Atmospheric Fate of Chlorobromomethane:  Rate Constant for the Reaction with OH, UV Spectrum, and Water Solubility

Orkin, Vladimir L.; Khamaganov, Victor G.; Guschin, A.; Huie, Robert E.; Kurylo, Michael J.

doi:10.1021/jp962428j

Cited by 47 publications

(80 citation statements)

References 19 publications

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“…absolute determinations by Orkin et al [1018], all of which are in good agreement. The recommended E/R is obtained from a fit to the data of DeMore and Orkin et al The A factor was then calculated.…”

Section: -94supporting

confidence: 60%

“…The recommended rate expression is derived from a fit to the data from the relative rate study of DeMore [376] (recalculated based on the current recommendation for the rate constant for the OH + CH 2 Cl 2 reference reaction). The results of Orkin et al [1017] are higher by a factor of 2 but have the same temperature dependence. They are encompassed within the 2σ confidence limits.…”

Section: -81mentioning

confidence: 62%

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Environmental effects of large igneous province magmatism: a Siberian perspective

Black

Lamarque

Shields

et al. 2015

Volcanism and Global Environmental Change

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Section: -94supporting

confidence: 60%

Section: -81mentioning

confidence: 62%

Environmental effects of large igneous province magmatism: a Siberian perspective

Black

Lamarque

Shields

et al. 2015

Volcanism and Global Environmental Change

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“…Unfortunately, this comparison is only possible for the reactions of Cl and OH with CF 3 CH 2 OCHF 2 and CF 3 CH 2 CHF 2 , since there have been no kinetic data reported previously Paper for PhysChemChemPhys on OH, Cl + ethers 15 Tokuhashi et al 15 Tokuhashi et al 15 Orkin et al 21 this work OH + CF 3 Smith 12 obtained using a relative rate technique. The data of Kambanis et al 8 for Cl + CF 3 CH 2 OCHF 2 (---◊---), and of Wallington and co-workers 13 for Cl + CF 3 CH 2 OCHF 2 (▽) and for Cl + CF 3 CHClOCHF 2 (▼) are also shown.…”

Section: Discussionmentioning

confidence: 95%

Rate constants and Arrhenius parameters for the reactions of OH radicals and Cl atoms with CF3CH2OCHF2, CF3CHClOCHF2 and CF3CH2OCClF2, using the discharge-flow/resonance fluorescence method

Beach

Hickson

Smith

et al. 2001

Phys. Chem. Chem. Phys.

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Rate constants have been determined for the reactions of OH radicals and Cl atoms with the three partially halogenated methyl-ethyl ethers, CF 3 CH 2 OCHF 2 , CF 3 CHClOCHF 2 and CF 3 CH 2 OCClF 2 , using discharge-flow techniques to generate the OH radicals and the Cl atoms and resonance fluorescence to observe changes in their relative concentrations in the presence of added ether. For each combination of radical and ether, experiments were carried out at three temperatures between 292 and 410 K, yielding the following Arrhenius expressions for the rate constants within this range of temperature: OH + CF 3 CH 2 OCHF 2 : k = (2.0 ± 0.8) × 10 -11 exp( -2110 ± 150 K / T) cm 3 molecule -1 s -1 OH + CF 3 CHClOCHF 2 : k = (4.5 ± 1.3) × 10 -13 exp( -940 ± 100 K / T) cm 3 molecule -1 s -1 OH + CF 3 CH 2 OCClF 2 : k = (1.6 ± 0.6) × 10 -12 exp( -1100 ± 125 K / T) cm 3 molecule -1 s -1 Cl + CF 3 CH 2 OCHF 2 : k = (6.1 ± 1.4) × 10 -12 exp( -1830 ± 90 K / T) cm 3 molecule -1 s -1 Cl + CF 3 CHClOCHF 2 : k = (7.8 ± 2.6) × 10 -11 exp( -2980 ± 130 K / T) cm 3 molecule -1 s -1 Cl + CF 3 CH 2 OCClF 2 : k = (2.2 ± 0.2) × 10 -11 exp( -2700 ± 40 K / T) cm 3 molecule -1 s -1 2 Paper for PhysChemChemPhys on OH, Cl + ethersThe results are compared with those obtained previously for the same and related reactions of OH radicals and Cl atoms, and the atmospheric implications of the results are considered briefly. IntroductionPartially halogenated ethers have uses both as potential replacements for chlorofluorocarbons 1 (CFCs) in a number of applications, and as quite widely used anaesthetics. 2 Consequently, studies of the kinetics of the reactions of these compounds with free radicals, especially OH, are useful, since the results aid our understanding of their atmospheric chemistry and allow their atmospheric lifetimes to be estimated. Less directly, they assist with the interpretation of laboratory experiments that are designed to reveal the mechanisms by which these ethers break down in the atmosphere. 3 Finally, evaluation of the rate constants and activation energies for these reactions can help with the construction of structure-activity relationships. In this context, one can, for example, compare the kinetic parameters for the reactions of a given radical with the substituted ethers with those for the reactions of the same radical with the corresponding substituted alkanes where the ether linkage is absent. Alternatively, one can explore how substitution of fluorine or chlorine atoms for hydrogen atoms affects the susceptibility of the molecule to attack by, for example, OH radicals or Cl atoms.Hydrofluoroethers (HFEs) are favoured as possible CFC replacements over other halogenated ethers as they contain no chlorine, which if released as atoms can catalytically destroy stratospheric ozone. Of course, HFEs are volatile and will inevitably be released into the atmosphere during use. Their oxidation, initiated predominantly by OH radicals, will lead to the formation of fluorinated esters and fluorinated formates. 4,5 The likely i...

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“…The absorption spectrum of C2H4BrCl is very similar with that of CH3Br between 195 nm and 280 nm and quite close to the CH3Cl below 195 nm. 28,29 This indicates that the electronic transitions of the two chromophores and the dynamics associated with the halogen forming channels could be considered independently as in the case of CH 2 BrCl. 5 This fact also can be confirmed by our experimental observations.…”

Section: Discussionmentioning

confidence: 99%

Photodissociation Dynamics of C₂H₄BrCl: Nonadiabatic Dynamics with Intrinsic C_sSymmetry

Lee

Paul

Hong

et al. 2009

Bulletin of the Korean Chemical Society

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The photodissociation dynamics of 1,2-bromochloroethane (C2H4BrCl) was investigated near 234 nm. A two-dimensional photofragment ion-imaging technique coupled with a [2+1] resonance-enhanced multiphoton ionization scheme was utilized to obtain speed and angular distributions of the nascent Br( 2 P3/2) and Br * ( 2 P1/2) atoms. The total translational energy distributions for the Br and Br * channels were well characterized by Gaussian functions with average translational energies of 100 and 84 kJ/mol, respectively. The recoil anisotropies for the Br and Br * channels were measured to be β = 0.49 ± 0.05 for Br and 1.55 ± 0.05 for Br * . The relative quantum yield for Br * was found to be ΦBr* = 0.33 ± 0.03. The probability of nonadiabatic transition between A' states was estimated to be 0.46. The relevant nonadiabatic dynamics is discussed in terms of interaction between potential energy surfaces in Cs symmetry.Key Words: Photodissociation dynamics, Alkyl halides, Curve-crossing, Cs symmetry, Ion-imaging

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Atmospheric Fate of Chlorobromomethane: Rate Constant for the Reaction with OH, UV Spectrum, and Water Solubility

Cited by 47 publications

References 19 publications

Environmental effects of large igneous province magmatism: a Siberian perspective

Environmental effects of large igneous province magmatism: a Siberian perspective

Rate constants and Arrhenius parameters for the reactions of OH radicals and Cl atoms with CF3CH2OCHF2, CF3CHClOCHF2 and CF3CH2OCClF2, using the discharge-flow/resonance fluorescence method

Photodissociation Dynamics of C₂H₄BrCl: Nonadiabatic Dynamics with Intrinsic C_sSymmetry

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Atmospheric Fate of Chlorobromomethane: Rate Constant for the Reaction with OH, UV Spectrum, and Water Solubility

Cited by 47 publications

References 19 publications

Environmental effects of large igneous province magmatism: a Siberian perspective

Environmental effects of large igneous province magmatism: a Siberian perspective

Rate constants and Arrhenius parameters for the reactions of OH radicals and Cl atoms with CF3CH2OCHF2, CF3CHClOCHF2 and CF3CH2OCClF2, using the discharge-flow/resonance fluorescence method

Photodissociation Dynamics of C2H4BrCl: Nonadiabatic Dynamics with Intrinsic CsSymmetry

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Photodissociation Dynamics of C₂H₄BrCl: Nonadiabatic Dynamics with Intrinsic C_sSymmetry