A Combined Experimental and Theoretical Study of the Reaction OH + 2-Butene in the 400-800 K Temperature Range.

Abstract

We report a combined experimental and theoretical study of the OH + cis-2-butene and OH + trans-2-butene reactions at combustion-relevant conditions: pressures of 1-20 bar and temperatures of 400-800 K. We probe the OH radical time histories by laser-induced fluorescence and analyze these experimental measurements with aid from time-dependent master-equation calculations. Importantly, our investigation covers a temperature range where experimental data on OH + alkene chemistry in general are lacking, and interpretation of such data is challenging due to the complexity of the competing reaction pathways. Guided by theory, we unravel this complex behavior and determine the temperature- and pressure-dependent rate coefficients for the three most important OH + 2-butene reaction channels at our conditions: H abstraction, OH addition to the double bond, and back-dissociation of the OH-butene adduct.