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Synthesis of Methanesulfonic Acid Directly from Methane: The Cation Mechanism or the Radical Mechanism?
Huidong Li1, Yucheng Hu1, Longfei Li2
1School of Science, Key Laboratory of High Performance Scientific Computation, Xihua University, Chengdu, 610039, P. R. China.
Abstract:
In 2019, Diaz-Urrutia and Ott developed a high-yield method for direct conversion of methane to methanesulfonic acid and proposed a cationic chain reaction mechanism. However, Roytman and Singleton questioned this mechanism, and they favored a free-radical mechanism. In the present paper, we studied both the cationic chain and radical mechanisms and found the radical mechanism is more favorable, since it has a much lower energy barrier. However, the radical mechanism has not considered the effect of ions for the reaction taking place in oleum. Thus, we studied a simple model of a protonated radical mechanism, which further lowers the energy barrier. Although the true mechanism for the CH4 + SO3 reaction could be more complicated in electrolyte solutions, this model should be helpful for the further study of the mechanism of this reaction.
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