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Mechanistic Study of the Aqueous Reaction of Organic Peroxides with HSO 3 − on the Surface of a Water Droplet
Author(s) -
Li Hao,
Wang Xiao,
Zhong Jie,
Chu Biwu,
Ma Qingxin,
Zeng Xiao Cheng,
Francisco Joseph S.,
He Hong
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202105416
Subject(s) - chemistry , aqueous solution , sulfate , inorganic chemistry , peroxide , atom (system on chip) , reaction mechanism , hydrogen peroxide , reaction rate , chemical reaction , photochemistry , catalysis , organic chemistry , computer science , embedded system
Aqueous reactions between organic peroxides and SO 2 are of intense interest in atmospheric science because of their ubiquitous implications for sulfate formation in secondary aerosols. However, the relative yields of the reaction products (inorganic vs. organic sulfates) remain controversial (i.e., 90 % vs. 40–70 % for inorganic sulfate) due in part to the lack of understanding of the underlying reaction mechanisms. Here, our computational results suggest that the reactions of HSO 3 − (dissolved SO 2 ) with organic peroxides are initiated on the surface of water nanodroplets and then proceed under two reaction pathways, in which the S atom of HSO 3 − attacks either the O1 or O2 atom of the peroxide group ‐O(O2)O(O1)H, leading to the formation of inorganic and organic sulfates, respectively. Notably, we find that thse reaction initiated by O1 atom exhibits a relatively low energy barrier and high reaction rate, which favours the formation of inorganic sulfate.