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

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

doi:10.1021/acs.energyfuels.0c00918

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

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

^*Corresponding author for this work

Mechanical Engineering

Research output: Contribution to journal › Article › peer-review

1 Citation (Scopus)

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.

Original language	English
Pages (from-to)	7439-7447
Number of pages	9
Journal	Energy and Fuels
Volume	34
Issue number	6
DOIs	https://doi.org/10.1021/acs.energyfuels.0c00918
Publication status	Published - 18 Jun 2020

Bibliographical 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.

ASJC Scopus subject areas

Chemical Engineering(all)
Fuel Technology
Energy Engineering and Power Technology

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10.1021/acs.energyfuels.0c00918

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

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. ",

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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 {\textcopyright} 2020 American Chemical Society. Copyright: Copyright 2020 Elsevier B.V., All rights reserved.",

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AU - Meijer, Anthony J.H.M.

AU - Pourkashanian, Mohamed

N1 - 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.

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N2 - 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.

AB - 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.

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

Abstract

Bibliographical note

ASJC Scopus subject areas

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