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

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 SO(2) using the quantum chemistry calculations. The results show that the barrier (9.7 kcal mol(−1)) of the HCHO + HSO(3)(−) reaction is higher than that (1.6 kcal mol(−1)) of the HCHO + SO(3)(2−) reaction, indicating that the HCHO + SO(3)(2−) reaction is easier to occur. For comparison, the reaction of acetaldehyde with dissolved SO(2) also was discussed. The barriers for the CH(3)CHO + HSO(3)(−) reaction and CH(3)CHO + SO(3)(2−) reaction are 16.6 kcal mol(−1), 2.5 kcal mol(−1), respectively. This result suggests that the reactivity of HCHO with dissolved SO(2) is higher than that of CH(3)CHO. The further oxidation of CH(2)(OH)SO(3)(−) and CH(3)CH(OH)SO(3)(−) by an OH radical and O(2) shows that the SO(5)˙(−) radical can be produced.