Journal of Physical Chemistry, Vol.98, No.28, 7029-7035, 1994
Rate-Constant Measurement of the Recombination Reaction C3H3+c3H3
Using the technique of infrared kinetic absorption spectroscopy, the second-order rate constant for the recombination reaction of the propargyl radical (C3H3 + C3H3) has been measured and found to have the value (1.2 +/- 0.2) x 10(-10) cm(3) molecule(-1) s(-1) at 295 K. The radical was produced in a flow cell by excimer laser flash photolysis (h = 193 nm) of the precursors C3H3Cl or C3H3Br and detected using time-resolved IR absorption. Absolute concentrations of C3H3 were determined by comparing the C3H3 absorption intensity with that of the Br atom. This calibration scheme was checked by producing methyl radicals by photolysis of methyl bromide and comparing the rate constant for methyl recombination thus obtained with literature values. The quantum yield for HCl production from the photodissociation of C3H3CI at 193 nm was determined to be 0.07 +/- 0.01.
Keywords:COLOR CENTER LASER;REACTION CH3+CH3-)C2H6;RADICAL REACTIONS;SPECTROSCOPY;PYROLYSIS;CHEMISTRY;BENZENE;DECOMPOSITION;TEMPERATURES;TRANSITION