Kinetics of gas-phase reactions of cyc-CF2CF2CF2CHFCH2 and trans-cyc-CF2CF2CF2CHFCHF  with OH radicals between 253 and 328 K

Zhang, Ni; Chen, Liang; Uchimaru, Tadafumi; Qing, Feiyao; Mizukado, Junji; Quan, Hengdao; Suda, Hiroyuki

doi:10.1016/j.cplett.2015.09.020

Cited by 10 publications

(4 citation statements)

References 16 publications

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“…By substituting these values into eq , the GWP values of cyc-CF 2 CF 2 CF 2 CFCH– for 20-, 100-, and 500-year time horizons are 67.77, 18.60, and 5.31, respectively. Our estimated GWP is well in agreement with the results reported by Liu et al In a 100-year time horizon, the GWP of cyc-CF 2 CF 2 CF 2 CHCH– was estimated as 107 by Guo et al Similarly, the GWPs of cyc-CF 2 CF 2 CF 2 CHFCH 2 and trans -cyc-CF 2 CF 2 CF 2 CHFCHF were estimated as 211 and 241 by Zhang et al, respectively. Further, Jia et al reported the GWPs of cyclo-CFCFCF 2 CF 2 –, cyclo-CHCFCF 2 CF 2 –, and cyclo-CHCHCF 2 CF 2 – for the 100-year time horizon to be 119, 76, and 20.…”

Section: Resultssupporting

confidence: 91%

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.

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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.

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Section: Resultssupporting

confidence: 91%

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.

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“…Figure exhibit the IR plots and 1 H NMR results, where the IR values of F6A, F7A, F8A, F6E, F7E, and F8E were found to correspond well with the experimentally reported data. − First, from Figure (g–i), it was observed that the absorption vibration peaks of each C–Cl bond were in good symmetry, the wave numbers of which were all within a range of 850–950 cm –1 . By comparing the FT-IR diagram of F6-1(g) and F7-1(i), C–Cl peaks showed a slight red shift.…”

Section: Resultssupporting

confidence: 75%

“…In this regard, Guo et al reported the rate constant ( k rate ) of F6A to be 2.94 ± 0.05 × 10 –13 s –1 (molec/cm 3 ) −1 through a relative experiment method, GWP 100 of which was 107. Similarly, Zhang et al explored the GWP 100 of F7A and cis-F8A to be 211 and 241, respectively. By adopting a CC bond, the k rate values of F6E, F7E, and F8E were reported to be 1.08 ± 0.04, 5.20 ± 0.09, and 1.01 ± 0.16 s –1 (molec/cm 3 ) −1 , respectively, the GWP 100 values of which were 15, 42, and 28, respectively.…”

Section: Introductionmentioning

confidence: 99%

Substitution Effects on the Reactivity and Thermostability of Five-Membered Ring Fluorides

Zhang

et al. 2022

ACS Omega

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Recently, five-membered ring fluorides (c-C 5 Fs) have been significantly desirable in green chlorofluorocarbon substitutes due to their practically flexible application in various fields and environmental friendliness. Detailed knowledge regarding different substitution effects on their environmental properties and thermal stability is very limited due to their high-cost experiments. Here, comprehensive density functional theory and ab initio molecular dynamics calculations were performed to explore the relative electrophilic and nucleophilic reactivity and thermostability of c-C 5 F chemicals. The electronic properties induced by substitution effects of c-C 5 Fs were first explored. The environmental friendliness of c-C 5 Fs including 1,1,2,2,3,3-hexafluorocyclopentane (F6A), 1,1,2,2,3,3,4-heptafluorocyclopentane (F7A), cis-1,1,2,2,3,3,4,5-octafluorocyclopentane (F8A), 3,3,4,4,5,5-hexafluorocyclopentene (F6E), 1,3,3,4,4,5,5-heptafluorocyclopentene (F7E), octafluorocyclopentene (F8E), 1-chloro-3,3,4,4,5,5-hexafluorocyclopent-1-ene (F6-1), and 1-chloro-2,3,3,4,4,5,5-heptafluorocyclopent-1-ene (F7-1) was validly confirmed. Besides, their thermal stabilities at 600 K temperature were concluded due to their flexible carbon skeletons, where both in-plane stability and slight aromaticity of F6E were in peculiar found to contribute substantially. We also would like to stress the future application of F6-1 due to its significant out-plane stability. This study may pave the way for the development of chlorofluorocarbon substitutes.

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“…According to these data, we make simple estimations of the atmospheric lifetime, the RE, the POCP, and the GWP of cyc-CF 2 CF 2 CF 2 CFCH–. The introduction of a >CC< double bond decreases the atmospheric lifetime of this compound to approximately one-fifth that of the corresponding saturated compound cyc-CF 2 CF 2 CF 2 CHFCH 2 – . Given a POCP value of 0.70, this compound’s potential influence on tropospheric ozone formation is considered insignificant, and the contribution of cyc-CF 2 CF 2 CF 2 CFCH– to the radiative forcing of climate change will be determined depending on its usage.…”

Section: Discussionmentioning

confidence: 99%

Atmospheric Chemistry of 1H-Heptafluorocyclopentene (cyc-CF₂CF₂CF₂CF═CH−): Rate Constant, Products, and Mechanism of Gas-Phase Reactions with OH Radicals, IR Absorption Spectrum, Photochemical Ozone Creation Potential, and Global Warming Potential

Liu

Qin

et al. 2016

J. Phys. Chem. A

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The rate constant for gas-phase reactions of OH radicals with 1H-heptafluorocyclopentene (cyc-CFCFCFCF═CH-) was measured using a relative rate method at 298 K: (5.20 ± 0.09) × 10 cm molecule s. The quoted uncertainty includes two standard deviations from the least-squares regression, the systematic error from the GC analysis, and the uncertainties of the rate constants of the reference compounds. The OH-radical-initiated oxidation of cyc-CFCFCFCF═CH- gives the main products COF, CO, and CO, leading to negligible environmental impact. For consumptions of cyc-CFCFCFCF═CH- of less than 54%, the yield of the formation of ([COF] + [CO] + [CO])/5 (based on the conservation of carbon) was 0.99 ± 0.02, which is very close to 100%. A possible degradation mechanism was proposed. The radiative efficiency (RE) of cyc-CFCFCFCF═CH- measured at room temperature was 0.215 W m ppb. The atmospheric lifetime of cyc-CFCFCFCF═CH- was calculated as 0.61 year, and the photochemical ozone creation potential (POCP) was negligible. The 20-, 100-, and 500-year time horizon global warming potentials (GWPs) were estimated as 153, 42, and 12, respectively.

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Kinetics of gas-phase reactions of cyc-CF2CF2CF2CHFCH2 and trans-cyc-CF2CF2CF2CHFCHF with OH radicals between 253 and 328 K

Cited by 10 publications

References 16 publications

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

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

Substitution Effects on the Reactivity and Thermostability of Five-Membered Ring Fluorides

Atmospheric Chemistry of 1H-Heptafluorocyclopentene (cyc-CF₂CF₂CF₂CF═CH−): Rate Constant, Products, and Mechanism of Gas-Phase Reactions with OH Radicals, IR Absorption Spectrum, Photochemical Ozone Creation Potential, and Global Warming Potential

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Kinetics of gas-phase reactions of cyc-CF2CF2CF2CHFCH2 and trans-cyc-CF2CF2CF2CHFCHF with OH radicals between 253 and 328 K

Cited by 10 publications

References 16 publications

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

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

Substitution Effects on the Reactivity and Thermostability of Five-Membered Ring Fluorides

Atmospheric Chemistry of 1H-Heptafluorocyclopentene (cyc-CF2CF2CF2CF═CH−): Rate Constant, Products, and Mechanism of Gas-Phase Reactions with OH Radicals, IR Absorption Spectrum, Photochemical Ozone Creation Potential, and Global Warming Potential

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

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

Atmospheric Chemistry of 1H-Heptafluorocyclopentene (cyc-CF₂CF₂CF₂CF═CH−): Rate Constant, Products, and Mechanism of Gas-Phase Reactions with OH Radicals, IR Absorption Spectrum, Photochemical Ozone Creation Potential, and Global Warming Potential