Synthesis of Methanesulfonic Acid Directly from Methane: The Cation Mechanism or the Radical Mechanism?
- 9 July 2021
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Physical Chemistry Letters
- Vol. 12 (28), 6486-6491
- https://doi.org/10.1021/acs.jpclett.1c01619
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.Funding Information
- National Natural Science Foundation of China (21877025, 21903018)
- U. S. National Science Foundation (CHE-1661604 and CHE-2134792)
- Sichuan Provincial Foundation for Distinguished Young Leaders of Disciplines in Science and Technology of China (2019JDJQ0051)
- Chunhui Program of the Ministry of Education of China (Z2017091)
- Natural Science Foundation of Hebei Province of China (B2019201128)
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