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Titolo:
Rate coefficients and mechanistic analysis for reaction of OH with vinyl chloride between 293 and 730 K
Autore:
Yamada, T; Siraj, M; Taylor, PH; Peng, JP; Hu, XH; Marshall, P;
Indirizzi:
Univ Dayton, Res Inst, Environm Sci & Engn Grp, Dayton, OH 43469 USA Univ Dayton Dayton OH USA 43469 ronm Sci & Engn Grp, Dayton, OH 43469 USA Univ N Texas, Dept Chem, Denton, TX 76203 USA Univ N Texas Denton TX USA 76203 N Texas, Dept Chem, Denton, TX 76203 USA
Titolo Testata:
JOURNAL OF PHYSICAL CHEMISTRY A
fascicolo: 41, volume: 105, anno: 2001,
pagine: 9436 - 9444
SICI:
1089-5639(20011018)105:41<9436:RCAMAF>2.0.ZU;2-Z
Fonte:
ISI
Lingua:
ENG
Soggetto:
TRANSITION-STATE-THEORY; RATE CONSTANTS; NITROUS-ACID; RADICALS; RANGE; CHLORINATION; CONDENSATION; ACETYLENE; KINETICS;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
41
Recensione:
Indirizzi per estratti:
Indirizzo: Taylor, PH Univ Dayton, Res Inst, Environm Sci & Engn Grp, 300 Coll Pk, Dayton, OH 43469 USA Univ Dayton 300 Coll Pk Dayton OH USA 43469 ayton, OH 43469 USA
Citazione:
T. Yamada et al., "Rate coefficients and mechanistic analysis for reaction of OH with vinyl chloride between 293 and 730 K", J PHYS CH A, 105(41), 2001, pp. 9436-9444

Abstract

The kinetics of the title reaction were investigated between 293 and 730 Kat 740 +/- 10 Torr in a helium bath gas. Absolute rate measurements were obtained using a laser photolysis/laser-induced fluorescence (LP/LIF) technique under slow flow conditions. Rate coefficients exhibited complex behavior with negative temperature dependence at temperatures below 560 K, a rapiddrop in rate between 560 and 620 K, and a positive temperature dependence above 620 K. The simple Arrhenius equation adequately describes the data atand below 560 K and is given by (in units of cm(3) molecule(-1) s(-1)) k(293-560 K) = (2.72 +/- 0.35) x 10(-12) exp(335 +/- 42)/T. Error limits are 2sigma values. The low-temperature values for k are within +/-2 sigma of the most recent measurements of this reaction obtained under atmospheric pressure conditions. Above 620 K, our measurement combined with the recent measurements of Liu et al.(8) to yield the following rate expression: k(620-1173 K) = (6.3 +/- 4.0) x 10(-11) exp(-2740 +/- 490)/T. Error limits are 2 sigma values. The rate data were interpreted using variational transition state theory and QRRK theory. OH addition to the beta site followed by adduct stabilization describes the low-temperature measurements. Ab initio-based transition state calculations for the H abstraction channel indicated that this mechanism is consistent with the rate measurements above 620 K. H abstraction is predicted to be the dominant reaction channel above temperatures of 800 K.

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Documento generato il 29/09/20 alle ore 10:31:48