Formation of H and D atoms in the pyrolysis of toluene-d sub s and toluene-. alpha. ,. alpha. ,. alpha. -d sub 3

Journal Article · Thu Mar 09 04:00:00 EST 1989 · Journal of Physical Chemistry; (USA)

DOI:https://doi.org/10.1021/j100342a033· OSTI ID:5091192

Rao, V S; Skinner, G B ^[1]

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1. Wright State Univ., Dayton, OH (USA)

Mixtures of l-20 ppm of toluene-d{sub 8} and C{sub 6}H{sub 5}CD{sub 3} in argon were pyrolyzed behind incident shock waves with a total pressure of {approx}0.4 atm and a temperature range of 1450-1790 K. D atom concentrations were measured for the first compound and both H and D for the second. The data indicate that an appreciable fraction of toluene dissociates via C{sub 6}H{sub 5}CO{sub 3} {yields} C{sub 6}H{sub 5} + CD{sub 3}, (5HD), with k{sub 5HD} = 2.0 {times} 10{sup 15} exp(-94 kcal/RT) s{sup {minus}1}, while the rate constant for C{sub 6}H{sub 5}CD{sub 3} {yields} C{sub 6}H{sub 5}CD{sub 2} + D, (1HD), was found to be k{sub 1HD} = 2.2 {times} 10{sup 14} exp(-86.4 kcal/RT), under experimental conditions. RRKM calculations were made to evaluate unimolecular falloff for these reactions and to calculate the corresponding rate constants for C{sub 7}H{sub 8}. For C{sub 6}H{sub 5}CH{sub 3} {yields} C{sub 6}H{sub 5} + CH{sub 3}, (5), we find that k{sub 5} = 1.5 {times} 10{sup 15} exp(-94.2 kcal/RT) s{sup {minus}1}, while for C{sub 6}H{sub 5}CH{sub 3} {yields} C{sub 6}H{sub 5}CH{sub 2} + H, (1), we find k{sub 1} = 2.5 {times} 10{sup 14} exp(-85.8 kcal/RT) s{sup {minus}1}, both under the experimental conditions given above.

• DOE Contract Number: AC02-76ER02944
• OSTI ID: 5091192
• Journal Information: Journal of Physical Chemistry; (USA), Journal Name: Journal of Physical Chemistry; (USA) Vol. 93:5; ISSN 0022-3654; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400800* -- Combustion
Pyrolysis
& High-Temperature Chemistry
ALKYLATED AROMATICS
ARGON
AROMATICS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DATA
DECOMPOSITION
DEUTERIUM COMPOUNDS
DISSOCIATION
ELEMENTS
EXPERIMENTAL DATA
FLUIDS
GASES
HYDROCARBONS
HYDROGEN COMPOUNDS
INFORMATION
KINETICS
LOW PRESSURE
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
PYROLYSIS
RARE GASES
REACTION KINETICS
SHOCK TUBES
THERMOCHEMICAL PROCESSES
TOLUENE
VERY HIGH TEMPERATURE