Kinetic study of gas phase reactions of OH with CF3CH2OH, CF3CF2CF2CH2OH, and CHF2CF2CH2OH using LP-LIF method

Indulkar, Yogesh N.; Sengupta, S.; Waghmode, Suresh B.; Kumar, Awadhesh; Dhanya, S.; Naik, Prakash D.

doi:10.1016/j.atmosenv.2011.09.022

Cited by 17 publications

(6 citation statements)

References 25 publications

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“…The Arrhenius parameters reported by Indulkar et al ( A and E a / R ) are in good agreement with those determined in this work over a wider temperature range ( T = 298–358 K). The rate coefficient at 298 K reported by Indulkar et al ((1.67 ± 0.23) 10 –13 cm 3 molecule –1 s –1 ) is also in good agreement, within the uncertainties, with that shown in Tables 2 and 4 of this paper ((1.85 ± 0.07) 10 –13 cm 3 molecule –1 s –1 ). Therefore, the conclusions of the manuscript remain unchanged.…”

supporting

confidence: 91%

“…In the process of publication of this work, Indulkar et al 39 reported the temperature dependence of the rate coefficient for the OH reaction with CHF 2 CF 2 CH 2 OH, k 1 , at temperatures above 298 K (T = 298−363 K) and at a single total pressure of ∼55 Torr in He by using the PLP/LIF technique. The Arrhenius parameters reported by Indulkar et al 39 (A and E a / R) are in good agreement with those determined in this work over a wider temperature range (T = 298−358 K).…”

Section: Notesmentioning

confidence: 99%

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Laboratory Studies of CHF₂CF₂CH₂OH and CF₃CF₂CH₂OH: UV and IR Absorption Cross Sections and OH Rate Coefficients between 263 and 358 K

et al. 2012

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Fluorinated alcohols, such as 2,2,3,3-tetrafluoropropanol (TFPO, CHF(2)CF(2)CH(2)OH) and 2,2,3,3,3-pentafluoropropanol (PFPO, CF(3)CF(2)CH(2)OH), can be potential replacements of hydrofluorocarbons with large global warming potentials, GWPs. IR absorption cross sections for TFPO and PFPO were determined between 4000 and 500 cm(-1) at 298 K. Integrated absorption cross sections (S(int), base e) in the 4000-600 cm(-1) range are (1.92 ± 0.34) × 10(-16) cm(2) molecule(-1) cm(-1) and (2.05 ± 0.50) × 10(-16) cm(2) molecule(-1) cm(-1) for TFPO and PFPO, respectively. Uncertainties are at a 95% confidence level. Ultraviolet absorption spectra were also recorded between 195 and 360 nm at 298 K. In the actinic region (λ > 290 nm), an upper limit of 10(-23) cm(2) molecule(-1) for the absorption cross sections (σ(λ)) was reported. Photolysis in the troposphere is therefore expected to be a negligible loss for these fluoropropanols. In addition, absolute rate coefficients for the reaction of OH radicals with CHF(2)CF(2)CH(2)OH (k(1)) and CF(3)CF(2)CH(2)OH (k(2)) were determined as a function of temperature (T = 263-358 K) by the pulsed laser photolysis/laser induced fluorescence (PLP-LIF) technique. At room temperature, the average values obtained were k(1) = (1.85 ± 0.07) × 10(-13) cm(3) molecule(-1) s(-1) and k(2) = (1.19 ± 0.03) × 10(-13) cm(3) molecule(-1) s(-1). The observed temperature dependence of k(1)(T) and k(2)(T) is described by the following expressions: (1.35 ± 0.23) × 10(-12) exp{-(605 ± 54)/T} and (1.36 ± 0.19) × 10(-12) exp{-(730 ± 43)/T} cm(3) molecule(-1) s(-1), respectively. Since photolysis of TFPO and PFPO in the actinic region is negligible, the tropospheric lifetime (τ) of these species can be approximated by the lifetime due to the homogeneous reaction with OH radicals. Global values of τ(OH) were estimated to be of 3 and 4 months for TFPO and PFPO, respectively. GWPs relative to CO(2) at a time horizon of 500 years were calculated to be 8 and 12 for TFPO and PFPO, respectively. Despite the higher GWP relative to CO(2), these species are not expected to significantly contribute to the greenhouse effect in the next decades since they are short-lived species and will not accumulate in the troposphere even as their emissions grow up.

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supporting

confidence: 91%

Section: Notesmentioning

confidence: 99%

Laboratory Studies of CHF₂CF₂CH₂OH and CF₃CF₂CH₂OH: UV and IR Absorption Cross Sections and OH Rate Coefficients between 263 and 358 K

et al. 2012

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“…As HFAs have been already proposed for broad commercial use as cleaning solvent in various industrial applications [1], it is essential to improve our knowledge of their atmospheric chemistry. The main degradation channel of fluorinated alcohols is the gas-phase reaction with OH radicals and therefore it is a subject of few recent studies [5][6][7][8]. An accurate knowledge of reaction kinetics is essential for the evaluation of the atmospheric lifetime of any HFA molecule to check whether it can be a suitable replacement for CFCs and HCFCs.…”

Section: Introductionmentioning

confidence: 99%

Theoretical studies on atmospheric chemistry of (CF3)2C(OH)CH3: Kinetics, mechanism and thermochemistry of gas phase reactions with OH radicals

Lily

Chandra

2015

Journal of Fluorine Chemistry

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“…The kinetics experimental set‐up, laser photolysis‐laser induced fluorescence (LP‐LIF), has been discussed in details in our previous publication . A short discussion is included in the supporting information.…”

Section: Discussionmentioning

confidence: 99%

Gas Phase OH Radical Reaction with 2‐Chloroethyl Vinyl Ether in the 256–333 K Temperature Range: A Combined LP‐LIF and Computational Study

2018

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The absolute rate coefficient for the gas phase reaction of OH radical with 2-chloroethyl vinyl ether (H 2 C = CH-O-CH 2 CH 2 Cl, 2ClEVE) has been measured using the laser photolysis (LP)laser induced fluorescence (LIF) technique. The kinetics measurements were done over the temperature range of 256-333 K. The bimolecular rate coefficients obtained, k(T), showed Arrhenius type behaviour which were fitted to the expression k(T) = (4.18 AE 0.55) 3 10 À12 exp[(700 AE 70)/T] cm 3 molecule À1 s À1 .The room temperature rate coefficient shows pressure independent behaviour in the range of 10-40 Torr. The reaction shows weak negative temperature dependence. A detail computational studies involving the energies and structures of the reactants, transition states and products were performed using Complete Basis Set (CBS) and Quadratic Configuration Interaction with Single and Double substitutions with a Triples contribution to the energy, QCISD(T), method to elucidate the reaction mechanism. The results suggest that the major pathways for the reaction proceeds through addition of OH radical to the C=C double bond and the H atom abstraction from the -O-CH 2 -group and they are competitive in nature. The tropospheric lifetime, radiative efficiency (RE) and the global warming potential (GWP) for 2-chloroethyl vinyl ether (2ClEVE) have been also determined.[a] Dr.

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Kinetic study of gas phase reactions of OH with CF3CH2OH, CF3CF2CF2CH2OH, and CHF2CF2CH2OH using LP-LIF method

Cited by 17 publications

References 25 publications

Laboratory Studies of CHF₂CF₂CH₂OH and CF₃CF₂CH₂OH: UV and IR Absorption Cross Sections and OH Rate Coefficients between 263 and 358 K

Laboratory Studies of CHF₂CF₂CH₂OH and CF₃CF₂CH₂OH: UV and IR Absorption Cross Sections and OH Rate Coefficients between 263 and 358 K

Theoretical studies on atmospheric chemistry of (CF3)2C(OH)CH3: Kinetics, mechanism and thermochemistry of gas phase reactions with OH radicals

Gas Phase OH Radical Reaction with 2‐Chloroethyl Vinyl Ether in the 256–333 K Temperature Range: A Combined LP‐LIF and Computational Study

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Kinetic study of gas phase reactions of OH with CF3CH2OH, CF3CF2CF2CH2OH, and CHF2CF2CH2OH using LP-LIF method

Cited by 17 publications

References 25 publications

Laboratory Studies of CHF2CF2CH2OH and CF3CF2CH2OH: UV and IR Absorption Cross Sections and OH Rate Coefficients between 263 and 358 K

Laboratory Studies of CHF2CF2CH2OH and CF3CF2CH2OH: UV and IR Absorption Cross Sections and OH Rate Coefficients between 263 and 358 K

Theoretical studies on atmospheric chemistry of (CF3)2C(OH)CH3: Kinetics, mechanism and thermochemistry of gas phase reactions with OH radicals

Gas Phase OH Radical Reaction with 2‐Chloroethyl Vinyl Ether in the 256–333 K Temperature Range: A Combined LP‐LIF and Computational Study

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Laboratory Studies of CHF₂CF₂CH₂OH and CF₃CF₂CH₂OH: UV and IR Absorption Cross Sections and OH Rate Coefficients between 263 and 358 K

Laboratory Studies of CHF₂CF₂CH₂OH and CF₃CF₂CH₂OH: UV and IR Absorption Cross Sections and OH Rate Coefficients between 263 and 358 K