Rate coefficients for cycloalkyl + O reactions and product branching in the decomposition of chemically activated cycloalkoxy radicals: an experimental and theoretical study

Literature Information

Publication Date 2010-06-03
DOI 10.1039/B925920A
Impact Factor 3.676
Authors

Karlheinz Hoyermann, Sven Maarfeld, Frank Nacke, Jörg Nothdurft, Matthias Olzmann, Jens Wehmeyer, Oliver Welz, Thomas Zeuch


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Abstract

The kinetics of cycloalkyl + O reactions were studied with respect to their rate coefficients and the product branching ratios from the decomposition of the chemically activated cycloalkoxy radicals. Rate coefficients for the reactions of cyclohexyl (c-C6H11), cycloheptyl (c-C7H13) and cyclooctyl (c-C8H15) radicals with oxygen atoms were determined with an experimental setup consisting of a discharge flow reactor with molecular beam sampling and REMPI/TOF-MS detection. The following rate coefficients were obtained (units: cm3/mol−1 s−1): k(c-C6H11 + O) = (1.33 ± 0.24) × 1014(T/298 K)0.11 (T = 250–600 K), k(c-C7H13 + O) = (1.85 ± 0.25) × 1014 (T = 298 K), k(c-C8H15 + O) = (1.56 ± 0.20) × 1014(T/298 K)0.66±0.15 (T = 268–363 K). Stable products were determined by quantitative FTIR spectroscopy. The decomposition of the cycloalkoxy radicals leads besides β-C–H bond fission (yields: 24% for c-C6H11O, 20–25% for c-C8H15O) mainly to alkyl radicals by ring-opening via β-C–C bond cleavage. These open-chain alkyl radicals further decompose mainly by β-C–C bond scission. An increase of the total pressure from 4 mbar to 1 bar had no effect on the product distribution for the reaction c-C6H11 + O, whereas for the reaction c-C8H15 + O further decomposition of the ring-opening product is significantly suppressed at 1 bar. The experimental results on the channel branching and its pressure dependence were rationalized with the statistical rate theory. A comparison of the experimental and modeling results indicates a significant influence of hindered internal rotations (HIRs) on the reactions of the ring-opening products. The harmonic approximation to describe these modes was shown to be inadequate, while a treatment as one-dimensional HIRs led to a significantly improved agreement between experimental and modeling results. Implications of our findings for the formation of secondary organic aerosol and high-temperature combustion are discussed.

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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