Atmospheric Chemistry of Fluorinated Alcohols:  Reaction with Cl Atoms and OH Radicals and Atmospheric Lifetimes

Hurley, M. D.; Wallington, Timothy J.; Andersen, Mads Peter; Ellis, David; Martin, Jonathan W.; Mabury, Scott A.

doi:10.1021/jp0373088

Cited by 85 publications

(142 citation statements)

References 30 publications

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“…These authors stated that the reported absorption cross sections of CF 3 CH 2 CH 2 OH were 5-10 % lower than those previously reported by Waterland et al [28] As shown in Figure 5 a, the band positions and shapes for CF 3 CH 2 CH 2 OH are in excellent agreement with the high-resolution spectrum [39] 760 0.123 RR/FTIR Sellevåg et al [6] 4-70 0.10 DF-PLP-FP/LIF Tokuhashi et al [40] CF 3 reported by Waterland et al [28] Therefore, s n is not resolution dependent between 0.004 and 1 cm À1 .…”

supporting

confidence: 74%

Atmospheric Lifetimes and Global Warming Potentials of CF₃CH₂CH₂OH and CF₃(CH₂)₂CH₂OH

et al. 2010

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A comprehensive study of several atmospheric degradation routes for two hydrofluoroalcohols, CF(3)(CH(2))(x=1,2)CH(2)OH, is presented. The gas-phase kinetics of their reactions with hydroxyl radicals (OH) and chlorine (Cl) atoms are investigated by absolute and relative techniques, respectively. The room-temperature rate coefficients (±σ, in cm(3) molecule(-1) s(-1)) k(OH) and k(Cl), are respectively (9.7±1.1)×10(-13) and (1.60±0.45)×10(-11) for CF(3)CH(2)CH(2)OH, and (2.62±0.32)×10(-12) and (8.71±0.24)×10(-11) for CF(3)(CH(2))(2)CH(2)OH. Average lifetimes of CF(3)CH(2)CH(2)OH and CF(3)(CH(2))(2)CH(2)OH due to the OH and Cl reactions are estimated to be 12 and 4 days, and greater than 20 and 4 years, respectively. Also, the IR and UV absorption cross sections of CF(3)(CH(2))(x=1,2)CH(2)OH are determined in the spectral ranges of 500-4000 cm(-1) and 200-310 nm. Photolysis of CF(3)(CH(2))(x=1,2)CH(2)OH in the actinic region (λ≥290 nm) is negligible compared to their homogeneous removal. Additionally, computational IR spectra are consistent with the experimental ones, thus giving high confidence in the obtained results. The lifetimes of CF(3)(CH(2))(x=1,2)CH(2)OH and IR spectra reported herein allow the calculation of the direct global warming potential of these hydrofluoroalcohols. The contribution of CF(3)(CH(2))(x)CH(2)OH to radiative forcing of climate change will be negligible.

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supporting

confidence: 74%

Atmospheric Lifetimes and Global Warming Potentials of CF₃CH₂CH₂OH and CF₃(CH₂)₂CH₂OH

et al. 2010

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“…Alcohols are affected by halogen atoms either by hydrogen abstraction in α-position (Wu et al, 2003) or by oxidation to aldehydes (Hurley et al, 2004).…”

Section: Related Mechanisms Of Halogen Chemistrymentioning

confidence: 99%

Halogenation processes of secondary organic aerosol and implications on halogen release mechanisms

et al. 2012

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Abstract. Reactive halogen species (RHS), such as X·, X 2 and HOX containing X = chlorine and/or bromine, are released by various sources like photo-activated sea-salt aerosol or from salt pans, and salt lakes. Despite many studies of RHS reactions, the potential of RHS reacting with secondary organic aerosol (SOA) and organic aerosol derived from biomass-burning (BBOA) has been neglected. Such reactions can constitute sources of gaseous organohalogen compounds or halogenated organic matter in the tropospheric boundary layer and can influence physicochemical properties of atmospheric aerosols.Model SOA from α-pinene, catechol, and guaiacol was used to study heterogeneous interactions with RHS. Particles were exposed to molecular chlorine and bromine in an aerosol smog-chamber in the presence of UV/VIS irradiation and to RHS, released from simulated natural halogen sources like salt pans. Subsequently, the aerosol was characterized in detail using a variety of physicochemical and spectroscopic methods. Fundamental features were correlated with heterogeneous halogenation, which results in new functional groups (FTIR spectroscopy), changes UV/VIS absorption, chemical composition (ultrahigh resolution mass spectroscopy (ICR-FT/MS)), or aerosol size distribution. However, the halogen release mechanisms were also found to be affected by the presence of organic aerosol. Those interaction processes, changing chemical and physical properties of the aerosol are likely to influence e.g. the ability of the aerosol to act as cloud condensation nuclei, its potential to adsorb other gases with low-volatility, or its contribution to radiative forcing and ultimately the Earth's radiation balance.

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“…[4][5][6] CF 3 CH 2 CH 2 OH is the one among the family of CF 3 (CH 2 ) x CH 2 OH, and its major atmospheric photooxidation product is CF 3 CH 2 CHO. [7][8][9][10] The major degradation process of CF 3 CH 2 CHO in atmosphere is initiated by the OH radicals. Experimental studies have been performed by some groups to determine the absolute and relative rate constants of the CF 3 CH 2 CHO + OH reaction.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Studies on Mechanism and Kinetics of the Hydrogen-Abstraction Reaction of CF₃CH₂CHO with OH Radicals

Ci¹,

Yu²,

Wan³

et al. 2011

Bulletin of the Korean Chemical Society

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The hydrogen abstraction reaction of CF 3 CH 2 CHO + OH has been studied theoretically by dual-level direct dynamics method. Two stable conformers, trans-and cis-CF 3 CH 2 CHO, have been located, and there are four distinct OH hydrogen-abstraction channels from t-CF 3 CH 2 CHO and two channels from c-CF 3 CH 2 CHO. The required potential energy surface information for the kinetic calculation was obtained at the MCG3-MPWB// M06-2X/aug-cc-pVDZ level. The rate constants, which were calculated using improved canonical transitionstate theory with small-curvature tunneling correction (ICVT/SCT) were fitted by a four-parameter Arrhenius equation. It is shown that the reaction proceeds predominantly via the H-abstraction from the -CHO group over the temperature range 200-2000 K. The calculated rate constants were in good agreement with the experimental data between 263 and 358 K.

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Atmospheric Chemistry of Fluorinated Alcohols: Reaction with Cl Atoms and OH Radicals and Atmospheric Lifetimes

Cited by 85 publications

References 30 publications

Atmospheric Lifetimes and Global Warming Potentials of CF₃CH₂CH₂OH and CF₃(CH₂)₂CH₂OH

Atmospheric Lifetimes and Global Warming Potentials of CF₃CH₂CH₂OH and CF₃(CH₂)₂CH₂OH

Halogenation processes of secondary organic aerosol and implications on halogen release mechanisms

Theoretical Studies on Mechanism and Kinetics of the Hydrogen-Abstraction Reaction of CF₃CH₂CHO with OH Radicals

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Atmospheric Chemistry of Fluorinated Alcohols: Reaction with Cl Atoms and OH Radicals and Atmospheric Lifetimes

Cited by 85 publications

References 30 publications

Atmospheric Lifetimes and Global Warming Potentials of CF3CH2CH2OH and CF3(CH2)2CH2OH

Atmospheric Lifetimes and Global Warming Potentials of CF3CH2CH2OH and CF3(CH2)2CH2OH

Halogenation processes of secondary organic aerosol and implications on halogen release mechanisms

Theoretical Studies on Mechanism and Kinetics of the Hydrogen-Abstraction Reaction of CF3CH2CHO with OH Radicals

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Atmospheric Lifetimes and Global Warming Potentials of CF₃CH₂CH₂OH and CF₃(CH₂)₂CH₂OH

Atmospheric Lifetimes and Global Warming Potentials of CF₃CH₂CH₂OH and CF₃(CH₂)₂CH₂OH

Theoretical Studies on Mechanism and Kinetics of the Hydrogen-Abstraction Reaction of CF₃CH₂CHO with OH Radicals