Kinetics and mechanism of the gas phase reaction of Cl atoms with iodobenzene

Andersen, Mads Peter; Ponomarev, D. A.; Nielsen, Ole John; Hurley, M. D.; Wallington, Timothy J.

doi:10.1016/s0009-2614(01)01318-5

Cited by 11 publications

(10 citation statements)

References 10 publications

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“…Such reactions proceed slowly with effective rate constants of the order of 10 -16 cm 3 molecule -1 s -1 via two reaction channels: hydrogen abstraction and adduct formation with the adduct undergoing rapid decomposition to reform the reactants. In dramatic contrast, the reactions of Cl atoms with C 6 H 5 Br and C 6 H 5 l proceed rapidly ( k Cl+C 6 H 5 Br = (1.3 ± 0.2) × 10 -11 , k Cl+C 6 H 5 I = (3.3 ± 0.7) × 10 -11 cm 3 molecule -1 s -1 ) to give C 6 H 5 Cl in a yield indistinguishable from 100%. , At first sight, it appears that the reactions of Cl atoms with C 6 H 5 Br and C 6 H 5 I proceed via a different mechanism from those with C 6 H 5 F and C 6 H 5 Cl. However, consideration of the thermochemistry associated with these reactions suggests that this might not be the case.…”

Section: Discussionmentioning

confidence: 98%

“…k -5b , then expression v can be reduced to k effective ) k 5a + k 5b k 8a /k 8 and no dependence on Cl atom steady-state concentration would be observed. If k 8 [Cl] ss , k -5b , then the effective rate constant Cl + C 6 H 5 F f products (5) Cl + CF 2 ClH f products…”

Section: Hencementioning

confidence: 99%

“…Kinetic and mechanistic data concerning the reaction of Cl atoms with aromatic compounds are needed to design and interpret such smog chamber studies. We have reported such data for C 6 H 6 , C 6 H 5 Cl, C 6 H 5 Br, and C 6 H 5 I . To complete our investigation of the reactivity of monohalobenzenes, we report here a study of the reaction of Cl atoms with C 6 H 5 F in 700 Torr of N 2 diluent at 296 K. The kinetics of the reaction of OH radicals with C 6 H 5 F were also studied as part of this work.…”

Section: Introductionmentioning

confidence: 99%

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Kinetics and Mechanism of the Gas-Phase Reaction of Cl Atoms and OH Radicals with Fluorobenzene at 296 K

et al. 2002

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Smog chamber/FTIR techniques were used to study the kinetics and mechanism of the reaction of Cl atoms and OH radicals with fluorobenzene, C6H5F, in 700 Torr of N2 or air diluent at 296 K. Reaction of Cl atoms with C6H5F proceeds via two pathways: H-atom abstraction to give HCl and the C6H4F radical and adduct formation to give the C6H5F−Cl adduct. At 296 K the rate constant for the abstraction channel is k 5a(Cl + C6H5F) = (1.1 ± 0.1) × 10-17 cm3 molecule-1 s-1. The C6H5F−Cl adduct undergoes rapid (k ∼ 108 s-1) decomposition to reform C6H5F and Cl atoms and reaction with Cl atoms via a mechanism which, at least in part, leads neither to production of C6H5Cl nor to reformation of C6H5F. As the steady-state Cl atom concentration is increased, the fraction of the C6H5F−Cl adduct undergoing reaction with Cl atoms increases causing an increase in the effective rate constant for the reaction of C6H5F with Cl atoms. The equilibrium between Cl atoms, C6H5F, and the C6H5F−Cl adduct is established rapidly and has an equilibrium constant estimated to be K 5b=[C6H5F−Cl]/[C6H5F][Cl] = (3.2 ± 2.4) × 10-18 cm3 molecule-1. An upper limit of k 9 < 6 × 10-17 cm3 molecule-1 s-1 was established for the reaction of the C6H5F−Cl adduct with O2. The reaction of OH radicals with C6H5F was studied and a rate constant of k(OH + C6H5F) = (7.9 ± 2.2) × 10-13 cm3 molecule-1 s-1 was determined. The results are discussed with respect to the available literature concerning reaction of Cl atoms and OH radicals with aromatic compounds. As part of this work, rate constants for reaction of OH radicals with 2-, 3-, and 4-fluorophenol of (6.3 ± 1.3) × 10-12, (2.3 ± 0.5) × 10-11, and (2.5 ± 0.5) × 10-11 cm3 molecule-1 s-1 were determined.

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Section: Discussionmentioning

confidence: 98%

Section: Hencementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Kinetics and Mechanism of the Gas-Phase Reaction of Cl Atoms and OH Radicals with Fluorobenzene at 296 K

et al. 2002

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“…6 C 6 F 5 OH is not expected to be present in the atmosphere at detectable levels; however, C 6 F 5 OH can serve as a model aromatic compound to help improve our understanding of the Cl-and OH-initiated reactions of aromatic compounds. We have previously studied the Cl atom and OH radical reactions of C 6 H 5 I, 7 C 6 H 5 F, 8 C 6 F 6 , 9 and C 6 F 5 H. 9 These reactions lead to aromatic Cl and OH adducts that have quite different atmospheric fates. The reactions of Cl atoms with C 6 H 5 F and C 6 F 5 H occur through two pathways, hydrogen abstraction and adduct formation.…”

Section: Introductionmentioning

confidence: 99%

“…7.28−8.39 mTorr C 6 F 5 OH, 1.08−1.80 mTorr C 2 H 2 , and either 109, 317, or 730 mTorr Cl 2 . When using C 2 H 4 as a reference compound, measurements were performed at initial concentrations of 8.89−9.28 mTorr C 6 F 5 OH, 5.17−5.25 mTorr C 2 H 4 , and either 109 or 730 mTorr Cl 2 in a total pressure of 700 Torr air.…”

mentioning

confidence: 97%

Atmospheric Chemistry of Pentafluorophenol: Kinetics and Mechanism of the Reactions of Cl Atoms and OH Radicals

et al. 2019

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Fourier transform infrared smog chamber techniques were used to study the kinetics and mechanisms of the reactions of Cl atoms and OH radicals with pentafluorophenol (C6F5OH) in 700 Torr total pressure of air or N2 diluent at 296 ± 2 K. Rate constants k(OH + C6F5OH) = (6.88 ± 1.37) × 10–12 cm3 molecule–1 s–1 and k(Cl + C6F5OH) = (2.52 ± 0.31) × 10–11 cm3 s–1 molecule–1 in 700 Torr air diluent were determined. In 700 Torr N2, the rate constant for the reaction of C6F5OH with Cl atoms is linearly dependent on the Cl atom concentration. Product studies on this reaction in both 700 Torr air and 700 Torr N2 diluent show the formation of nonconjugated products. The photolysis constant of C6F5OH was determined by 254 nm UV irradiation of a C6F5OH and CH3CHO mixture in 700 Torr air or N2 at 296 ± 2 K and yielded a photolysis rate constant of J(C6F5OH) = (2.83 ± 0.25) × 10–3 s–1. Results are discussed with respect to the atmospheric chemistry of other halogenated aromatic species.

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A theoretical study on the mechanism of the reaction between Cl atoms and nitrobenzene

Praña

Gomperts

Sordo

2004

Chemical Physics Letters

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Kinetics and mechanism of the gas phase reaction of Cl atoms with iodobenzene

Cited by 11 publications

References 10 publications

Kinetics and Mechanism of the Gas-Phase Reaction of Cl Atoms and OH Radicals with Fluorobenzene at 296 K

Kinetics and Mechanism of the Gas-Phase Reaction of Cl Atoms and OH Radicals with Fluorobenzene at 296 K

Atmospheric Chemistry of Pentafluorophenol: Kinetics and Mechanism of the Reactions of Cl Atoms and OH Radicals

A theoretical study on the mechanism of the reaction between Cl atoms and nitrobenzene

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