Hydroperoxyl

The hydroperoxyl radical, also known as the perhydroxyl radical, or HO₂^*, is the protonated form of superoxide.

Formation

Hydroperoxyl is formed through the transfer of a hydrogen atom to an oxygen atom.cite journal | title=Hydroperoxyl radical | journal=Glossary of Meteorology | accessdate=2008-08-18 ]

Equilibrium

The protonation/deprotonation equilibrium exhibits a pK(a) of around 4.80; consequently, about 0.3% of any superoxide present in the cytosol of a typical cell is in the protonated form. This ratio is rather accurately reflected by the published literature on the two species, as identified by a PubMed search; at the time of writing only 28 articles mention "HO₂^*," "hydroperoxyl" or "perhydroxyl" in their titles, as against 9228 mentioning superoxide. Here it is argued that this correlation is not justifiable: that HO₂^*'s biological and biomedical importance far exceeds the attention it has received. Several key observations of recent years are reviewed that can be explained much more economically when the participation of HO2* is postulated. It is suggested that a more widespread appreciation of the possible role of HO₂^* in biological systems would be of considerable benefit to biomedical research.

Because dielectric constant has a strong effect on pKa, and the dielectric constant of air is quite low, superoxide produced (photochemically) in the atmosphere is almost exclusively present as HO₂^*. As HO₂^* is quite reactive, it acts as a "cleanser" of the atmosphere by degrading certain organic pollutants. As such, the chemistry of HO₂^* is of considerable geochemical importance.

_____________________________________________ T Cp S delta-Hf _____ ________________ ________ K cal/mol K kcal/mol _____________________________________________ 200 7.99 51.51 3.22 298 8.34 54.75 3.00 300 8.35 54.81 3.00 400 8.89 57.88 2.80 500 9.47 59.33 2.63 600 10.00 61.10 2.50 700 10.43 62.68 2.40 800 10.77 64.09 2.31 900 11.06 65.38 2.23 1000 11.38 66.56 2.16 1100 11.63 67.65 2.11 1200 11.86 68.68 2.07 1300 12.08 69.63 2.04 1400 12.29 70.54 2.02 1500 12.48 71.39 2.00 1600 12.67 72.20 1.99 1700 12.85 72.98 1.99 1800 13.01 73.72 2.00 1900 13.17 74.42 2.01 2000 13.32 75.10 2.03 2100 13.46 75.76 2.05 2200 13.60 76.39 2.07 2300 13.72 76.99 2.10 2400 13.84 77.58 2.14 2500 13.95 78.15 2.17 2600 14.05 78.70 2.21 2700 14.15 79.23 2.25 2800 14.24 79.74 2.29 2900 14.32 80.25 2.33 3000 14.40 80.73 2.37

Effect on environment

Hydroperoxyl is responsible for the destruction of ozone in the stratosphere, and it is formed as a result of the oxidation of hydrocarbons in the troposphere.

References

*The standard enthalpy of formation and standard entropy values at 298 K were provided by Martin J. Rabinowitz of NASA Lewis Research Center
* [http://www.cem.msu.edu/~harrison/hydrides/HOBIG.gifHO₂^* molecule in action]