| Abstract
| - We report the study of the isomeric selective OH-initiated oxidation of 1,3-butadiene in the presence of O2and NO using the LP/LIF technique. The photolysis of monodeuterated 1-iodo-3-buten-2-ol provides onlyone of the possible OD-butadiene adducts, the minor addition channel product, simplifying the oxidationmechanism. We find, based on analysis of OD time-dependent traces that prompt rearrangement of initialβ-hydroxyalkyl radicals to α-hydroxyalkyl radicals occurs in agreement with RRKM/ME theoretical predictions.We report a rate constant of (3.3±1.0) × 10-11 cm3 molecules-1 s-1 for deuterium abstraction from theα-hydroxyalkyl radical at 298 ±2 K. Our approach demonstrates the feasibility of isomeric selective kineticstudies of the OH-initiated oxidation of unsaturated hydrocarbons.
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