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The OH-Initiated Oxidation of 1,3-Butadiene in the Presence of O₂ and NO: A Photolytic Route To Study Isomeric Selective Reactivity

Erin E. Greenwald,^† Jiho Park,^† Katie C. Anderson,^† Hahkjoon Kim,^† B. Jesse E. Reich,^† Stephen A. Miller,^† Renyi Zhang,^‡ and Simon W. North*^†

Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station, Texas 77842, and Department of Atmospheric Sciences, Texas A&M University, College Station, Texas 77842

J. Phys. Chem. A, 2005, 109 (35), pp 7915–7922

DOI: 10.1021/jp051545o

Publication Date (Web): August 13, 2005

†

Department of Chemistry.

‡

Department of Atmospheric Sciences.

Address correspondence to this author.

Abstract

We report the study of the isomeric selective OH-initiated oxidation of 1,3-butadiene in the presence of O₂ and NO using the LP/LIF technique. The photolysis of monodeuterated 1-iodo-3-buten-2-ol provides only one of the possible OD-butadiene adducts, the minor addition channel product, simplifying the oxidation mechanism. We find, based on analysis of OD time-dependent traces that prompt rearrangement of initial β-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 the α-hydroxyalkyl radical at 298 ±2 K. Our approach demonstrates the feasibility of isomeric selective kinetic studies of the OH-initiated oxidation of unsaturated hydrocarbons.

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