Computational studies on the mechanism and kinetics of Cl reaction with C<sub>2</sub>H<sub>5</sub>I

Jia, Xiujuan; Liu, Youjun; Sun, Jingyu; Sun, Hao; Wang, Fang; Su, Zhong‐Min; Pan, Xiumei; Wang, Rongshun

doi:10.1002/jcc.21516

Cited by 6 publications

(3 citation statements)

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“…The atmospheric lifetime of CH 3 CH 2 I (at 298 K) initiated by ⋅Cl was evaluated to be 206.68 day ([⋅Cl]=1.0×10 4 molecule cm −3 ) [39] according to the rate constant (5.60×10 −12 cm 3 molecule −1 s −1 ) obtained by Jia et al. [40] . This shows that ⋅OH is more favorable than ⋅Cl in the degradation of CH 3 CH 2 I. Bai et al [20] .…”

Section: Resultsmentioning

confidence: 99%

“…The atmospheric lifetime of CH 3 CH 2 I (at 298 K) initiated by * Cl was evaluated to be 206.68 day ([ * Cl] = 1.0 × 10 4 molecule cm À 3 ) [39] according to the rate constant (5.60 × 10 À 12 cm 3 molecule À 1 s À 1 ) obtained by Jia et al. [40] This shows that * OH is more favorable than * Cl in the degradation of CH 3 CH 2 I. Bai et al [20] have evaluated the NO [41][42][43][44] Comparing the atmospheric lifetimes of CH 3 I and CH 3 CH 2 I initiated by * OH or NO 3 * radicals, it can be found that the introduction of À CH 3 can significantly shorten the atmospheric residence time of iodoalkanes and accelerate the formation of reactive iodine-containing radicals, promoting the iodine cycling process in the atmospheric environment.…”

Section: Atmospheric Lifetimementioning

confidence: 99%

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Theoretical Study of the Hydroxyl‐Radical‐Initiated Degradation Mechanism, Kinetics, and Subsequent Evolution of Methyl and Ethyl Iodides in the Atmosphere

et al. 2023

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The degradation and transformation of iodinated alkanes are crucial in the iodine chemical cycle in the marine boundary layer. In this study, MP2 and CCSD(T) methods were adopted to study the atmospheric transformation mechanism and degradation kinetic properties of CH 3 I and CH 3 CH 2 I mediated by * OH radical. The results show that there are three reaction mechanisms including H-abstraction, I-substitution and I-abstraction. The H-abstraction channel producing * CH 2 I and CH 3 C • HI radicals are the main degradation pathways of CH 3 I and CH 3 CH 2 I, respectively. By means of the variational transition state theory and small curvature tunnel correction method, the rate constants and branching ratios of each reaction are calculated in the temperature range of 200-600 K. The results show that the tunneling effect contributes more to the reaction at low temperatures. Theoretical reaction rate constants of CH 3 I and CH 3 CH 2 I with * OH are calculated to be 1.42 × 10 À 13 and 4.44 × 10 À 13 cm 3 molecule À 1 s À 1 at T = 298 K, respectively, which are in good agreement with the experimental values. The atmospheric lifetimes of CH 3 I and CH 3 CH 2 I are evaluated to be 81.51 and 26.07 day, respectively. The subsequent evolution mechanism of * CH 2 I and CH 3 C • HI in the presence of O 2 , NO and HO 2 indicates that HCHO, CH 3 CHO, and I-atom are the main transformation end-products. This study provides a theoretical basis for insight into the diurnal conversion and environmental implications of iodinated alkanes.* and *OH [14,[19][20] in the atmospheric environment. Therefore, precise rate constants and subsequent reaction mechanism studies are needed to fully assess their environmental impact. The role of NO 3 * radical in the nocturnal transformation of CH 3 I and CH 3 CH 2 I has been explored by Nakano et al. [21][22] and Bai et al. [20] in experiment and theory, respectively. The results suggested that CH 3 I and CH 3 CH 2 I can be degraded in the atmosphere within a short time to serve as a source of reactive iodine compounds at night-time. Experimentally, Cotter et al. [14] inves-[a] X.

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Section: Resultsmentioning

confidence: 99%

Section: Atmospheric Lifetimementioning

confidence: 99%

Theoretical Study of the Hydroxyl‐Radical‐Initiated Degradation Mechanism, Kinetics, and Subsequent Evolution of Methyl and Ethyl Iodides in the Atmosphere

et al. 2023

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“…High concentrations of Cl atoms can be found in marine environments and urban areas with high levels of chloride‐containing aerosol 11. 12, 26 The reactions of FESs with Cl and OH radicals are important to evaluate the atmospheric lifetime of the FESs. CF 3 COOCH 2 CH 3 , CF 2 HCOOCH 3 , and CF 3 COOCH 3 are the typical FESs; thus, we take attention to the three FESs reactions with chlorine atoms and hydroxyl radicals.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Studies of the Reactions CF_xH_3−xCOOR+Cl and CF₃COOCH₃+OH

et al. 2015

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The mechanism and kinetics of the reactions of CF(3)COOCH(2)CH(3), CF(2)HCOOCH(3), and CF(3)COOCH(3) with Cl and OH radicals are studied using the B3LYP, MP2, BHandHLYP, and M06-2X methods with the 6-311G(d,p) basis set. The study is further refined by using the CCSD(T) and QCISD(T)/6-311++G(d,p) methods. Seven hydrogen-abstraction channels are found. All the rate constants, computed by a dual-level direct method with a small-curvature tunneling correction, are in good agreement with the experimental data. The tunneling effect is found to be important for the calculated rate constants in the low-temperature range. For the reaction of CF(3)COOCH(2)CH(3) +Cl, H-abstraction from the CH(2) group is found to be the dominant reaction channel. The standard enthalpies of formation for the species are also calculated. The Arrhenius expressions are fitted within 200-1000 K as kT(1) =8.4×10(-20) T (2.63) exp(381.28/T), kT(2) =2.95×10(-21) T (3.13) exp(-103.21/T), kT(3) =1.25×10(-23) T (3.37) exp(791.98/T), and kT(4) =4.53×10(-22) T (3.07) exp(465.00/T).

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