dc.contributor.author | Goldsmith, Claude | en_US |
dc.contributor.author | Ismail, Huzeifa | en_US |
dc.contributor.author | Green, William H. | en_US |
dc.date.accessioned | 2009-10-19T13:29:56Z | |
dc.date.available | 2009-10-19T13:29:56Z | |
dc.date.issued | 2009-07 | |
dc.date.submitted | 2009-06 | |
dc.identifier.issn | 1089-5639 | |
dc.identifier.uri | http://hdl.handle.net/1721.1/49463 | |
dc.description.abstract | This work reports experimental and theoretical first-order rate constants for the reaction of vinyl radical with C4H8 alkenes: 1-butene, 2-butene, and iso-butene. The experiments are performed over a temperature range of 300 K to 700 K at 100 Torr. Vinyl radicals (H[subscript 2]C=CH) were generated by laser photolysis of vinyl iodide (C[subscript 2]H[subscript ]3I) at 266 nm, and time-resolved absorption spectroscopy was used to probe vinyl radicals at 423.2 and 475 nm. Weighted Arrhenius fits to the experimental rate coefficients for 1-butene (k[subscript 1]), 2-butene (k[subscript 2]), and iso-butene (k[subscript 3]) yield k[subscript 1] = (1.3±0.3)× 10[superscript -12] cm[superscript 3] molecules[superscript -1] s[superscript -1] exp[-(2200 ± 120) K/T]; k2 = (1.7±0.3)× 10[superscript -12] cm[superscript 3] molecules[superscript -1] s[superscript -1] exp[-(2610 ± 120) K/T]; k[superscript 3] = (1.0±0.1)× 10[superscript -12] cm[superscript 3] molecules[superscript -1] s[superscript -1] exp[-(2130 ± 50) K/T], respectively. C6H11 potential energy surfaces (PES) for each system were calculated using the G3 method. RRKM/ME simulations were performed for each system to predict pressure dependent rate coefficients and branching fractions for the major channels. A generic rate rule for vinyl addition to various alkenes is recommended; a similar rate rule for the abstraction of H atoms by vinyl from alkenes is also provided. Some of the vinyl addition reactions exhibit anomalous Evans-Polanyi plots, similar to those reported for previous methyl addition reactions. | en_US |
dc.description.sponsorship | United States. Dept. of Energy (contract DE-FG02-98ER14914) | |
dc.description.sponsorship | United States. Dept. of Energy. Office of Basic Energy Sciences | |
dc.description.sponsorship | United States. Dept. of Energy. Chemical Sciences, Geosciences, and Energy Biosciences Division | |
dc.language.iso | en_US | en_US |
dc.publisher | American Chemical Society | |
dc.relation.isversionof | http://dx.doi.org/10.1021/jp9042039 | |
dc.rights | Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. | en_US |
dc.rights.uri | | en_US |
dc.source | Barbara Balkwill | en_US |
dc.title | Pressure and Temperature Dependence of the Reaction of Vinyl Radical with Alkenes III: Measured Rates and Predicted Product Distributions for Vinyl + Butene | en_US |
dc.type | Article | en_US |
dc.identifier.citation | Goldsmith, C. Franklin, Huzeifa Ismail, and William H. Green. “Pressure and Temperature Dependence of the Reaction of Vinyl Radical with Alkenes III: Measured Rates and Predicted Product Distributions for Vinyl + Butene†.” The Journal of Physical Chemistry A 113.47 (2009): 13357–13371. | en |
dc.contributor.department | Massachusetts Institute of Technology. Department of Chemical Engineering | en_US |
dc.contributor.department | Massachusetts Institute of Technology. Department of Chemistry | en_US |
dc.contributor.approver | Green, William H. | en_US |
dc.contributor.mitauthor | Goldsmith, Claude | en_US |
dc.contributor.mitauthor | Ismail, Huzeifa | en_US |
dc.contributor.mitauthor | Green, William H. | en_US |
dc.relation.journal | Journal of Physical Chemistry A | |
dc.eprint.version | Author's final manuscript | |
dc.type.uri | http://purl.org/eprint/type/SubmittedJournalArticle | en_US |
eprint.status | http://purl.org/eprint/status/PeerReviewed | en_US |
dspace.orderedauthors | Goldsmith, Claude; Ismail, Huzeifa; Green, William H. | |
dspace.orderedauthors | Goldsmith, Claude; Ismail, Huzeifa; Green, William H. | |
mit.license | PUBLISHER_POLICY | en_US |
mit.metadata.status | Complete | |