Kinetic study of reaction C2H5 + HO2 in a photolysis reactor with time-resolved Faraday rotation spectroscopy

Zhong, Hongtao; Yan, Chao; Teng, Chu C.; Ma, Guoming; Wysocki, Gerard; Ju, Yiguang

doi:10.1016/j.proci.2020.07.095

Kinetic study of reaction C₂H₅ + HO₂ in a photolysis reactor with time-resolved Faraday rotation spectroscopy

Journal Article · Wed Oct 14 00:00:00 EDT 2020 · Proceedings of the Combustion Institute

DOI:https://doi.org/10.1016/j.proci.2020.07.095· OSTI ID:1906176

Zhong, Hongtao ^[1]; ^[2]; Teng, Chu C. ^[2]; ^[2]; Wysocki, Gerard ^[2]; Ju, Yiguang ^[2]

Princeton Univ., NJ (United States); Princeton University
Princeton Univ., NJ (United States)

The rate constant and branching ratios of ethyl reaction with hydroperoxyl radical, C₂H₅ + HO₂ (1), a key radical-radical reaction for intermediate temperature combustion chemistry, were measured in situ for the first time in a photolysis Herriott cell by using mid-IR Faraday rotation spectroscopy (FRS) and UV-IR direct absorption spectroscopy (DAS). The microsecond time-resolved diagnostic technique in this work enabled the direct rate measurements of the target reaction at 40 and 80 mbar and reduced the experimental uncertainty considerably. C₂H₅ and HO₂ radicals were generated by the photolysis of (COCl)₂/C₂H₅I/CH₃OH/O₂/He mixture at 266 nm. By direct measurements of the transient profiles of C₂H₅, HO₂ and OH concentrations, the overall rate constant for this reaction at 297 K was determined as k₁(40 mbar) = (3.8 ± 0.8) × 10^–11 cm³ molecule^–1 s^–1 and k₁(80 mbar) = (4.1 ± 1.0) × 10^–11 cm³ molecule^–1 s^–1. As a result, the direct observation of hydroxyl radical (OH) indicated that OH formation channel was the major channel with a branching ratio of 0.8 ± 0.1.

View Accepted Manuscript (DOE)

Research Organization:: Princeton Univ., NJ (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Fusion Energy Sciences (FES); National Science Foundation (NSF)

Grant/Contract Number:: SC0020233

OSTI ID:: 1906176

Alternate ID(s):: OSTI ID: 1777052

Journal Information:: Proceedings of the Combustion Institute, Journal Name: Proceedings of the Combustion Institute Journal Issue: 1 Vol. 38; ISSN 1540-7489

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemical kinetics
Faraday rotation spectroscopy
Hydroperoxyl radical
Radical-radical reaction
Rate constant

Kinetic study of reaction C2H5 + HO2 in a photolysis reactor with time-resolved Faraday rotation spectroscopy

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Kinetic study of reaction C₂H₅ + HO₂ in a photolysis reactor with time-resolved Faraday rotation spectroscopy