Design and evaluation of surrogate mixtures for diesel based on the isolated droplet configuration

The development of simplified surrogate mixtures able to replicate combustion-related behaviors of chemically complex fuels is essential for their simulation with computational tools, a key step towards the design of high-efficiency and low-emission combustion applications. This work proposes to use the isolated droplet configuration as a benchmark to formulate and validate surrogates that capture the vaporization and soot production characteristics of a first-fill diesel and a diesel-biodiesel mixture. To that end, droplet vaporization experiments and a multicomponent model were coupled to produce blends matching the evaporation behavior, whereas the soot tendency was incorporated through tests at the ASTM D1322 smoke point lamp and the Oxygen Extended Sooting Index (OESI). The so-obtained surrogate blends were subsequently validated for both characteristics. Their evaporation curves proved to match remarkably well those obtained for the target fuels, with noticeable improvements when increasing the number of compounds in the mixture. As for the sooting behavior, the proposed blends achieved a good emulation in terms of the design parameter (OESI), confirming the validity of the proposed methodology. On the other hand, an additional and independent validation of the sooting propensity through the quantification of the mass of soot produced by isolated droplets under a high-temperature and reducing atmosphere revealed significantly higher soot yields for the surrogates when compared to the target fuels. These results highlight the relevance of the configuration used when designing and validating surrogates, since the same blends can provide substantial differences when evaluated through different sooting indices.     

Coupling of turbulence on the ignition of multicomponent sprays

This study examines the effect of turbulence on the ignition of multicomponent surrogate fuels and its role in modifying preferential evaporation in multiphase turbulent spray environments. To this end, two zero-dimensional droplet models are considered that are representative of asymptotic conditions of diffusion limit and the distillation limit are considered. The coupling between diffusion, evaporation and combustion is first identified using a scale analysis of 0D homogeneous batch reactor simulations. Subsequently, direct numerical simulations of homogeneously dispersed multicomponent droplets are performed for both droplet models, in decaying isotropic turbulence and at quiescent conditions to examine competing time scale effects arising from evaporation, ignition and turbulence. Results related to intra-droplet transport and effects of turbulence on autoignition and overall combustion are studied using an aviation fuel surrogate. Depending on the characteristic scale, it is shown that turbulence can couple through modulation of evaporation time or defer the ignition phase as a result of droplet cooling or gas-phase homogenization. Both preferential evaporation and turbulence are found to modify the ignition delay time, up to a factor of two. More importantly, identical droplet ignition behavior in homogeneous gas phase can imply fundamentally different combustion modes in heterogeneous environments.     

Evaluating a novel gasoline surrogate containing isopentane using a rapid compression machine and an engine

Simple surrogate formulations for gasoline are useful for modelling purposes and for comparing experimental results using a carefully designed fuel. Simple three-component surrogates based on primary reference fuels (PRF) and Toluene (TPRF) are frequently used to match the antiknock properties of actual gasoline fuels through the RON and MON. However, using PRF or TPRFs to test or to calibrate gasoline engines is still challenging, with the main difficulty being the capabilities of PRF fuels to match the physical properties of the road fuel such density, volatility (DVPE) and the distillation curve. To overcome such issues, an alternative to TPRF is presented in this work with a focus on premium fuel (RON98 EN228). This alternative consists of replacing some or all of isooctane by isopentane. In the event of total replacement, a three-component “THIP” (Toluene, Heptane, IsoPentane) surrogate fuel is produced. The physical and combustion properties of isopentane makes it easier to create surrogates that can match the DVPE, RON, MON and distillation characteristics of a real fuel. Furthermore, the use of isopentane allows the definition of a wider range of surrogate fuel compositions that can replicate the RON and MON of a given fuel. Surrogate formulations were developed at Shell Global Solutions that matched the RON, MON and selected physical properties of a reference premium gasoline (RPG). A Rapid Compression Machine (RCM) in PCFC was used to demonstrate that those surrogates can reproduce the essential autoignition characteristics of the selected RPG. Two mechanisms were used to predict RCM data and showed reasonable agreement, opening some perspective for further investigations. Finally, an engine test performed at Ferrari test facilities demonstrated that simple surrogates containing isopentane can be used to closely match the knock-limited combustion phasing of an RPG. In this paper, it is demonstrated such surrogates have advantages compared to TPRFs in being able to match the properties of a real fuel and that the surrogate approach is consistent with RCM data and engine results.     

Surrogate formulation for diesel and jet fuels using the minimalist functional group (MFG) approach

Surrogate fuels aim to reproduce real fuel combustion characteristics in order to enable predictive simulations and fuel/engine design. In this work, surrogate mixtures were formulated for three diesel fuels (Coryton Euro and Coryton US-2D certification grade and Saudi pump grade) and two jet fuels (POSF 4658 and POSF 4734) using the minimalist functional group (MFG) approach, a method recently developed and tested for gasoline fuels. The diesel and jet fuel surrogates were formulated by matching five important functional groups, while minimizing the surrogate components to two species. Another molecular parameter, called as branching index (BI), which denotes the degree of branching was also used as a matching criterion. The present works aims to test the ability of the MFG surrogate methodology for high molecular weight fuels (e.g., jet and diesel). ¹H Nuclear Magnetic Resonance (NMR) spectroscopy was used to analyze the composition of the groups in diesel fuels, and those in jet fuels were evaluated using the molecular data obtained from published literature. The MFG surrogates were experimentally evaluated in an ignition quality tester (IQT), wherein ignition delay times (IDT) and derived cetane number (DCN) were measured. Physical properties, namely, average molecular weight (AMW) and density, and thermochemical properties, namely, heat of combustion and H/C ratio were also compared. The results show that the MFG surrogates were able to reproduce the combustion properties of the above fuels, and we demonstrate that fewer species in surrogates can be as effective as more complex surrogates. We conclude that the MFG approach can radically simplify the surrogate formulation process, significantly reduce the cost and time associated with the development of chemical kinetic models, and facilitate surrogate testing.     

Combustion characteristics and detailed simulations of surrogates for a Tier II gasoline certification fuel

An experimental and numerical study of combustion of a gasoline certification fuel (‘indolene’), and four (S4) and five (S5) component surrogates for it, is reported for the configurations of an isolated droplet burning with near spherical symmetry in the standard atmosphere, and a single cylinder engine designed for advanced compression ignition of pre-vaporized fuel. The intent was to compare performance of the surrogate for these different combustion configurations and to assess the broader applicability of the kinetic mechanism and property database for the simulations. A kinetic mechanism comprised of 297 species and 16,797 reactions was used in the simulations that included soot formation and evolution, and accounted for unsteady transport, liquid diffusion inside the droplet, radiative heat transfer, and variable properties. The droplet data showed a clear preference for the S5 surrogate in terms of burning rate. The simulations showed generally very good agreement with measured droplet, flame, and soot shell diameters. Measurements of combustion timing, in-cylinder pressure, and mass-averaged gas temperature were also well predicted with a slight preference for the S5 surrogate. Preferential vaporization was not evidenced from the evolution of droplet diameter but was clearly revealed in simulations of the evolution of mixture fractions inside the droplets. The influence of initial droplet diameter (D_o) on droplet burning was strong, with S5 burning rates decreasing with increasing D_o due to increasing radiation losses from the flame. Flame extinction was predicted for D_o =3.0 mm as a radiative loss mechanism but not predicted for smaller D_o for the conditions of the simulations.     

Experimental and kinetic modeling study of combustion of JP-8, its surrogates and reference components in laminar nonpremixed flows

Experimental and numerical studies are carried out to construct reliable surrogates that can reproduce aspects of combustion of JP-8 and Jet-A. Surrogate fuels are defined as mixtures of few hydrocarbon compounds with combustion characteristics similar to those of commercial fuels. The combustion characteristics considered here are extinction and autoignition in laminar non premixed flows. The “reference” fuels used as components for the surrogates of jet fuels are n-decane, n-dodecane, methylcyclohexane, toluene, and o-xylene. Three surrogates are constructed by mixing these components in proportions to their chemical types found in jet fuels. Experiments are conducted in the counterflow system. The fuels tested are the components of the surrogates, the surrogates, and the jet fuels. A fuel stream made up of a mixture of fuel vapors and nitrogen is injected into a mixing layer from one duct of a counterflow burner. Air is injected from the other duct into the same mixing layer. The strain rate at extinction is measured as a function of the mass fraction of fuel in the fuel stream. The temperature of the air at autoignition is measured as a function of the strain rate at a fixed value of the mass fraction of fuel in the fuel stream. The measured values of the critical conditions of extinction and autoignition for the surrogates show that they are slightly more reactive than the jet fuels. Numerical calculations are carried out using a semi-detailed chemical-kinetic mechanism. The calculated values of the critical conditions of extinction and autoignition for the reference fuels and for the surrogates are found to agree well with experimental data. Sensitivity analysis is used to highlight key elementary reactions that influence the critical conditions of autoignition of an alkane fuel and an aromatic fuel.     

Experimental and kinetic modeling study of combustion of JP-8, its surrogates and components in laminar premixed flows

Experimental and kinetic modeling studies are carried out to characterize premixed combustion of jet fuels, their surrogates, and reference components in laminar nonuniform flows. In previous studies, it was established that the Aachen surrogate made up of 80 % n-decane and 20 % trimethylbenzene by weight, and surrogate C made up of 57 % n-dodecane, 21 % methylcyclohexane and 22 % o-xylene by weight, reproduce key aspects of combustion of jet fuels in laminar nonpremixed flows. Here, these surrogates and a jet fuel are tested in premixed, nonuniform flows. The counterflow configuration is employed, and critical conditions of extinction are measured. In addition, the reference components tested are n-heptane, n-decane, n-dodecane, methylcyclohexane, trimethylbenzene, and o-xylene. Measured critical conditions of extinction of the Aachen surrogate and surrogate C are compared with those for the jet fuel. In general the alkanes n-heptane, n-decane, and n-dodecane, and methylcyclohexane are found to be more reactive than the aromatics o-xylene and trimethylbenzene. Flame structure and critical conditions of extinction are predicted for the reference components and the surrogates using a semi-detailed kinetic model. The predicted values are compared with experimental data. Sensitivity analysis shows that the lower reactivity of the aromatic species arises from the formation of resonantly stabilized radicals. These radicals are found to have a scavenging effect. The present study on premixed flows together with previous studies on nonpremixed flows show that the Aachen surrogate and surrogate C reproduce many aspects of premixed and nonpremixed combustion of jet fuels.     

Simulation-driven formulation of transportation fuel surrogates

An alternative way to formulate transportation fuel surrogates using model predictions of gas-phase combustion targets is explored and compared to conventional approaches. Given a selection of individual fuel components, a multi-component chemical mechanism describing their oxidation kinetics, and a database of experimental measurements for key combustion quantities such as ignition delay times and laminar burning velocities, the optimal fractional amount of each fuel is determined as the one yielding the smallest error between experiments and model predictions. Using a previously studied three-component jet fuel surrogate containing n-dodecane, methyl-cyclohexane, and m-xylene as a case study, this article investigates in a systematic manner how the surrogate composition affects model predictions for ignition delay time and laminar burning velocities over a wide range of temperature, pressure and stoichiometry conditions, and compares the results to existing surrogate formulation techniques, providing new insights on how to define surrogates for simulation purposes. Finally, an optimisation algorithm is described to accelerate the identification of optimal surrogate compositions in this context.     

Catalytic ignition and autothermal combustion of JP-8 and its surrogates over a Pt/γ-Al2O3 catalyst

With the aim of utilizing JP-8 fuel for small scale portable power generation systems, catalytic combustion of JP-8 is studied. The surface ignition, extinction and autothermal combustion of JP-8, of a six-component surrogate fuel mixture, and the individual components of the surrogate fuel over a Pt/γ-Al₂O₃ catalyst are experimentally investigated in a packed bed flow reactor. The surrogate mixture exhibits similar ignition–extinction behavior and autothermal temperatures compared to JP-8 suggesting the possibility of using this surrogate mixture for detailed kinetics of catalytic combustion of JP-8. It is shown that JP-8 ignites at low temperatures in the presence of catalyst. Upon ignition, catalytic combustion of JP-8 and the surrogate mixture is self-sustained and robust combustion is observed under fuel lean as well as fuel rich conditions. It is shown that the ignition temperature of the hydrocarbon fuels increases with increasing equivalence ratio. Extinction is observed under fuel lean conditions, whereas sustained combustion was also observed for fuel rich conditions. The effect of dilution in the air flow on the catalytic ignition and autothermal temperatures of the fuel mixture is also investigated by adding helium to the air stream while keeping the flow rate and the equivalence ratio constant. The autothermal temperature decreases linearly as the amount of dilution in the flow is increased, whereas the ignition temperature shows no dependence on the dilution level under the range of our conditions, showing that ignition is dependent only on the type and relative concentration of the active species.     

Application of an aerosol shock tube to the measurement of diesel ignition delay times

Shock tube ignition delay times were measured for DF-2 diesel/21% O₂/argon mixtures at pressures from 2.3 to 8.0 atm, equivalence ratios from 0.3 to 1.35, and temperatures from 900 to 1300 K using a new experimental flow facility, an aerosol shock tube. The aerosol shock tube combines conventional shock tube methodology with aerosol loading of fuel-oxidizer mixtures. Significant efforts have been made to ensure that the aerosol mixtures were spatially uniform, that the incident shock wave was well-behaved, and that the post-shock conditions and mixture fractions were accurately determined. The nebulizer-generated, narrow, micron-sized aerosol size distribution permitted rapid evaporation of the fuel mixture and enabled separation of the diesel fuel evaporation and diffusion processes that occurred behind the incident shock wave from the chemical ignition processes that occurred behind the higher temperature and pressure reflected shock wave. This rapid evaporation technique enables the study of a wide range of low-vapor-pressure practical fuels and fuel surrogates without the complication of fuel cracking that can occur with heated experimental facilities. These diesel ignition delay measurements extend the temperature and pressure range of earlier flow reactor studies, provide evidence for NTC behavior in diesel fuel ignition delay times at lower temperatures, and provide an accurate data base for the development and comparison of kinetic mechanisms for diesel fuel and surrogate mixtures. Representative comparisons with several single-component diesel surrogate models are also given.     

On the importance of species selection for the formulation of fuel surrogates

Fuel surrogates are mixtures of simple compounds that emulate the combustion characteristics of more complex fuels, with the primary objective to enable detailed combustion modeling of very complex real fuels. Current efforts in surrogate development aim at optimizing the compositions of pure hydrocarbons to emulate multiple combustion related properties. In doing so, weights are assigned when defining optimization problem to reflect the importance of each property. In this study, we report on the relative importance of species selection and their weights on the overall performance of the optimized surrogate. Using experimental data of a reference jet fuel as target, we designed a study using a surrogate optimizer that imposes orthogonal perturbations on the surrogate components and weights and analyzed their impact on the optimized surrogate mixtures. Results from 3600 cases show that perturbations of surrogate components, rather than weights, induce far greater variability in the optimized composition and target property agreement. While the Derived Cetane Number (DCN) agreement shows a greater variability from the weight perturbation, the main reason for such high sensitivity is due to the wide range of values for pure component DCN of the individual components, which is also a result of the surrogate component selection. Further, the results show that the selection of surrogate components nearly predefines the overall shape of the distillation curves regardless of the weight values. The current study quantitatively supports the idea that appropriate selection of surrogate components that capture the physical and chemical characteristics of actual constituents of target fuel will increase the possibility of successful surrogate formulation and will mitigate the impact from arbitrary weight assignment.     

Experimental and kinetic modeling study of combustion of gasoline, its surrogates and components in laminar non-premixed flows

Experimental and numerical studies are carried out to construct surrogates that can reproduce selected aspects of combustion of gasoline in non premixed flows. Experiments are carried out employing the counterflow configuration. Critical conditions of extinction and autoignition are measured. The fuels tested are n-heptane, iso-octane, methylcyclohexane, toluene, three surrogates made up of these components, called surrogate A, surrogate B, and surrogate C, two commercial gasoline with octane numbers (ON) of 87 and 91, and two mixtures of the primary reference fuels, n-heptane and iso-octane, called PRF 87 and PRF 91. The combustion characteristics of the commercial gasolines, ON 87 and ON 91, are found to be nearly the same. Surrogate A and surrogate C are found to reproduce critical conditions of extinction and autoignition of gasoline: surrogate C is slightly better than surrogate A. Numerical calculations are carried out using a semi-detailed chemical-kinetic mechanism. The calculated values of the critical conditions of extinction and autoignition of the components of the surrogates agree well with experimental data. The octane numbers of the mixtures PRF 87 and PRF 91 are the same as those for the gasoline tested here. Experimental and numerical studies show that the critical conditions of extinction and autoignition for these fuels are not the same as those for gasoline. This confirms the need to include at least aromatic compounds in the surrogate mixtures. The present study shows that the semi-detailed chemical-kinetic mechanism developed here is able to predict key aspects of combustion of gasoline in non premixed flows, although further kinetic work is needed to improve the combustion chemistry of aromatic species, in particular toluene.     

Modelling biodiesel–diesel spray combustion using multicomponent vaporization coupled with detailed fuel chemistry and soot models

A multicomponent vaporization model is integrated with detailed fuel chemistry and soot models for simulating biodiesel–diesel spray combustion. Biodiesel, a fuel mixture comprised of fatty-acid methyl esters, is an attractive alternative to diesel fuel for use in compression-ignition engines. Accurately modelling of the spray, vaporization, and combustion of the fuel mixture is critical to predicting engine performance using biodiesel. In this study, a discrete-component vaporization model was developed to simulate the vaporization of biodiesel drops. The model can predict differences in the vaporization rates of different fuel components. The model was validated by use of experimental data of the measured biodiesel drop size history and spray penetration data obtained from a constant-volume chamber. Gas phase chemical reactions were simulated using a detailed reaction mechanism that also includes PAH reactions leading to the production of soot precursors. A phenomenological multi-step soot model was utilized to predict soot emissions from biodiesel–diesel combustion. The soot model considered various steps of soot formation and destruction, such as soot inception, surface growth, coagulation, and PAH condensation, as well as oxidation by oxygen and hydroxyl-containing molecules. The overall numerical model was validated with experimental data on flame structure and soot distributions obtained from a constant-volume chamber. The model was also applied to predict combustion, soot and NOx emissions from a diesel engine using different biodiesel–diesel blends. The engine simulation results were further analysed to determine the soot emissions characteristics by use of biodiesel–diesel fuels.     

Experimental comparison of soot formation in turbulent flames of Diesel and surrogate Diesel fuels

Soot formation is compared in turbulent diffusion flames burning a commercial Diesel and two Diesel surrogates containing n-decane and α-methylnaphthalene. A burner equipped with a high-efficiency atomisation system has been specially designed and allows the stabilisation of liquid fuels flames with similar hydrodynamics conditions. The initial surrogate composition (70% n-decane, 30% α-methylnaphthalene) was previously used in the literature to simulate combustion in Diesel engines. In this work, a direct comparison of Diesel and surrogates soot tendencies is undertaken and relies on soot and fluorescent species mappings obtained respectively by Laser-Induced Incandescence (LII) at 1064 nm and Laser-Induced Fluorescence at 532 nm. LIF was assigned to soot precursors and mainly to high-number ring Polycyclic Aromatic Hydrocarbons (PAH). The initial surrogate was found to form 40% more soot than the tested Diesel. Consequently, a second surrogate containing a lower α-methylnaphthalene concentration (20%) has been formulated. That composition which presents a Threshold Soot Index (TSI) very close to Diesel one is also consistent with our Diesel composition that indicates a relatively low PAH content. The spatially resolved measurements of soot and fluorescent soot precursors are quite identical (in shape and intensity) in the Diesel and in the second surrogate flames. Furthermore the concordance of the LII temporal decays suggests that a similar growth of the primary soot particles has occurred for Diesel and surrogates. In addition, the comparison of the LII fluence curves indicates that physical/optical properties of soot contained in the different flames might be similar. The chemical composition present at the surface of soot particles collected in Diesel and surrogate flames has been obtained by laser-desorption ionisation time-of-flight mass spectrometry. An important difference is found between Diesel and surrogate samples indicating the influence of the fuel composition on soot content.     

Counterflow ignition and extinction of FACE gasoline fuels

The demand for petroleum-derived gasoline in the transportation sector is on the rise. For better knowledge of gasoline combustion in practical combustion systems, this study presents experimental measurements and numerical prediction of autoignition temperatures and extinction limits of six FACE (fuels for advanced combustion engines) gasoline fuels in counterflow flames. Extinction limits were measured at atmospheric pressures while the experiments for autoignition temperatures were carried out at atmospheric and high pressures. For atmospheric pressure experiment, the fuel stream consists of the pre-vaporized fuel diluted with nitrogen, while a condensed fuel configuration is used for ignition experiment at higher chamber pressures. The oxidizer stream is pure air. Autoignition temperatures of the tested fuels are nearly the same at atmospheric pressure, while a huge difference is observed as the pressure is increased. Unlike the ignition temperatures at atmospheric pressures, minor difference exists in the extinction limits of the tested fuels. Simulations were carried out using a recently developed gasoline surrogate model. Both multi-component and n-heptane/isooctane mixtures were used as surrogates for the simulations. Overall, the n-heptane/isooctane surrogate mixtures are consistently more reactive as compared the multi-component surrogate mixtures. Transport weighted enthalpy and radical index analysis was used to explain the differences in extinction strain rates for the various fuels.     

Combustion of partially premixed spray jets

Gas turbines, liquid rocket motors, and oil-fired furnaces utilize the spray combustion of continuously injected liquid fuels. In most cases, the liquid spray is mixed with an oxidizer prior to combustion, and further oxidizer is supplied from the outside of the spray to complete diffusion combustion. This rich premixed spray is called “partially premixed spray.” Partially premixed sprays have not been studied systematically although they are of practical importance. In the present study, the burning behavior of partially premixed sprays was experimentally studied with a newly developed spray burner. A fuel spray and an oxidizer, diluted with nitrogen, was injected into the air. The overall equivalence ratio of the spray jet was set larger than unity to establish partially premixed spray combustion. In the present burner, the mean droplet diameter of the atomized liquid fuel could be varied without varying the overall equivalence ratio of the spray jet. Two combustion modes with and without an internal flame were observed. As the mean droplet diameter was increased or the overall equivalence ratio of the spray jet was decreased, the transition from spray combustion only with an external group flame to that with the internal premixed flame occurred. The results suggest that the internal flame was supported by flammable mixture through the vaporization of fine droplets, and the passage of droplet clusters deformed the internal flame and caused internal flame oscillation. The existence of the internal premixed flame enhanced the vaporization of droplets in the post-premixed-flame zone within the external diffusion flame.     

Autoignition of gasoline surrogate mixtures at intermediate temperatures and high pressures: Experimental and numerical approaches

Ignition-delay times were measured in shock-heated gases for a surrogate gasoline fuel comprised of ethanol/iso-octane/n-heptane/toluene at a composition of 40%/37.8%/10.2%/12% by liquid volume with a calculated octane number of 98.8. The experiments were carried out in stoichiometric mixtures in air behind reflected shock waves in a heated high-pressure shock tube. Initial reflected shock conditions were as follows: Temperatures of 690-1200 K, and pressures of 10, 30 and 50 bar, respectively. Ignition delay times were determined from CH^∗ chemiluminescence at 431.5 nm measured at a sidewall location. The experimental results are compared to simulated ignition delay times based on detailed chemical kinetic mechanisms. The main mechanism is based on the primary reference fuels (PRF) model, and sub-mechanisms were incorporated to account for the effect of ethanol and/or toluene. The simulations are also compared to experimental ignition-delay data from the literature for ethanol/iso-octane/n-heptane (20%/62%/18% by liquid volume) and iso-octane/n-heptane/toluene (69%/17%/14% by liquid volume) surrogate fuels. The relative behavior of the ignition delay times of the different surrogates was well predicted, but the simulations overestimate the ignition delay, mostly at low temperatures.     

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

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 NO_x 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 NO_x 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.