Investigation on addition and abstraction channels in Cl reactions with 1-butene and isobutene

Chu, Genbai; Chen, Jun; Shui, Miao; Xin, Jianting; Liu, Fuyi; Sheng, Liusi; Xu, T.; Cao, Liangcai; Gu, Yuqiu

doi:10.1016/j.ijms.2014.08.036

Cited by 3 publications

(1 citation statement)

References 42 publications

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“…These results indicate that the roaming path generates more vibrationally excited HCl than the abstraction path, consistent with the expectation according to consideration of the structures of the transition states, because the roaming transition state has an H−Cl distance of 2.37 Å9, much greater than the H−Cl distance of 1.59 Å for the transition state of H-abstraction30 and the equilibrium distance 1.275 Å of HCl. In the case of photolysis of acetaldehyde, the roaming transition state has a C−H distance of 1.722 Å, much greater than the equilibrium C−H distance of 1.093 Å of CH 4 31.…”

Section: Resultssupporting

confidence: 90%

New experimental evidence to support roaming in the reaction Cl + isobutene (i-C4H8)

Chen

Hung

Matsui

et al. 2017

Sci Rep

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The reaction Cl + isobutene (i-C4H8) was reported by Suits et al. to proceed via, in addition to abstraction, an addition-elimination path following a roaming excursion of Cl; a near-zero translational energy release and an isotropic angular distribution observed at a small collision energy characterized this mechanism. We employed a new experimental method to further characterize this roaming mechanism through observation of the internal distribution of HCl (v, J) and their temporal behavior upon irradiation of a mixture of Cl2C2O2 and i-C4H8 in He or Ar buffer gas. With 1–3 Torr buffer gas added to approach the condition of small collision energy, the intensities of emission of HCl (v = 1, 2) and the HCl production rates increased significantly; Ar shows a more significant effect than He because Ar quenches Cl more efficiently to reduce the collisional energy and facilitate the roaming path. According to kinetic modeling, the rate of addition-elimination (roaming) increased from kE ≈ 2 × 105 s−1 when little buffer gas was present to ~1.9 × 106 s−1 when 2–3 Torr of Ar was added, and the branching ratio for formation of [HCl (v = 2)]/[HCl (v = 1)] increased from 0.02 ± 0.01 for abstraction to 0.06 ± 0.01 for roaming.

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Section: Resultssupporting

confidence: 90%

New experimental evidence to support roaming in the reaction Cl + isobutene (i-C4H8)

Chen

Hung

Matsui

et al. 2017

Sci Rep

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Investigation into reactions of methyl methacrylate and ethyl acrylate with chlorine atom

Lin

et al. 2019

Chemosphere

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Infrared absorption of 1-chloro-2-methyl-2-propyl [⋅C(CH3)2CH2Cl] and 2-chloro-2-methylpropyl [⋅CH2C(CH3)2Cl] radicals produced in the addition reactions of Cl with isobutene (i-C4H8) in solid para-hydrogen

Chou

Lee

2016

The Journal of Chemical Physics

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The addition reactions of chlorine atom with isobutene (i-CH) in solid para-hydrogen (p-H) were investigated with infrared (IR) absorption spectra. When a p-H matrix containing Cl and isobutene was irradiated with ultraviolet light at 365 nm, intense lines in a set at 534.5, 1001.0, 1212.9, 1366.0, 2961.6, and 2934.7 cm, and several weaker others due to the 1-chloro-2-methyl-2-propyl radical, C(CH)CHCl, and those in a second set including intense ones at 642.7, 799.2, 1098.2, 1371.8, and 3027.3 cm due to the 2-chloro-2-methylpropyl radical, CHC(CH)Cl, appeared; the ratio of C(CH)CHCl to CHC(CH)Cl was approximately (3 ± 1):1. The observed wavenumbers and relative intensities agree with the vibrational wavenumbers and IR intensities predicted with the B3PW91/aug-cc-pVTZ method. That the Cl atom adds to both carbons of the C=C bond of isobutene with the terminal site slightly favored is consistent with the energies of products predicted theoretically, but is in contrast to the reaction of Cl + propene in solid p-H in which the addition of Cl to mainly the central C atom was previously reported. The role of the p-H matrix in affecting the reaction paths is discussed. Absorption lines of the complex i-CH⋅Cl and the dichloro-product anti-1,2-dichloro-2-methylpropane, a-CHClCCl(CH), are also characterized.

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Investigation on addition and abstraction channels in Cl reactions with 1-butene and isobutene

Cited by 3 publications

References 42 publications

New experimental evidence to support roaming in the reaction Cl + isobutene (i-C4H8)

New experimental evidence to support roaming in the reaction Cl + isobutene (i-C4H8)

Investigation into reactions of methyl methacrylate and ethyl acrylate with chlorine atom

Infrared absorption of 1-chloro-2-methyl-2-propyl [⋅C(CH3)2CH2Cl] and 2-chloro-2-methylpropyl [⋅CH2C(CH3)2Cl] radicals produced in the addition reactions of Cl with isobutene (i-C4H8) in solid para-hydrogen

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