Computational studies on the reactions of thiols, sulfides and disulfides with hydroperoxides. Relevance for jet fuel autoxidation

Christopher M. Parks, Anthony J.H.M. Meijer, Simon G. Blakey, Ehsan Alborzi, Mohamed Pourkashanian

Research output: Contribution to journalArticlepeer-review

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.

Original languageEnglish
Article number123326
Number of pages13
JournalFuel
Volume316
Early online date22 Jan 2022
DOIs
Publication statusPublished - 15 May 2022

Bibliographical note

Funding Information:
The research presented in this paper has been performed in the framework of the JETSCREEN project (JETfuel SCREENING and optimization) and has received funding from the European Union Horizon 2020 Programme under grant agreement n◦ 723525. The authors declare no competing financial interest.

Keywords

  • DFT
  • Fuel autoxidation
  • Reaction mechanisms
  • Sulfur oxidation

ASJC Scopus subject areas

  • Chemical Engineering(all)
  • Fuel Technology
  • Energy Engineering and Power Technology
  • Organic Chemistry

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