Stopped-flow studies of the mechanisms of ozone-alkene reactions in the gas phase: trans-2-butene

Martinez, Richard I.; Herron, John T.

doi:10.1021/j100327a017

Cited by 68 publications

(77 citation statements)

References 1 publication

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“…3). HO 2 formed by decomposition of the Criegee intermediate in the presence of O 2 [35] alongside OH radical formation from a 1,4-sigmatropic shift of the Criegee intermediate followed by bond fission [36] could cause secondary loss rates [37]. However, operating under excess alkene conditions and assuming 100% OH yield, this would lead to 2-6% error in the rate coefficient, despite OH yields of approximately 30-60% being reported [37,38].…”

Section: Resultsmentioning

confidence: 99%

Temperature‐dependent kinetics for the ozonolysis of selected chlorinated alkenes in the gas phase

Leather

McGillen

Ghalaieny

et al. 2010

Int J of Chemical Kinetics

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The ozonolysis of olefinic species is an important tropospheric process impacting on climate and human health. However, few studies have investigated these reactions as a function of temperature and even less information is available upon the effects of alkene heteroatomic substitution on the Arrhenius parameters. The electron-withdrawing capacity of substituents about the olefinic bond strongly influences the rate of alkene ozonolysis. To understand better the effect of these substitutions, the temperature-dependence of a series of ozonechloroalkene reactions is investigated. Experiments were conducted in the EXTreme RAnge (EXTRA) chamber, over the range of 292-409 K and 760 Torr. The experimentally determined rate coefficients were fitted using an Arrhenius-type analysis to yield the following activation energies: 30.80 ± 0.79, 23.18 ± 0.59, 65.2 ± 2.8, 116.9 ± 5.6, 29.5 ± 1.8, and 18.67 ± 0.96 kJ mol −1 and preexponential A-factors 1.22

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Section: Resultsmentioning

confidence: 99%

Temperature‐dependent kinetics for the ozonolysis of selected chlorinated alkenes in the gas phase

Leather

McGillen

Ghalaieny

et al. 2010

Int J of Chemical Kinetics

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“…hypothesised by Martinez and Herron (1988) that OH radical production can result from a 1,4-sigmatropic shift within the C.I. followed by bond fission (Fig.…”

Section: Referencementioning

confidence: 99%

“…possible is • CH 2 OO • , which is formed during the ozonolysis of ethene and terminal alkenes, or the C.I. may be either monosub- Martinez and Herron (1988), hypothesis of OH radical production from a 1,4-sigmatropic shift within the CI, followed by bond fission. Table 1.…”

Section: Introductionmentioning

confidence: 99%

Measurements of OH and HO<sub>2</sub> yields from the gas phase ozonolysis of isoprene

et al. 2010

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Abstract. The reactions of ozone with alkenes are an important source of hydroxyl (OH) radicals; however, quantification of their importance is hindered by uncertainties in the absolute OH yield. Hydroxyl radical yields for the gas-phase ozonolysis of isoprene are determined in this paper by four different methods: (1) The use of cyclohexane as an OH scavenger, and the production of cyclohexanone, (2) The use of 1,3,5-trimethylbenzene as an OH tracer, and the diminution in its concentration, (3) A kinetic method in which the OH yield was obtained by performing a series of pseudo-first-order experiments in the presence or absence of an OH scavenger (cyclohexane), (4) The OH and HO 2 yields were determined by fitting the temporal OH and HO 2 profiles following direct detection of absolute OH and HO 2 concentrations by laser induced fluorescence at low pressure (Fluorescence Assay by Gas Expansion-FAGE). The following OH yields for the ozonolysis of isoprene were obtained, relative to alkene consumed, for each method: (1) Scavenger (0.25±0.04), (2) Tracer (0.25±0.03), (3) Kinetic study (0.27±0.02), and (4) Direct observation (0.26±0.02), the error being one standard deviation. An averaged OH yield of 0.26±0.02 is recommended at room temperature and atmospheric pressure and this result is compared with recent literature determinations. The HO 2 yield was directly determined for the first time using FAGE to be 0.26±0.03.

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“…cm6 molec-' s-' [lo] [2,3,4,5,11,12,13,14] on the ozone reactions of propene, 2-butene and 2,3-dimethyl2-butene, has provided conflicting conclusions as to the amounts of these radical products. OH produced by the reaction of ozone with isoprene is both important to smog formation in the atmoshere, and can complicate the standard 03/hydrocarbon/dark experiment, because much of the hydrocarbon that appears to be reacting with 0 3 is actually lost via reaction with OH.…”

Section: Experimental Systemmentioning

confidence: 99%

Atmospheric photooxidation of isoprene part II: The ozone‐isoprene reaction

Paulson

Flagan

Seinfeld

1992

Int J of Chemical Kinetics

172

137

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A series of experiments have been performed to study the ozone-isoprene reaction in a smog chamber by adding externally produced 0 3 to the hydrocarbon in the dark. A chemical tracer, methyl cyclohexane, was added to probe the OH formation in the system. O(3P) formation was also examined using the known distribution of products that are unique to the 0(3P)-isoprene reaction (part I). The results provide clear evidence that both OH and O(3P) are produced by the 03-isoprene reaction directly in large quantities; about 0.68 2 0.15 and 0.45 2 0.20 per 03-isoprene reaction, respectively. These additional radicals severely complicate the analysis of the 0 3 reaction, hence, computer kinetic modeling was necessary to ascertain the products of the 0 3 reaction itself, corrected for OH and O(3P) reactions. The product distribution, which differs dramatically from that published previously, is: 67 2 9% methacrolein, 26 2 6% methyl vinyl ketone, and 7 2 3% propene, accounting for 100 * 10% of the reacted isoprene. Applicability of these results to the gas-phase 0 3 reaction with other unsaturated hydrocarbons is briefly discussed.

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Stopped-flow studies of the mechanisms of ozone-alkene reactions in the gas phase: trans-2-butene

Cited by 68 publications

References 1 publication

Temperature‐dependent kinetics for the ozonolysis of selected chlorinated alkenes in the gas phase

Temperature‐dependent kinetics for the ozonolysis of selected chlorinated alkenes in the gas phase

Measurements of OH and HO<sub>2</sub> yields from the gas phase ozonolysis of isoprene

Atmospheric photooxidation of isoprene part II: The ozone‐isoprene reaction

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Stopped-flow studies of the mechanisms of ozone-alkene reactions in the gas phase: trans-2-butene

Cited by 68 publications

References 1 publication

Temperature‐dependent kinetics for the ozonolysis of selected chlorinated alkenes in the gas phase

Temperature‐dependent kinetics for the ozonolysis of selected chlorinated alkenes in the gas phase

Measurements of OH and HO&lt;sub&gt;2&lt;/sub&gt; yields from the gas phase ozonolysis of isoprene

Atmospheric photooxidation of isoprene part II: The ozone‐isoprene reaction

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Measurements of OH and HO<sub>2</sub> yields from the gas phase ozonolysis of isoprene