期刊
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
卷 23, 期 9, 页码 5176-5186出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/d0cp06033j
关键词
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资金
- European Union's Horizon 2020 research and innovation programme, through the EUROCHAMP-2020 Infrastructure Activity Grant [730997]
- UEFISCDI [PN-III-P4-ID-PCE-2016-4-0807, PN-III-P2-2.1-PED2019-4972]
- FANTEL
The reactivity of epoxides with chlorine atoms was evaluated using experimental determinations, theoretical calculations, and SAR estimations in this study. It was found that adding a CH2 group increases the reactivity towards chlorine atoms. Theoretical calculations were in good agreement with experimental findings, and the importance of considering geometrical distribution and ring influence for improving SAR calculations was discussed.
Evaluating the reactivity of epoxides in the gas phase is very important due to their wide distribution in the atmosphere, potential health implications and atmospheric impact. The kinetic rate constants for the oxidation of epoxides have been very little studied until now. From the experimental data obtained in this work has been observed that there is an increase in reactivity towards chlorine atoms as a CH2 group is added to the hydrocarbon chain. The Structure Activity Relationship (SAR) method usually provides a good approximation of the rate constant for a wide series of compounds especially for those without complex structure and multiple organic functions. However, a good determination of the factors included in SAR estimations depends largely on the database of these compounds, which in the case of epoxides is very limited. The SAR estimation method also does not take into account other possible factors that could affect reactivity, such as the geometry of the molecule. The aim of this work is to further evaluate the reactivity of epoxides with chlorine atoms using experimental determinations, theoretical calculations and SAR estimations. For this, rate coefficients have been measured at 298 +/- 2 K and 1000 +/- 4 mbar pressure of synthetic air in a 1080 l Quartz Reactor (QUAREC) and a 480 l Duran glass reactor for the reaction of chlorine atoms with cyclohexene oxide (CHO), 1,2-epoxyhexane (12EHX), 1,2-epoxybutane (12EB), trans-2,3-epoxybutane (tEB) and cis-2,3-epoxybutane (cEB). Theoretical calculations for the reactions studied are in good agreement with our experimental findings and provide insights about the position of the H atom abstraction and reactivity trends for a series of epoxides. The importance of taking into consideration the geometrical distribution and the ring influence to improve SAR calculations is discussed.
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