Formation of D atoms in the pyrolysis of toluene-d/sub 8/ behind shock waves: kinetics of the reaction C/sub 7/D/sub 8/ + H. -->. C/sub 7/D/sub 7/H + D
Abstract
Dilute mixtures (5-20 ppm) of toluene-d/sub 8/ in argon were pyrolyzed behind reflected shock waves at temperatures of 1410-1730 K and total pressures of 3 atm. In a second group of experiments, mixtures of 20 ppm toluene-d/sub 8/ and 5 ppm neopentane (which acted as a source of H atoms) were similarly pyrolyzed at 1200-1460 K. Progress of the reaction was followed by analysis for H and D atoms by using resonance absorption spectroscopy. For the reaction C/sub 6/D/sub 5/CD/sub 3/ ..-->.. C/sub 6/D/sub 5/CD/sub 2/ + D under the experimental conditions, k/sub 1D/ = 1.1 x 10/sup 14/ exp(-82000 cal/RT) s/sup -1/. After allowance for isotope effects and unimolecular falloff, the high-pressure rate constant for the reaction C/sub 6/H/sub 5/CH/sub 3/ ..-->.. C/sub 6/H/sub 5/CH/sub 2/ + H is calculated to be k/sub 1infinity/. For the reaction D + C/sub 6/D/sub 5/CD/sub 3/ ..-->.. C/sub 6/D/sub 5/CD/sub 2/ +- D/sub 2/, K/sub 2D2/ = 2.1 x 10/sup 15/ exp(-15000 cal/RT) mol/sup -1/ cm/sup 3/ s/sup -1/ over the range 1300-1800 K, with an uncertainty of a factor of 1.5, while after correction for isotope effects the rate constant for H + C/sub 6/H/sub 5/CH ..-->.. C/sub 6/H/sub 5/CH/sub 2/more »
- Authors:
- Publication Date:
- Research Org.:
- Wright State Univ., Dayton, OH
- OSTI Identifier:
- 6155388
- Resource Type:
- Journal Article
- Journal Name:
- J. Phys. Chem.; (United States)
- Additional Journal Information:
- Journal Volume: 88:19
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 2-2-DIMETHYLPROPANE; PYROLYSIS; HYDROGEN; CHEMICAL REACTION KINETICS; TOLUENE; ABSORPTION SPECTROSCOPY; ACCURACY; ARGON; DATA ANALYSIS; DEUTERIUM COMPOUNDS; EXPERIMENTAL DATA; MEDIUM PRESSURE; QUANTITY RATIO; TEMPERATURE DEPENDENCE; TIME DEPENDENCE; VERY HIGH TEMPERATURE; ALKANES; ALKYLATED AROMATICS; AROMATICS; CHEMICAL REACTIONS; DATA; DECOMPOSITION; ELEMENTS; FLUIDS; GASES; HYDROCARBONS; HYDROGEN COMPOUNDS; INFORMATION; KINETICS; NONMETALS; NUMERICAL DATA; ORGANIC COMPOUNDS; RARE GASES; REACTION KINETICS; SPECTROSCOPY; THERMOCHEMICAL PROCESSES; 400301* - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)
Citation Formats
Rao, V S, and Skinner, G B. Formation of D atoms in the pyrolysis of toluene-d/sub 8/ behind shock waves: kinetics of the reaction C/sub 7/D/sub 8/ + H. -->. C/sub 7/D/sub 7/H + D. United States: N. p., 1984.
Web. doi:10.1021/j150663a035.
Rao, V S, & Skinner, G B. Formation of D atoms in the pyrolysis of toluene-d/sub 8/ behind shock waves: kinetics of the reaction C/sub 7/D/sub 8/ + H. -->. C/sub 7/D/sub 7/H + D. United States. https://doi.org/10.1021/j150663a035
Rao, V S, and Skinner, G B. 1984.
"Formation of D atoms in the pyrolysis of toluene-d/sub 8/ behind shock waves: kinetics of the reaction C/sub 7/D/sub 8/ + H. -->. C/sub 7/D/sub 7/H + D". United States. https://doi.org/10.1021/j150663a035.
@article{osti_6155388,
title = {Formation of D atoms in the pyrolysis of toluene-d/sub 8/ behind shock waves: kinetics of the reaction C/sub 7/D/sub 8/ + H. -->. C/sub 7/D/sub 7/H + D},
author = {Rao, V S and Skinner, G B},
abstractNote = {Dilute mixtures (5-20 ppm) of toluene-d/sub 8/ in argon were pyrolyzed behind reflected shock waves at temperatures of 1410-1730 K and total pressures of 3 atm. In a second group of experiments, mixtures of 20 ppm toluene-d/sub 8/ and 5 ppm neopentane (which acted as a source of H atoms) were similarly pyrolyzed at 1200-1460 K. Progress of the reaction was followed by analysis for H and D atoms by using resonance absorption spectroscopy. For the reaction C/sub 6/D/sub 5/CD/sub 3/ ..-->.. C/sub 6/D/sub 5/CD/sub 2/ + D under the experimental conditions, k/sub 1D/ = 1.1 x 10/sup 14/ exp(-82000 cal/RT) s/sup -1/. After allowance for isotope effects and unimolecular falloff, the high-pressure rate constant for the reaction C/sub 6/H/sub 5/CH/sub 3/ ..-->.. C/sub 6/H/sub 5/CH/sub 2/ + H is calculated to be k/sub 1infinity/. For the reaction D + C/sub 6/D/sub 5/CD/sub 3/ ..-->.. C/sub 6/D/sub 5/CD/sub 2/ +- D/sub 2/, K/sub 2D2/ = 2.1 x 10/sup 15/ exp(-15000 cal/RT) mol/sup -1/ cm/sup 3/ s/sup -1/ over the range 1300-1800 K, with an uncertainty of a factor of 1.5, while after correction for isotope effects the rate constant for H + C/sub 6/H/sub 5/CH ..-->.. C/sub 6/H/sub 5/CH/sub 2/ + H/sub 2/ over the range 600-1800 K can be expressed by the non-Arrhenius equation k/sub 2/ = 7.6 x 10/sup -5/T/sup 5.5/ exp(-340 cal/RT) mol/sup -1/ cm/sup 3/ s/sup -1/, with an uncertainty of a factor of 2. Data were also obtained on the exchange reaction by which H atoms add to the ring of C/sub 6/D/sub 5/CD/sub 3/, and D atoms are eliminated. For this reaction k/sub 4D = 3.5 x 10/sup 13/ exp(-3700 cal/RT) mol/sup -1/ cm/sup 3/ s/sup -1/ in the range 1200-1500 K, with an estimated uncertainty of a factor of 1.5. 15 references, 4 figures.},
doi = {10.1021/j150663a035},
url = {https://www.osti.gov/biblio/6155388},
journal = {J. Phys. Chem.; (United States)},
number = ,
volume = 88:19,
place = {United States},
year = {Thu Sep 13 00:00:00 EDT 1984},
month = {Thu Sep 13 00:00:00 EDT 1984}
}