Ozone and temperature
The mechanism describing the formation of the ozone layer was described by British mathematician Sydney Chapman in 1930. Molecular oxygen absorbs high energy sunlight in the UV-C region, at wavelengths shorter than about 240 nm. Radicals produced from the homolytically split oxygen molecules combine with molecular oxygen to form ozone. Ozone in turn is photolysed much more rapidly than molecular oxygen as it has a stronger absorption that occurs at longer wavelengths, where the solar emission is more intense. Ozone (O3) photolysis produces O and O2. The oxygen atom product combines with atmospheric molecular oxygen to reform O3, releasing heat. The rapid photolysis and reformation of ozone heats the stratosphere resulting in a temperature inversion. This increase of temperature with altitude is characteristic of the stratosphere; its resistance to vertical mixing means that it is stratified. Within the stratosphere temperatures increase with altitude (see temperature inversion); the top of the stratosphere has a temperature of about 270 K (−3°C or 26.6°F).
This vertical stratification, with warmer layers above and cooler layers below, makes the stratosphere dynamically stable: there is no regular convection and associated turbulence in this part of the atmosphere. However, exceptionally energetic convection processes, such as volcanic eruption columns and overshooting tops in severe supercell thunderstorms, may carry convection into the stratosphere on a very local and temporary basis. Overall the attenuation of solar UV at wavelengths that damage DNA by the ozone layer allows life to exist on the surface of the planet outside of the ocean. All air entering the stratosphere must pass through the tropopause, the temperature minimum that divides the troposphere and stratosphere. The rising air is literally freeze dried; the stratosphere is a very dry place. The top of the stratosphere is called the stratopause, above which the temperature decreases with height.
Sydney Chapman gave a correct description of the source of stratospheric ozone and its ability to generate heat within the stratosphere; he also wrote that ozone may be destroyed by reacting with atomic oxygen, making two molecules of molecular oxygen. We now know that there are additional ozone loss mechanisms, and that these mechanisms are catalytic meaning that a small amount of the catalyst can destroy a great number of ozone molecules. The first is due to the reaction of hydroxyl radicals (•OH) with ozone. •OH is formed by the reaction of electronically excited oxygen atoms produced by ozone photolysis, with water vapor. While the stratosphere is dry, additional water vapor is produced in situ by the photochemical oxidation of methane (CH4). The HO2 radical produced by the reaction of OH with O3 is recycled to OH by reaction with oxygen atoms or ozone. In addition, solar proton events can significantly affect ozone levels via radiolysis with the subsequent formation of OH. Nitrous oxide (N2O) is produced by biological activity at the surface and is oxidised to NO in the stratosphere; the so-called NOx radical cycles also deplete stratospheric ozone. Finally, chlorofluorocarbon molecules are photolysed in the stratosphere releasing chlorine atoms that react with ozone giving ClO and O2. The chlorine atoms are recycled when ClO reacts with O in the upper stratosphere, or when ClO reacts with itself in the chemistry of the Antarctic ozone hole.
Paul J. Crutzen, Mario J. Molina and F. Sherwood Rowland were awarded the Nobel Prize in Chemistry in 1995 for their work describing the formation and decomposition of stratospheric ozone.