Sulfuric Acid Formation via HSO Oxidation by HO in the Atmosphere.

With the help of quantum mechanical methods, the formation of HSO by the oxidation of HSO with HO was studied theoretically. Both stepwise and concerted mechanisms were calculated. It was found that the direct oxidation of HSO by HO alone requires prohibitive activation energies of >38.6 kcal/mol. However, the addition of one water molecule exhibits a strong catalytic effect that dramatically reduces the overall reaction barrier to 6.2 (2.3 with PCM) kcal/mol. The deprotonated HSO species also reduces the overall reaction barrier to 5.6 (-5.8 with PCM) kcal/mol. Both of these proceed via concerted pathways. On the other hand, the stepwise mechanisms generally produce intermediates with a hydroperoxy group (-O-O-H), which is a result of a nucleophilic attack by the oxygens of HO. While studying the catalytic effect of water, a previously unknown hydroperoxy intermediate (HOO)S(OH), where sulfur is coordinated with three OH groups, was found. This work also reveals a rearrangement step of another hydroperoxy intermediate (HOO)SO to HSO that was found in earlier experimental studies. For all of the mechanisms calculated, the final HSO is formed with a significant exothermicity of >60 kcal/mol. In general, even without sunlight, it was found that the formation of sulfuric acid by hydrogen peroxide can occur in a heterogeneous moisturized environment.