Elucidating NO coupling effects on ignition of toluene reference fuels by chemical functional group analysis

Abstract

Derived cetane number (DCN), Research and Motor Octane Numbers (RON and MON) have been fundamentally analyzed using Quantitative Structure-Property Relationship (QSPR) regression models with key chemical functional groups. Both RON and MON exhibit strong sensitivities to the abundances of (CH2)n and benzyl-type groups but lack sensitivity to the CH3 group, most dominant in real gasolines. Residual and EGR gases contain NOx known to synergize with fuel autoignition chemistry. Two TRF mixtures having high and low aromatic content but sharing the same RON and MON values were used to evaluate NOx coupling effects. DCN measurements with NO addition were found to be strongly correlated with the abundance of the (CH2)n group. Similar experiments of 200 ppm NO in a Rapid Compression Machine show promotion (inhibition) of ignition for the high (low) aromatic TRF fuel. Kinetic modeling attributes the promotion to the NONO2 interconversion reactions, NO + HO2 = NO2 + OH, CH3 + NO2 = CH3O + NO and NO2 + H = NO + OH. The inhibitive effect relates specifically to low temperature kinetics and high NO loading conditions, leading to the formation of meta-stable species (e.g. CH3 + NO2 (+M) = CH3NO2 (+M)) that decelerate the rate of conversion of HO2 to more reactive OH radicals. The coupling of NO with real gasolines depends on chemical composition and temperature conditions not only encompassed by RON and MON criteria, but by the chemical functional group characteristics. The relevance of this finding to the significance of preferential vaporization of multi-component gasolines on low-speed pre-ignition (LSPI) is discussed. Within the context of chemical functional group distributions of five distillation cuts of a marketed ethanol-free gasoline determined by NMR spectroscopy, the analyses identify considerable variations of key functionalities with fuel distillation properties, indicating chemical kinetic autoignition behaviors that are dependent on preferential vaporization.