Kinetic analysis of n-decane–hydrogen blend combustion in premixed and non-premixed supersonic flows

Numerical analysis of ignition and combustion of an n-decane–hydrogen fuel blend in a premixed supersonic flow and in a model scramjet duct is performed using a reduced reaction mechanism built especially to describe the oxidation of blended n-C₁₀H₂₂–H₂ fuel in air at the temperature T₀ > 900–1000 K in the pressure range P₀ = 0.1–13 atm. The developed kinetic mechanism involves the principal reactions responsible for chain mechanism development both for n-decane and for hydrogen oxidation. It has been shown that using blended n-C₁₀H₂₂–H₂ fuel makes it possible to enhance the ignition and combustion both in premixed and in non-premixed supersonic fuel–air flows compared to burning pure hydrogen–air and n-decane–air mixtures. This allows high combustion completeness in the scramjet duct at the distance of ～1 m even at extremely low air temperature T₀ = 1000 K and pressure P₀ = 0.3 atm. This is due to the interaction of kinetics of the formation of highly reactive atoms and radicals, carriers of chain mechanism, in H₂–air and n-C₁₀H₂₂–air mixtures.     

Effects of preferential and differential diffusion on the mutual annihilation of two premixed hydrogen–air flames

The unsteady process of upstream head-on quenching of two laminar premixed hydrogen–air flames at different equivalence ratios in one dimension is investigated numerically in the presence of preferential and differential diffusion effects. Important chemical and transport characteristics of the mutual annihilation process are studied during the two primary stages of upstream mutual annihilation, preheat layers' and reaction layers' interactions. Because of the diffusive mobility of the fuel, hydrogen, relative to heat and the oxidizer, preferential and differential diffusion effects result in a shift in the equivalence ratio in the reaction zone to leaner conditions. This shift, in turn, affects the subsequent reaction layers' interactions through qualitative and quantitative changes in the rates of reactants' consumption and radicals' production. Another consequence of this shift is the presence of excess and ‘unburnt’ fuel or oxidizer at the end of the mutual annihilation process. The process of mutual annihilation occurs over time scales that are significantly shorter than characteristic residence times associated with flames.     

Ignition of a vapor-gas mixture by a moving small-size source

A theoretical analysis of the ignition of a liquid fuel vapor-air mixture by a moving small source of heating was performed. A gas-phase model of the ignition with consideration given to heat transfer, liquid fuel evaporation, diffusion and convective motion of fuel vapor in the oxidizer medium, crystallization of the heating source, kinetics of the vaporization and ignition processes, temperature dependence of the thermophysical characteristics of the interacting substances, and character of motion of the heating source in the vapor-gas mixture was developed. The values of the ignition delay time τ _d , the main characteristic of the process, were determined. It was established how τ _d depends on the initial temperature, heating source sizes, velocity and trajectory of the heating source, and ambient air temperature.     

Gas-phase autoignition of a spherical volume of fuel in an oxidative medium

A mathematical model of the ignition of unmixed of fuel and oxidizer (a finite spherical volume of fuel surrounded by an infinite oxidizer medium) was developed. The regularities of the autoignition of this system were examined. It was demonstrated that the temperature maximum arising at the fuel-oxidizer interface propagates with increasing amplitude and velocity toward the center of the spherical volume and that the time it takes to attain the maximum temperature (below the autoignition threshold) and the ignition delay time (above the threshold) depend on the parameter δ nonmonotonically, more specifically, exhibit well-pronounced maxima     

Isomer-specific influences on ignition and intermediates of two C5 ketones in an RCM

Ketones have been considered as potential biofuels and main components of blend stock for internal engines. To better understand the chemical kinetics of ketones, ignition delay times of 2-pentanone (propyl methyl ketone, PMK) and 3-pentanone (diethyl ketone, DEK) were measured at temperatures of 895–1128 K under 10 and 20 bar, at equivalence ratios (?) of 0.5 and 1.0 in a rapid compression machine (RCM). To explore the impact of carbonyl functionality and resonance stabilized structures of fuel radicals on their combustion kinetics, high-temperature pyrolysis at 1130 K and relatively low-temperature oxidation at 950 K studies were performed in an RCM, and the time-resolved species concentration profiles under these two conditions were quantified using a fast sampling system and gas chromatography (GC). A new kinetic model containing low-temperature reactions was built aiming at predicting the pyrolysis and oxidation behaviors of both ketones. The consumption pathways of the resonance stabilization fuel radicals through oxygen addition and following reactions are promoted since the decomposition rates of these radicals are about 4 orders magnitudes lower than regular fuel radicals. The occurrences of the so-called “addition-dissociation reactions”, i.e., ketones reacting with a hydrogen yielding aldehyde or reacting with a methyl radical yielding shorter-chain-length ketones, are verified in pyrolysis experiments. Based on experiments and model analysis, the carbonyl functionality in both ketones is preserved during the process of β-scissions of fuel radicals and α-scissions of fuel-related acyl radicals, resulting in the direct formation of CO and ketene. However, the position of carbonyl functionality has a significant impact on the species pools.     

Ignition of a floating droplet of organic coal–water fuel

The results of experimental investigations are presented for the ignition of droplets (particles) of organic coal–water fuels (OCWFs) floating in a flow of an oxidizer using a special combustion chamber from high-temperature quartz glass. The temperature and the velocity of motion of the oxidizer vary in the ranges of 500–900 K and 0.5–3 m/s. The initial sizes (radii) of fuel droplets amounted to 0.3–1.5 mm. As the basic OCWF components, particles (of 80–100 µm in size) of brown coal “B2,” water, mazut, and waste castor and compressor oils are used. With use of the system of high-velocity video registration, the conditions providing for floating of OCWF particles without initiation of burning and with the subsequent steady ignition are established. Four modes of OCWF-droplet ignition with different trajectories of their motion in the combustion chamber are singled out. The times of the OCWF-ignition delay in dependence on the size of fuel particles and oxidizer temperatures are determined. The deviations of the OCWF-ignition-delay times obtained under conditions of suspension of a droplet on the thermocouple junction and while floating in the oxidizer flow are established.     

Direct ignition and S-curve transition by in situ nano-second pulsed discharge in methane/oxygen/helium counterflow flame

A well-defined plasma assisted combustion system with novel in situ discharge in a counterflow diffusion flame was developed to study the direct coupling kinetic effect of non-equilibrium plasma on flame ignition and extinction. A uniform discharge was generated between the burner nozzles by placing porous metal electrodes at the nozzle exits. The ignition and extinction characteristics of CH₄/O₂/He diffusion flames were investigated by measuring excited OH¹ and OH PLIF, at constant strain rates and O₂ mole fraction on the oxidizer side while changing the fuel mole fraction. It was found that ignition and extinction occurred with an abrupt change of OH¹ emission intensity at lower O₂ mole fraction, indicating the existence of the conventional ignition-extinction S-curve. However, at a higher O₂ mole fraction, it was found that the in situ discharge could significantly modify the characteristics of ignition and extinction and create a new monotonic and fully stretched ignition S-curve. The transition from the conventional S-curves to a new stretched ignition curve indicated clearly that the active species generated by the plasma could change the chemical kinetic pathways of fuel oxidation at low temperature, thus resulting in the transition of flame stabilization mechanism from extinction-controlled to ignition-controlled regimes. The temperature and OH radical distributions were measured experimentally by the Rayleigh scattering technique and PLIF technique, respectively, and were compared with modeling. The results showed that the local maximum temperature in the reaction zone, where the ignition occurred, could be as low as 900 K. The chemical kinetic model for the plasma–flame interaction has been developed based on the assumption of constant electric field strength in the bulk plasma region. The reaction pathways analysis further revealed that atomic oxygen generated by the discharge was critical to controlling the radical production and promoting the chain branching effect in the reaction zone for low temperature ignition enhancement.     

Comprehensive ignition characterization of a non-toxic hypergolic hybrid rocket propellant

This paper describes a comprehensive characterization of ignition properties of a metal-hydride based non-toxic hypergolic hybrid rocket propellant. The propellant consists of Rocket Grade Hydrogen Peroxide (RGHP) as oxidizer, high-density Polyethylene (HDPE) as fuel and sodium borohydride (NaBH₄) as the additive, embedded in the HDPE matrix. Ignition quality was characterized as ignition delay, ignition probability and flame spread. In a drop-test setup, ignition characteristics were determined as a function of seven parameters: RGHP concentration, additive loading, oxidizer droplet impact velocity, oxidizer droplet volume, pressure, diluent gas, and environmental exposure. The parameters encompass thermo-chemical, fluid/droplet dynamics and environmental factors affecting ignition. Ignition delays as low as 3 ms were observed, one of the lowest using non-toxic hypergolic hybrid propellants in open-air. An overwhelming majority of conditions tested yielded <10 ms ignition delays and 100% ignition success. All conditions tested affected ignition to varying degrees with RGHP concentration, NaBH₄ loading and drop impact velocity significantly affecting ignition. Further, contrary to expectations, exposing sanded fuel samples to humidity for a few h enhanced ignition instead of hampering it and exposure for 24 h did not lead to ignition degradation. Tests with diluent gases other than air (at atmospheric and elevated pressures) revealed that atmospheric oxygen played a negligible role in the reaction process. This proved that oxygen for the initial ignition event was obtained from RGHP decomposition, with atmospheric oxygen playing no role in ignition performance. Aside from demonstrating excellent ignition characteristics, our results further show a need to go beyond thermo-chemical properties and to consider aspects of ignition other than ignition delay in hypergolic propellant research to enable a complete understanding of the ignition processes. The comprehensive ignition characterization demonstrates the chosen propellant's ability to overcome ignition challenges in hybrid rockets and serves as a proof of concept for its further development.     

Nonpremixed ignition of H2/air in a mixing layer with a vortex

The ignition of a laminar non-premixed H₂/air mixing layer with an embedded vortex was computationally studied with detailed chemistry and transport. The initial vortex velocity and pressure fields were specified based on the stream function of an incompressible nonviscous vortex. The fuel side is pure hydrogen at 300 K, and the oxidizer side is air at 2000 K. The vortex evolution process was found to consist of two ignition events. The first ignition occurs in a diffusion mode with chain branching reactions dominating. The second ignition takes place in the premixed mode, with more chemical reactions involved, and is significantly affected by the heat and species generated in the first ignition event. The coupling between the most reactive mixture fraction and scalar dissipation rate was verified to be crucial to the ignition delay. The effects of the vortex strength, characteristic size, and its center location were individually investigated. For all vortex cases, the ignition delay was shorter than that of the 1D case. Furthermore, the ignition delay has a nonmonotonic dependence on all the vortex parameters.     

Chemical kinetic interactions of NO with a multi-component gasoline surrogate: Experiments and modeling

This work reports an experimental and modeling study on the chemical kinetic interactions of NO with a multi-component gasoline surrogate, namely PACE-20, using a twin-piston rapid compression machine at a stochiometric fuel loading with 20% EGR (exhaust gas recirculation) by mass, pressures of 20 and 40 bar, and temperatures from 700 to 930 K. Five NO concentrations are investigated, namely 0, 20, 50, 70 and 150 ppm, where NO addition effects are characterized through changes in PACE-20 ignition reactivity and heat release characteristics. Experiments indicate that within the low-temperature regime, NO promotes low-temperature heat release rate and main ignition reactivity at low addition levels, with saturation or even inhibiting effects observed at >50 ppm NO addition, while within the NTC/intermediate-temperature regime, adding NO only promotes reactivity. A recently updated, detailed chemical kinetic model with chemistry specific to NOx/hydrocarbons interaction incorporated is used to simulate the experiments, and reasonable agreement is obtained. In-depth sensitivity and rate of production analyses are further performed. The results indicate that NO interacts with PACE-20 via two types of interaction: (a) direct interactions between NO and PACE-20 derivatives, primarily through NO+HO₂↔NO₂+OH and RO₂+NO↔RO+NO₂, and (b) indirect interactions between PACE-20 derivatives and NO₂ produced from the direct interactions, primarily through R+NO₂↔RO+NO. The observed NO inhibiting effect at low temperatures and 150 ppm NO addition is attributed to the lack of HO₂ radicals to sustain NO consumption via NO+HO₂↔NO₂+OH, and the take-up of inhibiting pathways via RO₂+NO↔RO+NO₂. The results also indicate that even with the presence of multiple fuel components, NOx/hydrocarbons interactions are highly selective, and are mainly initiated by the interactions between NO and RO₂ radicals from cyclopentane and ethanol, as well as between NO₂ and R radicals from toluene, 1,2,4-trimethylbenzene and 1-hexene. Further studies on these interactive reactions are therefore highly recommended.     

Experimental and numerical study of premixed, lean ethylene flames

Ethylene is a key intermediate in the combustion mechanisms of most practical fuels. It plays also an important role in the formation of aromatic hydrocarbons and soot particules. The latter has motivated many experimental and numerical studies carried out on rich ethylene-air mixtures. Less studies have been devoted to lean mixtures, and the development of strategies based on lean, premixed flames to reduce soot and NO_x production requires additional experimental data in lean conditions. In this work, the chemical structure of lean premixed ethylene-oxygen-nitrogen flames stabilized on a flat-flame burner at atmospheric pressure was determined experimentally. The species mole fraction profiles were also computed by the Premix code (Chemkin II version) and four detailed reaction mechanisms. A very good agreement was observed for the main flame properties: reactants consumption, final products (CO₂, H₂O) and the main intermediates: CO and H₂. Marked differences occurred in the prediction of active intermediate species present in small concentrations. Pathways analyses were performed to identify the origins of these discrepancies. It was shown that the same reactions were involved in the four mechanisms to describe the consumption of ethylene, but with marked differences in their relative importance. C₂H₃ and CH₂HCO are the main radicals formed in this first step and their consumption increases the differences between the mechanisms either by the use of different kinetic data for common reactions or by differences in the nature of the consumption reactions.     

Comparative study on ethyl butanoate reactivity – Experimental investigation and kinetic modeling of the C6 ethyl ester

Ethyl butanoate is a representative for oxygenated hydrocarbons as they are discussed as future liquid fuels from sustainable production pathways. An in-depth understanding of the influence of oxygen on the reactivity of those fuel candidates is mandatory for the molecular design and their application in internal combustion engines. Towards this goal, ignition delay times for ethyl butanoate were measured at conditions relevant to internal combustion engines using a shock tube and a rapid compression machine. These experiments were conducted for stoichiometric mixtures with air-like conditions at pressures of 20, 30 and 40 bar and a total temperature range of 680–1260 K. A negative temperature coefficient regime was found where the ignition delay times increased with increasing temperatures for all covered pressures. To further understand the kinetics of ethyl butanoate and the influence of the ester functional group, a detailed kinetic mechanism was developed and validated against the measured ignition delay times. A good agreement between the measured data and the prediction by the newly developed mechanism was achieved. The findings of this work were then used to compare ethyl butanoate to di-ethyl carbonate, methyl pentanoate and n-heptane, which also show a seven-heavy-atom-membered main chain and have all been kinetically studied before. The differences between the molecular structures and their effect on the kinetic pathways was discussed to extract information for future fuel design. It was found that especially the inhibting effect of oxgen atoms on six-membered internal H-atom migration reactions has a significant impact on the fuel’s reactivity.     

Ignition of non-premixed cyclohexane and mono-alkylated cyclohexane flames

Ignition temperatures of non-premixed cyclohexane, methylcyclohexane, ethylcyclohexane, n-propylcyclohexane, and n-butylcyclohexane flames were measured in the counterflow configuration at atmospheric pressure, a free-stream fuel/N₂ mixture temperature of 373 K, a local strain rate of 120 s^?1, and fuel mole fractions ranging from 1% to 10%. Using the recently developed JetSurf 2.0 kinetic model, satisfactory predictions were found for cyclohexane, methyl-, ethyl-, and n-propyl-cyclohexane flames, but the n-butylcyclohexane data were overpredicted by 20 K. The results showed that cyclohexane flames exhibit the highest ignition propensity among all mono-alkylated cyclohexanes and n-hexane due to its higher reactivity and larger diffusivity. The size of mono-alkyl group chain was determined to have no measurable effect on ignition, which is a result of competition between fuel reactivity and diffusivity. Detailed sensitivity analyses showed that flame ignition is sensitive primarily to fuel diffusion and also to H₂/CO and C₁–C₃ hydrocarbon kinetics.     

A kinetic investigation on low-temperature ignition of propane with ozone addition in an RCM

To extend the temperature for propane ignition to a lower region (< 680 K), ozone (O₃) was used as an ignition promoter to investigate the low-temperature chemistry of propane. Ignition delay times for propane containing varying concentrations of O₃ (0, 100, and 1000 ppm) were measured at 25 bar, 654–882 K, and equivalence ratios of 0.5 and 1.0 in a rapid compression machine (RCM). Species profiles during propane ignition with varying O₃ concentrations were recorded using a fast sampling system combined with a gas chromatograph (GC). A kinetic model for propane ignition with O₃ was developed. O₃ shortened ignition delay times of propane significantly, and the NTC behavior was weakened. O atoms released from O₃ reacted with propane through hydrogen abstraction reactions, which led to the fast production of OH radicals. The following oxidation of fuel radicals generated additional OH radicals. Consequently, the inhibition caused by the slow chemistry of hydrogen peroxide (H₂O₂) in the NTC region was weakened in the presence of O₃. Experimental results with O₃ addition can provide extra constraints on the low-temperature chemistry of propane. Species profiles during propane ignition at 730 K with 1000 ppm O₃ addition showed the production of propanal (C₂H₅CHO), acetone (CH₃COCH₃), and acetaldehyde (CH₃CHO) was promoted significantly. Model analyses indicated that O₃ shifted the oxidation temperature of propane to a lower region, in which reactions of ROO radicals (NC₃H₇O₂ and IC₃H₇O₂) tend to generate RO radicals (NC₃H₇O and IC₃H₇O). The promotion of RO radicals led to the fast production of C₂H₅CHO, CH₃COCH₃, and CH₃CHO. The corresponding species profile highlighted the reaction relevant to ROO and RO radicals (NC₃H₇O + O₂ = C₂H₅CHO + HO₂ and 2 IC₃H₇O₂ = 2 IC₃H₇O + O₂). Rate constants of these reactions were updated, which can potentially improve the performance of the core mechanism under lower temperatures and provide references for model development of larger hydrocarbons.     

High pressure ignition delay times of H2/CO mixture in carbon dioxide and argon diluent

Ignition Delay Time (IDT) plays a significant role in combustion process of advanced power cycles such as direct-fired supercritical carbon dioxide (sCO₂) cycle. In this cycle, fuel and oxidizer are heavily diluted with carbon dioxide (CO₂) and autoignite at a combustor inlet pressure range of 10–30 MPa and a temperature range of 900–1500 K. A fuel candidate for sCO₂ power cycle applications is syngas (H₂/CO mixture); however, its ignition properties at these conditions are not studied. Moreover, the existing chemical kinetics models have not been evaluated for H₂/CO mixtures applications relevant to elevated pressure conditions and under large dilution levels of CO₂. Therefore, two tasks are performed in this study. First, IDTs of a H₂/CO=95:5 mixture at stoichiometric and rich (Φ=2) conditions are measured in a high-pressure shock tube under 95.5% CO₂ dilution level and at 10 MPa and 20 MPa for a temperature range of 1161–1365 K. For the experimental conditions considered in this work, Aramco 2.0, FFCM-1, HP-Mech and USC Mech II kinetic models are capable of capturing IDT data. Second, similar experiments are conducted by replacing the CO₂ dilute gas with Argon (Ar) to understand the chemical effect of CO₂ on IDT globally. Sensitivity analysis results reveal that for both diluents, reaction H + O₂(+M)=HO₂(+M) is the most important reaction in controlling ignition. Further, a rate of production analysis shows that CO₂ has a competing effect on OH radical production. On one hand, CO₂ accelerates the consumption of H radicals through H + O₂+CO₂→HO₂+CO₂ therefore hindering HO₂+HOH+OH reaction for OH production. On the other hand, CO₂ is shown to enhance OH production through H₂O₂+M=OH+OH+M. These kinetic effects from CO₂ cancel out, therefore CO₂ does not significantly alter the IDT globally when compared to the Ar bath case. This is confirmed by both experimental results and simulation.     

Ignition and combustion behavior of zirconium-based pyrotechnic igniters and pyrotechnic delays under aging

Pyrotechnic materials often necessitate high reliability and stability to be utilized in energetic devices. However, prolonged storage of these materials degrades their performance in many ways and results in failure of these devices. Only a few studies have focussed on their burning characteristics, and reported limited understanding on the effect of aging on this behavior of such materials. In this study, ignition and combustion behavior of pyrotechnic materials based on zirconium (Zr) as fuel and potassium perchlorate (KClO₄) or iron(III) oxide (Fe₂O₃) as oxidant are investigated, for various aging conditions. Pristine samples are compared with samples subjected to aging under 91 °C (thermally aged) and seasonal changes (naturally aged). The ignition delay time as a function of maximum wire temperature is obtained through high-speed combustion photography for these samples. Surface features and oxide content are analyzed using scanning electron microscopy and x-ray photoelectron spectroscopy techniques. Results indicate that ignition delay time increases significantly with aging period for both pyrotechnic igniter and pyrotechnic delay samples. However, this time reduces as the maximum wire temperature is increased for all samples. Naturally aged samples exhibit longer ignition delay times and higher metal oxide content when compared to thermally aged ones. Both pre-oxidation of metallic fuel and prior thermal decomposition of oxidizer play an important role in causing this behavior with aged samples.     

Low-Temperature Flameless Combustion of a Large Drop of <Emphasis Type="Italic">n</Emphasis>-Dodecane under Microgravity Conditions

The forced ignition, combustion, and spontaneous ignition of a drop of n-dodecane in an atmosphere of air at a normal pressure under microgravity conditions were studied based on a physicomathematical model of drop combustion and a detailed kinetic mechanism of the oxidation and combustion of n-dodecane C₁₂H₂₆. The selection of n-dodecane was related to the Russian–American experiment CFI (Cool Flame Investigation) Zarevo performed in 2017 aboard the International Space Station with the use of the large drops of this hydrocarbon. The analysis carried out deepens our knowledge about the flameless combustion of a large drop under the conditions of microgravity. The calculations showed that, after the radiation extinction of a hot flame, the drop can continue to evaporate because of the exothermic low-temperature oxidation of fuel vapor with repeated blue flame flashes at a characteristic temperature of 980–1000 K. A detailed analysis of the calculation results showed that the regular splashes of temperature resulted from the thermal decomposition of hydrogen peroxide—branching with the release of hydroxyl radicals.     

An experimental and modeling study of the shock tube ignition of a mixture of n-heptane and n-propylbenzene as a surrogate for a large alkyl benzene

Alkyl aromatics are an important chemical class in gasoline, jet and diesel fuels. In the present work, an n-propylbenzene and n-heptane mixture is studied as a possible surrogate for large alkyl benzenes contained in diesel fuels. To evaluate it as a surrogate, ignition delay times have been measured in a heated high pressure shock tube (HPST) for a mixture of 57% n-propylbenzene/43% n-heptane in air (≈21% O₂, ≈79% N₂) at equivalence ratios of 0.29, 0.49, 0.98 and 1.95 and compressed pressures of 1, 10 and 30 atm over a temperature range of 1000–1600 K. The effects of reflected-shock pressure and equivalence ratio on ignition delay time were determined and common trends highlighted. A combined n-propylbenzene and n-heptane reaction mechanism was assembled and simulations of the shock tube experiments were carried out. The simulation results showed very good agreement with the experimental data for ignition delay times. Sensitivity and reaction pathway analyses have been performed to reveal the important reactions responsible for fuel oxidation under the shock tube conditions studied. It was found that at 1000 K, the main consumption pathways for n-propylbenzene are abstraction reactions on the alkyl chain, with particular selectivity to the allylic site. In comparison at 1500 K, the unimolecular decomposition of the fuel is the main consumption pathway.     

A comparative reactivity study of 1-alkene fuels from ethylene to 1-heptene

A comparative reactivity study of 1-alkene fuels from ethylene to 1-heptene has been performed using ignition delay time (IDT) measurements from both a high-pressure shock tube and a rapid compression machine, at an equivalence ratio of 1.0 in ‘air’, at a pressure of 30 atm in the temperature range of 600–1300 K. At low temperatures (< 950 K), the results show that 1-alkenes with longer carbon chains show higher fuel reactivity, with 1-pentene being the first fuel to show negative temperature coefficient (NTC) behavior followed by 1-hexene and 1-heptene. At high temperatures (> 950 K), the experimental results show that all of the fuels except propene show very similar fuel reactivity, with the IDTs of propene being approximately four times longer than for all of the other 1-alkenes. To analyze the experimental results, a chemistry mechanism has been developed using consistent rate constants for these alkenes. At 650 K, flux analyses show that hydroxyl radicals add to the double bond, followed by addition to molecular oxygen producing hydroxy?alkylperoxy radicals, which can proceed via the Waddington mechanism or alternate internal H-atom isomerizations in chain branching similar to those for alkanes. We have found that the major chain propagation reaction pathways that compete with chain branching pathyways mainly produce hydroxyl rather than hydroperoxyl radicals, which explains the less pronounced NTC behavior for larger 1-alkenes compared to their corresponding alkanes. At 1200 K, flux analyses show that the accumulation of hydroperoxyl radicals is important for the auto-ignition of 1-alkenes from propene to 1-heptene. The rate of production of hydroperoxyl radicals for 1-alkenes from 1-butene to 1-heptene is higher than that for propene, which is due to the longer carbon chain facilitating hydroperoxyl radical formation via more efficient reaction pathways. This is the major reason that propene presents lower fuel reactivity than the other 1-alkenes at high temperatures.     

Ignition enhancement by addition of NO and NO2 from a N2/O2 plasma torch in a supersonic flow

The effects of NO and NO₂ produced by using a plasma jet (PJ) of a N₂/O₂ mixture on ignition of hydrogen, methane, and ethylene in a supersonic airflow were experimentally and numerically investigated. Numerical analysis of ignition delay time showed that the addition of a small amount of NO or NO₂ drastically reduced ignition delay times of hydrogen and hydrocarbon fuels at a relatively low initial temperature. In particular, NO and NO₂ were more effective than O radicals for ignition of a CH₄/air mixture at 1200 K or lower. These ignition enhancement effects were examined by including the low temperature chemistry. Ignition tests by a N₂/O₂ PJ in a supersonic flow (M = 1.7) for using hydrogen, methane, and ethylene injected downstream of the PJ were conducted. The results showed that the ignitability of the N₂/O₂ PJ is affected by the composition of the feedstock and that pure O₂ is not the optimum condition for downstream fuel injection. This result of ignition tests with downstream fuel injection demonstrated a significant difference in ignition characteristics of the PJ from the ignition tests with upstream fuel injection.