A direct study of the reaction of CH2( 3B1)-radicals with toluene in the temperature range 296 K

K. Heberger, F. Temps, S. Völker, M. Wolf, H. Gg Wagner

Research output: Contribution to journalArticle

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Abstract

The reaction (1) between CH2-radicals in the triplet electronic ground state,3B1 (≡3CH2), and toluene (T) 3CH2+T→products was studied in the gas phase at temperatures from 296 K≤T≤623 K. The overall rate constant of the reaction was measured between 472 K≤T≤623 K using the discharge flow Laser Magnetic Resonance method. The direct experimental results (±2°) were described by the expression K1 exp=(9.4±1.6)·1013·exp[-(4530±100)K/T]cm3/mol·s. Allowing for the [3CH2] decay to occur both via direct reaction with the reactant as well as via partial equilibration between theand ã 1A1 (≡1CH2) excited electronic states followed by reactions of 1CH2 with T, the Arrhenius expression for the direct 3CH2 reaction in the temperature range investigated was found to be (k1b+k1c)=(6.0±1.8)·1013·exp[-(36.8±1.4), kJ mol-1/R·T] cm3/mol·s. The main reaction channels were deduced from the results of an end product study together with a comparison of the Arrhenius parameters to data obtained in this laboratory for related reactions of 3CH2. The end product distribution indicates that at room temperature abstraction of an H-atom from the CH3 group of toluene (reaction 1c) dominates over addition of the 3CH2 to the aromatic ring, whereas for T≥450 K the addition channel (reaction 1b) dominates. In combustion systems the role of 1CH2 has to be taken into account as well.

Original languageEnglish
Pages (from-to)29-35
Number of pages7
JournalSymposium (International) on Combustion
Volume23
Issue number1
DOIs
Publication statusPublished - 1991

Fingerprint

Toluene
toluene
Electronic states
Magnetic resonance
Temperature
Ground state
temperature
Rate constants
Gases
Atoms
Lasers
products
electronics
magnetic resonance
vapor phases
ground state
rings
decay
room temperature

ASJC Scopus subject areas

  • Chemical Engineering(all)
  • Fluid Flow and Transfer Processes
  • Physical and Theoretical Chemistry
  • Energy Engineering and Power Technology
  • Fuel Technology
  • Mechanical Engineering

Cite this

A direct study of the reaction of CH2( 3B1)-radicals with toluene in the temperature range 296 K. / Heberger, K.; Temps, F.; Völker, S.; Wolf, M.; Wagner, H. Gg.

In: Symposium (International) on Combustion, Vol. 23, No. 1, 1991, p. 29-35.

Research output: Contribution to journalArticle

Heberger, K. ; Temps, F. ; Völker, S. ; Wolf, M. ; Wagner, H. Gg. / A direct study of the reaction of CH2( 3B1)-radicals with toluene in the temperature range 296 K. In: Symposium (International) on Combustion. 1991 ; Vol. 23, No. 1. pp. 29-35.
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abstract = "The reaction (1) between CH2-radicals in the triplet electronic ground state,3B1 (≡3CH2), and toluene (T) 3CH2+T→products was studied in the gas phase at temperatures from 296 K≤T≤623 K. The overall rate constant of the reaction was measured between 472 K≤T≤623 K using the discharge flow Laser Magnetic Resonance method. The direct experimental results (±2°) were described by the expression K1 exp=(9.4±1.6)·1013·exp[-(4530±100)K/T]cm3/mol·s. Allowing for the [3CH2] decay to occur both via direct reaction with the reactant as well as via partial equilibration between theand {\~a} 1A1 (≡1CH2) excited electronic states followed by reactions of 1CH2 with T, the Arrhenius expression for the direct 3CH2 reaction in the temperature range investigated was found to be (k1b+k1c)=(6.0±1.8)·1013·exp[-(36.8±1.4), kJ mol-1/R·T] cm3/mol·s. The main reaction channels were deduced from the results of an end product study together with a comparison of the Arrhenius parameters to data obtained in this laboratory for related reactions of 3CH2. The end product distribution indicates that at room temperature abstraction of an H-atom from the CH3 group of toluene (reaction 1c) dominates over addition of the 3CH2 to the aromatic ring, whereas for T≥450 K the addition channel (reaction 1b) dominates. In combustion systems the role of 1CH2 has to be taken into account as well.",
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N2 - The reaction (1) between CH2-radicals in the triplet electronic ground state,3B1 (≡3CH2), and toluene (T) 3CH2+T→products was studied in the gas phase at temperatures from 296 K≤T≤623 K. The overall rate constant of the reaction was measured between 472 K≤T≤623 K using the discharge flow Laser Magnetic Resonance method. The direct experimental results (±2°) were described by the expression K1 exp=(9.4±1.6)·1013·exp[-(4530±100)K/T]cm3/mol·s. Allowing for the [3CH2] decay to occur both via direct reaction with the reactant as well as via partial equilibration between theand ã 1A1 (≡1CH2) excited electronic states followed by reactions of 1CH2 with T, the Arrhenius expression for the direct 3CH2 reaction in the temperature range investigated was found to be (k1b+k1c)=(6.0±1.8)·1013·exp[-(36.8±1.4), kJ mol-1/R·T] cm3/mol·s. The main reaction channels were deduced from the results of an end product study together with a comparison of the Arrhenius parameters to data obtained in this laboratory for related reactions of 3CH2. The end product distribution indicates that at room temperature abstraction of an H-atom from the CH3 group of toluene (reaction 1c) dominates over addition of the 3CH2 to the aromatic ring, whereas for T≥450 K the addition channel (reaction 1b) dominates. In combustion systems the role of 1CH2 has to be taken into account as well.

AB - The reaction (1) between CH2-radicals in the triplet electronic ground state,3B1 (≡3CH2), and toluene (T) 3CH2+T→products was studied in the gas phase at temperatures from 296 K≤T≤623 K. The overall rate constant of the reaction was measured between 472 K≤T≤623 K using the discharge flow Laser Magnetic Resonance method. The direct experimental results (±2°) were described by the expression K1 exp=(9.4±1.6)·1013·exp[-(4530±100)K/T]cm3/mol·s. Allowing for the [3CH2] decay to occur both via direct reaction with the reactant as well as via partial equilibration between theand ã 1A1 (≡1CH2) excited electronic states followed by reactions of 1CH2 with T, the Arrhenius expression for the direct 3CH2 reaction in the temperature range investigated was found to be (k1b+k1c)=(6.0±1.8)·1013·exp[-(36.8±1.4), kJ mol-1/R·T] cm3/mol·s. The main reaction channels were deduced from the results of an end product study together with a comparison of the Arrhenius parameters to data obtained in this laboratory for related reactions of 3CH2. The end product distribution indicates that at room temperature abstraction of an H-atom from the CH3 group of toluene (reaction 1c) dominates over addition of the 3CH2 to the aromatic ring, whereas for T≥450 K the addition channel (reaction 1b) dominates. In combustion systems the role of 1CH2 has to be taken into account as well.

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