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An Experimental and Kinetic Modeling Study of the Reaction of CHF3 with Methane

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journal contribution
posted on 15.09.2006, 00:00 by Hai Yu, Eric M. Kennedy, John C. Mackie, Bogdan Z. Dlugogorski
The gas-phase reaction of CHF3 with CH4 has been studied experimentally and computationally. The motivation behind the study is that reaction of CHF3 with CH4 provides a possible route for synthesis of CH2CF2 (C2H2F2). Experiments are carried out in a plug flow, isothermal α-alumina reactor at atmospheric pressure over the temperature range of 973−1173 K. To assist in understanding the reaction mechanism and the role of the reactor material involved in the reaction of CHF3 with CH4, the reaction of CHF3 with CH4, pyrolysis of CH4, and pyrolysis of CHClF2 have been studied in the presence of α-alumina or α-AlF3 particles under various conditions. Under all conditions studied for the reaction of CHF3 and CH4, the major products are C2F4, C2H2F2, and HF. Minor products include C2H2, C2H4, C2H3F, C2HF3, C3F6, CO2, and H2. C2H6, CH2F2, and CHF2CHF2 are detected in trace amounts. The initial step is the gas-phase unimolecular decomposition of CHF3, producing CF2 and HF. It is proposed that CF2 decomposes on the surface of α-alumina, producing F radicals that are responsible for the activation of CH4. A reaction scheme developed on the basis of the existing NIST HFC and GRI-Mech 3.0 mechanisms is used to model the reaction of CHF3 with CH4. Generally satisfactory agreement between experimental and modeling results is obtained on the conversion levels of CHF3 and CH4 and rates of formation of major products. Using the software package AURORA, the reaction pathways leading to the formation of major products are elucidated.