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• W2471620072 abstract "We report an improved measurement for the rate constant of methane dissociation in argon (CH4 + Ar = CH3 + H + Ar) behind reflected shock waves. The experiment was conducted using a sub-parts per million sensitivity CH3 diagnostic recently developed in our laboratory based on ultraviolet cavity-enhanced absorption spectroscopy. The high sensitivity of this diagnostic allowed for measurements of quantitatively resolved CH3 time histories during the initial stage of CH4 pyrolysis, where the reaction system is clean and free from influences of secondary reactions and temperature change. This high sensitivity also allowed extension of our measurement range to much lower temperatures (<1500 K). The current-reflected shock measurements were performed at temperatures between 1487 and 1866 K and pressures near 1.7 atm, resulting in the following Arrhenius rate constant expression for the title reaction: k(1.7 atm) = 3.7 × 10(16) exp(-42 200 K/T) cm(3)/mol·s, with a 2σ uncertainty factor of 1.25. The current data are in good consensus with various theoretical and review studies, but at the low temperature end they suggest a slightly higher (up to 35%) rate constant compared to these previous results. A re-evaluation of previous and current experimental data in the falloff region was also performed, yielding updated expressions for both the low-pressure limit and the high-pressure limit rate constants and improved agreement with all existing data." @default.
• W2471620072 created "2016-07-22" @default.
• W2471620072 creator A5039442806 @default.
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• W2471620072 date "2016-07-12" @default.
• W2471620072 modified "2023-09-29" @default.
• W2471620072 title "Improved Shock Tube Measurement of the CH₄ + Ar = CH₃ + H + Ar Rate Constant using UV Cavity-Enhanced Absorption Spectroscopy of CH₃" @default.
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• W2471620072 doi "https://doi.org/10.1021/acs.jpca.6b02572" @default.
• W2471620072 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/27380878" @default.
• W2471620072 hasPublicationYear "2016" @default.
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