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Oxidation Kinetics of Alkyl Sulfates and Sulfonates by Sulfate Radical (SO4•-) in the Aqueous Phase: Deactivating Role of Sulfur Functional Groups | |
Lai, Donger1; Schaefer, Thomas2; Zhang, Yimu2; Li, Yong Jie3![]() ![]() ![]() | |
2025-01-07 | |
Source Publication | ACS Earth and Space Chemistry
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ISSN | 2472-3452 |
Volume | 9Issue:1Pages:158-168 |
Abstract | The sulfate radical (SO) is a potent oxidant known to efficiently oxidize many organic compounds in the aqueous phase. To date, reactions of SO with alkyl sulfates and sulfonates, which are common organosulfur compounds found in atmospheric aerosols and cloud droplets, are not well understood. Here, we employed a laser flash photolysis-long path absorption (LFP-LPA) technique to measure the temperature-dependent oxidation kinetics of organosulfur compounds initiated by SO in the aqueous phase. These compounds included five alkyl sulfates, namely, methyl sulfate (MS), ethyl sulfate (ES), octyl sulfate (OS), decyl sulfate (DS), and dodecyl sulfate (SDS), as well as three sulfonates, namely, methanesulfonate (MSA), hydroxymethanesulfonate (HMS), and 2-hydroxyethylsulfonate (HES). Our kinetic data revealed that the second-order rate constants of these organosulfur compounds were in the range of 10 to 10 L mol s and exhibited a positive temperature-dependency across the range of 278 to 318 K. Upon oxidation, the hydrogen abstraction is likely the dominant pathway. Moreover, alkyl sulfates and sulfonates generally exhibit smaller reactivities compared to other organic compounds with the same carbon number, such as alcohols. This reduced reactivity could be explained by the strong electron-withdrawing nature of sulfur functional groups (i.e., −OSO in alkyl sulfates and −SO in sulfonates). Among the two sulfur functional groups, −SO shows a stronger deactivating effect than −OSO, likely due to the higher charge density of the former. Overall, the findings of this work fill a gap in the understanding of the SO oxidation kinetics in organosulfur compounds. |
Keyword | Aqueous-phase Oxidation Organosulfates Sulfate And Sulfite Functional Groups Sulfate Radical Sulfonates |
DOI | 10.1021/acsearthspacechem.4c00313 |
URL | View the original |
Indexed By | SCIE |
Language | 英語English |
WOS Research Area | Chemistry ; Geochemistry & Geophysics |
WOS Subject | Chemistry, Multidisciplinary ; Geochemistry & Geophysics |
WOS ID | WOS:001392245500001 |
Publisher | AMER CHEMICAL SOC, 1155 16TH ST, NW, WASHINGTON, DC 20036 |
Scopus ID | 2-s2.0-85214511588 |
Fulltext Access | |
Citation statistics | |
Document Type | Journal article |
Collection | Faculty of Science and Technology DEPARTMENT OF CIVIL AND ENVIRONMENTAL ENGINEERING DEPARTMENT OF OCEAN SCIENCE AND TECHNOLOGY |
Corresponding Author | Herrmann, Hartmut; Chan, Man Nin |
Affiliation | 1.Department of Earth and Environmental Sciences, Faculty of Science, The Chinese University of Hong Kong, Hong Kong, 999077, Hong Kong 2.Atmospheric Chemistry Department (ACD), Leibniz Institute for Tropospheric Research (TROPOS), Leipzig, 04318, Germany 3.Department of Civil and Environmental Engineering, Department of Ocean Science and Technology, Centre for Regional Oceans, Faculty of Science and Technology, University of Macau, Taipa, Macau, 999078, Macao 4.School of Environmental Science and Engineering, Shandong University, Qingdao, 266237, China 5.The Institute of Environment, Energy, and Sustainability, The Chinese University of Hong Kong, Hong Kong, 999077, Hong Kong |
Recommended Citation GB/T 7714 | Lai, Donger,Schaefer, Thomas,Zhang, Yimu,et al. Oxidation Kinetics of Alkyl Sulfates and Sulfonates by Sulfate Radical (SO4•-) in the Aqueous Phase: Deactivating Role of Sulfur Functional Groups[J]. ACS Earth and Space Chemistry, 2025, 9(1), 158-168. |
APA | Lai, Donger., Schaefer, Thomas., Zhang, Yimu., Li, Yong Jie., Herrmann, Hartmut., & Chan, Man Nin (2025). Oxidation Kinetics of Alkyl Sulfates and Sulfonates by Sulfate Radical (SO4•-) in the Aqueous Phase: Deactivating Role of Sulfur Functional Groups. ACS Earth and Space Chemistry, 9(1), 158-168. |
MLA | Lai, Donger,et al."Oxidation Kinetics of Alkyl Sulfates and Sulfonates by Sulfate Radical (SO4•-) in the Aqueous Phase: Deactivating Role of Sulfur Functional Groups".ACS Earth and Space Chemistry 9.1(2025):158-168. |
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