Rate constants for the reaction of OH radicals with n-propyl, n-butyl, iso-butyl and tert-butyl vinyl ethers

Thiault, G.; Mellouki, Abdelwahid

doi:10.1016/j.atmosenv.2006.05.011

Cited by 33 publications

(22 citation statements)

References 10 publications

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“…Apart from this, it will be difficult for us to discuss the reason behind such discrepancy. In the same study, they have also measured rate coefficient for reaction of OH radical with n‐propyl vinyl ether which matches very well with the values using absolute method and relative rate method . The various k values for other vinyl ethers are given in Table for comparison.…”

Section: Resultsmentioning

confidence: 91%

“…This allows the transfer of negative charge from the O atom to the olefinic linkage by p‐π conjugation, which adds extra stability to a molecule. The reaction of alkyl vinyl ethers with OH radical is well studied experimentally as well as theoretically by various groups. In these molecules, apart from the OH radical addition to C=C bond, H‐abstraction by OH radical is also operative at normal temperature and hence the rate coefficient is comparatively higher than corresponding simple ethers.…”

Section: Introductionmentioning

confidence: 99%

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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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Section: Resultsmentioning

confidence: 91%

Section: Introductionmentioning

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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“…To date, relevant kinetic and mechanistic studies have mostly focused on the simplest vinyl ethers. Reactions of methyl vinyl ether (MVE), ethyl vinyl ether (EVE), n-propyl vinyl ether (n-PVE), n-butyl vinyl ether (n-BVE), iso-butyl vinyl ether (i-BVE) and tert-butyl vinyl ether (t-BVE) with O 3 , OH and NO 3 have extensively been reported in the literature [1,3,18,[21][22][23][24][25][26][27][28][29][30][31][32]. However, only few studies of the reaction of 2-MPE with OH, NO 3 and Cl were reported recently [2].…”

Section: Introductionmentioning

confidence: 99%

Atmospheric Chemistry of 2-Methoxypropene and 2-Ethoxypropene: Kinetics and Mechanism Study of Reactions with Ozone

Xing

Tsona

et al. 2018

Atmosphere

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Rate coefficients at ambient temperature and atmospheric pressure for the reaction of ozone with 2-methoxypropene (2-MPE) and 2-ethoxypropene (2-EPE) were determined in an evacuable 100 L Teflon reaction chamber using absolute and relative rate methods. The product experiments were carried out using a 50 L Teflon reaction chamber in conjunction with FTIR as the detection technique. The rate coefficients (k in units of cm 3 molecule −1 s −1 ) obtained are 1.18 ± 0.13 × 10 −17 and 1.89 ± 0.23 × 10 −17 for reactions with 2-MPE and 2-EPE, respectively. The effects of the alkoxy group on the gas-phase reactivity of alkyl vinyl ethers toward ozone are compared and discussed. The major ozonolysis products are methyl acetate, formaldehyde and CO 2 for 2-MPE, and ethyl acetate, formaldehyde and CO 2 for 2-EPE. Possible mechanisms for the two vinyl ethers are proposed based on the observed reaction products. Additionally, atmospheric lifetimes of 32 h and 21 h for 2-MPE and 2-EPE were estimated based on the measured rate constants and the ambient tropospheric concentration of ozone, respectively. The obtained values of the lifetimes indicate that the reaction with ozone is an important loss process for these vinyl ethers in the atmosphere, especially in polluted areas.

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“…8 Upon their release into the atmosphere, vinyl ethers undergo either photolysis or photochemical oxidation by OH radicals and ozone during daytime and by nitrate radicals (NO 3 ) and ozone during the nighttime. 5,[9][10][11][12] Reactions with Cl atoms may also be important in certain locations during certain times of the year. 13 Some experimental and theoretical studies on the reaction of ozone with selected vinyl ethers have been performed.…”

Section: Introductionmentioning

confidence: 99%

Matrix isolation study of the early intermediates in the ozonolysis of selected vinyl ethers

Xing

Tang

et al. 2017

RSC Adv.

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Rate constants for the reaction of OH radicals with n-propyl, n-butyl, iso-butyl and tert-butyl vinyl ethers

Cited by 33 publications

References 10 publications

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

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

Atmospheric Chemistry of 2-Methoxypropene and 2-Ethoxypropene: Kinetics and Mechanism Study of Reactions with Ozone

Matrix isolation study of the early intermediates in the ozonolysis of selected vinyl ethers

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