Theoretical study of the oxidation reactions of sulfurous acid/sulfite with ozone to produce sulfuric acid/sulfate with atmospheric implications

Abstract

Herein, theoretical studies were performed on the atmospheric oxidation of sulfurous acid (H₂SO₃) and sulfite ions (HSO₃⁻) by ozone (O₃) to produce sulfuric acid and hydrosulfate ions. The most favorable path for the H₂SO₃ + O₃ reaction has been found to be initiated from concerted H-abstraction and oxygen addition, with an overall energy barrier of 18.3 kcal mol⁻¹. On the other hand, the most favorable path for the HSO₃⁻ + O₃ reaction is initiated from oxygen addition, with an overall energy barrier of only 0.3 kcal mol⁻¹. Kinetic simulations were performed to estimate the significance of these reactions in the formation of atmospheric sulfate and destruction of the ozone layer. The results provide new insight into the missing source of atmospheric sulfate and particulate matter.