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A platform for research: civil engineering, architecture and urbanism
Theoretical investigation on atmospheric reaction mechanism, kinetics and SAR estimations of four-carbon ketones and alcohols
https://orcid.org/0000-0002-0896-9356
https://orcid.org/0000-0002-0644-9971
Abstract The oxidation mechanism, thermochemistry and kinetics of 3-hydroxy-2-butanone (3H2B) and 2-methyl-1-propanol (2M1P) initiated by NO3 radicals were theoretically investigated at the CCSD(T)//BH&HLYP/6–311++G(d,p) level. The thermodynamic calculation results show that the channels of α-CH and α-CH2 sites are dominant for 3H2B and 2M1P. The strategy of experiment-SAR-DFT combined was proposed for the first time to discuss reaction kinetic information. The estimated rate constants of hydroxylketones and saturated alcohols with the total carbon number of four to six were provided by using the SAR method. The revised and supplemented group substituent factors F(–CH<) and F(–CH2OH) were provided to the original NO3 database, and the values obtained are 1.67 and 18.3. The rate constants for H-atom abstraction reactions of 3H2B and 2M1P with NO3 were evaluated over the temperature range of 250–350 K to verify the experiment-SAR-DFT strategy. The calculated values of 3H2B and 2M1P are 6.93 × 10−16 and 2.67 × 10−15 cm3 molecule−1 s−1 at 298 K, which are in close agreement with the reported experimental results and updated estimated values. Our theoretical research outcomes further attest that the new group substituent factor F(–CH2OH) is reliable. The nighttime atmospheric lifetime of 3H2B and 2M1P were estimated to be around 33 and 9 days, indicating that 3H2B has an effect on the atmospheric environment at night. The results can improve the reliability and accuracy of NO3 radicals kinetic data required to predict the contributions of 3H2B and 2M1P to the atmospheric environment.
Graphical abstract The optimal reaction sites of 3H2B and 2M1P with NO3 radicals were determined based on thermodynamic and kinetic data. The obtained total theoretical rate constants of two reactions at room temperature were compared with experimental results and the estimated SAR values in this manuscript. The reasons for deviations were explained to realize the strategy of experiment-SAR-DFT combination. Display Omitted
Highlights The mechanism, thermochemistry and kinetics of 3H2B and 2M1P initiated by NO3 radicals were investigated. The strategy of experiment-SAR-DFT combined was proposed to discuss reaction kinetic information. The revised and supplemented group substituent factors F(–CH<) and F(–CH2OH) were provided. The HKs and SAs with total carbon number of four to six were estimated. The tropospheric lifetimes of 3H2B and 2M1P were predicted.
Theoretical investigation on atmospheric reaction mechanism, kinetics and SAR estimations of four-carbon ketones and alcohols
https://orcid.org/0000-0002-0896-9356
https://orcid.org/0000-0002-0644-9971
Abstract The oxidation mechanism, thermochemistry and kinetics of 3-hydroxy-2-butanone (3H2B) and 2-methyl-1-propanol (2M1P) initiated by NO3 radicals were theoretically investigated at the CCSD(T)//BH&HLYP/6–311++G(d,p) level. The thermodynamic calculation results show that the channels of α-CH and α-CH2 sites are dominant for 3H2B and 2M1P. The strategy of experiment-SAR-DFT combined was proposed for the first time to discuss reaction kinetic information. The estimated rate constants of hydroxylketones and saturated alcohols with the total carbon number of four to six were provided by using the SAR method. The revised and supplemented group substituent factors F(–CH<) and F(–CH2OH) were provided to the original NO3 database, and the values obtained are 1.67 and 18.3. The rate constants for H-atom abstraction reactions of 3H2B and 2M1P with NO3 were evaluated over the temperature range of 250–350 K to verify the experiment-SAR-DFT strategy. The calculated values of 3H2B and 2M1P are 6.93 × 10−16 and 2.67 × 10−15 cm3 molecule−1 s−1 at 298 K, which are in close agreement with the reported experimental results and updated estimated values. Our theoretical research outcomes further attest that the new group substituent factor F(–CH2OH) is reliable. The nighttime atmospheric lifetime of 3H2B and 2M1P were estimated to be around 33 and 9 days, indicating that 3H2B has an effect on the atmospheric environment at night. The results can improve the reliability and accuracy of NO3 radicals kinetic data required to predict the contributions of 3H2B and 2M1P to the atmospheric environment.
Graphical abstract The optimal reaction sites of 3H2B and 2M1P with NO3 radicals were determined based on thermodynamic and kinetic data. The obtained total theoretical rate constants of two reactions at room temperature were compared with experimental results and the estimated SAR values in this manuscript. The reasons for deviations were explained to realize the strategy of experiment-SAR-DFT combination. Display Omitted
Highlights The mechanism, thermochemistry and kinetics of 3H2B and 2M1P initiated by NO3 radicals were investigated. The strategy of experiment-SAR-DFT combined was proposed to discuss reaction kinetic information. The revised and supplemented group substituent factors F(–CH<) and F(–CH2OH) were provided. The HKs and SAs with total carbon number of four to six were estimated. The tropospheric lifetimes of 3H2B and 2M1P were predicted.
Theoretical investigation on atmospheric reaction mechanism, kinetics and SAR estimations of four-carbon ketones and alcohols
https://orcid.org/0000-0002-0896-9356
https://orcid.org/0000-0002-0644-9971
Abstract The oxidation mechanism, thermochemistry and kinetics of 3-hydroxy-2-butanone (3H2B) and 2-methyl-1-propanol (2M1P) initiated by NO3 radicals were theoretically investigated at the CCSD(T)//BH&HLYP/6–311++G(d,p) level. The thermodynamic calculation results show that the channels of α-CH and α-CH2 sites are dominant for 3H2B and 2M1P. The strategy of experiment-SAR-DFT combined was proposed for the first time to discuss reaction kinetic information. The estimated rate constants of hydroxylketones and saturated alcohols with the total carbon number of four to six were provided by using the SAR method. The revised and supplemented group substituent factors F(–CH<) and F(–CH2OH) were provided to the original NO3 database, and the values obtained are 1.67 and 18.3. The rate constants for H-atom abstraction reactions of 3H2B and 2M1P with NO3 were evaluated over the temperature range of 250–350 K to verify the experiment-SAR-DFT strategy. The calculated values of 3H2B and 2M1P are 6.93 × 10−16 and 2.67 × 10−15 cm3 molecule−1 s−1 at 298 K, which are in close agreement with the reported experimental results and updated estimated values. Our theoretical research outcomes further attest that the new group substituent factor F(–CH2OH) is reliable. The nighttime atmospheric lifetime of 3H2B and 2M1P were estimated to be around 33 and 9 days, indicating that 3H2B has an effect on the atmospheric environment at night. The results can improve the reliability and accuracy of NO3 radicals kinetic data required to predict the contributions of 3H2B and 2M1P to the atmospheric environment.
Graphical abstract The optimal reaction sites of 3H2B and 2M1P with NO3 radicals were determined based on thermodynamic and kinetic data. The obtained total theoretical rate constants of two reactions at room temperature were compared with experimental results and the estimated SAR values in this manuscript. The reasons for deviations were explained to realize the strategy of experiment-SAR-DFT combination. Display Omitted
Highlights The mechanism, thermochemistry and kinetics of 3H2B and 2M1P initiated by NO3 radicals were investigated. The strategy of experiment-SAR-DFT combined was proposed to discuss reaction kinetic information. The revised and supplemented group substituent factors F(–CH<) and F(–CH2OH) were provided. The HKs and SAs with total carbon number of four to six were estimated. The tropospheric lifetimes of 3H2B and 2M1P were predicted.
Theoretical investigation on atmospheric reaction mechanism, kinetics and SAR estimations of four-carbon ketones and alcohols
Wang, Quyang (author) / Ni, Shuang (author) / Bai, Fengyang (author) / Pan, Xiumei (author)
Atmospheric Environment ; 271
2021-12-18
Article (Journal)
Electronic Resource
English
Kinetics and mechanism of reaction between polyfluorinated alcohols and thionyl chloride
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Gas chromatographic separation of cyclic alcohols and ketones
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