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** Chlorofluorocarbon**
Chlorofluorocarbons (CFCs) are fully halogenated paraffin hydrocarbons that contain
only carbon, chlorine, and fluorine, produced as volatile derivative of methane, ethane,
and propane. They are also commonly known by the DuPont brand 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. Because CFCs contribute 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).
1.Structure, properties and production
As in simpler alkanes, carbon in the CFCs bonds with tetrahedral symmetry. Because the fluorine
and chlorine atoms differ greatly in size and effective charge from hydrogen and from each other,
the methane-derived CFCs deviate from perfect tetrahedral symmetry.
The physical properties of 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 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). 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, and their boiling points make them suitable as refrigerants. 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 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. Illustrative is the synthesis of chlorodifluoromethane from chloroform:
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.
3.Applications
CFCs and HCFCs are used in a variety of 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, propellants in medicinal applications and degreasing
solvents.
*Hydro-chlorofluorocarbons (HCFCs): when derived from methane and ethane these compounds
have the formula CClmFnH4mn and C2ClxFyH6xy, where m, n, x, and y are nonzero.
*And bromofluorocarbons 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 CFmH4m, C2FmH6m, C3FmH8m, and C4FmH10m, where m
is nonzero.
4.1.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, easier equation that can be applied to get the correct molecular formula of the
CFC/R/Freon class compounds is this 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
hydrogen, 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 ;-
5.Environmental impacts
As previously discussed, CFCs were phased out via the Montreal Protocol due to their part in ozone
depletion. However, the atmospheric impacts of CFCs are not limited to its role as an active ozone
reducer. This anthropogenic compound is also a greenhouse gas, with a much higher potential to
enhance the greenhouse effect than CO2.
Infrared absorption bands trap heat from escaping earth's atmosphere. In the case of CFCs, the
strongest of these bands are located in the spectral region 7.815.3 m referred to as an
atmospheric window due to the relative transparency of the atmosphere within this region. The
strength of CFC bands and the unique susceptibility of the atmosphere, at which the compound
absorbs and emits radiation, are two factors that contribute to CFCs' "super" greenhouse
effect. Another such factor is the low concentration of the compound. Because CO2 is close to
saturation with high concentrations, it takes more of the substance to enhance the greenhouse
effect. Conversely, the low concentration of CFCs allow their effects to increase linearly with mass.
Using CFCs or SF6 as a tracer of ocean circulation allows for the derivation of rates for ocean
processes due to the time-dependent source function. The elapsed time since a subsurface water
mass was last in contact with the atmosphere is the tracer-derived age. Estimates of age can be
derived based on the partial pressure of an individual compound and the ratio of the partial
pressure of CFCs to each other (or SF6).
pCFC = [CFC]/F(T,S)
where [CFC] is the measured CFC concentration (pmol kg1) and F is the solubility of CFC gas in
seawater as a function of temperature and salinity. The CFC partial pressure is expressed in units
of 1012 atmospheres or parts-per-trillion (ppt). The solubility measurements of CFC-11 and CFC-12
have been previously measured by Warner and Weiss Additionally, the solubility measurement of
CFC-113 was measured by Bu and Warner and SF6 by Wanninkhof et al. and Bullister et al. Theses
authors mentioned above have expressed the solubility, F, at a total pressure of 1 atm as:
where F = solubility expressed in either mol l1 or mol kg1 atm1 T = absolute temperature S =
salinity in parts per thousand (ppt) a1, a2, a3, b1, b2, and b3 are constants to be determined from the
least squares fit to the solubility measurements. This equation is derived from the integrated Van 't
Hoff equation and the logarithmic Setchenow salinity dependence.
It can be noted that the solubility of CFCs increase with decreasing temperature at approximately
1% per degree Celsius.
Once the partial pressure of the CFC (or SF6) is derived, it is then compared to the atmospheric
time histories for CFC-11, CFC-12, or SF6 in which the pCFC directly corresponds to the year with
the same. The difference between the corresponding date and the collection date of the seawater
sample is the average age for the water parcel. The age of a parcel of water can also be calculated
using the ratio of two CFC partial pressures or the ratio of the SF6 partial pressure to a CFC partial
pressure.