Shock tube studies on the high temperature chemical kinetics of allyl radicals:: reactions with C2H2, CH4, H2 and C3H5 at 1000-1400 K

Rate constants of various allyl radical reactions have been measured at combustion relevant temperatures of 1000 to 1400 K. Time resolved absorption spectroscopy was used under reflected shock wave conditions in highly diluted mixtures of the reagents in argon. Studies on the thermal dissociation of 1,5-hexadiene as a precursor reaction of allyl radicals showed pressure dependence between 0.35 and 14bar with temperature dependent approach of the high pressure limit. Very weak temperature dependence for the C3H5 + C3H5 combination is established and thermal dissoziations rates of allyl itself were measured above 1170 K. Experimental rate constant for the C3H5 + H-2 and C3H5 + CH4 abstraction reactions are reported first time. The important reaction of allyl with acetylene was now measured directly in a combustion relevant temperature range, 1060-1320 K, resulting in k = 10((13.6 +/- 6.5)) exp [-(90 +/- 10) kJmol(-1)/RT] cm(3) Mol(-1) s(-1). Branching between two product channels occurs with 95% towards C5H6 + H. Absolute high temperature UV absorption spectra are reported for allyl and cyclopentadiene.