Atmospheric chemistry of perfluorocyclopentene (cyc-CF 2 CF 2 CF 2 CF=CF−): Kinetics, products and mechanism of gas-phase reactions with OH radicals, and atmospheric implications

Zhang, Ni; Uchimaru, Tadafumi; Guo, Qin; Qing, Feiyao; Chen, Liang; Mizukado, Junji

doi:10.1016/j.atmosenv.2017.04.012

Cited by 15 publications

(33 citation statements)

References 33 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The inset shows an expanded view of the room-temperature results. Included for comparison are the relative rate results from Zhang et al (open circles CH 3 F reference compound, open triangles CH 2 F 2 reference compound), and their reported Arrhenius fit (dashed line) and the results from Wallington and Hurley (open square). Note that the Wallington and Hurley rate coefficient is not visible in the zoomed-in range of the inset.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Atmospheric Chemistry of c-C₅HF₇ and c-C₅F₈: Temperature-Dependent OH Reaction Rate Coefficients, Degradation Products, Infrared Spectra, and Global Warming Potentials

et al. 2021

View full text Add to dashboard Cite

c-C 5 HF 7 (1H-heptafluorocyclopentene) and c-C 5 F 8 (perfluorocyclopentene) are potent greenhouse gases presently used as replacement compounds in Si etching. A thorough understanding of their potential impact on climate and air quality necessitates studies of their atmospheric reactivity, radiative properties, and atmospheric degradation pathways. The predominant atmospheric removal process for these compounds is expected to be via reaction with the OH radical. In this study, rate coefficients, k, for the gas-phase reaction of the OH radical with c-C 5 HF 7 and c-C 5 F 8 were measured over a range of temperatures (242−370 K) and pressures (50−100 Torr, He) using a pulsed laser photolysis−laser-induced fluorescence technique. In addition, a complementary relative rate technique, employing multiple reference compounds, was used to study the reactions between 273 and 372 K at 100 Torr (He) total pressure. Reaction rate coefficients were found to be independent of pressure over this range of conditions with k 1 (296 K) = (4.59 ± 0.10) × 10 −14 cm 3 molecule −1 s −1 and k 1 (T) = (4.00 ± 0.40) × 10 −13 exp(−(631 ± 30)/T) cm 3 molecule −1 s −1 for c-C 5 HF 7 and k 2 (296 K) = (4.90 ± 0.14) × 10 −14 cm 3 molecule −1 s −1 and k 2 (T) = (3.59 ± 0.4) × 10 −13 exp(−(591 ± 25)/T) cm 3 molecule −1 s −1 for c-C 5 F 8 . Stable end-products were measured following the OH radical-initiated degradation of c-C 5 HF 7 and c-C 5 F 8 in the presence of O 2 . F(O)CCF 2 CF 2 CF 2 CH(O), CF 2 O, and CO 2 were observed as the major end-products in the oxidation of c-C 5 HF 7 with molar yields of 0.64, 1.27, and 0.53, respectively. For c-C 5 F 8 , F(O)CCF 2 CF 2 CF 2 CF(O), CF 2 O, and CO 2 were observed with molar yields of 0.66, 0.63, and 0.43, respectively. The total carbon mass balance in both systems was 1.0 ± 0.15. The high yield of a C5-dicarbonyl endproduct is consistent with a ring opening at the carbon−carbon double bond site for both c-C 5 HF 7 and c-C 5 F 8 . A comparison of the present kinetic and degradation product results with previously published studies is presented. A rate coefficient upper limit for the gas-phase reaction of O 3 with c-C 5 HF 7 and c-C 5 F 8 of 1 × 10 −21 cm 3 molecule −1 s −1 was measured as part of this work. Atmospheric lifetimes for c-C 5 HF 7 and c-C 5 F 8 are estimated to be 252 and 236 days, respectively. Infrared absorption spectra of c-C 5 HF 7 and c-C 5 F 8 were also measured and found to agree, to within 5%, with results from previous studies. The well-mixed and lifetime adjusted radiative efficiencies (RE, W m −2 ppb −1 ) and 100 year time horizon global warming potential (GWP) for c-C 5 HF 7 are 0.35, 0.24, and 46.7 and for c-C 5 F 8 are 0.38, 0.25, and 46.2, respectively.

show abstract

Section: Resultsmentioning

confidence: 99%

“…Liu et al and Zhang et al have reported laboratory kinetic studies of the OH + c -C 5 HF 7 and c -C 5 F 8 reactions, respectively: …”

Section: Introductionmentioning

confidence: 99%

Atmospheric Chemistry of c-C₅HF₇ and c-C₅F₈: Temperature-Dependent OH Reaction Rate Coefficients, Degradation Products, Infrared Spectra, and Global Warming Potentials

et al. 2021

View full text Add to dashboard Cite

show abstract

“…Since H2013 the lifetime of octafluorocyclopentene has been revised upward from 31 days to 1.1 years (WMO, 2019). We do not have the absorption spectrum and our recommended RE of 0.25 W m −2 ppb −1 is from N Zhang et al (2017) who use a lifetime of 0.715 years. For the five remaining compounds with lifetimes of 31 days or less the new RE values are the same (after rounding) as in H2013 (see Table S12 for RE values with more significant figures).…”

Section: Fully Fluorinated Speciesmentioning

confidence: 99%

Updated Global Warming Potentials and Radiative Efficiencies of Halocarbons and Other Weak Atmospheric Absorbers

Hodnebrog

Aamaas

Fuglestvedt

et al. 2020

Reviews of Geophysics

View full text Add to dashboard Cite

Human activity has led to increased atmospheric concentrations of many gases, including halocarbons, and may lead to emissions of many more gases. Many of these gases are, on a per molecule basis, powerful greenhouse gases, although at present‐day concentrations their climate effect is in the so‐called weak limit (i.e., their effect scales linearly with concentration). We published a comprehensive review of the radiative efficiencies (RE) and global warming potentials (GWP) for around 200 such compounds in 2013 (Hodnebrog et al., 2013, https://doi.org/10.1002/rog.20013). Here we present updated RE and GWP values for compounds where experimental infrared absorption spectra are available. Updated numbers are based on a revised “Pinnock curve”, which gives RE as a function of wave number, and now also accounts for stratospheric temperature adjustment (Shine & Myhre, 2020, https://doi.org/10.1029/2019MS001951). Further updates include the implementation of around 500 absorption spectra additional to those in the 2013 review and new atmospheric lifetimes from the literature (mainly from WMO (2019)). In total, values for 60 of the compounds previously assessed are based on additional absorption spectra, and 42 compounds have REs which differ by >10% from our previous assessment. New RE calculations are presented for more than 400 compounds in addition to the previously assessed compounds, and GWP calculations are presented for a total of around 250 compounds. Present‐day radiative forcing due to halocarbons and other weak absorbers is 0.38 [0.33–0.43] W m−2, compared to 0.36 [0.32–0.40] W m−2 in IPCC AR5 (Myhre et al., 2013, https://doi.org/10.1017/CBO9781107415324.018), which is about 18% of the current CO2 forcing.

show abstract

“…Our estimated overall rate constant is in good agreement with the rate constant of (5.20 ± 0.09) × 10 −14 cm 3 molecule −1 s −1 at 298.15 K reported by Liu et al, 9 which supports the agreement between the theoretically calculated and experimentally measured rate constants. Zhang et al 18 also reported similar rate constant values of (4.43 ± 0.10) × 10 −14 cm 3 molecule −1 s −1 and (4.43 ± 0.10) × 10 −14 cm 3 molecule −1 s −1 for the reaction of cyc-1-CF 2 CF 2 CF 2 CFCF− with the • OH radical both experimentally and theoretically, respectively, at 298 K. Previously, Jia et al 30 reported the rate constants of cyclo-CFCFCF 2 CF 2 −, cyclo-CHCFCF 2 CF 2 −, and cyclo-CH CHCF 2 CF 2 − reactions with • OH radicals and the values are (3.79 ± 0.11) × 10 −14 , (6.15 ± 0.16) × 10 −14 , and (1.73 ± 0.03) × 10 −13 cm 3 molecule −1 s −1 at 298 K, respectively. Their reported rate constants are in good agreement with our estimated rate constants.…”

Section: Optimized Structures and Vibration Frequenciesmentioning

confidence: 99%

“…From these studies, they observed the low GWPs of cyc-CF 2 CF 2 CF 2 CHCH− and that the major degradation products, e.g., COF 2 , CO, and CO 2 , are formed from the secondary reaction of radical intermediates formed from the oxidation of cyc-CF 2 CF 2 CF 2 CHCH−. Zhang et al 18 investigated the kinetics of perfluorocyclopentene (cyc-1-CF 2 CF 2 CF 2 CFCF−) with the • OH radical using the relative rate technique and CCSD(T)/BHandHLYP method. They calculated the experimental rate constant of (4.43 ± 0.10) × 10 −14 cm 3 molecule −1 s −1 at 298 K, which is in good agreement with the theoretical rate constant of 4.3 × 10 −14 cm 3 molecule −1 s −1 .…”

Section: Introductionmentioning

confidence: 99%

Tropospheric Oxidation of 1H-Heptafluorocyclopentene (cyc-CF₂CF₂CF₂CF═CH−) with OH Radicals: Reaction Mechanism, Kinetics, and Global Warming Potentials

Gogoi

Paul

Mishra

et al. 2021

ACS Earth Space Chem.

View full text Add to dashboard Cite

Assessment of the atmospheric chemistry and environmental impact of 1H-heptafluorocyclopentene (i.e., cyc-CF 2 CF 2 CF 2 CF CH) appears essential before its wide-scale applications. So, in this present work, we have investigated the • OH radical-initiated oxidation of cyc-CF 2 CF 2 CF 2 CFCH− using the density functional theory. We have used M11/6-311++G(d,p) level of theory for geometry optimization and frequency calculations. The energetics and rate constant calculations indicate that the pathway concerning the • OH radical addition reaction with the CC bond is more favorable than the H-and F-abstraction reactions with the • OH radical. The canonical transition state theory has been employed to calculate the rate constant within the temperature range of 250−450 K and 1 atm pressure. The estimated overall rate constant value is 7.14 × 10 −14 cm 3 molecule −1 s −1 at 298.15 K, which agrees well with the previously reported experimental rate constant value of (5.20 ± 0.09) × 10 −14 cm 3 molecule −1 s −1 at 298.15 K. Moreover, we have determined the branching ratio percentage and found that the • OH radical addition reaction contributes 99.99% to the overall rate constant. The calculated atmospheric lifetime is 0.44 years. Furthermore, the radiative efficiency (RE) is determined to be 0.132 W m −2 ppb −1 and the photochemical ozone creation potential (POCPs) is also calculated as 0.82. Finally, global warming potentials (GWPs) for 20, 100, and 500 years are estimated as 67. 77, 18.60, and 5.31, respectively.

show abstract

Atmospheric chemistry of perfluorocyclopentene (cyc-CF 2 CF 2 CF 2 CF=CF−): Kinetics, products and mechanism of gas-phase reactions with OH radicals, and atmospheric implications

Cited by 15 publications

References 33 publications

Atmospheric Chemistry of c-C₅HF₇ and c-C₅F₈: Temperature-Dependent OH Reaction Rate Coefficients, Degradation Products, Infrared Spectra, and Global Warming Potentials

Atmospheric Chemistry of c-C₅HF₇ and c-C₅F₈: Temperature-Dependent OH Reaction Rate Coefficients, Degradation Products, Infrared Spectra, and Global Warming Potentials

Updated Global Warming Potentials and Radiative Efficiencies of Halocarbons and Other Weak Atmospheric Absorbers

Tropospheric Oxidation of 1H-Heptafluorocyclopentene (cyc-CF₂CF₂CF₂CF═CH−) with OH Radicals: Reaction Mechanism, Kinetics, and Global Warming Potentials

Contact Info

Product

Resources

About

Atmospheric chemistry of perfluorocyclopentene (cyc-CF 2 CF 2 CF 2 CF=CF−): Kinetics, products and mechanism of gas-phase reactions with OH radicals, and atmospheric implications

Cited by 15 publications

References 33 publications

Atmospheric Chemistry of c-C5HF7 and c-C5F8: Temperature-Dependent OH Reaction Rate Coefficients, Degradation Products, Infrared Spectra, and Global Warming Potentials

Atmospheric Chemistry of c-C5HF7 and c-C5F8: Temperature-Dependent OH Reaction Rate Coefficients, Degradation Products, Infrared Spectra, and Global Warming Potentials

Updated Global Warming Potentials and Radiative Efficiencies of Halocarbons and Other Weak Atmospheric Absorbers

Tropospheric Oxidation of 1H-Heptafluorocyclopentene (cyc-CF2CF2CF2CF═CH−) with OH Radicals: Reaction Mechanism, Kinetics, and Global Warming Potentials

Contact Info

Product

Resources

About

Atmospheric Chemistry of c-C₅HF₇ and c-C₅F₈: Temperature-Dependent OH Reaction Rate Coefficients, Degradation Products, Infrared Spectra, and Global Warming Potentials

Atmospheric Chemistry of c-C₅HF₇ and c-C₅F₈: Temperature-Dependent OH Reaction Rate Coefficients, Degradation Products, Infrared Spectra, and Global Warming Potentials

Tropospheric Oxidation of 1H-Heptafluorocyclopentene (cyc-CF₂CF₂CF₂CF═CH−) with OH Radicals: Reaction Mechanism, Kinetics, and Global Warming Potentials