Show simple item record

dc.contributor.authorKHALED, Fethi
dc.contributor.authorGiri, Binod
dc.contributor.authorLiu, Dapeng
dc.contributor.authorAssaf, Emmanuel
dc.contributor.authorFittschen, Christa
dc.contributor.authorFarooq, Aamir
dc.date.accessioned2019-04-04T08:31:34Z
dc.date.available2019-04-04T08:31:34Z
dc.date.issued2019-02-15
dc.identifier.citationKhaled F, Giri BR, Liu D, Assaf E, Fittschen C, et al. (2019) Insights into the Reactions of Hydroxyl Radical with Diolefins from Atmospheric to Combustion Environments. The Journal of Physical Chemistry A 123: 2261–2271. Available: http://dx.doi.org/10.1021/acs.jpca.8b10997.
dc.identifier.issn1089-5639
dc.identifier.issn1520-5215
dc.identifier.doi10.1021/acs.jpca.8b10997
dc.identifier.urihttp://hdl.handle.net/10754/631805
dc.description.abstractHydroxyl radicals and olefins are quite important from combustion and atmospheric chemistry standpoint. Large amounts of olefinic compounds are emitted into the earth’s atmosphere from both biogenic and anthropogenic sources. Olefins make a significant share in the tranportation fuels (e.g., up to 20% by volume in gasoline), and they appear as important intermediates during hydrocarbon oxidation. As olefins inhibit low-temperature heat release, they have caught some attention for their applicability in future advanced combustion engine technology. Despite their importance, the literature data for the reactions of olefins are quite scarce. In this work, we have measured the rate coefficients for the reaction of hydroxyl radicals (OH) with several diolefins, namely 1,3-butadiene, cis-1,3-pentadiene, trans-1,3-pentadiene, and 1,4-pentadiene, over a wide range of experimental conditions (T = 294 – 468 K and p ~ 53 mbar; T = 881 – 1348 K and p ~ 1 – 2.5 bar). We obtained the low-T data in a flow reactor using laser flash photolysis and laser induced fluorescence (LPFR/LIF), and the high-T data were obtained with a shock tube and UV laser-absorption (ST/LA). At low temperatures, we observed differences in the reactivity of cis- and trans-1,3-pentadiene, but these molecules exhibited similar reactivity at high temperatures. Similar to monoolefins + OH reactions, we observed negative temperature dependence for dienes + OH reactions at low temperatures – revealing that OH-addition channels prevail at low temperatures. Except for 1,4-pentadiene + OH reaction, which shows evidence of significant H-abstraction reactions even at low-temperatures, other diolefins studied here almost exclusively undergo addition reaction with OH radicals at the low-temperature end of our experiments; whereas the reactions mainly switch to hydrogen abstraction at high temperatures. These reactions show complex Arrhenius behaviour as a result of many possible chemical pathways in such a convoluted system.
dc.description.sponsorshipResearch reported in this work was funded by King Abdullah University of Science and Technology (KAUST). Work in Lille was funded by by the French ANR agency under contract No. ANR-11-LabX-0005-01 CaPPA (Chemical and Physical Properties of the Atmosphere) and the Région Hauts-de-France, the Ministère de l'Enseignement Supérieur et de la Recherche and the European Fund for Regional Economic Development (CPER Climibio).
dc.publisherAmerican Chemical Society (ACS)
dc.relation.urlhttps://pubs.acs.org/doi/10.1021/acs.jpca.8b10997
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Physical Chemistry A, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acs.jpca.8b10997.
dc.titleInsights into the Reactions of Hydroxyl Radical with Diolefins from Atmospheric to Combustion Environments
dc.typeArticle
dc.contributor.departmentChemical Kinetics & Laser Sensors Laboratory
dc.contributor.departmentClean Combustion Research Center
dc.contributor.departmentMechanical Engineering Program
dc.contributor.departmentPhysical Science and Engineering (PSE) Division
dc.identifier.journalThe Journal of Physical Chemistry A
dc.eprint.versionPost-print
dc.contributor.institutionUniversité Lille, CNRS, UMR 8522 – PC2A – Physicochimie des Processus de Combustion et de l’Atmosphère, F-59000 Lille, France
kaust.personKhaled, Fathi
kaust.personGiri, Binod
kaust.personLiu, Dapeng
kaust.personFarooq, Aamir
refterms.dateFOA2020-02-15T00:00:00Z
dc.date.published-online2019-02-15
dc.date.published-print2019-03-21


Files in this item

Thumbnail
Name:
acs.jpca.8b10997.pdf
Size:
395.6Kb
Format:
PDF
Description:
Accepted Manuscript

This item appears in the following Collection(s)

Show simple item record