A theoretical study on the formation and oxidation mechanism of hydroxyalkylsulfonate in the atmospheric aqueous phase

Abstract

Hydroxymethanesulfonate (HMS) is an important organosulfur compound in the atmosphere. In this work, we studied the formation mechanism of HMS via the reaction of formaldehyde with dissolved SO₂ using the quantum chemistry calculations. The results show that the barrier (9.7 kcal mol⁻¹) of the HCHO + HSO₃⁻ reaction is higher than that (1.6 kcal mol⁻¹) of the HCHO + SO₃²⁻ reaction, indicating that the HCHO + SO₃²⁻ reaction is easier to occur. For comparison, the reaction of acetaldehyde with dissolved SO₂ also was discussed. The barriers for the CH₃CHO + HSO₃⁻ reaction and CH₃CHO + SO₃²⁻ reaction are 16.6 kcal mol⁻¹, 2.5 kcal mol⁻¹, respectively. This result suggests that the reactivity of HCHO with dissolved SO₂ is higher than that of CH₃CHO. The further oxidation of CH₂(OH)SO₃⁻ and CH₃CH(OH)SO₃⁻ by an OH radical and O₂ shows that the SO₅˙⁻ radical can be produced.