Density Functional Theory Calculations on Copper-Mediated Peroxide Decomposition Reactions: Implications for Jet Fuel Autoxidation

Research output: Contribution to journalArticlepeer-review

Authors

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

Colleges, School and Institutes

External organisations

  • University of Sheffield
  • Department of Mechanical Engineering

Abstract

The presence of metal impurities in jet fuel can lead to a reduction in the thermal stability of the fuel. Density functional theory (DFT) calculations are reported on the reactions of hydroperoxides with both bare Cu(I) ions and Cu(naphthenate). The reaction of Cu(naphthenate) and cumene hydroperoxide forms one product complex. The release of alkoxy radicals (RO - ) from the product complex is energetically feasible. This provides a low-energy route to radical formation when compared to hydroperoxide fission. The reaction mechanisms reported here for the copper-catalyzed hydroperoxide decomposition can be used to improve current chemical kinetic models for fuel autoxidation.

Bibliographic note

Funding Information: The work described in this paper was funded by the EU Clean Sky 2 programme FINCAP (Fuel INjector Coking and Autoxidation Prediction), grant number 755606. Publisher Copyright: Copyright © 2020 American Chemical Society. Copyright: Copyright 2020 Elsevier B.V., All rights reserved.

Details

Original languageEnglish
Pages (from-to)7439-7447
Number of pages9
JournalEnergy and Fuels
Volume34
Issue number6
Publication statusPublished - 18 Jun 2020