Details
| Original language | English |
|---|---|
| Pages (from-to) | 5176-5186 |
| Number of pages | 11 |
| Journal | Physical Chemistry Chemical Physics |
| Volume | 23 |
| Issue number | 9 |
| Publication status | Published - 19 Feb 2021 |
| Externally published | Yes |
Abstract
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 CH2group 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) andcis-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.
ASJC Scopus subject areas
- Physics and Astronomy(all)
- General Physics and Astronomy
- Chemistry(all)
- Physical and Theoretical Chemistry
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In: Physical Chemistry Chemical Physics, Vol. 23, No. 9, 19.02.2021, p. 5176-5186.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Experimental and theoretical study of the reactivity of a series of epoxides with chlorine atoms at 298 K
AU - Tovar, Carmen M.
AU - Haack, Alexander
AU - Barnes, Ian
AU - Bejan, Iustinian Gabriel
AU - Wiesen, Peter
N1 - Funding Information: The authors acknowledge the financial support provided by the European Union's Horizon 2020 research and innovation programme, through the EUROCHAMP-2020 Infrastructure Activity Grant (grant agreement no. 730997). IGB acknowledges the PN-III-P4-ID-PCE-2016-4-0807 and PN-III-P2-2.1-PED2019-4972 UEFISCDI projects. CMT wish to acknowledge to FANTEL for a PhD scholarship.
PY - 2021/2/19
Y1 - 2021/2/19
N2 - 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 CH2group 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) andcis-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.
AB - 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 CH2group 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) andcis-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.
UR - http://www.scopus.com/inward/record.url?scp=85102681580&partnerID=8YFLogxK
U2 - 10.1039/d0cp06033j
DO - 10.1039/d0cp06033j
M3 - Article
C2 - 33624654
AN - SCOPUS:85102681580
VL - 23
SP - 5176
EP - 5186
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
SN - 1463-9076
IS - 9
ER -