Kinetics and Mechanism of the Reaction of Chlorine Atoms with n-Pentanal

Kinetics and Mechanism of the Reaction of Chlorine Atoms with n-Pentanal

The kinetics and mechanism of the reaction Cl + CH3(CH2)3CHO was investigated using absolute (PLP−LIF) and relative rate techniques in 8 Torr of argon or 800−950 Torr of N2 at 295 ± 2 K. The absolute rate experiments gave k[Cl+CH3(CH2)3CHO] = (2.31 ± 0.35) × 10-10 in 8 Torr of argon, while relative...

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Veröffentlicht in:The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2008-02, Vol.112 (8), p.1741-1746
Hauptverfasser: Iwasaki, E, Nakayama, T, Matsumi, Y, Takahashi, K, Wallington, T. J, Hurley, M. D, Kaiser, E. W
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container_end_page 1746
container_issue 8
container_start_page 1741
container_title The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory
container_volume 112
creator Iwasaki, E
Nakayama, T
Matsumi, Y
Takahashi, K
Wallington, T. J
Hurley, M. D
Kaiser, E. W
description The kinetics and mechanism of the reaction Cl + CH3(CH2)3CHO was investigated using absolute (PLP−LIF) and relative rate techniques in 8 Torr of argon or 800−950 Torr of N2 at 295 ± 2 K. The absolute rate experiments gave k[Cl+CH3(CH2)3CHO] = (2.31 ± 0.35) × 10-10 in 8 Torr of argon, while relative rate experiments gave k[Cl+CH3(CH2)3CHO] = (2.24 ± 0.20) × 10-10 cm3 molecule-1 s-1 in 800−950 Torr of N2. Additional relative rate experiments gave k[Cl+CH3(CH2)3C(O)Cl] = (8.74 ± 1.38) × 10-11 cm3 molecule-1 s-1 in 700 Torr of N2. Smog chamber Fourier transform infrared (FTIR) techniques indicated that the acyl-forming channel accounts for 42 ± 3% of the reaction. The results are discussed with respect to the literature data and the importance of long range (greater than or equal to two carbon atoms along the aliphatic chain) effects in determining the reactivity of organic molecules toward chlorine atoms.
doi_str_mv 10.1021/jp077525z
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