Site-Specific Rate Constant Measurements for Primary and Secondary H- and D-Abstraction by OH Radicals: Propane and n -Butane

Handle URI:
http://hdl.handle.net/10754/347271
Title:
Site-Specific Rate Constant Measurements for Primary and Secondary H- and D-Abstraction by OH Radicals: Propane and n -Butane
Authors:
Badra, Jihad; Nasir, Ehson F.; Farooq, Aamir ( 0000-0001-5296-2197 )
Abstract:
Site-specific rate constants for hydrogen (H) and deuterium (D) abstraction by hydroxyl (OH) radicals were determined experimentally by monitoring the reaction of OH with two normal and six deuterated alkanes. The studied alkanes include propane (C3H8), propane 2,2 D2 (CH 3CD2CH3), propane 1,1,1-3,3,3 D6 (CD 3CH2CD3), propane D8 (C3D 8), n-butane (n-C4H10), butane 2,2-3,3 D4 (CH3CD2CD2CH3), butane 1,1,1-4,4,4 D6 (CD3CH2CH2CD3), and butane D10 (C4D10). Rate constant measurements were carried out over 840-1470 K and 1.2-2.1 atm using a shock tube and OH laser absorption. Previous low-temperature data were combined with the current high-temperature measurements to generate three-parameter fits which were then used to determine the site-specific rate constants. Two primary (P1,H and P 1,D) and four secondary (S00,H, S00,D, S 01,H, and S01,D) H- and D-abstraction rate constants, in which the subscripts refer to the number of C atoms connected to the next-nearest-neighbor C atom, are obtained. The modified Arrhenius expressions for the six site-specific abstractions by OH radicals are P1,H = 1.90 × 10-18T2.00 exp(-340.87 K/T) cm 3molecule-1s-1 (210-1294 K); P1,D= 2.72 × 10-17 T1.60 exp(-895.57 K/T) cm 3molecule-1s-1 (295-1317 K); S00,H = 4.40 × 10-18 T1.93 exp(121.50 K/T) cm 3molecule-1s-1 (210-1294 K); S00,D = 1.45 × 10-20 T2.69 exp(282.36 K/T) cm 3molecule-1s-1 (295-1341 K); S01,H = 4.65 × 10-17 T1.60 exp(-236.98 K/T) cm 3molecule-1s-1 (235-1407 K); S01,D = 1.26 × 10-18 T2.07 exp(-77.00 K/T) cm 3molecule-1s-1 (294-1412 K). © 2014 American Chemical Society.
KAUST Department:
Clean Combustion Research Center; Physical Sciences and Engineering (PSE) Division
Citation:
Site-Specific Rate Constant Measurements for Primary and Secondary H- and D-Abstraction by OH Radicals: Propane and n -Butane 2014, 118 (26):4652 The Journal of Physical Chemistry A
Publisher:
American Chemical Society
Journal:
The Journal of Physical Chemistry A
Issue Date:
3-Jul-2014
DOI:
10.1021/jp503849b
Type:
Article
ISSN:
1089-5639; 1520-5215
Additional Links:
http://pubs.acs.org/doi/abs/10.1021/jp503849b
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Clean Combustion Research Center

Full metadata record

DC FieldValue Language
dc.contributor.authorBadra, Jihaden
dc.contributor.authorNasir, Ehson F.en
dc.contributor.authorFarooq, Aamiren
dc.date.accessioned2015-03-30T06:29:49Zen
dc.date.available2015-03-30T06:29:49Zen
dc.date.issued2014-07-03en
dc.identifier.citationSite-Specific Rate Constant Measurements for Primary and Secondary H- and D-Abstraction by OH Radicals: Propane and n -Butane 2014, 118 (26):4652 The Journal of Physical Chemistry Aen
dc.identifier.issn1089-5639en
dc.identifier.issn1520-5215en
dc.identifier.doi10.1021/jp503849ben
dc.identifier.urihttp://hdl.handle.net/10754/347271en
dc.description.abstractSite-specific rate constants for hydrogen (H) and deuterium (D) abstraction by hydroxyl (OH) radicals were determined experimentally by monitoring the reaction of OH with two normal and six deuterated alkanes. The studied alkanes include propane (C3H8), propane 2,2 D2 (CH 3CD2CH3), propane 1,1,1-3,3,3 D6 (CD 3CH2CD3), propane D8 (C3D 8), n-butane (n-C4H10), butane 2,2-3,3 D4 (CH3CD2CD2CH3), butane 1,1,1-4,4,4 D6 (CD3CH2CH2CD3), and butane D10 (C4D10). Rate constant measurements were carried out over 840-1470 K and 1.2-2.1 atm using a shock tube and OH laser absorption. Previous low-temperature data were combined with the current high-temperature measurements to generate three-parameter fits which were then used to determine the site-specific rate constants. Two primary (P1,H and P 1,D) and four secondary (S00,H, S00,D, S 01,H, and S01,D) H- and D-abstraction rate constants, in which the subscripts refer to the number of C atoms connected to the next-nearest-neighbor C atom, are obtained. The modified Arrhenius expressions for the six site-specific abstractions by OH radicals are P1,H = 1.90 × 10-18T2.00 exp(-340.87 K/T) cm 3molecule-1s-1 (210-1294 K); P1,D= 2.72 × 10-17 T1.60 exp(-895.57 K/T) cm 3molecule-1s-1 (295-1317 K); S00,H = 4.40 × 10-18 T1.93 exp(121.50 K/T) cm 3molecule-1s-1 (210-1294 K); S00,D = 1.45 × 10-20 T2.69 exp(282.36 K/T) cm 3molecule-1s-1 (295-1341 K); S01,H = 4.65 × 10-17 T1.60 exp(-236.98 K/T) cm 3molecule-1s-1 (235-1407 K); S01,D = 1.26 × 10-18 T2.07 exp(-77.00 K/T) cm 3molecule-1s-1 (294-1412 K). © 2014 American Chemical Society.en
dc.publisherAmerican Chemical Societyen
dc.relation.urlhttp://pubs.acs.org/doi/abs/10.1021/jp503849ben
dc.rightsArchived with thanks to The Journal of Physical Chemistry A. Copyright © 2014 American Chemical Societyen
dc.titleSite-Specific Rate Constant Measurements for Primary and Secondary H- and D-Abstraction by OH Radicals: Propane and n -Butaneen
dc.typeArticleen
dc.contributor.departmentClean Combustion Research Centeren
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalThe Journal of Physical Chemistry Aen
dc.eprint.versionPost-printen
dc.contributor.institutionFuel Technology R&D Division, Saudi Aramco Research and Development Center, Dhahran 31311, Saudi Arabiaen
dc.contributor.affiliationKing Abdullah University of Science and Technology (KAUST)en
kaust.authorBadra, Jihaden
kaust.authorNasir, Ehson Fawaden
kaust.authorFarooq, Aamiren
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