Journal of Physical Chemistry p. 6313 - 6319 (1988)
Update date:2022-08-17
Topics:
Rao
Skinner, Gordon B.
Five sets of experiments were carried out to determine the rate constant for dissociation of C2H3 at high temperatures. In all cases the measurements involved absorption of H or D Lyman-α radiation in argon-diluted gas mixtures reacting behind shock waves. For pyrolysis of vinyl bromide at 0.5-atm total pressure we found for C2H3 + Ar → C2H2 + H + Ar, k = 7.0 × 1013 exp(-28 kcal/RT) mol-1 cm3 s-1 at 1380-1750 K. For the same reaction initiated from vinyl iodide at 0.5-atm total pressure and 1060-1370 K, we found k = 3.5 × 1014 exp(-33 kcal/RT) mol-1 cm3 s-1. In three sets of experiments in which H atoms reacted with C2D2 to produce D atoms, we obtained values of k∞ for the reaction H + C2H2 → C2H3 of 8 × 1011, 1.2 × 1012, and 3.4 × 1012 mol-1 cm3 s-1 in the temperature range 1200-1900 K, with no clearly visible temperature dependence. All of the experimental values lie 3-10 times lower than those deduced from earlier work at high temperatures or based on ab initio calculations for the vinyl radical.
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