Journal of Physical Chemistry A, Vol.101, No.11, 2138-2146, 1997
Kinetics of C-2 Reactions During High-Temperature Pyrolysis of Acetylene
The kinetics of C-2 radical reactions during the first stage of acetylene high-temperature pyrolysis was studied by monitoring C, C-2 and C-3 radicals. Quantitative C-2 detection was performed by ring dye laser absorption spectroscopy, C atoms were measured by applying atomic resonance absorption spectroscopy, and C-3 radicals were monitored by their emission using a combination of a spectrograph and an intensified CCD camera system. The experiments were performed behind reflected shock waves and cover the temperature range of 2580-4650 K at pressures around 2 bar. In the first part of the study initial mixtures containing Ar with 5-50 ppm C2H2 were used. In this very low concentration range, rate coefficients for the following four reactions were determined : [GRAPHICS] Furthermore, this experiments indicate that a modification of the JANAF(1) thermodynamic data of either C, C-2 or C-3 seems to be necessary. In the second part, some experiments with relatively high initial acetylene concentrations up to 500 ppm C2H2 in Ar were carried out to check the validity of a more complex mechanism for the acetylene pyrolysis. Finally in a third part, a perturbation study was performed by adding 1000 ppm H-2 to the initial mixtures of Ar with 20 and 50 ppm of C2H2. For the most important perturbation reactions, [GRAPHICS] ificant amounts of dissolved HBr.
Keywords:LASER-INDUCED FLUORESCENCE;BOND-DISSOCIATION ENERGY;LIFETIME MEASUREMENTS;C2;RADICALS;ETHYLENE;SYSTEMS