Kinetic Study of the Oxidation of Stabilized and the Chemically Activated Secondary Ethyl Radical of Methyl Ethyl Sulfide (CH3SCH•CH3)| Chapter 3 | Progress in Chemical Science Research Vol. 4

 The reaction between activated CH3S CH•CH3 and molecular oxygen is investigated using the quantum Rice-Ramsperger-Kassel (QRRK) theory to account for future reactions, collisions, and deactivation. Hydroxyl radicals initiate the oxidation of methyl ethyl sulphide (CH3SCH2CH3) and MES during combustion (methylthioethane). Finding stable and unstable byproducts of the oxidation of the activated secondary radical of methyl ethyl sulphide is the goal.

Using the CBS-QB3 and G3MP2B3 composite and M062X/6-311+G(2d, p) DFT techniques, the thermochemical properties of reactants, products, and transition states were examined. The calculations for kinetic and thermochemical parameters use these thermochemical properties. The thermochemical characteristics of products, reactants, and transition states that were determined using the CBS-QB3 calculation method are used to determine kinetic parameters. It has been discovered that the reaction of CH3SCH•CH3 and O2 produces an energised peroxy adduct, CH3SCH(OO•)CH3, with a calculated well depth of 30.2 kcal/mol at the CBS-QB3 level of theory. Under conditions of high pressure and low temperature, isomerization and stabilisation of the CH3SCH(OO•)CH3 adduct are significant, whereas under conditions of atmospheric pressure and temperatures between above 600 and 800 K, Temperatures below 500 K are found to be crucial for the stabilisation of the CH3SCH(OO•)CH3 adduct, while temperatures between 500 and 900 K are ideal for the intramolecular hydrogen shift and isomerization of the CH3SCH(OO•)CH3 adduct, and temperatures above 800 K are crucial for all subsequent reaction pathways. It is recommended that the temperature should be between 600 and 800 K for this oxidation reaction to occur under pressures of 1-4 atm. A novel mechanism for the CH3SCH(OO•)CH3 adduct is seen, with the peroxyl oxygen radical binding to sulphur causing the creation of oxygen-sulfur and oxygen-carbon double bonds.

Author(s) Details:

Guanghui Song,
Department of Chemical, Biological and Pharmaceutical Engineering, New Jersey Institute of Technology, University Heights, Newark, NJ-07102, USA.

Joseph W. Bozzelli,
Department of Chemical, Biological and Pharmaceutical Engineering, New Jersey Institute of Technology, University Heights, Newark, NJ-07102, USA.

Hebah Abdel-Wahab,
Department of Chemical, Biological and Pharmaceutical Engineering, New Jersey Institute of Technology, University Heights, Newark, NJ-07102, USA.

Tamara Gund,
Department of Chemical, Biological and Pharmaceutical Engineering, New Jersey Institute of Technology, University Heights, Newark, NJ-07102, USA.

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