Kinetics of Cl atom reactions with butadienes including isoprene

Notario, Alberto; Bras, G. Le; Mellouki, Abdelwahid

doi:10.1016/s0009-2614(97)01303-1

Cited by 34 publications

(37 citation statements)

References 12 publications

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“…It is a product of industrial processes [28,29], tobacco smoke [30], and motor vehicle exhaust [31]. It can react in the atmosphere with OH [32], Cl [33] and O 3 [34][35][36] forming a series of products. In 1999, Kramp et al [36] performed experimental studies on the reaction of ozone with 1,3-butadiene at room temperature and atmosphere pressure.…”

Section: Introductionmentioning

confidence: 99%

Theoretical study for ozonolysis of 1,3-butadiene

Liu

Huang

et al. 2010

Journal of Molecular Structure: THEOCHEM

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Section: Introductionmentioning

confidence: 99%

Theoretical study for ozonolysis of 1,3-butadiene

Liu

Huang

et al. 2010

Journal of Molecular Structure: THEOCHEM

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“…[17][18][19][20] The reaction of 1,3-butadiene with the hydroxyl radical is considered to be the dominant chemical loss process during the daytime, with lifetimes of 1 and 4.5 h for OH concentrations of approximately 2 × 10 6 and 8 × 10 5 molecule cm -3 . 20,21 A generic mechanism for the OHinitiated oxidation of 1,3-butadiene is shown below: Under atmospheric conditions, the butadiene-OH adducts react with O 2 to form peroxy radicals that subsequently react in the presence of NO to form alkoxy radicals and NO 2 .…”

Section: Introductionmentioning

confidence: 99%

Experimental and Ab Initio Dynamical Investigations of the Kinetics and Intramolecular Energy Transfer Mechanisms for the OH + 1,3-Butadiene Reaction between 263 and 423 K at Low Pressure

et al. 2008

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The rate constants for the reaction of the OH radical with 1,3-butadiene and its deuterated isotopomer has been measured at 1-6 Torr total pressure over the temperature range of 263-423 K using the discharge flow system coupled with resonance fluorescence/laser-induced fluorescence detection of OH. The measured rate constants for the OH + 1,3-butadiene and OH + 1,3-butadiene-d 6 reactions at room temperature were found to be (6.98 ( 0.28) × 10 -11 and (6.94 ( 0.38) × 10 -11 cm 3 molecule -1 s -1 , respectively, in good agreement with previous measurements at higher pressures. An Arrhenius expression for this reaction was determined to be k 1 II (T) ) (7.23 ( 1.2) ×10 -11 exp [(664 ( 49)/T] cm 3 molecule -1 s -1 at 263-423 K. The reaction was found to be independent of pressure between 1 and 6 Torr and over the temperature range of 262-423 K, in contrast to previous results for the OH + isoprene reaction under similar conditions. To help interpret these results, ab initio molecular dynamics results are presented where the intramolecular energy redistribution is analyzed for the product adducts formed in the OH + isoprene and OH + butadiene reactions.

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“…The rate constant between isoprene and Cl has been studied using a relative rate method 16 -18 or absolute rate measurements. [19][20][21] The branching ratio for H-abstraction of the initial reaction has been inferred from the HCl formation yield, with a value between 13% and 17% for the initial Cl-isoprene reaction. 16,19,20 a͒ Electronic mail: zhang@ariel.tamu.edu Some of those studies have identified the final products of the Cl-isoprene reactions, including CO, CO 2 , formyl chloride ͑HCOCl͒, formic acid, methyl-glyoxal, hydrogen chloride, and 1-chloro-3-methyl-3-buten-2-one ͑CMBO͒.…”

Section: Introductionmentioning

confidence: 99%

C–C bond fission pathways of chloroalkenyl alkoxy radicals

Zhang

Allen

2003

The Journal of Chemical Physics

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Density-functional theory and ab initio molecular orbital calculations have been employed to determine the structures and energetics of the chloroalkenyl alkoxy radicals arising from Cl-initiated reactions of isoprene as well as the transition states and products of their decomposition reactions. Geometry optimizations of the various species were performed at the Becke three parameter Lee-Yang-Parr ͑B3LYP͒/6-31G(d, p) level, and single-point energies were computed using second-order Møller-Plesset and coupled-cluster theory with single and double excitations including perturbative corrections for the triple excitations. The activation and reaction energies of C-C bond scission of the alkoxy radicals are in the ranges of 12-25 and Ϫ3 -22 kcal mol Ϫ1 , respectively. Using the obtained activation barriers and transition state structures, we have calculated the high-pressure limit decomposition rates of the chloroalkenyl alkoxy radicals using transition state theory, ranging from 1ϫ10 Ϫ5 to 2ϫ10 4 s Ϫ1 . The results indicate that C-C bond decomposition of the chloroalkenyl alkoxy radicals is rather slow and likely plays a minor role in the Cl-isoprene reactions. Implications of the present results on the formation yields of methyl vinyl ketone, methacrolein, and 1-chloro-3-methyl-3-buten-2-one are discussed.

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Kinetics of Cl atom reactions with butadienes including isoprene

Cited by 34 publications

References 12 publications

Theoretical study for ozonolysis of 1,3-butadiene

Theoretical study for ozonolysis of 1,3-butadiene

Experimental and Ab Initio Dynamical Investigations of the Kinetics and Intramolecular Energy Transfer Mechanisms for the OH + 1,3-Butadiene Reaction between 263 and 423 K at Low Pressure

C–C bond fission pathways of chloroalkenyl alkoxy radicals

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