Computational studies on the reactions of thiols, sulfides and disulfides with hydroperoxides. Relevance for jet fuel autoxidation. (15th May 2022)

• Record Type: Journal Article
• Authors: Parks, Christopher M.; Meijer, Anthony J.H.M.; Blakey, Simon G.; Alborzi, Ehsan; Pourkashanian, Mohamed
• Is Part Of: Fuel. Volume 316(2022)
• Publication Date: 2022-05-15
• Subjects: DFT -- Fuel autoxidation -- Sulfur oxidation -- Reaction mechanisms; Fuel -- Periodicals; Coal -- Periodicals; Coal; Fuel; Periodicals; 662.6
• DOI: 10.1016/j.fuel.2022.123326
• Languages: English
• ISSNs: 0016-2361

Abstract

Graphical abstract: Highlights: DFT studies on hydroperoxide oxidation of sulfur species. Mechanistic pathways were modelled and interpreted. Pathways modelled here provide a substantial library for the improvement of current chemical kinetic models. Abstract: Density Functional Theory calculations (DFT) are reported on the reactions of hydroperoxides with different classes of sulfur: thiols (RSH), sulfides (RSR) and disulfides (RSSR), all of which are important trace species in the auto-oxidation of jet fuel. It is shown that thiols can react under auto-oxidation conditions with hydroperoxides to form sulfonic acids and alcohols. In contrast, it is shown that disulfide species are more likely to form thiyl radicals, which are less likely to be important for the direct autoxidation of fuels due to prohibitive reaction barriers. The reaction mechanisms reported here for sulfur oxidation and the associated calculated thermodynamic data can be used to extend the applicability of current chemical kinetic models for fuel autoxidation, which are currently treated as a single elementary reaction despite the range of sulfur species found in fuels.