The reaction of CH, + C1, produces predominantly CH3CI + HCI, which above 1200 K goes to olefins, aromatics, and HCI. Results obtained in laboratory experiments and detailed modeling of the chlorine-catalyzed polymerization of methane a t 1260 and 1310 K are presented. The reaction can be separated into two stages, the chlorination of methane and pyrolysis of methylchloride.
Previously measured rates of hydrogenolysis of propylene, toluene, and xylene fit −d[RCH3]/dt=10(11.5±1)−(55±3)/θ[RCH3][H2]1/2 mole liter−1·sec−1 (where θ is 2.3RT kcal mole−1) over an unusually wide range of conditions. In the case of toluene, for example, the range is 107 in rate, 105 in hydrogen pressure, and 500°C in temperature. We propose the mechanism H2⇄2H,H+RCH3⇄RH+CH3,CH3+H2⇄CH4+H,giving −d[RCH3]/dt=K11/2k2[RCH3][H2]1/2. Substitution of values for K1 and k2 gives rate constants and Arrhenius parameters in excellent agreement with all reliable data.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.