Competing Channels in the Propene + OH Reaction: Experiment and Validated Modeling over a Broad Temperature and Pressure Range

Claudia Kappler 1 , 1 , Judit Zádor, Oliver Welz 2 , 2 , Ravi X. Fernandez 3 , 3 , Matthias Olzmann 4 , 4  and Craig A. Taatjes 5 , 5
  • 1  Karlsruher Institut für Technologie (KIT), Institut für Physikalische Chemie, Karlsruhe, Deutschland
  • 2  Sandia National Laboratories, Combustion Research Facility, Livermore, CA 94551-0969, U.S.A.
  • 3  RWTH Aachen, Physico-Chemical Fundamentals of Combustion, Aachen, Deutschland
  • 4  Karlsruher Institut für Technologie (KIT), Institut für Physikalische Chemie, Karlsruhe, Deutschland
  • 5  Sandia National Laboratories, Combustion Research Facility, Livermore, CA 94551-0969, U.S.A.

Abstract

Although the propene + OH reaction has been in the center of interest of numerous experimental and theoretical studies, rate coefficients have never been determined experimentally between 600 and ∼750 K, where the reaction is governed by the complex interaction of addition, back-dissociation and abstraction. In this work OH time-profiles are measured in two independent laboratories over a wide temperature region (200–950 K) and are analyzed incorporating recent theoretical results. The datasets are consistent both with each other and with the calculated rate coefficients. We present a simplified set of reactions validated over a broad temperature and pressure range, that can be used in smaller combustion models for propene + OH. In addition, the experimentally observed kinetic isotope effect for the abstraction is rationalized using ab initio calculations and variational transition-state theory. We recommend the following approximate description of the OH + C3H6 reaction

C3H6 + OH ⇆ C3H6OH (R1a,R-1a)

C3H6 + OH → C3H5 + H2O (R1b)

k1a (200 K ≤ T ≤ 950 K; 1 bar ≤ P) = 1.45 × 10-11 (T/K)-0.18e460 K/T cm3 molecule-1 s-1

k-1a (200 K ≤ T ≤ 950 K; 1 bar ≤ P) = 5.74 × 1012e-12690 K/T s-1

k1b (200 K ≤ T ≤ 950 K) = 1.63 × 10-18 (T/K)2.36e-725 K/T cm3 molecule-1 s-1

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Founded in 1887, the Zeitschrift für Physikalische Chemie covers the main developments in physical chemistry, placing with an emphasis on experimental research. It represents a combination ofdiscusses reaction kinetics and spectroscopy, surface research and electrochemistry, thermodynamics and the structure analysis of matter in its various conditions, among other topics.

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