Tropospheric photooxidation of CF&amp;lt;sub&amp;gt;3&amp;lt;/sub&amp;gt;CH&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt;CHO and CF&amp;lt;sub&amp;gt;3&amp;lt;/sub&amp;gt;(CH&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt;)&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt;CHO initiated by Cl atoms and OH radicals

Antiñolo, María; Jiménez, Elena; Notario, Alberto; Martı́nez, Ernesto; Albaladejo, José

doi:10.5194/acp-10-1911-2010

Cited by 25 publications

(16 citation statements)

References 31 publications

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“…This increase in k OH and k Cl with the length of the hydrocarbon chain has also been observed for the OH and Cl rate coefficients for partially fluorinated aldehydes CF 3 (CH 2 ) x CHO. [18] Regarding the degradation products of reactions (1) and (2), mechanistic studies carried out both in the absence and presence of NO x on the OH and Cl reactions with CF 3 CH 2 OH [6,25,26] and CF 3 CH 2 CH 2 OH [7][8][9] confirm that the main reaction pathway proceeds via hydrogen atom abstraction from the CH 2 group adjacent to the OH group, since the main primary product was the corresponding aldehyde. Theoretical studies recently performed by our group on the Cl-initiated reaction with CF 3 CH 2 OH [26] are consistent with the experimental observa- Table 2S of the Supporting Information.…”

Section: Resultsmentioning

confidence: 96%

“…The experimental setup employed in this study has been recently described by AntiÇolo et al [18] Typically, spectra were obtained from the co-addition of 16 interferograms, which required about 1 min of acquisition time. A White-type gas cell was used with a fixed optical path length of 8 m. IR spectra were recorded under static conditions from diluted mixtures of CF 3 The absorption cross section (base 10) at each wavenumber, s n , was obtained by applying the Beer-Lambert law as described in AntiÇolo et al [18] by plotting the absorbance versus HFA concentration [Eq. (9)]:…”

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confidence: 99%

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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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Section: Resultsmentioning

confidence: 96%

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confidence: 99%

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

et al. 2010

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“…The second experimental system, based on Fourier transform infrared (FTIR) spectroscopy, was employed for determining the IR absorption cross sections, σe v , of HFO-1243zf and their integrated values over a specific wavenumber range, S int . The experimental setups, techniques, and methodologies are described in detail in previous works (Jiménez et al 2007(Jiménez et al , 20052010;Antiñolo et al 2010Antiñolo et al , 2012. Only a brief description is given below.…”

Section: Techniques and Methodologiesmentioning

confidence: 99%

Hydroxyl radical reaction rate coefficients as a function of temperature and IR absorption cross sections for CF3CH=CH2 (HFO-1243zf), potential replacement of CF3CH2F (HFC-134a)

González

Jiménez

Ballesteros

et al. 2014

Environ Sci Pollut Res

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CF3CH=CH2 (hydrofluoroolefin, HFO-1243zf) is a potential replacement of high global-warming potential (GWP) hydrofluorocarbon (HFC-134a, CF3CFH2). Both the atmospheric lifetime and the radiative efficiency of HFO-1243zf are parameters needed for estimating the GWP of this species. Therefore, the aim of this work is (i) to estimate the atmospheric lifetime of HFO-1243zf from the reported OH rate coefficients, k OH, determined under tropospheric conditions and (ii) to calculate its radiative efficiency from the reported IR absorption cross sections. The OH rate coefficient at 298 K also allows the estimation of the photochemical ozone creation potential (ε(POCP)). The pulsed laser photolysis coupled to a laser-induced fluorescence technique was used to determine k OH for the reaction of OH radicals with HFO-1243zf as a function of pressure (50-650 Torr of He) and temperature (263-358 K). Gas-phase IR spectra of HFO-1243zf were recorded at room temperature using a Fourier transform IR spectrometer between 500 and 4,000 cm(-1). At all temperatures, k OH did not depend on bath gas concentration (i.e., on the total pressure between 50 and 650 Torr of He). A slight but noticeable T dependence of k OH was observed in the temperature range investigated. The observed behavior is well described by the following Arrhenius expression: k OH(T) = (7.65 ± 0.26) × 10(-13) exp [(165 ± 10) / T] cm(3) molecule(-1) s(-1). Negligible IR absorption of HFO-1243zf was observed at wavenumbers greater than 1,700 cm(-1). Therefore, IR absorption cross sections, [Formula: see text], were determined in the 500-1,700 cm(-1) range. Integrated [Formula: see text] were determined between 650 and 1,800 cm(-1) for comparison purposes. The main diurnal removal pathway for HFO-1243zf is the reaction with OH radicals, which accounts for 64% of the overall loss by homogeneous reactions at 298 K. Globally, the lifetime due to OH reaction (τ OH) was estimated to be 8.7 days under the assumption of a well-mixed atmosphere. Assuming other removal pathways, the atmospheric lifetime (τ) was estimated to be ∼6 days. Considering the estimated τ OH and the measured IR absorption cross sections of HFO-1243zf in the atmospheric window (720-1,250 cm(-1)), its lifetime corrected radiative efficiency was calculated to be 0.019 W m(-2) ppbv(-1). GWP100 years for the HFO investigated, 0.29, is negligible compared to that of HFC-134a, the HFC to be potentially replaced (GWP100 years = 1,300, Hodnebrog et al. (Rev Geophys 51:300-378, 2013)). ε POCP for HFO-1243zf was estimated to be around 1 order of magnitude lower than that for ethylene. In conclusion, HFO-1243zf is fast degraded in the atmosphere, and it does not appreciably contribute to global warming and local/regional air pollution. Therefore, HFO-1243zf can be a suitable replacement for HFC-134a in air conditioning units.

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“…All of them have previously been described in detail (Jim enez et al, 2005;Antiñolo et al, 2010Antiñolo et al, , 2014 and only a brief overview is given in the subsequent subsections.…”

Section: Methodsmentioning

confidence: 99%

“…The UV and IR absorption spectroscopy systems have already been described in detail elsewhere (Jim enez et al, 2005;Antiñolo et al, 2010).…”

Section: Uv and Ir Absorption Spectroscopy Systemsmentioning

confidence: 99%

Atmospheric degradation of 2-chloroethyl vinyl ether, allyl ether and allyl ethyl ether: Kinetics with OH radicals and UV photochemistry

et al. 2017

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Tropospheric photooxidation of CF<sub>3</sub>CH<sub>2</sub>CHO and CF<sub>3</sub>(CH<sub>2</sub>)<sub>2</sub>CHO initiated by Cl atoms and OH radicals

Cited by 25 publications

References 31 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

Hydroxyl radical reaction rate coefficients as a function of temperature and IR absorption cross sections for CF3CH=CH2 (HFO-1243zf), potential replacement of CF3CH2F (HFC-134a)

Atmospheric degradation of 2-chloroethyl vinyl ether, allyl ether and allyl ethyl ether: Kinetics with OH radicals and UV photochemistry

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Tropospheric photooxidation of CF&lt;sub&gt;3&lt;/sub&gt;CH&lt;sub&gt;2&lt;/sub&gt;CHO and CF&lt;sub&gt;3&lt;/sub&gt;(CH&lt;sub&gt;2&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;CHO initiated by Cl atoms and OH radicals

Cited by 25 publications

References 31 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

Hydroxyl radical reaction rate coefficients as a function of temperature and IR absorption cross sections for CF3CH=CH2 (HFO-1243zf), potential replacement of CF3CH2F (HFC-134a)

Atmospheric degradation of 2-chloroethyl vinyl ether, allyl ether and allyl ethyl ether: Kinetics with OH radicals and UV photochemistry

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Tropospheric photooxidation of CF<sub>3</sub>CH<sub>2</sub>CHO and CF<sub>3</sub>(CH<sub>2</sub>)<sub>2</sub>CHO initiated by Cl atoms and OH radicals

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

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