Reflected shock tube studies of high-temperature rate constants for OH + C2H2 and OH + C2H4

The reflected shock tube technique with multi-pass absorption spectrometric detection of OH-radicals at 308 nm (corresponding to a total path length of approximately 4.9 m) has been used to study the reactions, OH + C(2)H(2)--> products (1) and OH + C(2)H(4)--> C(2)H(3) + H(2)O (2). The present optical configuration gives a S/N ratio of approximately 1 at approximately 0.5-1.0 x 10(12) radicals cm(-3). Hence, kinetics experiments could be performed at [OH](0) = approximately 4-20 ppm thereby minimizing secondary reactions. OH was produced rapidly from the dissociations of either CH(3)OH or NH(2)OH (hydroxylamine). A mechanism was then used to obtain profile fits that agreed with the experiment to within <+/-5%. The derived Arrhenius expressions, in units of cm(3) molecule(-1) s(-1) are: k(1) = (1.03 +/- 0.24) x 10(-10) exp(-7212 +/- 417 K/T) for 1509-2362 K and k(2) = (10.2 +/- 5.8) x 10(-10) exp(-7411 +/- 871 K/T) for 1463-1931 K. The present study is the first ever direct measurement for reaction (1) at temperatures >1275 K while the present results extend the temperature range for (2) by approximately 700 K. These values are compared with earlier determinations and with recent theoretical calculations. The calculations agree with the present data for both reactions to within +/-10% over the entire T-range.