H-Abstraction by OH from Large Branched Alkanes: Overall Rate Measurements and Site-Specific Tertiary Rate Calculations

Handle URI:
http://hdl.handle.net/10754/622833
Title:
H-Abstraction by OH from Large Branched Alkanes: Overall Rate Measurements and Site-Specific Tertiary Rate Calculations
Authors:
Liu, Dapeng ( 0000-0002-9267-6192 ) ; Khaled, Fathi; Giri, Binod; Assaf, Emmanuel; Fittschen, Christa; Farooq, Aamir ( 0000-0001-5296-2197 )
Abstract:
Reaction rate coefficients for the reaction of hydroxyl (OH) radicals with nine large branched alkanes (i.e., 2-methyl-3-ethyl-pentane, 2,3-dimethyl-pentane, 2,2,3-trimethylbutane, 2,2,3-trimethyl-pentane, 2,3,4-trimethyl-pentane, 3-ethyl-pentane, 2,2,3,4-tetramethyl-pentane, 2,2-dimethyl-3-ethyl-pentane, and 2,4-dimethyl-3-ethyl-pentane) are measured at high temperatures (900-1300 K) using a shock tube and narrow-line-width OH absorption diagnostic in the UV region. In addition, room-temperature measurements of six out of these nine rate coefficients are performed in a photolysis cell using high repetition laser-induced fluorescence of OH radicals. Our experimental results are combined with previous literature measurements to obtain three-parameter Arrhenius expressions valid over a wide temperature range (300-1300 K). The rate coefficients are analyzed using the next-nearest-neighbor (N-N-N) methodology to derive nine tertiary (T003, T012, T013, T022, T023, T111, T112, T113, and T122) site-specific rate coefficients for the abstraction of H atoms by OH radicals from branched alkanes. Derived Arrhenius expressions, valid over 950-1300 K, are given as (the subscripts denote the number of carbon atoms connected to the next-nearest-neighbor carbon): T003 = 1.80 × 10-10 exp(-2971 K/T) cm3 molecule-1 s-1; T012 = 9.36 × 10-11 exp(-3024 K/T) cm3 molecule-1 s-1; T013 = 4.40 × 10-10 exp(-4162 K/T) cm3 molecule-1 s-1; T022 = 1.47 × 10-10 exp(-3587 K/T) cm3 molecule-1 s-1; T023 = 6.06 × 10-11 exp(-3010 K/T) cm3 molecule-1 s-1; T111 = 3.98 × 10-11 exp(-1617 K/T) cm3 molecule-1 s-1; T112 = 9.08 × 10-12 exp(-3661 K/T) cm3 molecule-1 s-1; T113 = 6.74 × 10-9 exp(-7547 K/T) cm3 molecule-1 s-1; T122 = 3.47 × 10-11 exp(-1802 K/T) cm3 molecule-1 s-1.
KAUST Department:
Clean Combustion Research Center
Citation:
Liu D, Khaled F, Giri BR, Assaf E, Fittschen C, et al. (2017) H-Abstraction by OH from Large Branched Alkanes: Overall Rate Measurements and Site-Specific Tertiary Rate Calculations. The Journal of Physical Chemistry A. Available: http://dx.doi.org/10.1021/acs.jpca.6b10576.
Publisher:
American Chemical Society (ACS)
Journal:
The Journal of Physical Chemistry A
Issue Date:
10-Jan-2017
DOI:
10.1021/acs.jpca.6b10576
Type:
Article
ISSN:
1089-5639; 1520-5215
Sponsors:
We acknowledge the funding support from Saudi Aramco under the FUELCOM program and by King Abdullah University of Science and Technology (KAUST). Financial support by the French ANR agency under contract no. ANR-11-LabEx-0005-01 CaPPA (Chemical and Physical Properties of the Atmosphere) is acknowledged.
Additional Links:
http://pubs.acs.org/doi/full/10.1021/acs.jpca.6b10576
Appears in Collections:
Articles; Clean Combustion Research Center

Full metadata record

DC FieldValue Language
dc.contributor.authorLiu, Dapengen
dc.contributor.authorKhaled, Fathien
dc.contributor.authorGiri, Binoden
dc.contributor.authorAssaf, Emmanuelen
dc.contributor.authorFittschen, Christaen
dc.contributor.authorFarooq, Aamiren
dc.date.accessioned2017-02-06T07:36:57Z-
dc.date.available2017-02-06T07:36:57Z-
dc.date.issued2017-01-10en
dc.identifier.citationLiu D, Khaled F, Giri BR, Assaf E, Fittschen C, et al. (2017) H-Abstraction by OH from Large Branched Alkanes: Overall Rate Measurements and Site-Specific Tertiary Rate Calculations. The Journal of Physical Chemistry A. Available: http://dx.doi.org/10.1021/acs.jpca.6b10576.en
dc.identifier.issn1089-5639en
dc.identifier.issn1520-5215en
dc.identifier.doi10.1021/acs.jpca.6b10576en
dc.identifier.urihttp://hdl.handle.net/10754/622833-
dc.description.abstractReaction rate coefficients for the reaction of hydroxyl (OH) radicals with nine large branched alkanes (i.e., 2-methyl-3-ethyl-pentane, 2,3-dimethyl-pentane, 2,2,3-trimethylbutane, 2,2,3-trimethyl-pentane, 2,3,4-trimethyl-pentane, 3-ethyl-pentane, 2,2,3,4-tetramethyl-pentane, 2,2-dimethyl-3-ethyl-pentane, and 2,4-dimethyl-3-ethyl-pentane) are measured at high temperatures (900-1300 K) using a shock tube and narrow-line-width OH absorption diagnostic in the UV region. In addition, room-temperature measurements of six out of these nine rate coefficients are performed in a photolysis cell using high repetition laser-induced fluorescence of OH radicals. Our experimental results are combined with previous literature measurements to obtain three-parameter Arrhenius expressions valid over a wide temperature range (300-1300 K). The rate coefficients are analyzed using the next-nearest-neighbor (N-N-N) methodology to derive nine tertiary (T003, T012, T013, T022, T023, T111, T112, T113, and T122) site-specific rate coefficients for the abstraction of H atoms by OH radicals from branched alkanes. Derived Arrhenius expressions, valid over 950-1300 K, are given as (the subscripts denote the number of carbon atoms connected to the next-nearest-neighbor carbon): T003 = 1.80 × 10-10 exp(-2971 K/T) cm3 molecule-1 s-1; T012 = 9.36 × 10-11 exp(-3024 K/T) cm3 molecule-1 s-1; T013 = 4.40 × 10-10 exp(-4162 K/T) cm3 molecule-1 s-1; T022 = 1.47 × 10-10 exp(-3587 K/T) cm3 molecule-1 s-1; T023 = 6.06 × 10-11 exp(-3010 K/T) cm3 molecule-1 s-1; T111 = 3.98 × 10-11 exp(-1617 K/T) cm3 molecule-1 s-1; T112 = 9.08 × 10-12 exp(-3661 K/T) cm3 molecule-1 s-1; T113 = 6.74 × 10-9 exp(-7547 K/T) cm3 molecule-1 s-1; T122 = 3.47 × 10-11 exp(-1802 K/T) cm3 molecule-1 s-1.en
dc.description.sponsorshipWe acknowledge the funding support from Saudi Aramco under the FUELCOM program and by King Abdullah University of Science and Technology (KAUST). Financial support by the French ANR agency under contract no. ANR-11-LabEx-0005-01 CaPPA (Chemical and Physical Properties of the Atmosphere) is acknowledged.en
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/full/10.1021/acs.jpca.6b10576en
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in 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 http://pubs.acs.org/doi/full/10.1021/acs.jpca.6b10576.en
dc.titleH-Abstraction by OH from Large Branched Alkanes: Overall Rate Measurements and Site-Specific Tertiary Rate Calculationsen
dc.typeArticleen
dc.contributor.departmentClean Combustion Research Centeren
dc.identifier.journalThe Journal of Physical Chemistry Aen
dc.eprint.versionPost-printen
dc.contributor.institutionUniversité Lille , CNRS, UMR 8522 - PC2A - Physicochimie des Processus de Combustion et de l'Atmosphère, F-59000 Lille, France.en
kaust.authorLiu, Dapengen
kaust.authorKhaled, Fathien
kaust.authorGiri, Binoden
kaust.authorFarooq, Aamiren
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