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二阶动力学硫酸盐自由基(SO)氧化一些大气相关有机化合物的速率系数。

Second-Order Kinetic Rate Coefficients for the Aqueous-Phase Sulfate Radical (SO) Oxidation of Some Atmospherically Relevant Organic Compounds.

机构信息

Department of Environmental Toxicology, University of California Davis, Davis, California 95616, United States.

Department of Chemistry, University of California Davis, Davis, California 95616, United States.

出版信息

J Phys Chem A. 2022 Sep 22;126(37):6517-6525. doi: 10.1021/acs.jpca.2c04964. Epub 2022 Sep 7.

Abstract

The sulfate anion radical (SO) is a reactive oxidant formed in the autoxidation chain of sulfur dioxide, among other sources. Recently, new formation pathways toward SO and other reactive sulfur species have been reported. This work investigated the second-order rate coefficients for the aqueous SO oxidation of the following important organic aerosol compounds (): 2-methyltetrol, 2-methyl-1,2,3-trihydroxy-4-sulfate, 2-methyl-1,2-dihydroxy-3-sulfate, 1,2-dihydroxyisoprene, 2-methyl-2,3-dihydroxy-1,4-dinitrate, 2-methyl-1,2,4-trihydroxy-3-nitrate, 2-methylglyceric acid, 2-methylglycerate, lactic acid, lactate, pyruvic acid, pyruvate. The rate coefficients of the unknowns were determined against that of a reference in pure water in a temperature range of 298-322 K. The decays of each reagent were measured with nuclear magnetic resonance (NMR) and high-performance liquid chromatography-high-resolution mass spectrometry (HPLC-HRMS). Incorporating additional SO reactions into models may aid in the understanding of organosulfate formation, radical propagation, and aerosol mass sinks.

摘要

硫酸根阴离子自由基(SO)是二氧化硫自动氧化链中形成的一种反应性氧化剂,还有其他来源。最近,已经报道了 SO 和其他活性硫物种的新形成途径。这项工作研究了以下重要有机气溶胶化合物()在水溶液中被 SO 氧化的二级速率系数:2-甲基四醇、2-甲基-1,2,3-三羟基-4-硫酸盐、2-甲基-1,2-二羟基-3-硫酸盐、1,2-二羟基异戊二烯、2-甲基-2,3-二羟基-1,4-二硝酸盐、2-甲基-1,2,4-三羟基-3-硝酸盐、2-甲基甘油酸、2-甲基甘油酸酯、乳酸、乳酸盐、丙酮酸、丙酮酸。在 298-322 K 的温度范围内,通过在纯水中与参考物质的反应,确定了未知物的速率系数。每个试剂的衰减都通过核磁共振(NMR)和高效液相色谱-高分辨率质谱(HPLC-HRMS)进行测量。将更多的 SO 反应纳入模型中,可能有助于理解有机硫酸盐的形成、自由基传播和气溶胶质量汇。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/819b/9511566/21bd3de0f80f/jp2c04964_0006.jpg

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