Laminar flame propagation of acetone and 2-butanone at normal to high pressures: Insight into fuel molecular structure effects of ketones

This work reports an experimental and kinetic modeling investigation on the laminar flame propagation of acetone and 2-butanone at normal to high pressures. The experiments were performed in a high-pressure constant-volume cylindrical combustion vessel at 1–10 atm, 423 K and equivalence ratios of 0.7–1.5. A kinetic model of acetone and 2-butanone combustion was developed from our recent pentanone model [Li et al., Proc. Combust. Inst. 38 (2021) 2135–2142] and validated against experimental data in this work and in literature. Together with our recently reported data of 3-pentanone, remarkable fuel molecular structure effects were observed in the laminar flame propagation of the three C₃C₅ ketones. The laminar burning velocity increases in the order of acetone, 2-butanone and 3-pentanone, while the pressure effects in laminar burning velocity reduces in the same order. Modeling analysis was performed to provide insight into the key pathways in flames of acetone and 2-butanone. The differences in radical pools are concluded to be responsible for the observed fuel molecular structure effects on laminar burning velocity. The favored formation of methyl in acetone flames inhibits its reactivity and leads to the slowest laminar flame propagation, while the easiest formation of ethyl in 3-pentanone flames results in the highest reactivity and fastest laminar flame propagation. Furthermore, the LBVs of acetone and 3-pentanone exhibit the strongest and weakest pressure effects respectively, which can be attributed to the influence of fuel molecular structures through two crucial pressure-dependent reactions CH₃ + H (+M) = CH₄ (+M) and C₂H₄ + H (+M) = C₂H₅ (+M).     

A combustion chemistry study of tetramethylethylene in a laminar premixed low-pressure hydrogen flame

The combustion chemistry of tetramethylethylene (TME) was studied in a premixed laminar low-pressure hydrogen flame by combined photoionization molecular-beam mass spectrometry (PI-MBMS) and photoelectron photoion coincidence (PEPICO) spectroscopy at the Swiss Light Source (SLS) of the Paul Scherrer Institute in Villigen, Switzerland. This hexene isomer with the chemical formula C₆H₁₂ has a special structure with only allylic CH bonds. Several combustion intermediate species were identified by their photoionization and threshold photoelectron spectra, respectively. The experimental mole fraction profiles were compared to modeling results from a recently published kinetic reaction mechanism that includes a TME sub-mechanism to describe the TME/H₂ flame structure. The first stable intermediate species formed early in the flame front during the combustion of TME are 2-methyl-2-butene (C₅H₁₀) at a mass-to-charge ratio (m/z) of 70, 2,3-dimethylbutane (C₆H₁₄) at m/z 86, and 3-methyl-1,2-butadiene (C₅H₈) at m/z 68. Isobutene (C₄H₈) is also a dominant intermediate in the combustion of TME and results from consumption of 2-methyl-2-butene. In addition to these hydrocarbons, some oxygenated species are formed due to low-temperature combustion chemistry in the consumption pathway of TME under the investigated flame conditions.     

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.     

Insight into fuel isomeric effects on laminar flame propagation of pentanones

Laminar flame propagation was investigated for pentanone isomers/air mixtures (3-pentanone, 2-pentanone and 3-methyl-2-butanone) in a high-pressure constant-volume cylindrical combustion vessel at 393–423 K, 1–10 atm and equivalence ratios of 0.6–1.5, and in a heat flux burner at 393 K, 1 atm and equivalence ratios of 0.6–1.5. Two kinds of methods generally show good agreement, both of which indicate that the laminar burning velocity increases in the order of 3-methyl-2-butanone, 2-pentanone and 3-pentanone. A kinetic model of pentanone isomers was developed and validated against experimental data in this work and in literature. Modeling analysis was performed to provide insight into the flame chemistry of the three pentanone isomers. H-abstraction reactions are concluded to dominate fuel consumption, and further decomposition of fuel radicals eventually produces fuel-specific small radicals. The differences in radical pools are concluded to be responsible for the observed fuel isomeric effects on laminar burning velocity. Among the three pentanone isomers, 3-pentanone tends to produce ethyl and does not prefer to produce methyl and allyl in flames, thus it has the highest reactivity and fastest laminar flame propagation. On the contrary, 3-methyl-2-butanone tends to produce allyl and methyl instead of ethyl, and consequently has the lowest reactivity and slowest laminar flame propagation.     

The effects of burner stabilization on Fenimore NO formation in low-pressure, fuel-rich premixed CH4/O2/N2 flames

We investigate the effects of varying the degree of burner stabilization on Fenimore NO formation in fuel-rich low-pressure flat CH₄/O₂/N₂ flames. Towards this end, axial profiles of flame temperature and OH, NO and CH mole fractions are measured using laser-induced fluorescence (LIF). The experiments are performed at equivalence ratios between 1.3 and 1.5. The flame temperature is seen to decrease by 200-300 K, with a concomitant decrease in OH mole fraction, upon reducing the total flow rate from 5 to 3 L/min, thus increasing stabilization. At equivalence ratios between 1.3 and 1.5, this decrease in flow rate lowers the maximum CH mole fraction by a factor of 2, and the NO mole fraction by ∼40% in all flames studied. Integrating the reaction rate for CH + N₂ to estimate Fenimore NO formation, using the rate coefficient in GRI-Mech 3.0, and the measured temperatures and CH profiles show very good agreement with the measured NO mole fraction for ? = 1.3 and 1.4, supporting the current choice for this rate. This agreement also shows that the increase in residence time caused by increased stabilization is an important factor in the ultimate impact of the changes in CH mole fraction on NO formation. The results at ? = 1.5 suggest that substantial quantities of fixed nitrogen species, e.g., HCN, are only slowly oxidized in the post-flame zone under these conditions, leading to a significant discrepancy between the measured NO mole fraction and that obtained by integrating over the CH profile. Detailed calculations using GRI-Mech 3.0 predict the experimental results at ? = 1.3 nearly quantitatively, but show increasing differences with the measurements for both CH and NO profiles with increasing equivalence ratio.     

Benzene formation in premixed fuel-rich 1,3-butadiene flames

Detailed kinetic modeling and flame-sampling molecular-beam time-of-flight mass spectrometry are combined to unravel important pathways leading to the formation of benzene in a premixed laminar low-pressure 1,3-butadiene flame. The chemical kinetic model developed is compared with new experimental results obtained for a rich (? = 1.8) 1,3-butadiene/O₂/Ar flame at 30 Torr and with flame data for a similar but richer (? = 2.4) flame reported by Cole et al. [Combust. Flame 56 (1) (1984) 51-70]. The newer experiment utilizes photoionization by tunable vacuum-ultraviolet synchrotron radiation, which allows for the identification and separation of combustion species by their characteristic ionization energies. Predictions of mole fractions as a function of distance from the burner of major combustion intermediates and products are in overall satisfactory agreement with experimentally observed profiles. The accurate predictions of the propargyl radical and benzene mole fractions permit an assessment of potential benzene formation pathways. The results indicate that C₆H₆ is formed mainly by the C₃H₃ + C₃H₃ and i-C₄H₅ + C₂H₂ reactions, which are roughly of equal importance. Smaller contributions arise from C₃H₃ + C₃H₅. However, given the experimental and modeling uncertainties, other pathways cannot be ruled out.     

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.     

An experimental study of the rich premixed ethylbenzene flame at low pressure

A slightly sooting premixed ethylbenzene flame with an equivalence ratio of 1.90 was investigated at low pressure (4.0 kPa) using molecular-beam mass spectrometry (MBMS) and tunable synchrotron vacuum ultraviolet (VUV) photoionization. Basing on the ionization threshold measurements of photoionization efficiency (PIE) spectra, combustion intermediates up to C₁₉H₁₂ were identified, including a number of radicals and isomeric species. Mole fraction profiles of observed flame species were evaluated from the measurements of burner scan at the photon energies near ionization thresholds. Besides, the flame temperature profile was measured by a Pt/Pt-13%Rh thermocouple. From the intermediate identification and mole fraction measurements, the degradation of ethylbenzene, as well as the formation of some interested polycyclic aromatic hydrocarbons (PAHs), was discussed in detail. It is suggested that the formation of most typical PAHs observed in this work can be related to the H-abstraction/C₂H₂-addition (HACA) mechanism. Furthermore, the high concentration levels of intermediates in this flame is ascribed to the weak C-C bonds in the sidechain of ethylbenzene, which provides a potential explanation of the high sooting tendencies of ethylbenzene and other monocyclic aromatic fuels with complex sidechain structure. This study is anticipated to be constructive for combustion investigations of aromatic fuels, and the discussion is hoped to be helpful for further modeling studies concerning PAHs formation in combustion process.     

An experimental and kinetic modeling study of premixed nitroethane flames at low pressure

An experimental and kinetic modeling study is reported on three premixed nitroethane/oxygen/argon flames at low pressure (4.655 kPa) with the equivalence ratios (Φ) of 1.0, 1.5 and 2.0. Over 30 flame species were identified with tunable synchrotron vacuum ultraviolet photoionization mass spectrometry, with their mole fractions quantified as the function of the height above burner. The flame temperature profiles were measured with a Pt–6%Rh/Pt–30%Rh thermocouple. A detailed kinetic mechanism with 115 species and 730 reactions was proposed and validated against experimental results. The computed predictions have shown satisfactory agreement with the experimental results. Basing on the rate-of-production analysis, the reaction pathways that feature the combustion of nitroethane were revealed, including the primary decomposition of C–N bond fission, the oxidation of C2 and C1 hydrocarbons and the formation of nitrogenous species. The presence of NO₂ and NO has been proved to be important for these processes.     

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.     

NO and OH* emission characteristics of very-lean to stoichiometric ammonia–hydrogen–air swirl flames

One of the main concerns regarding ammonia combustion is its tendency to yield high nitric oxide (NO) emissions. Burning ammonia under slightly rich conditions reduces the NO mole fraction to a low level, but the penalties are poor combustion efficiency and unburnt ammonia. As an alternative solution, this paper reports the experimental investigation of premixed swirl flames fueled with ammonia-hydrogen mixtures under very-lean to stoichiometric conditions. A gas analyzer was used to measure the NO mole fraction in the flame and post flame regions, and it was found that low NO emissions (as low as 100 ppm) in the exhaust were achieved under very lean conditions (? ≈ 0.40). Low NO emission was also possible at higher equivalence ratios, e.g. ? = 0.65, for very large ammonia fuel fractions (X_NH3 > 0.90). 1-D flame simulations were performed to elaborate on experimental findings and clarify the observations of the chemical kinetics. In addition, images of OH* chemiluminescence intensity were captured to identify the flame structure. It was found that, for some conditions, the OH* chemiluminescence intensity can be used as a proxy for the NO mole fraction. A monotonic relationship was discovered between OH* chemiluminescence intensities and NO mole fraction for a wide range of ammonia-hydrogen blends (0.40 < ? < 0.90 and 0.25 < X_NH3 < 0.90), making it possible to use the low-cost OH* chemiluminescence technique to qualify NO emission of flames fueled with hydrogen-enriched ammonia blends.     

Cup-burner flame structure and extinguishment by CF3Br and C2HF5 in microgravity

The effects of fire-extinguishing agents CF₃Br and C₂HF₅ on the structure and extinguishing processes of microgravity cup-burner flames have been studied numerically. Propane and a propane–ethanol–water fuel mixture, prescribed for a Federal Aviation Administration (FAA) aerosol can explosion simulator test, were used as the fuel. The time-dependent, two-dimensional numerical code, which includes a detailed kinetic model (177 species and 2986 reactions), diffusive transport, and a gray-gas radiation model, revealed unique flame structure and predicted the minimum extinguishing concentration of agent when added to the air stream. The peak reactivity spot (i.e., reaction kernel) at the flame base stabilized a trailing flame. The calculated flame temperature along the trailing flame decreased downstream due to radiative cooling, causing local extinction at <1250 K and flame tip opening. As the mole fraction of agent in the coflow (X_a) was increased gradually: (1) the premixed-like reaction kernel weakened (i.e., lower heat release rate) (but nonetheless formed at higher temperature); (2) the flame base stabilized increasingly higher above the burner rim, parallel to the axis, until finally blowoff-type extinguishment occurred; (3) the calculated maximum flame temperature remained at nearly constant (≈1700 K) or mildly increased; and (4) the total heat release of the entire flame decreased (inhibited) for CF₃Br but increased (enhanced) for C₂HF₅. In the lifted flame base with added C₂HF₅, H₂O (formed from hydrocarbon-O₂ combustion) was converted further to HF and CF₂O through exothermic reactions, thus enhancing the heat-release rate peak. In the trailing flame, “two-zone” flame structure developed: CO₂ and CF₂O were formed primarily in the inner and outer zones, respectively, while HF was formed in both zones. As a result, the unusual (non-chain branching) reactions and the combustion enhancement (increased total heat release) due to the C₂HF₅ addition occurred primarily in the trailing diffusion flame.     

An experimental study on the formation of polycyclic aromatic hydrocarbons in laminar coflow non-premixed methane/air flames doped with four isomeric butanols

Experimental measurements were conducted for temperatures and mole fractions of C1–C16 combustion intermediates in laminar coflow non-premixed methane/air flames doped with 3.9% (in volume) 1-butanol, 2-butanol, iso-butanol and tert-butanol, respectively. Synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS) technique was utilized in the measurements of species mole fractions. The results show that the variant molecular structures of butyl alcohols have led to different efficiencies in the formation of polycyclic aromatic hydrocarbons (PAHs) that may cause the variations in sooting tendency. Detailed species information suggests that the presence of allene and propyne promotes benzene formation through the C₃H₃ + C₃H₄ reactions and consequently PAH formation through the additions of C2 and C3 species to benzyl or phenyl radicals. As a matter of fact, PAHs formed from the 1-butanol doped flame are the lowest among the four investigated flames, because 1-butanol mainly decomposes to ethylene and oxygenates rather than C3 hydrocarbon species. Meanwhile, the tert-butanol doped flame generates the largest quantities of allene and propyne among the four flames and therefore is the sootiest one.     

Critical temperature and reactant mass flux for radiative extinction of ethylene microgravity spherical diffusion flames at 1 bar

In microgravity combustion, where buoyancy is not present to accelerate the flow field and strain the flame, radiative extinction is of fundamental importance, and has implications for spacecraft fire safety. In this work, the critical point for radiative extinction is identified for normal and inverse ethylene spherical diffusion flames via atmospheric pressure experiments conducted aboard the International Space Station, as well as with a transient numerical model. The fuel is ethylene with nitrogen diluent, and the oxidizer is an oxygen/nitrogen mixture. The burner is a porous stainless-steel sphere. All experiments are conducted at constant reactant flow rate. For normal flames, the ambient oxygen mole fraction was varied from 0.2 to 0.38, burner supply fuel mole fraction from 0.13 to 1, total mass flow rate, ṁ_total, from 0.6 to 12.2 mg/s, and adiabatic flame temperature, T_ad, from 2000 to 2800 K. For inverse flames, the ambient fuel mole fraction was varied from 0.08 to 0.12, burner supply oxygen mole fraction from 0.4 to 0.85, ṁ_total from 2.3 to 11.3 mg/s, and T_ad from 2080 to 2590 K. Despite this broad range of conditions, all flames extinguish at a critical extinction temperature of 1130 K, and a fuel-based mass flux of 0.2 g/m²-s for normal flames, and an oxygen-based mass flux of 0.68 g/m²-s for inverse flames. With this information, a simple equation is developed to estimate the flame size (i.e., location of peak temperature) at extinction for any atmospheric-pressure ethylene spherical diffusion flame given only the reactant mass flow rate. Flame growth, which ultimately leads to radiative extinction if the critical extinction point is reached, is attributed to the natural development of the diffusion-limited system as it approaches steady state and the reduction in the transport properties as the flame temperature drops due to increasing flame radiation with time (radiation-induced growth.)     

Experimental and numerical investigation of ester droplet combustion: Application to butyl acetate

This paper presents an experimental and numerical study of the combustion of isolated n‑butyl acetate droplets in the standard atmosphere. Numerical simulations are reported using a model that incorporates unsteady gas and liquid transport, variable properties, and radiation. Three skeletal mechanisms of n‑butyl acetate, derived from a large detailed mechanism comprised of 819 species and 52,698 reactions, were used in the numerical simulations to evaluate the influence of the kinetic mechanism on burning. The reduced mechanisms comprised 212 species and 5413 reactions, 157 species and 3089 reactions, and 105 species and 1035 reactions. The numerical model did not include soot formation, though qualitatively mild sooting was noted only for droplets larger than 0.7 mm. The numerical predictions were in good agreement with experimental measurements of droplet and flame diameters. Flame extinction was numerically predicted which was attributed to a decrease of the characteristic diffusion time relative to the chemical time as droplet burned. Effects of initial droplet diameter on the evolution of maximum gas temperature (T_max) and peak mole fractions of CO₂ and CO are also examined numerically.     

Probing O2 dependence of hydroperoxy-butyl reactions via isomer-resolved speciation

Degenerate chain-branching mechanisms of n-alkanes are centered on the formation of hydroperoxy-alkyl radicals (̇QOOH), formed via ̇R + O₂ reactions, and the ensuing competition between unimolecular decomposition and second-O₂-addition. Quantitative measurements of partially oxidized intermediates formed via reactions of ̇QOOH provide critical constraints that are required for accurate modeling of combustion chemistry. To examine the influence of temperature and oxygen concentration on intermediates from unimolecular decomposition of ̇QOOH, isomer-resolved speciation measurements were conducted on n-butane oxidation at 835 Torr in a jet-stirred reactor (JSR) from 500 – 900 K. Resulting from negative-temperature coefficient behavior, cyclic ether formation peaked at two temperatures, 650 K and 800 K, which were selected for separate experiments to quantify the O₂-dependence of species profiles using O₂ concentrations of 4.2 · 10¹⁷ – 1.1 · 10¹⁹ molecules cm^–3.Utilizing vacuum-ultraviolet absorption spectroscopy and electron-impact mass spectrometry, cyclic ether isomers were quantified separately, including explicit resolution of cis- and trans- isomers of 2,3-dimethyloxirane. Stereoisomers of 2-butene were also quantified explicitly. For all cyclic ethers, a common trend in O₂-dependence emerged: species concentrations reach a maximum near 3.0 · 10¹⁸ molecules cm^–3 (equivalence ratio of 0.5). Although quantitative disparities are evident, chemical kinetics modeling qualitatively reproduces the O₂ dependence of species at 650 K. However, at 800 K, weak dependence on O₂ is predicted, which is in contrast with the measurements. Two carbonyls, diacetyl and methyl vinyl ketone, were also quantified and follow similar dependence on [O₂] and temperature as the cyclic ethers, which indicates some fraction forms via ̇QOOH-mediated reactions. The discrepancies between the measured and model-predicted species profiles indicate that sub-mechanisms for important intermediates may require additional elementary reactions, including stereochemical-specific reactions, to improve the fidelity of n-alkane combustion modeling.     

Experimental and kinetic modeling study of the positive ions in premixed ethylene flames over a range of equivalence ratios

Understanding the ion chemistry in flames is crucial for developing ion sensitive technologies for controlling combustion processes. In this work, we measured the spatial distributions of positive ions in atmospheric-pressure burner-stabilized premixed flames of ethylene/oxygen/argon mixtures in a wide range of equivalence ratios ϕ = 0.4÷1.5. A flame sampling molecular beam system coupled with a quadrupole mass spectrometer was used to obtain the spatial distributions of cations in the flames, and a high mass resolution time-of-flight mass spectrometer was utilized for the identification of the cations having similar m/z ratios. The measured profiles of the flame ions were corrected for the contribution of hydrates formed during sampling in the flames slightly upstream the flame reaction zone. We also proposed an updated ion chemistry model and verified it against the experimental profiles of the most abundant cations in the flames. Our model is based on the kinetic mechanism available in the literature extended with the reactions for C₃H₅⁺ cation. Highly accurate W2-F12 quantum chemical calculations were used to obtain a reliable formation enthalpy of C₃H₅⁺. The model was found to reproduce properly the measured relative abundance of the key oxygenated cations (viz., CH₅O⁺, C₂H₃O⁺) in the whole range of equivalence ratios employed, and the C₃H₅⁺ cation abundance in the richest flame with ϕ=1.5, but significantly underpredicts the relative mole fraction of C₃H₃⁺, which becomes a key species under fuel-rich conditions. Apart from this, several aromatic and cyclic C_xH_y cations dominating under fuel-rich conditions were identified. We also considered the most important directions for the further refinement of the mechanism.     

Probing the low-temperature chemistry of methyl hexanoate: Insights from oxygenate intermediates

Understanding the combustion of methyl esters is crucial to elucidate kinetic pathways and predict combustion parameters, soot yields, and fuel performance of biodiesel, however most kinetic studies of methyl esters have focused on smaller, surrogate model esters. Methyl hexanoate is a larger methyl ester approaching the chain length of methyl esters found in biodiesel and has not received as much research attention as other smaller esters. The purpose of this work is to present the first atmospheric pressure combustion data of methyl hexanoate, CH₃CH₂CH₂CH₂CH₂COOCH₃. Mixtures of 2% methyl hexanoate in O₂ and N₂ are studied using a plug flow reactor at atmospheric pressure, wall temperatures from 573 to 973 K, residence times from roughly 1-2 s., and fuel equivalence ratios of 1, 1.5, and 2. Exhaust gases are analyzed by a gas chromatograph-mass spectrometer system and species mole fractions are presented. The literature model shows satisfactory agreement with the experimental species profiles and improvements for future mechanistic studies are suggested. In particular, this work proposes new unimolecular decomposition pathways of methyl hexanoate to form methanol or methyl acetate. Furthermore, the experiment detected three unsaturated esters that are direct products of the low temperature oxidation chemistry and it provides more insight into branching ratios for the formation of methyl hexanoate radicals and for the decomposition of hydroperoxyalkyl radicals.     

Lean or ultra-lean stretched planar methane/air flames

Lean premixed combustion has potential advantages of reducing pollutants and improving fuel economy. In some lean engine concepts, the fuel is directly injected into the combustion chamber resulting in a distribution of lean fuel/air mixtures. In this case, very lean mixtures can burn when supported by hot products from more strongly burning flames. This study examines the downstream interaction of opposed jets of a lean-limit CH₄/air mixture vs. a lean H₂/air flame. The CH₄ mixtures are near or below the lean flammability limit. The flame composition is measured by laser-induced Raman scattering and is compared to numerical simulations with detailed chemistry and molecular transport including the Soret effect. Several sub-limit lean CH₄/air flames supported by the products from the lean H₂/air flame are studied, and a small amount of CO₂ product (around 1% mole fraction) is formed in a “negative flame speed” flame where the weak CH₄/air mixture diffuses across the stagnation plane into the hot products from the H₂/air flame. Raman scattering measurements of temperature and species concentration are compared to detailed simulations using GRI-3.0, C₁, and C₂ chemical kinetic mechanisms, with good agreement obtained in the lean-limit or sub-limit flames. Stronger self-propagating CH₄/air mixtures result in a much higher concentration of product (around 6% CO₂ mole fraction), and the simulation results are sensitive to the specific chemical mechanism. These model-data comparisons for stronger CH₄/air flames improve when using either the C₂ or the Williams mechanisms.