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Browsing Centre for Atmospheric Chemistry by Author "Anderson, Rebecca S."
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Item Open Access Carbon kinetic isotope effects in the gas-phase reactions of aromatic hydrocarbons with the OH radical at 296 ± 4 K(AGU, 2004) Anderson, Rebecca S.; Iannone, Richard; Thompson, Alexandra E.; Rudolph, Jochen; Huang, LinThe carbon kinetic isotope effects (KIEs) of the room temperature reactions of benzene and several light alkyl benzenes with OH radicals were studied in a reaction chamber at ambient pressure using gas chromatography coupled with online combustion and isotope ratio mass spectrometry (GCC‐IRMS). The KIEs are reported in per mil according to $\varepsilon$ (‰) = (KIE − 1) × 1000, where KIE = k12/k13. The following average KIEs were obtained, (all in ‰): benzene 7.53 ± 0.50; toluene 5.95 ± 0.28; ethylbenzene 4.34 ± 0.28; o‐xylene 4.27 ± 0.05, p‐xylene 4.83 ± 0.81; o‐ethyltoluene 4.71 ± 0.12 and 1,2,4‐trimethylbenzene 3.18 ± 0.09. Our KIE value for benzene + OH agrees with the only reported value known to us [Rudolph et al., 2000]. It is shown that measurements of the stable carbon isotope ratios of light aromatic compounds should be extremely useful to study atmospheric processing by the OH radical.Item Open Access Laboratory measurements of the 12C/13C kinetic isotope effects in the gas-phase reactions of unsaturated hydrocarbons with Cl atoms at 298 ± 3 K(Springer Netherlands, 2007) Anderson, Rebecca S.; Huang, Lin; Iannone, Richard; Rudolph, J.The carbon kinetic isotope effects (KIEs) in the reactions of several unsaturated hydrocarbons with chlorine atoms were measured at room temperature and ambient pressure using gas chromatography combustion isotope ratio mass spectrometry (GCC-IRMS). All measured KIEs, defined as the ratio of the rate constants for the unlabeled and labeled hydrocarbon reaction k 12/k 13, are greater than unity or normal KIEs. The KIEs, reported in per mil according to Cl ɛ = (k 12/k 13−1) × 1000‰ with the number of experimental determinations in parenthesis, are as follows: ethene, 5.65 ± 0.34 (1); propene, 5.56 ± 0.18 (2); 1-butene, 5.93 ± 1.16 (1); 1-pentene, 4.86 ± 0.63 (1); cyclopentene, 3.75 ± 0.14 (1); toluene, 2.89 ± 0.31 (2); ethylbenzene, 2.17 ± 0.17 (2); o-xylene, 1.85 ± 0.54 (2). To our knowledge, these are the first reported KIE measurements for reactions of unsaturated NMHC with Cl atoms. Relative rate constants were determined concurrently to the KIE measurements. For the reactions of cyclopentene and ethylbenzene with Cl atoms, no rate constant has been reported in refereed literature. Our measured rate constants are: cyclopentene (7.32 ± 0.88) relative to propene (2.68 ± 0.32); ethylbenzene (1.15 ± 0.04) relative to o-xylene (1.35 ± 0.21), all × 10−10 cm3 molecule−1 s−1. The KIEs in reactions of aromatic hydrocarbons with Cl atoms are similar to previously reported KIEs in Cl-reactions of alkanes with the same numbers of carbon atoms. Unlike the KIEs for previously studied gas-phase hydrocarbon reactions, the KIEs for alkene–Cl reactions do not exhibit a simple inverse dependence on carbon number. This can be explained by competing contributions of normal and inverse isotope effects of individual steps in the reaction mechanism. Implications for the symmetries of the transition state structures in these reactions and the potential relevance of Cl-atom reactions on stable carbon isotope ratios of atmospheric NMHC are discussed