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Improved Shock Tube Measurement of the CH4 + Ar = CH3 + H + Ar Rate Constant using UV Cavity-Enhanced Absorption Spectroscopy of CH3

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High Temperature Gasdynamics Laboratory, Mechanical Engineering, Stanford University, California 94305, United States
*E-mail: [email protected]. Phone: +1-(650)-725-2072. Fax: +1-(650)-723-1748.
Cite this: J. Phys. Chem. A 2016, 120, 28, 5427–5434
Publication Date (Web):July 5, 2016
https://doi.org/10.1021/acs.jpca.6b02572
Copyright © 2016 American Chemical Society
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    Abstract

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    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 × 1016 exp(−42 200 K/T) cm3/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.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpca.6b02572.

    • Details on the optimization of the k1 falloff rate expression

    • Table of the intermediate falloff data of k1 selected as optimization targets

    • Optimal solution of A0, E0, and A∞ and corresponding uncertainty analysis

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