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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; Herrmann, Hartmut2,4; Chan, Man Nin1,5
2025-01-07
Source PublicationACS Earth and Space Chemistry
ISSN2472-3452
Volume9Issue: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.

KeywordAqueous-phase Oxidation Organosulfates Sulfate And Sulfite Functional Groups Sulfate Radical Sulfonates
DOI10.1021/acsearthspacechem.4c00313
URLView the original
Indexed BySCIE
Language英語English
WOS Research AreaChemistry ; Geochemistry & Geophysics
WOS SubjectChemistry, Multidisciplinary ; Geochemistry & Geophysics
WOS IDWOS:001392245500001
PublisherAMER CHEMICAL SOC, 1155 16TH ST, NW, WASHINGTON, DC 20036
Scopus ID2-s2.0-85214511588
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Document TypeJournal article
CollectionFaculty of Science and Technology
DEPARTMENT OF CIVIL AND ENVIRONMENTAL ENGINEERING
DEPARTMENT OF OCEAN SCIENCE AND TECHNOLOGY
Corresponding AuthorHerrmann, Hartmut; Chan, Man Nin
Affiliation1.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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