Kinetic studies of Cl-atom reactions with selected aromatic compounds using the photochemical reactor-FTIR spectroscopy technique

Shi, Junbo; Bernhard, Mary Jo

doi:10.1002/(sici)1097-4601(1997)29:5<349::aid-kin5>3.0.co;2-u

Cited by 57 publications

(53 citation statements)

References 31 publications

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“…Sokolov et al determined an upper limit of 2.5 x 10 -16 cm 3 molecule -1 s -1 for HCl formation at room temperature [8]. This is below a prior measured total rate constant of 9.8 x 10 -16 cm 3 molecule -1 s -1 by Shi and Bernhard [9]. A potential reaction path under these conditions is formation of dichlorocyclohexadienyl radicals by addition.…”

Section: Introductionmentioning

confidence: 86%

Kinetic studies of the reaction of atomic chlorine with chlorobenzene

Gao

Marshall

2009

Chemical Physics Letters

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The rate constant k1 for Cl + C6H5Cl → products has been studied via the pulsed laser photolysis -time-resolved resonance fluorescence technique over 710 -1030 K.The results may be summarized as k1 = (1.36 ± 0.47) x 10 -10 cm 3 molecule -1 s -1 exp{-(42.5 ± 2.5) kJ mol -1 /RT}. The quoted uncertainties are ±1σ, and the 95% confidence limit for k1 is ±21%. The major pathway is proposed to be formation of HCl and chlorophenyl radicals. Density functional calculations suggest the most favorable product is 3-chlorophenyl arising from attack meta to the C-Cl bond.

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Section: Introductionmentioning

confidence: 86%

Kinetic studies of the reaction of atomic chlorine with chlorobenzene

Gao

Marshall

2009

Chemical Physics Letters

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“…For light alkenes, there may be an additional impact on δ 13 C due to reaction with ozone (Iannone et al, 2003) (Shi and Bernhard, 1997), the KIE measurement method used in this work is not suitable for this reaction.…”

Section: Atmospheric Relevancementioning

confidence: 99%

“…b Experimental rate constant calculated using literature rate constants and uncertainties for the reference compound (Atkinson and Aschmann, 1985;Coquet and Ariya, 2000;Ezell et al, 2002;Fantechi et al, 1998;Shi and Bernhard, 1997;Smith et al, 2002;Stutz et al, 1998;Wallington et al, 1989) Uncertainty shown is the error of the mean KIE value for compounds with two KIE measurements, and the uncertainty from the standard error of the plot of Equation (1) for compounds with only one KIE measurement. b Iannone et al, (2003) c Mean Cl k value with 1σ standard error of the k values determined using relative rate analysis for compounds measured more than once.…”

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confidence: 99%

“…q Smith et al, (2002). (Hooshiyar and Niki, 1995) c Shi and Bernhard, (Shi and Bernhard, 1997) d Chatwick et al, (Chadwick et al, 2001) e Anderson et al, (Anderson et al, 2004a) f Anderson et al, (Anderson et al, 2004b) g Atkinson and Arey, (Atkinson and Arey, 2003) 33 (Anderson et al, 2004a;Anderson et al, 2004b;Rudolph et al, 2000), literature Cl-reaction KIE values (Anderson et al, submitted 2006), and literature rate constant data (Aschmann and Atkinson, 1995;Atkinson and Arey, 2003;Atkinson, 1997;Chadwick et al, 2001;Coquet and Ariya, 2000;Hooshiyar and Niki, 1995;Shi and Bernhard, 1997;Stutz et al, 1998;Wallington et al, 1989). b Uncertainties are the standard deviations determined using the reported uncertainties in the literature data and in the KIEs from this work.…”

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confidence: 99%

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Laboratory measurements of the 12C/13C kinetic isotope effects in the gas-phase reactions of unsaturated hydrocarbons with Cl atoms at 298 ± 3 K

et al. 2006

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Abstract. 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 ε = (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. transition state structure. IntroductionThe impact of chlorine atom chemistry on the removal of unsaturated hydrocarbons from the atmosphere has been studied in a significant number of publications (Boudries and Bottenheim, 2000;Jobson et al., 1994;Ramacher et al., 1999;Rudolph et al., 1999;Wingenter et al., 1999). Although reactions with hydroxyl radicals and ozone are far more important on the global scale, particularly in continental mid-latitudes, it is agreed that at high latitudes during Polar Sunrise and in coastal environments in the marine boundary layer, where concentrations of Cl atoms can reach levels of up to 10 5 cm -3 (Chang et al., 2004;Singh et al., 1996), Cl-atom chemistry can significantly increase the removal rate of NMHC from the atmosphere.The usefulness of stable carbon isotope ratio measurements for investigating the OH chemistry of both saturated and unsaturated nonmethane hydrocarbons (NMHC) has been demonstrated recently (Rudolph et al., 2000;Rudolph et al., 2002;Rudolph et al., 2003;Saito et al., 2002;Thompson et al., 2003;Tsunogai et al., 1999). To accurately interpret the isotope ratio measurements of unsaturated hydrocarbons, knowledge of the kinetic isotope fractionations associated with their chemical removal is necessary.Measurements have been reported of the 12 C/ 13 C-KIEs in the reactions of alkenes and aromatic hydrocarbons with OH radicals (Anderson et al., 2004a;Anderson et al., 2004b;Rudolph et al., 2000) and in the reactions of alkenes with ozone (Iannone et al., 2003).To best interpret measurements of NMHC from environments with elevated Cl-atom ExperimentThe method for measuring carbon KIEs for the reactions of NMHC + Cl is similar to the method used for measuring OH-reaction KIEs which has been described in detail in a previous publication . The method required only a few minor changes to generate Cl atoms rather than OH radicals, described recently ( For each experiment, before the Cl-atom reaction was initiated, two or three measurements of the reaction chamber contents were made to verify sufficient stability in both the concentration and stable isotope ratios of the hydrocarbons. From all of the hydrocarbons, the mean relative standard deviation of the individual hydrocarbon concentration measurements was 1.5%, with relative standard deviations ranging from 0.5-3.0%. The mean standard deviation of the stable carbon isotope compositions...

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“…At the late stage of irradiation, radical reactions play very important role for chlorinated aromatic hydrocarbon decomposition. Because rate constants of Cl radicals with chlorinated aromatic hydrocarbons (usually 1.0 × 10 -15 ~ 1.0 × 10 -16 ) (Shi & Bernhard, 1997) are much smaller than those of OH radicals ( 1.0 × 10 -12 ~1.0 × 10 -13 ), Cl radical addition reaction followed by peroxyl radical reaction pathway is not so important for chlorinated aromatic hydrocarbon decomposition in air mixture; on the contrary, OH radical reaction pathway is more important for chlorinated aromatic hydrocarbon decomposition in low or high humidity air mixture (Sun et al, 2007c …”

Section: General Mechanism Of Chlorinated Aromatic Hydrocarbons (Cl-amentioning

confidence: 99%

Organic Pollutants Treatment from Air Using Electron Beam Generated Nonthermal Plasma – Overview

Sun¹,

Chmielewski²

2012

Organic Pollutants Ten Years After the Stockholm Convention - Environmental and Analytical Update

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Kinetic studies of Cl-atom reactions with selected aromatic compounds using the photochemical reactor-FTIR spectroscopy technique

Cited by 57 publications

References 31 publications

Kinetic studies of the reaction of atomic chlorine with chlorobenzene

Kinetic studies of the reaction of atomic chlorine with chlorobenzene

Laboratory measurements of the 12C/13C kinetic isotope effects in the gas-phase reactions of unsaturated hydrocarbons with Cl atoms at 298 ± 3 K

Organic Pollutants Treatment from Air Using Electron Beam Generated Nonthermal Plasma – Overview

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