Pulsed laser photolysis vacuum UV laser-induced fluorescence kinetic study of the reactions of Cl(2P3/2) atoms with ethyl formate, n-propyl formate, and n-butyl formate

Ide, Tomoyuki; Iwasaki, Erika; Matsumi, Yutaka; Xing, Jiangkuan; Takahashi, Kenshi; Wallington, Timothy J.

doi:10.1016/j.cplett.2008.11.030

Cited by 7 publications

(6 citation statements)

References 9 publications

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“…Therefore, a three parameter fit was used to obtain the Arrhenius expression, and it is k(200−400 K) = (2.97 × 10 −18 )T 2.4 exp[−(390/T)] cm 3 molecule −1 s −1 . The computed rate coefficient at 298 K is 9.53 × 10 −12 cm 3 molecule −1 s −1 , which is in very good agreement with all the available reported rate coefficients reported by Notario et al 1 [(1.34 ± 0.15) × 10 −11 cm 3 molecule −1 s −1 at 298 K and 15−60 Torr in He as buffer gas, measured using the PLP-RF technique]; Sellevag and Nielsen 2 [(1.10 ± 0.07) × 10 −11 cm 3 molecule −1 s −1 at 298 K and 760 Torr in N 2 as buffer gas, measured using the relative rate technique]; Wallington et al 3 [(9.57 ± 1.3) × 10 −12 cm 3 molecule −1 s −1 at 298 K and 700 Torr in N 2 as buffer gas, measured using PLP-RF technique]; and Ide et al 4 [(9.50 ± 0.3) × 10 −12 cm 3 molecule −1 s −1 at 298 K and 7 Torr in Ar as buffer gas, measured using PLP/VUV-LIF technique]. Also, the computed rate coefficient is in very good agreement with the experimentally measured rate coefficient at 298 K, in the present investigation.…”

Section: Ratementioning

confidence: 99%

“…Wallington et al 3 studied the reaction of ethyl formate with Cl atoms using the PLP-RF technique at 298 K and 700 Torr in N 2 as buffer gas, and they reported the rate coefficient to be (9.57 ± 1.3) × 10 −12 cm 3 molecule −1 s −1 . Recently, Ide et al 4 studied the reaction of ethyl formate with Cl atoms using the PLP/VUV-LIF technique at 298 K and 7 Torr in Ar as buffer gas, and they reported the rate coefficient to be (9.50 ± 0.3) × 10 −12 cm 3 molecule −1 s −1 .…”

Section: + → CL C H Oc(o)h Products 2mentioning

confidence: 99%

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Experimental and Computational Investigation on the Gas Phase Reaction of Ethyl Formate with Cl Atoms

2014

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The rate coefficient for the gas-phase reaction of Cl atoms with ethyl formate was measured over the temperature range of 268-343 K using relative rate methods, with ethyl chloride as a reference compound. The temperature dependent relative rate coefficients for the ethyl formate + Cl reaction were measured, and the modified Arrhenius expression kethyl formate(268-343) = (2.54 ± 0.57) × 10(-23) T(4.1) exp {-(981 ± 102)/T} cm(3) molecule(-1) s(-1) was obtained with 2σ error limits. The room temperature rate coefficient for the title reaction is (9.84 ± 0.79) × 10(-12) cm(3) molecule(-1) s(-1), which is in good agreement with reported values. To complement the experimental measurement, computational methods were used to calculate the rate coefficient for the ethyl formate + Cl reaction atoms using canonical variational transition state theory (CVT) with small curvature tunneling (SCT) and the CCSD (T)/cc-pVDZ//M062X/6-31+g(d,p) level of theory. The temperature dependent Arrhenius expression was obtained to be 2.97 × 10(-18) T(2.4) exp[-(390/T)] cm(3) molecule(-1) s(-1) over the temperature range of 200-400 K. The thermodynamic parameters and branching ratio were calculated. Also, the atmospheric lifetime and global warming potentials (GWPs) were calculated for ethyl formate.

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Section: Ratementioning

confidence: 99%

Section: + → CL C H Oc(o)h Products 2mentioning

confidence: 99%

Experimental and Computational Investigation on the Gas Phase Reaction of Ethyl Formate with Cl Atoms

2014

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“…We have not included data for alkyl iodides because an especially stable adduct appears to form, along with some displacement on iodine. ,, Regioselectivity studies show that abstraction of the aldehydic hydrogen from acetaldehyde is dominant to an extent that assigning (a small) k (CH 3 CHO) would be unreliable . However, for longer chain aldehydes, abstraction at more remote carbons begins to compete. , Similarly, reaction occurs predominantly at the acyl hydrogen of small alkyl formates, , but the increase in rate constant for longer-chain formates again suggests some reaction at sites more remote from the ester function. , For methyl acetate, only k (CH 3 OCOCH 3 ) for the dominant process can be assigned; however, a value is available for CH 2 (CH 3 )CO 2 CH 3 . For all of the alcohols listed, it is assumed that endothermic abstraction from the O–H group is trivial.…”

Section: Introductionmentioning

confidence: 99%

Evolution of Structure–Reactivity Correlations for the Hydrogen Abstraction Reaction by Chlorine Atom

Poutsma

2013

J. Phys. Chem. A

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Empirical structure-reactivity correlations are developed for log k(298), the gas-phase rate constants for the reaction (Cl(•) + HCR(3) → ClH + CR(3)(•)). It has long been recognized that correlation with Δ(r)H is weak. The poor performance of the linear Evans-Polanyi formulation is illustrated and was little improved by adding a quadratic term, for example, by making its slope smoothly dependent on Δ(r)H [η ≡ (Δ(r)H - Δ(r)H(min))/(Δ(r)H(max) - Δ(r)H(min))]. The "polar effect" ((δ-)Cl---H---CR(3)(δ+))(++) has also been long discussed, but there is no formalization of this dependence based on widely available independent variable(s). Using the sum of Hammett constants for the R substituents also gave at best modest correlations, either for σ(para) or for its dissection into F (field/inductive) and R (resonance) effects. Much greater success was achieved by combining these approaches with the preferred independent variable set being either [(Δ(r)H)(2), Δ(r)H, ΣF, and ΣR] or [η, Δ(r)H, ΣF, and ΣR]. For 64 rate constants that span 7 orders of magnitude, these correlation formulations give r(2) > 0.87 and a mean unsigned deviation of <0.5 log k units, with even better performance if primary, secondary, and tertiary reaction centers are treated separately.

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Section: Kineticsmentioning

confidence: 65%

“…Based on the observed reactivity, it was very evident that the obtained kinetic data for the reaction of PB with OH radicals and Cl atoms follow the reactivity trend of the other homologous esters. 66 Moreover, the reactivity was found to increase as the number of −CH 2 − increases on either side of the ester linkage. This in turn proved that the reaction rate coefficients increase as the most prominent reactive sites (R2, R3, R4, and R5) in the ester molecule (PB) become highly reactive.…”

Section: The Journal Of Physical Chemistry Amentioning

confidence: 96%

Cl Atoms and OH Radicals Initiated Kinetic and Mechanistic Study on the Degradation of Propyl Butanoate under Tropospheric Conditions

Gupta

Rajakumar

2019

J. Phys. Chem. A

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The reactivity of various OVOCs (mainly esters) in the troposphere leads to the generation of various organics, which in turn leads to an increase in the cloud acidity of the Earth's atmosphere. Hence, it becomes necessary to understand the mechanistic aspects of the reaction of these molecules with dominant atmospheric agents. In this study, the tropospheric degradation of one s u c h e s t e r , p r o p y l b u t a n o a t e ( P B ; CH 3 CH 2 CH 2 COOCH 2 CH 2 CH 3 ) was studied with OH radicals and Cl atoms at the CCSD(T)//M06-2x/6-311+G-(2d,2p) and CCSD(T)//BHandHLYP/6-311+G(2d,2p) level of theories over the studied temperature range of 200−400 K. The Arrhenius expressions obtained using the CVT/SCT/ISPE method were calculated as k PB + Cl (200−400 K) = 1.3 × 10 −14 T 1.3 exp[1335/T] cm 3 molecule −1 s −1 and k PB + OH (200−400 K) = 1.8 × 10 −26 T 4.6 exp[4469/T] cm 3 molecule −1 s −1 . The obtained kinetics was also well validated against the SAR (structure−activity relationship)-based rate coefficients. The most prominent H-abstraction reaction channels were investigated for the PB + OH/Cl reaction. The abstraction of H atoms attached to the carbon atom present in the β-position to the ester (−C(O)O−) functionality was found to go via the lowest energy activation barriers for the reaction of PB toward both OH radicals and Cl atoms. The product degradation channels were also elucidated in an O 2 /NO x -rich environment. Moreover, to gauge the impact of the emitted PB on the troposphere, atmospheric lifetimes, radiative efficiencies, global warming potentials, and photochemical ozone creation potentials were also calculated and are included in the manuscript.

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Pulsed laser photolysis vacuum UV laser-induced fluorescence kinetic study of the reactions of Cl(2P3/2) atoms with ethyl formate, n-propyl formate, and n-butyl formate

Cited by 7 publications

References 9 publications

Experimental and Computational Investigation on the Gas Phase Reaction of Ethyl Formate with Cl Atoms

Experimental and Computational Investigation on the Gas Phase Reaction of Ethyl Formate with Cl Atoms

Evolution of Structure–Reactivity Correlations for the Hydrogen Abstraction Reaction by Chlorine Atom

Cl Atoms and OH Radicals Initiated Kinetic and Mechanistic Study on the Degradation of Propyl Butanoate under Tropospheric Conditions

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