Temterature dependence of the reactions of CH radicals with unsaturated hydrocarbons

Michael R. Berman; J. W. Fleming; A. B. Harvey; Ming-Chang Lin

doi:10.1016/0301-0104(82)85147-1

Temterature dependence of the reactions of CH radicals with unsaturated hydrocarbons

Michael R. Berman^*, J. W. Fleming, A. B. Harvey, Ming-Chang Lin

^*Corresponding author for this work

Department of Applied Chemistry

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Abstract

The temperature dependences of the reactions of CH (X²Π) with several unsaturated hydrocarbons were studied. CH radicals were generated by multiple-photon dissociation of CHBr₃ at 266 nm. The CH concentration was monitored by its laser-induced fluorescence at 430 nm. The rate constants for the reactions of CH with C₂H₂ and C₂H₄ were found to increase with decreasing temperature. These rate constants were measured between 171 and 657 and 160 and 652 K, respectively, and found to be kC₂ H₂ = (3.49 ± 0.42) × 10^-10 exp [(61 ± 36)/T] and kC₂H₄ = (2.23 ± 0.27) × 10^-10 exp [(173 ± 35)/T] cm³ molecule^-1 s^-1. The rate constant for reaction with benzene was found to be temperature independent in the range 297-674 K with kC₆H₆ = (4.3 ± 0.3) × 10^-10 cm³ molecule^-1 s^-1. The rate constant for the reaction of CH + toluene was determined to be kC₆H₅CH₃ = (5.0 ± 0.4)× 10^-10 cm³ molecule^-1 s^-1. Comparison of these results with earlier room-temperature measurements which used 193 nm photolysis indicates that VUV photolysis of unsaturated hydrocarbon reactants could systematically affect those measured rate constants.

Original language	English
Pages (from-to)	27-33
Number of pages	7
Journal	Chemical Physics
Volume	73
Issue number	1-2
DOIs	https://doi.org/10.1016/0301-0104(82)85147-1
State	Published - 1 Dec 1982

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title = "Temterature dependence of the reactions of CH radicals with unsaturated hydrocarbons",

abstract = "The temperature dependences of the reactions of CH (X2Π) with several unsaturated hydrocarbons were studied. CH radicals were generated by multiple-photon dissociation of CHBr3 at 266 nm. The CH concentration was monitored by its laser-induced fluorescence at 430 nm. The rate constants for the reactions of CH with C2H2 and C2H4 were found to increase with decreasing temperature. These rate constants were measured between 171 and 657 and 160 and 652 K, respectively, and found to be kC2 H2 = (3.49 ± 0.42) × 10-10 exp [(61 ± 36)/T] and kC2H4 = (2.23 ± 0.27) × 10-10 exp [(173 ± 35)/T] cm3 molecule-1 s-1. The rate constant for reaction with benzene was found to be temperature independent in the range 297-674 K with kC6H6 = (4.3 ± 0.3) × 10-10 cm3 molecule-1 s-1. The rate constant for the reaction of CH + toluene was determined to be kC6H5CH3 = (5.0 ± 0.4)× 10-10 cm3 molecule-1 s-1. Comparison of these results with earlier room-temperature measurements which used 193 nm photolysis indicates that VUV photolysis of unsaturated hydrocarbon reactants could systematically affect those measured rate constants.",

author = "Berman, {Michael R.} and Fleming, {J. W.} and Harvey, {A. B.} and Ming-Chang Lin",

year = "1982",

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doi = "10.1016/0301-0104(82)85147-1",

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T1 - Temterature dependence of the reactions of CH radicals with unsaturated hydrocarbons

AU - Berman, Michael R.

AU - Fleming, J. W.

AU - Harvey, A. B.

AU - Lin, Ming-Chang

PY - 1982/12/1

Y1 - 1982/12/1

N2 - The temperature dependences of the reactions of CH (X2Π) with several unsaturated hydrocarbons were studied. CH radicals were generated by multiple-photon dissociation of CHBr3 at 266 nm. The CH concentration was monitored by its laser-induced fluorescence at 430 nm. The rate constants for the reactions of CH with C2H2 and C2H4 were found to increase with decreasing temperature. These rate constants were measured between 171 and 657 and 160 and 652 K, respectively, and found to be kC2 H2 = (3.49 ± 0.42) × 10-10 exp [(61 ± 36)/T] and kC2H4 = (2.23 ± 0.27) × 10-10 exp [(173 ± 35)/T] cm3 molecule-1 s-1. The rate constant for reaction with benzene was found to be temperature independent in the range 297-674 K with kC6H6 = (4.3 ± 0.3) × 10-10 cm3 molecule-1 s-1. The rate constant for the reaction of CH + toluene was determined to be kC6H5CH3 = (5.0 ± 0.4)× 10-10 cm3 molecule-1 s-1. Comparison of these results with earlier room-temperature measurements which used 193 nm photolysis indicates that VUV photolysis of unsaturated hydrocarbon reactants could systematically affect those measured rate constants.

AB - The temperature dependences of the reactions of CH (X2Π) with several unsaturated hydrocarbons were studied. CH radicals were generated by multiple-photon dissociation of CHBr3 at 266 nm. The CH concentration was monitored by its laser-induced fluorescence at 430 nm. The rate constants for the reactions of CH with C2H2 and C2H4 were found to increase with decreasing temperature. These rate constants were measured between 171 and 657 and 160 and 652 K, respectively, and found to be kC2 H2 = (3.49 ± 0.42) × 10-10 exp [(61 ± 36)/T] and kC2H4 = (2.23 ± 0.27) × 10-10 exp [(173 ± 35)/T] cm3 molecule-1 s-1. The rate constant for reaction with benzene was found to be temperature independent in the range 297-674 K with kC6H6 = (4.3 ± 0.3) × 10-10 cm3 molecule-1 s-1. The rate constant for the reaction of CH + toluene was determined to be kC6H5CH3 = (5.0 ± 0.4)× 10-10 cm3 molecule-1 s-1. Comparison of these results with earlier room-temperature measurements which used 193 nm photolysis indicates that VUV photolysis of unsaturated hydrocarbon reactants could systematically affect those measured rate constants.

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Temterature dependence of the reactions of CH radicals with unsaturated hydrocarbons

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