Massive ozone depletions were first observed in 1975 over the Antarctic and more recently over the Arctic. Although the reactions in Equation 3.38 and Equation 3.39 appear to account for most of the ozone destruction observed at low to middle latitudes, Equation 3.37 requires intense sunlight to generate chlorine atoms, and sunlight is in very short supply during the polar winters. At high latitudes (near the poles), therefore, a different set of reactions must be responsible for the depletion.
Recent research has shown that, in the absence of oxygen atoms, chlorine monoxide can react with stratospheric nitrogen dioxide in a redox reaction to form chlorine nitrate (ClONO2). When chlorine nitrate is in the presence of trace amounts of HCl or adsorbed on ice particles in stratospheric clouds, additional redox reactions can occur in which chlorine nitrate produces Cl2 or HOCl (hypochlorous acid):
Equation 3.42
HCl(g) + ClONO2(g) → Cl2(g) + HNO3(g)
Equation 3.43
H2O(g) + ClONO2(g) → HOCl(g) + HNO3(g)
Both Cl2 and HOCl undergo cleavage reactions by even weak sunlight to give reactive chlorine atoms. When the sun finally rises after the long polar night, relatively large amounts of Cl2 and HOCl are present and rapidly generate high levels of chlorine atoms. The reactions shown in Equation 3.38 and Equation 3.39 then cause ozone levels to fall dramatically.
Stratospheric ozone levels decreased about 2.5% from 1978 to 1988, which coincided with a fivefold increase in the widespread use of CFCs since the 1950s. If the trend were allowed to continue, the results could be catastrophic. Fortunately, many countries have banned the use of CFCs in aerosols. In 1987, representatives from 43 nations signed the Montreal Protocol, committing themselves to reducing CFC emissions by 50% by the year 2000. Later, representatives from a large number of countries, alarmed by data showing the rapid depletion of stratospheric chlorine, agreed to phase out CFCs completely by the early 21st century; the United States banned their use in 1995. The projected effects of these agreements on atmospheric chlorine levels are shown in Figure 3.17 “Projected Effects of International Agreements on Atmospheric Chlorine Levels”. Because of the very slow rate at which CFCs are removed from the stratosphere, however, stratospheric chlorine levels will not fall to the level at which the Antarctic ozone hole was first observed until about 2050. The scientific community recognized Molina and Rowland’s work in 1995, when they shared the Nobel Prize in Chemistry.
Figure 3.17 Projected Effects of International Agreements on Atmospheric Chlorine Levels
The graph plots atmospheric chlorine content in chlorine atoms per 109 molecules of O2 plus N2 from 1960 to 1990 (actual data) and 1990 to 2080 (estimated for various schemes for regulating CFC emissions).
Manufacturing companies are now under great political and economic pressure to find alternatives to the CFCs used in the air-conditioning units of cars, houses, and commercial buildings. One approach is to use hydrochlorofluorocarbons (HCFCs), hydrocarbons in which only some of the hydrogen atoms are replaced by chlorine or fluorine, and hydrofluorocarbons (HFCs), which do not contain chlorine (Table 3.4 “Selected HCFCs and HFCs”). The C–H bonds in HCFCs and HFCs act as “handles” that permit additional chemical reactions to occur. Consequently, these substances are degraded more rapidly, and most are washed out of the atmosphere before they can reach the stratosphere.
Table 3.4 Selected HCFCs and HFCs
| Name | Molecular Formula | Industrial Name |
|---|---|---|
| chlorodifluoromethane | CHClF2 | HCFC-22 (freon-22) |
| 1-chloro-1,1-difluoroethane | CH3CClF2 | HCFC-141b |
| 2,2-dichloro-1,1,1-trifluoroethane | CHCl2CF3 | HCFC-123 |
| 1,1,1,2-tetrafluoroethane | CH2FCF3 | HFC-134a |
HFCs are used as a replacement for CFCs. The molecular structure of HFC-134a is shown in this ball-and-stick model.
Nonetheless, the small fraction of HCFCs that reaches the stratosphere will deplete ozone levels just as CFCs do, so they are not the final answer. Indeed, the 1990 London amendment to the Montreal Protocol specifies that HCFCs must be phased out by 2040. Finding a suitable replacement for refrigerants is just one of the challenges facing chemists in the 21st century.