New insights into fuel blending effects: Intermolecular chemical kinetic interactions affecting autoignition times and intermediate-temperature heat release

Song Cheng, S. Scott Goldsborough, Chiara Saggese, Scott W. Wagnon, William J. Pitz

Research output: Journal article publicationJournal articleAcademic researchpeer-review

9 Citations (Scopus)


Fuel blending effects on chemically-dominated fuel properties, such as gasoline anti-knock quality, are influenced by fundamental chemical kinetic interactions between the blending agent and the base fuel. Historically, quantification of such interactions has focused on direct changes to the radical pool, including ȮH and HO2, while intermolecular chemical kinetic interactions pertaining to carbon-containing, non-fuel-specific intermediates are typically overlooked. In this regard, this work aims to derive new insight into intermolecular chemical kinetic interactions that are intrinsic to fuel blending effects, via a case study on blends of 0–30% ethanol (by volume) into FGF-LLNL (a multi-component gasoline surrogate for FACE-F research gasoline) using a rapid compression machine at a diluted/stoichiometric fuel loading, compressed pressure of 40 bar and low- to intermediate-temperature regimes that are representative of boosted SI engine operation. Ethanol blending effects on the intermediate temperature heat release (ITHR) of FGF-LLNL are characterized using experimental measurements, where ethanol is found to promote the extent of ITHR and suppress the transition from ITHR to main ignition. Chemical kinetic modeling is undertaken using recently updated gasoline surrogate and alcohol models. Sensitivity analyses on ITHR characteristics further corroborate the ethanol blending effects, and highlight the significant dependence of ITHR on both fuel-specific and non-fuel-specific reactions. An approach allowing comprehensive characterization of the complex intermolecular chemical kinetic interactions between constituents in a fuel blend is then proposed. Application of the approach to FGF-LLNL/E0–E30 reveals that ethanol perturbs the heat release and autoignition characteristics of FGF-LLNL not only by directly changing the ȮH and HO2 radical pools via fuel-specific reactions, but also indirectly through intermolecular interactions where participating intermediates can be produced and consumed by various sub-chemistries. Disabling the intermolecular interactions in carbon-containing species between ethanol and FGF-LLNL sub-chemistries leads to somewhat slower ITHR evolution and lower ignition reactivity. The role of the individual intermolecular interaction is also characterized using the proposed approach. Finally, implications of intermolecular interactions for future studies that aim to improve model performance are highlighted, where it is found that further investigations on the acetaldehyde sub-model and FGF-LLNL/ethanol interactive chemical reactions (e.g., FGF-LLNL+CH3O2 and RO2+ethanol) are needed for chemistry models to accurately predict fuel blending behavior.

Original languageEnglish
Article number111559
JournalCombustion and Flame
Publication statusPublished - Nov 2021
Externally publishedYes


  • Autoignition
  • Fuel blending effects
  • Intermediate temperature heat release
  • Intermolecular chemical kinetic interactions
  • Simulated molecular tagging

ASJC Scopus subject areas

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


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