<i>Ab initio</i> chemical kinetics of Isopropyl acetate oxidation with OH radicals

<p dir="ltr">Global reactivity descriptors of isopropyl acetate (IPA) and thermo-kinetic aspects of its oxidation via OH radicals have been studied. Transition state theory (TST) was utilized to estimate the bimolecular rate constants. Ten oxidation pathways have been investigated, a...

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Main Author: Mohamed A. Abdel-Rahman (5450786) (author)
Other Authors: Mohamed F. Shibl (1975762) (author), Abolfazl Shiroudi (1783840) (author), Mohamed A. M. Mahmoud (12421996) (author)
Published: 2023
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author Mohamed A. Abdel-Rahman (5450786)
author2 Mohamed F. Shibl (1975762)
Abolfazl Shiroudi (1783840)
Mohamed A. M. Mahmoud (12421996)
author2_role author
author
author
author_facet Mohamed A. Abdel-Rahman (5450786)
Mohamed F. Shibl (1975762)
Abolfazl Shiroudi (1783840)
Mohamed A. M. Mahmoud (12421996)
author_role author
dc.creator.none.fl_str_mv Mohamed A. Abdel-Rahman (5450786)
Mohamed F. Shibl (1975762)
Abolfazl Shiroudi (1783840)
Mohamed A. M. Mahmoud (12421996)
dc.date.none.fl_str_mv 2023-07-15T03:00:00Z
dc.identifier.none.fl_str_mv 10.1080/17518253.2023.2233539
dc.relation.none.fl_str_mv https://figshare.com/articles/journal_contribution/_i_Ab_initio_i__chemical_kinetics_of_Isopropyl_acetate_oxidation_with_OH_radicals/25187621
dc.rights.none.fl_str_mv CC BY 4.0
info:eu-repo/semantics/openAccess
dc.subject.none.fl_str_mv Chemical sciences
Physical chemistry
Theoretical and computational chemistry
Isopropyl acetate
oxidation
thermochemistry
chemical kinetics
dc.title.none.fl_str_mv <i>Ab initio</i> chemical kinetics of Isopropyl acetate oxidation with OH radicals
dc.type.none.fl_str_mv Text
Journal contribution
info:eu-repo/semantics/publishedVersion
text
contribution to journal
description <p dir="ltr">Global reactivity descriptors of isopropyl acetate (IPA) and thermo-kinetic aspects of its oxidation via OH radicals have been studied. Transition state theory (TST) was utilized to estimate the bimolecular rate constants. Ten oxidation pathways have been investigated, and all of them are exothermic. The potential energy diagram has been sketched using different pre- and post-reactive complexes for all reaction pathways. Rate coefficient calculations were obtained directly by connecting the separated reactants with different transition states. The results indicate that the reaction of IPA with OH radicals occurs in the ground state rather than the excited state, and the rate constants obtained directly and from the effective approach are the same, which confirmed the accuracy of the estimated pre-reactive complexes and the reaction mechanism. Rate constants and branching ratios show that hydrogen atom abstraction from the <i>iso</i> C − H (C<sub>2</sub> atom) bond is the most kinetically preferable route up to 1000 K, while at higher temperatures, H-atom abstraction from the out-of-plane CH<sub>3</sub> group (C<sub>3</sub> atom) became the most dominant route with high competition with that of the in-plane CH<sub>3</sub> group (C<sub>4</sub> atom).</p><h2>Other Information</h2><p dir="ltr">Published in: Green Chemistry Letters and Reviews<br>License: <a href="http://creativecommons.org/licenses/by/4.0/" target="_blank">http://creativecommons.org/licenses/by/4.0/</a><br>See article on publisher's website: <a href="https://dx.doi.org/10.1080/17518253.2023.2233539" target="_blank">https://dx.doi.org/10.1080/17518253.2023.2233539</a></p>
eu_rights_str_mv openAccess
id Manara2_a8bd1dc68715ee11437fc44bc1c20173
identifier_str_mv 10.1080/17518253.2023.2233539
network_acronym_str Manara2
network_name_str Manara2
oai_identifier_str oai:figshare.com:article/25187621
publishDate 2023
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rights_invalid_str_mv CC BY 4.0
spelling <i>Ab initio</i> chemical kinetics of Isopropyl acetate oxidation with OH radicalsMohamed A. Abdel-Rahman (5450786)Mohamed F. Shibl (1975762)Abolfazl Shiroudi (1783840)Mohamed A. M. Mahmoud (12421996)Chemical sciencesPhysical chemistryTheoretical and computational chemistryIsopropyl acetateoxidationthermochemistrychemical kinetics<p dir="ltr">Global reactivity descriptors of isopropyl acetate (IPA) and thermo-kinetic aspects of its oxidation via OH radicals have been studied. Transition state theory (TST) was utilized to estimate the bimolecular rate constants. Ten oxidation pathways have been investigated, and all of them are exothermic. The potential energy diagram has been sketched using different pre- and post-reactive complexes for all reaction pathways. Rate coefficient calculations were obtained directly by connecting the separated reactants with different transition states. The results indicate that the reaction of IPA with OH radicals occurs in the ground state rather than the excited state, and the rate constants obtained directly and from the effective approach are the same, which confirmed the accuracy of the estimated pre-reactive complexes and the reaction mechanism. Rate constants and branching ratios show that hydrogen atom abstraction from the <i>iso</i> C − H (C<sub>2</sub> atom) bond is the most kinetically preferable route up to 1000 K, while at higher temperatures, H-atom abstraction from the out-of-plane CH<sub>3</sub> group (C<sub>3</sub> atom) became the most dominant route with high competition with that of the in-plane CH<sub>3</sub> group (C<sub>4</sub> atom).</p><h2>Other Information</h2><p dir="ltr">Published in: Green Chemistry Letters and Reviews<br>License: <a href="http://creativecommons.org/licenses/by/4.0/" target="_blank">http://creativecommons.org/licenses/by/4.0/</a><br>See article on publisher's website: <a href="https://dx.doi.org/10.1080/17518253.2023.2233539" target="_blank">https://dx.doi.org/10.1080/17518253.2023.2233539</a></p>2023-07-15T03:00:00ZTextJournal contributioninfo:eu-repo/semantics/publishedVersiontextcontribution to journal10.1080/17518253.2023.2233539https://figshare.com/articles/journal_contribution/_i_Ab_initio_i__chemical_kinetics_of_Isopropyl_acetate_oxidation_with_OH_radicals/25187621CC BY 4.0info:eu-repo/semantics/openAccessoai:figshare.com:article/251876212023-07-15T03:00:00Z
spellingShingle <i>Ab initio</i> chemical kinetics of Isopropyl acetate oxidation with OH radicals
Mohamed A. Abdel-Rahman (5450786)
Chemical sciences
Physical chemistry
Theoretical and computational chemistry
Isopropyl acetate
oxidation
thermochemistry
chemical kinetics
status_str publishedVersion
title <i>Ab initio</i> chemical kinetics of Isopropyl acetate oxidation with OH radicals
title_full <i>Ab initio</i> chemical kinetics of Isopropyl acetate oxidation with OH radicals
title_fullStr <i>Ab initio</i> chemical kinetics of Isopropyl acetate oxidation with OH radicals
title_full_unstemmed <i>Ab initio</i> chemical kinetics of Isopropyl acetate oxidation with OH radicals
title_short <i>Ab initio</i> chemical kinetics of Isopropyl acetate oxidation with OH radicals
title_sort <i>Ab initio</i> chemical kinetics of Isopropyl acetate oxidation with OH radicals
topic Chemical sciences
Physical chemistry
Theoretical and computational chemistry
Isopropyl acetate
oxidation
thermochemistry
chemical kinetics