used as refrigerants, propellants (in aerosol applications), gaseous fire suppression systems, and solvents. As a result of CFCs contributing to ozone depletion in the upper atmosphere, the manufacture of such compounds has been phased out under the Montreal Protocol, and they are being replaced with other products such as hydrofluorocarbons (HFCs) and hydrofluoroolefins (HFOs) including R-410A, R-134a and R-1234yf.

Structure, properties and production

As in simpler alkanes, carbons in CFCs bond with tetrahedral symmetry. Because the fluorine and chlorine atoms differ greatly in size and effective charge from hydrogen and from each other, methane-derived CFCs deviate from perfect tetrahedral symmetry. The physical properties of CFCs and HCFCs can be affected by changes in the number and identity of the halogen atoms. They are generally volatile, but less so than their parent alkanes. The decreased volatility is attributed to the molecular polarity induced by the halides, which induces intermolecular interactions. Thus, methane boils at −161 °C whereas the fluoromethanes boil between −51.7 (CF2H2) and −128 °C (CF4). CFCs still have higher boiling points because the chloride is even more polarizable than fluoride. Because of their polarity, CFCs are useful solvents, and their boiling points make them suitable as refrigerants. 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 higher than their 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. Written below is the synthesis of chlorodifluoromethane from chloroform:

HCCl3 + 2 HF → HCF2Cl + 2 HCl Brominated derivatives are generated by free-radical reactions of hydrochlorofluorocarbons, replacing C–H bonds with C–Br bonds. The production of the anesthetic 2-bromo-2-chloro-1,1,1-trifluoroethane ("halothane") is written out below:

CF3CH2Cl + Br2 → CF3CHBrCl + HBr

Applications CFCs and HCFCs are used in various applications because of their low toxicity, reactivity and flammability. 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, aerosol 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.

Classes of compounds and Numbering System Chlorofluorocarbons (CFCs): when derived from methane and ethane, these compounds have the formulae CClmF4−m and C2ClmF6−m, where m is nonzero. Hydro-chlorofluorocarbons (HCFCs): when derived from methane and ethane, these compounds have the formula CClmFnH4−m−n and C2ClxFyH6−x−y, where m, n, x, and y are nonzero. Bromofluorocarbons (BFCs): have formulae similar to the CFCs and HCFCs, but also include bromine. Hydrofluorocarbons (HFCs): when derived from methane, ethane, propane, and butane, these compounds have the respective formulae CFmH4−m, C2FmH6−m, C3FmH8−m, and C4FmH10−m, where m is nonzero.

Numbering system A special numbering system is used for fluorinated alkanes, prefixed with Freon-, R-, CFC- and HCFC-, where 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), and the remaining atoms are chlorine. Freon-12, for example, indicates a methane derivative (only two numbers) containing two fluorine atoms (the second 2) and no hydrogen (1 − 1 = 0). It is therefore CCl2F2. Another equation that can be applied to get the correct molecular formula of the CFC/R/Freon class compounds is to take the numbering and add 90 to it. The resulting value will give the number of carbons as the first numeral, the second numeral gives the number of hydrogen atoms, and the third numeral gives the number of fluorine atoms. The rest of the unaccounted carbon bonds are occupied by chlorine atoms. The value of this equation is always a three figure number. An easy example is that of CFC-12, which gives: 90+12=102 -> 1 carbon, 0 hydrogens, 2 fluorine atoms, and hence 2 chlorine atoms resulting in CCl2F2. The main advantage of this method of deducing the molecular composition in comparison with the method described in the paragraph above is that it gives the number of carbon atoms of the molecule. Freons containing bromine are signified by four numbers. Isomers, which are common for ethane and propane derivatives, are indicated by letters following the numbers:

Reactions The reaction of the CFCs which is responsible for the depletion of ozone, 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-B radiation, 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.

Impact as greenhouse gases

CFCs were phased out via the Montreal Protocol due to their part in ozone depletion.

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