FTIR gas-phase kinetic study of the reactions of Cl atoms with (CH3)2CCHC(O)H and CH3CHCHC(O)OCH3

Blanco, Marı́a B.; Barnes, Ian; Teruel, Mariano A.

doi:10.1016/j.cplett.2010.02.023

Cited by 15 publications

(14 citation statements)

References 25 publications

(31 reference statements)

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“…Our result confirms that the structure of unsaturated aldehydes has a very small impact on their reactivity towards Cl atoms, as was previously observed (Ullerstam et al, 2001, Colmenar et al, 2015) opposite to their reactivity towards OH and NO 3 radicals (Tables S1 and S2). The reactivity towards Cl seems to be fairly independent of the substitution on the olefinic carbons for unsaturated aldehydes, as stated by Blanco et al, 2010.…”

Section: Kinetic Studymentioning

confidence: 60%

“…However, data for other unsaturated aldehydes and their corresponding alkenes are available. The rate coefficients of the reactions of Cl with crotonaldehyde and 3-methyl-2-butenal (see Table 4) are 34% and 36% lower than those with trans-2-butene (3.58×10 −10 cm 3 molecule −1 s −1 provided by Kaiser et al, 2007) and 2-methyl-propene (3.38×10 −10 cm 3 molecule −1 s −1 provided by Blanco et al, 2010), respectively. This may be due to the negative inductive effect of the carbonyl-containing group, which may deactivate the double bond toward the Cl atom addition.…”

Section: Kinetic Studymentioning

confidence: 96%

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An experimental study of the gas-phase reaction between Cl atoms and trans-2-pentenal: Kinetics, products and SOA formation

et al. 2021

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The gas-phase reaction of trans-2-pentenal (T2P) with Cl atoms was studied at atmospheric pressure and room temperature. A rate coefficient of (2.56±0.83)×10 -10 cm 3 molecule -1 s -1 was obtained using the relative rate method and isoprene, cyclohexane and ethanol as reference compounds. The kinetic study was carried out using a 300-L Teflon bag simulation chamber (IMT Lille Douai-France) and a 16-L Pyrex cell (UCLM-Ciudad Real-Spain), both coupled to the Fourier transform infrared (FTIR) technique. Gas-phase products and secondary organic aerosol (SOA) formation were studied at UCLM using a 16-L Pyrex cell and a 264-L quartz simulation chamber coupled to the FTIR and gas-chromatography-mass spectrometry (GC-MS) techniques. HCl, CO, and propanal were identified as products formed from the studied reaction and quantified by FTIR, being the molar yield of the latter (5.2±0.2)%. Formic acid was identified as a secondary product and was quantified by FTIR with a yield of (6.2±0.4)%.In addition, 2-chlorobutanal and 2-pentenoic acid were identified, but not quantified, by GC-MS as products. The SOA formation was investigated using a fast mobility particle sizer spectrometer. The observed SOA yields reached maximum values of around 7% at high particle mass concentrations. This work provides the first study of the formation of gaseous and particulate products for the reaction of Cl with T2P. A reaction mechanism is suggested to explain the formation of the observed gaseous products. The results are discussed in terms of the structure-reactivity relationship, and the atmospheric implications derived from this study are commented as well.

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Section: Kinetic Studymentioning

confidence: 60%

Section: Kinetic Studymentioning

confidence: 96%

An experimental study of the gas-phase reaction between Cl atoms and trans-2-pentenal: Kinetics, products and SOA formation

et al. 2021

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“…These rate constants are close to collisioncontrolled, and it is possible that in this regime substitution on the carbon chain induces very small changes in reaction rate constants. 50 A similar reason can explain why the rate constant for Cl reaction with MnPE differs very weakly from that of Cl reaction with butane, (2.11 ± 0.18) × 10 −10 cm 3 molecule −1 s −1 . 51 Comparison of the reactivity of the three oxidants toward MnPE shows that the rate constant for the reaction with Cl is larger than those of reactions with OH (by 2 orders of magnitude) and NO 3 (by 5 orders of magnitude).…”

Section: Resultsmentioning

confidence: 83%

Gas-Phase Reaction of Methyl n-Propyl Ether with OH, NO₃, and Cl: Kinetics and Mechanism

et al. 2017

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Rate constants at room temperature (293 ± 2 K) and atmospheric pressure for the reaction of methyl n-propyl ether (MnPE), CHOCHCHCH, with OH and NO radicals and the Cl atom have been determined in a 100 L FEP-Teflon reaction chamber in conjunction with gas chromatography-flame ionization detector (GC-FID) as the detection technique. The obtained rate constants k (in units of cm molecule s) are (9.91 ± 2.30) × 10, (1.67 ± 0.32) × 10, and (2.52 ± 0.14) × 10 for reactions with OH, NO, and Cl, respectively. The products of these reactions were investigated by gas chromatography-mass spectrometry (GC-MS), and formation mechanisms are proposed for the observed reaction products. Atmospheric lifetimes of the studied ether, calculated from rate constants of the different reactions, reveal that the dominant loss process for MnPE is its reaction with OH, while in coastal areas and in the marine boundary layer, MnPE loss by Cl reaction is also important.

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“…The rate constant of AA reaction with Cl is 8 times higher than the reaction with OH, 4 orders of magnitude higher than that for the reaction with NO 3 , and 8 orders of magnitude higher than that for the reaction with O 3 . It is necessary to mention that the rate constant for the reaction with Cl is close to the gas kinetic limited value from gas collision theory, which means that the reaction probability in this case is high regardless of the collision site and that the compound chemical structure plays a limited role in determining the reaction rate constant …”

Section: Results and Discussionmentioning

confidence: 85%

“…It is necessary to mention that the rate constant for the reaction with Cl is close to the gas kinetic limited value from gas collision theory, which means that the reaction probability in this case is high regardless of the collision site and that the compound chemical structure plays a limited role in determining the reaction rate constant. 50 3.2. Atmospheric Implications.…”

Section: Resultsmentioning

confidence: 99%

Gas-Phase Oxidation of Allyl Acetate by O₃, OH, Cl, and NO₃: Reaction Kinetics and Mechanism

Wang

Zhu

et al. 2018

J. Phys. Chem. A

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Allyl acetate (AA) is widely used as monomer and intermediate in industrial chemicals synthesis. To evaluate the atmospheric outcome of AA, kinetics and mechanism of its gas-phase reaction with main atmospheric oxidants (O, OH, Cl, and NO) have been investigated in a Teflon reactor at 298 ± 3 K. Both absolute and relative rate methods were used to determine the rate constants for AA reactions with the four atmospheric oxidants. The obtained rate constants (in units of cm molecule s) are (1.8 ± 0.3) × 10, (3.1 ± 0.7) × 10, (2.5 ± 0.5) × 10, and (1.1 ± 0.4) × 10, for reactions with O, OH, Cl, and NO respectively. While results for reactions with O, OH and Cl are in good agreement with previous studies, the kinetics for the reaction with NO is reported for the first time in this study. On the basis of determined rate constants, the tropospheric lifetimes of AA are τ = 9 days, τ = 5 h, τ = 5 days, τ = 2 days. On the basis of the products study, reaction mechanisms for these oxidations have been proposed and the reaction products were detected using thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS) and Fourier transform infrared spectroscopy (FTIR). Results show that the main products formed in these reactions are carbonyl compounds. In particular, 2-oxoethyl acetate was detected in all four AA oxidation reactions. Compared to previous studies, several new products were determined for reactions with OH and Cl. These results form a set of comprehensive kinetic data for AA reactions with main atmospheric oxidants and provide a better understanding of the degradation and atmospheric outcome of unsaturated acetate esters in the troposphere, during both daytime and nighttime.

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FTIR gas-phase kinetic study of the reactions of Cl atoms with (CH3)2CCHC(O)H and CH3CHCHC(O)OCH3

Cited by 15 publications

References 25 publications

An experimental study of the gas-phase reaction between Cl atoms and trans-2-pentenal: Kinetics, products and SOA formation

An experimental study of the gas-phase reaction between Cl atoms and trans-2-pentenal: Kinetics, products and SOA formation

Gas-Phase Reaction of Methyl n-Propyl Ether with OH, NO₃, and Cl: Kinetics and Mechanism

Gas-Phase Oxidation of Allyl Acetate by O₃, OH, Cl, and NO₃: Reaction Kinetics and Mechanism

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FTIR gas-phase kinetic study of the reactions of Cl atoms with (CH3)2CCHC(O)H and CH3CHCHC(O)OCH3

Cited by 15 publications

References 25 publications

An experimental study of the gas-phase reaction between Cl atoms and trans-2-pentenal: Kinetics, products and SOA formation

An experimental study of the gas-phase reaction between Cl atoms and trans-2-pentenal: Kinetics, products and SOA formation

Gas-Phase Reaction of Methyl n-Propyl Ether with OH, NO3, and Cl: Kinetics and Mechanism

Gas-Phase Oxidation of Allyl Acetate by O3, OH, Cl, and NO3: Reaction Kinetics and Mechanism

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Product

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Gas-Phase Reaction of Methyl n-Propyl Ether with OH, NO₃, and Cl: Kinetics and Mechanism

Gas-Phase Oxidation of Allyl Acetate by O₃, OH, Cl, and NO₃: Reaction Kinetics and Mechanism