Gas-phase chemistry of atmospheric Cl atoms: a PLP-RF kinetic study with a series of ketones

Albaladejo, José; Notario, Alberto; Cuevas, Carlos A.; Jiménez, Elena; Cabañas, Beatriz; Martı́nez, Ernesto

doi:10.1016/s1352-2310(02)00921-4

Cited by 33 publications

(43 citation statements)

References 27 publications

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“…(cm 3 molecule −1 s −1 ), respectively, one can assume a reactivity ratio trans-2-heptenal/1-hexene <0.5 which is similar to the other two unsaturated aldehydes, in light of the probable value for the Cl+1-hexene constant, >4.83×10 −10 cm 3 molecule −1 s −1 . The deactivation effects observed in this work for aldehydes is smaller than those found for reactions of ketones (both saturated and unsaturated) and the corresponding alkanes with Cl atoms (Albaladejo et al, 2003). The reason may reside in the fact that the CHO group is a reactive site itself (and so it contributes to the global rate constant) while reactions on the CO group are not expected.…”

Section: Resultscontrasting

confidence: 63%

Kinetic study of the gas-phase reaction of atomic chlorine with a series of aldehydes

Rodrı́guez

Rodrı́guez²,

Notario

et al. 2005

Atmos. Chem. Phys.

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Abstract. The reactions of Cl atoms with a series of unsaturated aldehydes have been investigated for the first time using a relative method. In order to obtain additional information for a qualitative structure versus reactivity discussion, we have also determined the rate coefficients for the reactions of atomic chlorine with their respective saturated aldehydes. These relative measurements were performed at room temperature and atmospheric pressure of air and N 2 , by using ethane, propene and 1-butene as reference compounds. The weighted average relative rate constants obtained, k Cl ±2σ (in units of cm 3 molecule −1 s −1 ) were: trans-2-pentenal (1.31±0.19)×10 −10 ; trans-2-hexenal (1.92±0.22)×10 −10

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Section: Resultscontrasting

confidence: 63%

Kinetic study of the gas-phase reaction of atomic chlorine with a series of aldehydes

Rodrı́guez

Rodrı́guez²,

Notario

et al. 2005

Atmos. Chem. Phys.

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“…The gas mixtures were irradiated with the pulsed excimer laser at 351 nm to produce Cl( 2 P j ) atoms from Cl 2 photolysis. Cl( 2 P 3/2 ) atoms were directly detected by the PLP-LIF technique at 134.72 nm that corresponds to the 3p 5 [Cl] 0 . Tunable VUVradiation around 135 nm was generated by four-wave difference frequency mixing (ω vuv = 2ω 1 -ω 2 ) in 35 Torr of Kr, using two dye lasers pumped by a single XeCl excimer laser (Lambda Physik, COMPex 201, FL3002 and Scanmate 2E).…”

Section: Plp-lif Measurement Of K 1 At Nagoyamentioning

confidence: 99%

“…Cl + cyclohexanone → products (1) Literature data for k 1 span a range of approximately a factor of 3 [3][4][5][6]. There has been just one study of the UV spectrum of cyclohexanone [7].…”

Section: Introductionmentioning

confidence: 99%

Atmospheric chemistry of cyclohexanone: UV spectrum and kinetics of reaction with chlorine atoms

Iwasaki¹,

Matsumi²,

Takahashi³

et al. 2008

Int J of Chemical Kinetics

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Absolute and relative rate techniques were used to study the reactivity of Cl atoms with cyclohexanone in 6 Torr of argon or 800-950 Torr of N 2 at 295 ± 2 K. The absolute rate experiments gave k(Cl + cyclohexanone) = (1.88 ± 0.38) × 10 −10 , whereas the relative rate experiments gave k(Cl + cyclohexanone) = (1.66 ± 0.26) × 10 −10 cm 3 molecule −1 s −1 . Cyclohexanone has a broad UV absorption band with a maximum cross section of (4.0 ± 0.3) × 10 −20 cm 2 molecule −1 near 285 nm. The results are discussed with respect to the literature data.

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“…where t is the lifetime of HFA due to each loss process in the troposphere (i.e., t OH and t Cl , due to reactions (1) and (2), respectively, and t wet , due to the removal by wet deposition , [31] t HFA would be 7 days for CF 3 CH 2 CH 2 OH and 1 day for CF 3 (CH 2 ) 2 CH 2 OH.…”

mentioning

confidence: 99%

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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Gas-phase chemistry of atmospheric Cl atoms: a PLP-RF kinetic study with a series of ketones

Cited by 33 publications

References 27 publications

Kinetic study of the gas-phase reaction of atomic chlorine with a series of aldehydes

Kinetic study of the gas-phase reaction of atomic chlorine with a series of aldehydes

Atmospheric chemistry of cyclohexanone: UV spectrum and kinetics of reaction with chlorine atoms

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

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Gas-phase chemistry of atmospheric Cl atoms: a PLP-RF kinetic study with a series of ketones

Cited by 33 publications

References 27 publications

Kinetic study of the gas-phase reaction of atomic chlorine with a series of aldehydes

Kinetic study of the gas-phase reaction of atomic chlorine with a series of aldehydes

Atmospheric chemistry of cyclohexanone: UV spectrum and kinetics of reaction with chlorine atoms

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

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