Null cycle

In atmospheric chemistry, a null cycle is a catalytic cycle that simply interconverts chemical species without leading to net production or removal of any component. In the stratosphere, null cycles are very important in contrasting series of reactions that lead to net depletion in the ozone layer.^[1]

One such cycle involves the nitrogen oxide species, which are the most responsible for ozone depletion in the stratosphere.^[2] The catalytic cycle is:

NO + O₃ → NO₂ + O₂
NO₂ + O → NO + O₂
Net: O + O₃ → 2O₂

while the corresponding null cycle competes due to the possible photolysis of NO₂ which allows conservation of the odd oxygen species:

NO + O₃ → NO₂ + O₂
NO₂ + hν → NO + O
Net: O₃ + hν → O + O₂

Since O and O₃ can exchange rapidly, the last cycle does not affect the rate of consumption of ozone which thus decreases during the day when photolysis can occur. NO can also react with other free radicals, such as chlorine and bromine, providing pathways that lead to null cycles:

Cl + O₃ → ClO + O₂
ClO + NO → Cl + NO₂
NO₂ + hν → NO + O
Net: O₃ + hν → O + O₂

Other null cycles, also termed holding cycles, produce reservoirs, effectively holding up the reactive species. An example is the formation of dinitrogen pentoxide:

NO₂ + NO₃ → N₂O₅

This can lock up about 10% of the NO_x family of species present in the atmosphere, limiting their ability to participate in the ozone-destructing catalytic cycles.^[3]

References

1. Holloway, Ann M.; Wayne, Richard P. (2010). Atmospheric Chemistry. Royal Society of Chemistry. p. 145. ISBN 9781847558077.
2. "NOAA Study Shows Nitrous Oxide Now Top Ozone-Depleting Emission". NOAA. 2009-08-27. Retrieved 2012-05-23.
3. Girard, James (2009). Principles of Environmental Chemistry (2 ed.). Jones & Bartlett Learning. pp. 135–136. ISBN 9780763759391.