Articles | Volume 22, issue 5
https://doi.org/10.5194/acp-22-3693-2022
© Author(s) 2022. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/acp-22-3693-2022
© Author(s) 2022. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
18 Mar 2022
Research article |
| 18 Mar 2022
| 18 Mar 2022
OH-initiated atmospheric degradation of hydroxyalkyl hydroperoxides: mechanism, kinetics, and structure–activity relationship
Long Chen
State Key Lab of Loess and Quaternary Geology (SKLLQG), Institute of Earth Environment, Chinese Academy of Sciences (CAS), Xi'an, 710061, China
CAS Center for Excellence in Quaternary Science and Global Change, Xi'an, 710061, China
Yu Huang
CORRESPONDING AUTHOR
State Key Lab of Loess and Quaternary Geology (SKLLQG), Institute of Earth Environment, Chinese Academy of Sciences (CAS), Xi'an, 710061, China
CAS Center for Excellence in Quaternary Science and Global Change, Xi'an, 710061, China
Yonggang Xue
State Key Lab of Loess and Quaternary Geology (SKLLQG), Institute of Earth Environment, Chinese Academy of Sciences (CAS), Xi'an, 710061, China
CAS Center for Excellence in Quaternary Science and Global Change, Xi'an, 710061, China
Zhihui Jia
School of Materials Science and Engineering, Shaanxi Normal University, Xi'an, Shaanxi, 710119, China
Wenliang Wang
School of Chemistry and Chemical Engineering, Key Laboratory for Macromolecular Science of Shaanxi Province, Shaanxi Normal University, Xi'an, Shaanxi, 710119, China
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The mechanisms and kinetics of the formation of highly oxidized products from the multi-generation ·OH oxidation of styrene in the absence and presence of NOx are studied using the quantum chemistry methods. The calculations show that the volatility of the multi-generation ·OH oxidation products significantly decreases with increasing the number of ·OH oxidation steps.
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Quantum chemical methods are applied to gain insight into the oligomerization reaction mechanisms and kinetics of distinct stabilized Criegee intermediate (SCI) reactions with hydroperoxide esters, where calculations show that SCI addition reactions with hydroperoxide esters proceed through the successive insertion of SCIs to form oligomers that involve SCIs as the repeating unit. The saturated vapor pressure of the formed oligomers decreases monotonically with the increasing number of SCIs.
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The mechanisms and kinetics of the formation of highly oxidized products from the multi-generation ·OH oxidation of styrene in the absence and presence of NOx are studied using the quantum chemistry methods. The calculations show that the volatility of the multi-generation ·OH oxidation products significantly decreases with increasing the number of ·OH oxidation steps.
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Quantum chemical methods are applied to gain insight into the oligomerization reaction mechanisms and kinetics of distinct stabilized Criegee intermediate (SCI) reactions with hydroperoxide esters, where calculations show that SCI addition reactions with hydroperoxide esters proceed through the successive insertion of SCIs to form oligomers that involve SCIs as the repeating unit. The saturated vapor pressure of the formed oligomers decreases monotonically with the increasing number of SCIs.
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In this study, we report the long-term measurement of organic carbon (OC) and elementary carbon (EC) in PM2.5 with hourly time resolution conducted at a regional site in Shanghai from 2016 to 2020. The results from this study provide critical information about the long-term trend of carbonaceous aerosol, in particular secondary OC, in one of the largest megacities in the world and are helpful for developing pollution control measures from a long-term planning perspective.
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Short summary
Quantum chemical methods are applied to gain insight into the detailed mechanisms of OH-initiated oxidation of distinct HHPs. The dominant pathway is H-abstraction from the -OOH group in the initiation reactions of the OH radical with HOCH2OOH and HOC(CH3)2OOH. H-abstraction from -CH group is competitive with that from the -OOH group in the reaction of the OH radical with HOCH(CH3)OOH. The barrier of H-abstraction from the -OOH group is slightly increased as the methyl group number increases.
Quantum chemical methods are applied to gain insight into the detailed mechanisms of...
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