Kinetics Study of Acid-Catalyzed Sulfate Esterification Reactions for Atmospherically Relevant Polyols
Kinetics Study of Acid-Catalyzed Sulfate Esterification Reactions for Atmospherically Relevant Polyols
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大气相关多元醇酸催化硫酸酯化反应的动力学研究
DOI：
10.1021/acsearthspacechem.2c00306
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发表时间：
2022
影响因子：
3.4
通讯作者：
Elrod, Matthew J.
中科院分区：
文献类型：
--
作者：
Mohammed, Aziz C.;Sheffield, Sunniva B.;Elrod, Matthew J.
广泛的实验室和实地研究已经确定有机硫酸盐是二次有机气溶胶（SOA）的重要成分。然而，这些有机硫酸盐在大气中形成的机制仍然不确定。采用核磁共振体动力学方法测定了一系列多元醇酸催化硫酸酯化反应的速率常数。核磁共振数据表明，虽然在末端羟基上发生的反应比在内部羟基上发生的反应要快，但在一系列多元醇中没有其他明显的结构反应性趋势。这些结果表明，邻近的羟基并没有显著改变硫酸盐酯化率从那些先前确定的单醇。对典型大气SOA酸度的动力学数据外推表明，多元醇的硫酸盐酯化反应不太可能是有机硫酸盐的重要来源。这一结论与先前对单醇的研究一致，该研究对这种反应类型的动力学不可行性作出了类似的结论。
Extensive laboratory and field studies have identified organosulfates as important constituents of secondary organic aerosol (SOA). However, the mechanisms by which these organosulfates form in the atmosphere remain uncertain. The rate constants for the acid-catalyzed sulfate esterification reactions of a series of polyols were measured via bulk kinetics experiments using nuclear magnetic resonance (NMR) spectroscopy. The NMR data indicated that while reactions that occurred at a terminal hydroxyl site were somewhat faster than reactions at internal hydroxyl sites, there were no other significant structure–reactivity trends among the series of polyols. These results suggest that neighboring hydroxyl groups do not significantly modify the sulfate esterification rates from those previously determined for monoalcohols. Extrapolation of the kinetics data to typical atmospheric SOA acidities suggests that sulfate esterification reactions of polyols are unlikely to be a significant source of organosulfates. This conclusion is consistent with a previous study of monoalcohols which made similar conclusions about the kinetic infeasibility of this reaction type.
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影响因子：
5
作者：
Hughes, Dagen D.;Christiansen, Megan B.;Stone, Elizabeth A.
通讯作者：
Stone, Elizabeth A.
DOI：
10.1039/c3cp54859g
发表时间：
2014-03
期刊：
Physical chemistry chemical physics : PCCP
影响因子：
--
作者：
L. Schöne;J. Schindelka;Edyta Szeremeta;T. Schaefer;D. Hoffmann;K. Rudzinski;R. Szmigielski;H. He
通讯作者：
L. Schöne;J. Schindelka;Edyta Szeremeta;T. Schaefer;D. Hoffmann;K. Rudzinski;R. Szmigielski;H. He
影响因子：
3.4
作者：
Aoki, Erika;Sarrimanolis, Jon N.;Elrod, Matthew J.
通讯作者：
Elrod, Matthew J.
酸度过多。
DOI：
--
发表时间：
1978
期刊：
影响因子：
--
作者：
R. A. Cox;K. Yates
通讯作者：
K. Yates