Combined experimental and numerical study on the extinction limits of non-premixed H2/CH4 counterflow flames with varying oxidizer composition

Chemical reaction mechanisms with detailed kinetics are an important topic in combustion science and an essential prerequisite for the accurate modeling of reactive flows in combustors. Besides isolating and studying individual reactions, the development of reaction mechanisms is often based on well-defined experimental observables, such as the laminar burning velocity and the ignition delay time. While many optimization targets are associated with premixed combustion, the extinction strain rate (ESR) of non-premixed flames in the counterflow configuration is another well-defined experimental observable which, however, often receives less attention. In order to reduce the scarcity of corresponding datasets for the emerging fuel hydrogen and its blends with methane, this work reports ESR measurements for H₂, CH₄/H₂ and CH₄ counterflow diffusion flames considering a variation of the oxygen content in the oxidizer stream between 14 % and 21 %. The experimental investigation is complemented by calculations with a 1D counterflow model utilizing a temperature-control continuation method in order to determine the extinction limits numerically. The simulations are performed with six different well-established chemical reaction mechanisms. It is shown from both, experimental and numerical results, that with the substitution of CH₄ by H₂ the ESR increases and further, that the ESR decreases with a reduction of the oxygen content in the oxidizer stream. In addition, decreasing flame temperatures are observed at extinction as the H₂ content increases. Overall, all mechanisms are able to qualitatively recover the trends found for varying H₂ contents, fuel mole fraction, and oxygen content in the oxidizer. However, significant quantitative deviations are observed between the numerical results regarding the ESR values and the deviations are larger than for other important flame characteristics, such as the laminar burning velocity. The results suggest that the ESR could be a useful optimization target for further improving chemical reaction mechanisms which underlines the importance of datasets such as the one presented in this work.     

Radiation intensity imaging measurements of methane and dimethyl ether turbulent nonpremixed and partially premixed jet flames

Quantitative time-dependent images of the infrared radiation intensity from methane and dimethyl ether (DME) turbulent nonpremixed and partially premixed jet flames are measured and discussed in this work. The fuel compositions (CH₄/H₂/N₂, C₂H₆O/H₂/N₂, CH₄/air, and C₂H₆O/air) and Reynolds numbers (15,200–46,250) for the flames were selected following the guidelines of the International Workshop on Measurement and Computation of Turbulent Nonpremixed Flames (TNF Workshop). The images of the radiation intensity are acquired using a calibrated high speed infrared camera and three band-pass filters. The band-pass filters enable measurements of radiation from water vapor and carbon dioxide over the entire flame length and beyond. The images reveal localized regions of high and low intensity characteristic of turbulent flames. The peak mean radiation intensity is approximately 15% larger for the DME nonpremixed flames and 30% larger for the DME partially premixed flames in comparison to the corresponding methane flames. The trends are explained by a combination of higher temperatures and longer stoichiometric flame lengths for the DME flames. The longer flame lengths are attributed to the higher density of the DME fuel mixtures based on existing flame length scaling relationships. The longer flame lengths result in larger volumes of high temperature gas and correspondingly higher path-integrated radiation intensities near and downstream of the stoichiometric flame length. The radiation intensity measurements acquired with the infrared camera agree with existing spectroscopy measurements demonstrating the quantitative nature of the present imaging technique. The images provide new benchmark data of turbulent nonpremixed and partially premixed jet flames. The images can be compared with results of large eddy simulations rendered in the form of quantitative images of the infrared radiation intensity. Such comparisons are expected to support the evaluation of models used in turbulent combustion and radiation simulations.     

The role of particles in the inhibition of counterflow diffusion flames by iron pentacarbonyl

Laser light scattering and thermophoretic sampling have been used to investigate particle formation in counterflow diffusion flames inhibited by iron pentacarbonyl Fe(CO)₅. Three CH₄-O₂-N₂ reactant mixtures are investigated, with Fe(CO)₅ added to the fuel or the oxidizer stream in each. Flame calculations that incorporate only gas-phase chemistry are used to assist in interpretation of the experimental results. In flames with the inhibitor added on the flame side of the stagnation plane, the region of particle formation overlaps with the region of high H-atom concentration, and particle formation may interfere with the inhibition chemistry. When the inhibitor is added on the non-flame side of the stagnation plane, significant condensation of metal or metal oxide particles is found, and implies that particles prevent active inhibiting species from reaching the region of high radical concentration. As the inhibitor loading increases, the maximum scattering cross section increases sharply, and the difference between the measured and predicted inhibition effect widens, suggesting that particle formation is the cause of the deviation. Laser-based particle size measurements and thermophoretic sampling in low strain rate flames show that the particles have diameters between 10 nm and 30 nm. Thermophoresis affects the nanoparticle distribution in the flames, in some cases causing particles to cross the stagnation plane. The scattering magnitude in the counterflow diffusion flames appears to be strongly dependent on the residence time, and relatively independent of the peak flame temperature.     

Effects of H2 and H preferential diffusion and unity Lewis number on superadiabatic flame temperatures in rich premixed methane flames

The structures of freely propagating rich CH₄/air and CH₄/O₂ flames were studied numerically using a relatively detailed reaction mechanism. Species diffusion was modeled using five different methods/assumptions to investigate the effects of species diffusion, in particular H₂ and H, on superadiabatic flame temperature. With the preferential diffusion of H₂ and H accounted for, significant amount of H₂ and H produced in the flame front diffuse from the reaction zone to the preheat zone. The preferential diffusion of H₂ from the reaction zone to the preheat zone has negligible effects on the phenomenon of superadiabatic flame temperature in both CH₄/air and CH₄/O₂ flames. It is therefore demonstrated that the superadiabatic flame temperature phenomenon in rich hydrocarbon flames is not due to the preferential diffusion of H₂ from the reaction zone to the preheat zone as recently suggested by Zamashchikov et al. [V.V. Zamashchikov, I.G. Namyatov, V.A. Bunev, V.S. Babkin, Combust. Explosion Shock Waves 40 (2004) 32]. The suppression of the preferential diffusion of H radicals from the reaction zone to the preheat zone drastically reduces the degree of superadiabaticity in rich CH₄/O₂ flames. The preferential diffusion of H radicals plays an important role in the occurrence of superadiabatic flame temperature. The assumption of unity Lewis number for all species leads to the suppression of H radical diffusion from the reaction zone to the preheat zone and significant diffusion of CO₂ from the postflame zone to the reaction zone. Consequently, the degree of superadiabaticity of flame temperature is also significantly reduced. Through reaction flux analyses and numerical experiments, the chemical nature of the superadiabatic flame temperature phenomenon in rich CH₄/air and CH₄/O₂ flames was identified to be the relative scarcity of H radical, which leads to overshoot of H₂O and CH₂CO in CH₄/air flames and overshoot of H₂O in CH₄/O₂ flames.     

Numerical study of premixed twin edge flames in a counterflow field

Characteristics of premixed edge flames established in a counterflow field with a stretch-rate gradient were numerically investigated by solving three-dimensional governing equations with detailed chemistry in the general curvilinear coordinates system. Local mole fractions of radicals, such as OH or CH, at the flame edge of a CH₄/air mixture were found to be larger than those in other parts of the flame. On the other hand, local mole fractions of radicals in the flame edge of a C₃H₈/air mixture were smaller than those in other parts. These numerical results agreed well with the experimental results of the present authors. Moreover, it was elucidated that two flame edges of twin counterflow flames did not merge at the edge even in the case of the CH₄/air mixture. The ratio of the local stretch rate at the flame edge to the extinction stretch rate for planar twin flames with the same equivalence ratio was 0.6 for the CH₄/air mixture and 0.7 for the C₃H₈/air mixture. These numerical results also agreed with results of the past experiments. Moreover, as for relatively low stretch-rate gradients, the stretch-rate gradient had no strong influence on the characteristics of the edge flames.     

Influence of H2 on the response of lean premixed CH4 flames to high strained flows

A combined experimental and numerical investigation on the effects of H₂ addition to lean-premixed CH₄ flames in highly strained counterflow fields (with strain rates up to 8000 s⁻¹) using preheated flows indicate significant enhancement of lean flammability limits and extinction strain rates for relatively small amounts of H₂ addition. Numerical modeling of the counterflow opposed jet configuration used in this study indicated extinction strain rates which were within 5% of experimentally measured values for equivalence ratios ranging from 0.75 to less than 0.4. Both experimental and numerical results indicate that increasing H₂ in the fuel significantly increases flame speeds and thus extinction strain rates. Furthermore, increasing H₂ decreases the dependency of extinction equivalence ratio on the strain rate of the flow. For all of the mixtures investigated, extinction temperatures depend primarily on equivalence ratio and not fuel composition for the range of H₂ content studied, which suggests that extinction can be correlated to flame temperature and O₂ concentration. Nonetheless, H₂ addition greatly increases the maximum allowable strain rate before extinction temperatures are reached. Inspection of the model-predicted species profiles suggest that the enhancement of CH₄ burning rates with H₂ addition is driven by early H₂ breakdown increasing radical production rates early in the flame zone to enhance CH₄ ignition under conditions where otherwise CH₄ combustion might be prone to undergo extinction.     

Numerical investigation on NO formation in laminar counterflow methane/n-heptane dual fuel flames

To understand the fundamental mechanisms of NO formation in natural gas-diesel dual fuel combustion, a numerical study on NO formation in laminar counterflow methane (CH₄)/n-heptane (n-C₇H₁₆) dual fuel flames is conducted. The results reveal that the flame structure and NO formation vary with the fuel equivalence ratio. For a given n-C₇H₁₆/air mixture, the NO emission index decreases with increasing the equivalence ratio of the CH₄/air mixture (φ(CH₄/air)). The NO formation route analysis suggests that the prompt and thermal routes dominate the NO formation. The increase in φ(CH₄/air) causes the decrease in the contribution of the prompt route to overall NO formation. NO formation by prompt route is mainly caused by rich n-C₇H₁₆ combustion. As φ(CH₄/air) increases, the mole fractions of the radicals (OH, O and H) related to CH formation in the reaction zone of rich n-C₇H₁₆/air flame branch are decreased, which reduces the formation of NO by prompt route.     

A mechanistic study of Soret diffusion in hydrogen–air flames

The separate and combined effects of Soret diffusion of the hydrogen molecule (H₂) and radical (H) on the structure and propagation speed of the freely-propagating planar premixed flames, and the strain-induced extinction response of premixed and nonpremixed counterflow flames, were computationally studied for hydrogen–air mixtures using a detailed reaction mechanism and transport properties. Results show that, except for the conservative freely-propagating planar flame, Soret diffusion of H₂ increases the fuel concentration entering the flame structure and as such modifies the mixture stoichiometry and flame temperature, which could lead to substantial increase (decrease) of the flame speed for the lean (rich) mixtures respectively. On the other hand, Soret diffusion of H actively modifies its concentration and distribution in the reaction zone, which in turn affects the individual reaction rates. In particular, the reaction rates of the symmetric, twin, counterflow premixed flames, especially at near-extinction states, can be increased for lean flames but decreased for rich flames, whose active reaction regions are respectively located at, and away from, the stagnation surface. However, such a difference is eliminated for the single counterflow flame stabilized by an opposing cold nitrogen stream, as the active reaction zone up to the state of extinction is always located away from the stagnation surface. Finally, the reaction rate is increased in general for diffusion flames because the bell-shaped temperature distribution localizes the H concentration to the reaction region which has the maximum temperature.     

Effects of Lewis number and preferential diffusion on flame characteristics in 80%H2/20%CO syngas counterflow diffusion flames diluted with He and Ar

Numerical study is conducted to grasp flame characteristics in H₂/CO syngas counterflow diffusion flames diluted with He and Ar. An effective fuel Lewis number, applicable to premixed burning regime and even to moderately stretched diffusion flames, is suggested through the comparison among fuel Lewis number, effective Lewis number, and effective fuel Lewis number. Flame characteristics with and without the suppression of the diffusivities of H, H₂, and He are compared in order to clarify the important role of preferential diffusion effects through them. It is found that the scarcity of H and He in reaction zone increases flame temperature whereas that of H₂ deteriorates flame temperature. Impact of preferential diffusion of H, H₂, and He in flame characteristics is also addressed to reaction pathways for the purpose of displaying chemical effects.     

Effect of CO2/N2/CH4 dilution on NO formation in laminar coflow syngas diffusion flames

The effect of CO₂/N_2/CH₄ dilution on NO formation in laminar coflow H₂/CO syngas diffusion flames was experimentally and numerically investigated. The results reveal that the NO emission index increases with H₂/CO mole ratio. In all cases, CO₂/N₂/CH₄ dilution can reduce the peak temperature of syngas flame and have the ability to reduce peak flame temperature is decreased in the following order: CO₂>N₂>CH₄. CO₂/N₂ dilution reduces the NO formation in syngas flame while CH₄ dilution promotes the NO formation. Besides, the dilution of CO₂/N₂/CH₄ can reduce the peak mole fraction of OH and its variations with H₂/CO mole ratio and dilution ratio show the same trend as the peak flame temperature variations. The height of the flame with CO₂ and N₂ dilution increases with dilution ratio. The flame with CH₄ dilution becomes higher and wider with the increase of dilution ratio.     

A numerical study on NOx formation in laminar counterflow CH4/air triple flames

Formation of NO_x in counterflow methane/air triple flames at atmospheric pressure was investigated by numerical simulation. Detailed chemistry and complex thermal and transport properties were employed. Results indicate that in a triple flame, the appearance of the diffusion flame branch and the interaction between the diffusion flame branch and the premixed flame branches can significantly affect the formation of NO_x, compared to the corresponding premixed flames. A triple flame produces more NO and NO₂ than the corresponding premixed flames due to the appearance of the diffusion flame branch where NO is mainly produced by the thermal mechanism. The contribution of the N₂O intermediate route to the total NO production in a triple flame is much smaller than those of the thermal and prompt routes. The variation in the equivalence ratio of the lean or rich premixed mixture affects the amount of NO formation in a triple flame. The interaction between the diffusion and the premixed flame branches causes the NO and NO₂ formation in a triple flame to be higher than in the corresponding premixed flames, not only in the diffusion flame branch region but also in the premixed flame branch regions. However, this interaction reduces the N₂O formation in a triple flame to a certain extent. The interaction is caused by the heat transfer and the radical diffusion from the diffusion flame branch to the premixed flame branches. With the decrease in the distance between the diffusion flame branch and the premixed flame branches, the interaction is intensified.     

An experimental and numerical study on characteristics of laminar premixed H2/CO/CH4/air flames

The effects of variations in the fuel composition on the characteristics of H₂/CO/CH₄/air flames of gasified biomass are investigated experimentally and numerically. Experimental measurements and numerical simulations of the flame front position and temperature are performed in the premixed stoichiometric H₂/CO/CH₄/air opposed-jet flames with various H₂ and CO contents in the fuel. The adiabatic flame temperatures and laminar burning velocities are calculated using the EQUIL and PREMIX codes of Chemkin collection 3.5, respectively. Whereas the flame structures of the laminar premixed stoichiometric H₂/CO/CH₄/air opposed-jet flames are simulated using the OPPDIF package with the GRI-Mech 3.0 chemical kinetic mechanisms and detailed transport properties. The measured flame front position and temperature of the stoichiometric H₂/CO/CH₄/air opposed-jet flames are closely predicted by the numerical calculations. Detailed analysis of the calculated chemical kinetic structures reveals that the reaction rate of reactions (R38), (R46), and (R84) increase with increasing H₂ content in the fuel mixture. It is also found that the increase in the laminar flame speed with H₂ addition is most likely due to an increase in active radicals during combustion (chemical effect), rather than from changes in the adiabatic flame temperature (thermal effect). Chemical kinetic structure and sensitivity analyses indicate that for the stoichiometric H₂/CO/CH₄/air flames with fixed H₂ concentration in the fuel mixture, the reactions (R99) and (R46) play a dominant role in affecting the laminar burning velocity as the CO content in the fuel is increased.     

A reaction mechanism for gasoline surrogate fuels for large polycyclic aromatic hydrocarbons

This work aims to develop a reaction mechanism for gasoline surrogate fuels (n-heptane, iso-octane and toluene) with an emphasis on the formation of large polycyclic aromatic hydrocarbons (PAHs). Starting from an existing base mechanism for gasoline surrogate fuels with the largest chemical species being pyrene (C₁₆H₁₀), this new mechanism is generated by adding PAH sub-mechanisms to account for the formation and growth of PAHs up to coronene (C₂₄H₁₂). The density functional theory (DFT) and the transition state theory (TST) have been adopted to evaluate the rate constants for several PAH reactions. The mechanism is validated in the premixed laminar flames of n-heptane, iso-octane, benzene and ethylene. The characteristics of PAH formation in the counterflow diffusion flames of iso-octane/toluene and n-heptane/toluene mixtures have also been tested for both the soot formation and soot formation/oxidation flame conditions. The predictions of the concentrations of large PAHs in the premixed flames having available experimental data are significantly improved with the new mechanism as compared to the base mechanism. The major pathways for the formation of large PAHs are identified. The test of the counterflow diffusion flames successfully predicts the PAH behavior exhibiting a synergistic effect observed experimentally for the mixture fuels, irrespective of the type of flame (soot formation flame or soot formation/oxidation flame). The reactions that lead to this synergistic effect in PAH formation are identified through the rate-of-production analysis.     

The effects of hydrogen addition on soot formation in counterflow diffusion n-heptane flames

The effects of H₂ addition on soot formation are investigated in counterflow diffusion n-heptane flames. Three effects including chemical, thermal, and dilution are fully isolated and characterized by additions of H₂, He, and Ar. Soot volume fractions are measured using LE-calibrated LII technique, and flame temperatures are measured using OH-TLAF method along with a thermocouple. Numerical simulations are conducted with a detailed mechanism with soot model. The simulated soot volume fractions and flame temperatures are in good agreement with experimental data. The experimental results show that H₂ addition can greatly reduce the soot formation. It is also found that the chemical and dilution effects suppress soot formation, while the thermal effect with increasing flame temperature promotes soot formation. Kinetic analysis suggests that HACA growth rate could be the dominant factor that controls the final soot formation through the three effects due to H₂ addition.     

A mechanistic evaluation of Soret diffusion in heptane/air flames

The influence of Soret diffusion on the structure and response of n-heptane/air flames is investigated numerically with detailed reaction mechanism and transport. Unstretched freely-propagating planar premixed flames as well as stretched counterflow premixed and diffusion flames are studied, with emphasis on the separate and combined Soret effects of heptane and its oppositely-directed decomposition species H₂ and H, as well as those of the major species O₂, N₂, CO₂ and H₂O. Results show that, in the unstretched case for which the flame temperature remains at its adiabatic value, Soret diffusion primarily affects the chemical kinetics embedded in the flame structure and the net effect is small; while in the stretched cases, its impact is mainly through those of heptane and the secondary fuel H₂ in modifying the flame temperature, with substantial effects, while H₂ and H also affect the chemical kinetics especially when the active reaction zone is localized. The dilution/enrichment of the reactant concentrations in the flame through the Soret diffusion of the major species O₂, N₂, CO₂ and H₂O further exert finite effects on the flame burning intensity.     

Kinetic modeling study of hydrogen addition to premixed dimethyl ether-oxygen-argon flames

The chemical composition of flames was examined systematically for a series of laminar, premixed low-pressure Dimethyl ether (DME)-oxygen-argon flames blended with hydrogen. The effects of hydrogen addition to the DME base flame were seen to result in interesting differences. The flame is analyzed with a comprehensive kinetic model that combines the chemistries of hydrogen and DME combustion. The results indicated that the reduction of CH₃OCH₃ mole fraction in the blend is the dominant factor for the reduction of CH₃OCH₃ and CO mole fractions in the flame. The rate of the primary reactions related to CH₃OCH₃ and CO increases obviously with the addition of hydrogen. When the volume fractions of H₂ to the total of DME and H₂ exceeds 40%, H₂ will change from an intermediate species to a reactant, which means the effect of H₂ on the premixed combustion will be more significant. The free radicals in the radical pool, such as H, O and OH radicals, increase as hydrogen is added, which promote the combustion process. The mole fraction of CH₂O is decreased as hydrogen is added. Less soot precursors (acetylene (C₂H₂)) were produced with the addition of H₂.     

The calculation of ion currents in hydrocarbon flames

The calculation of ion currents in hydrocarbon flames was attempted to test a mechanism involving temperature dependence. Values of [CH] and [O] in the flame are available in some cases of permixed methaneoxygen flames, but not for the diffusion flame of H₂ and air containing hydrocarbon. For the latter cases a relationship between [CH₄] and [CH] was sought, using the kinetics of the stages CH₄ → CH₃ → CH₂ → CH → CHO⁺ and of the competitive combustion to oxygenated products. An approximate value of the ionization efficiency (φ) of CH₄ was calculated and found to agree with experimental determinations in premixed CH₄O₂ and diffusion H₂air plus CH₄ flames. The maximum saturation current was calculated for a premixed CH₄O₂ flame using literature data, and a modified method was applied to a H₂air diffusion flame. The shape of the hydrogen flame ionization detector response curve was calculated from the data of H₂ oxidation kinetics and the ionization path CH₄ → CHO⁺. The calculated curve was a reasonable representation of the experimental observations, and the calculated maximum response was within an order of magnitude of the observed value.     

A detailed numerical study of NOx kinetics in low calorific value H2/CO syngas flames

The present study provides an extensive and detailed numerical analysis of NO_x chemical kinetics in low calorific value H₂/CO syngas flames utilizing predictions by five chemical kinetic mechanisms available out of which four deal with H₂/CO while the fifth mechanism (GRI 3.0) additionally accounts for hydrocarbon chemistry. Comparison of predicted axial NO profiles in premixed flat flames with measurements at 1 bar, 3.05 bar and 9.15 bar shows considerably large quantitative differences among the various mechanisms. However, at each pressure, the quantitative reaction path diagrams show similar NO formation pathways for most of the mechanisms. Interestingly, in counterflow diffusion flames, the quantitative reaction path diagrams and sensitivity analyses using the various mechanisms reveal major differences in the NO formation pathways and reaction rates of important reactions. The NNH and N₂O intermediate pathways are found to be the major contributors for NO formation in all the reaction mechanisms except GRI 3.0 in syngas diffusion flames. The GRI 3.0 mechanism is observed to predict prompt NO pathway as the major contributing pathway to NO formation. This is attributed to prediction of a large concentration of CH radical by the GRI 3.0 as opposed to a relatively negligible value predicted by all other mechanisms. Also, the back-conversion of NNH into N₂O at lower pressures (2–4 bar) was uniquely observed for one of the five mechanisms. The net reaction rates and peak flame temperatures are used to correlate and explain the differences observed in the peak [NO] at different pressures. This study identifies key reactions needing assessment and also highlights the need for experimental data in syngas diffusion flames in order to assess and optimize H₂/CO and nitrogen chemistry.     

Computational and experimental study of the effects of adding dimethyl ether and ethanol to nonpremixed ethylene/air flames

Two sets of axisymmetric laminar coflow flames, each consisting of ethylene/air nonpremixed flames with various amounts (up to 10%) of either dimethyl ether (CH₃-O-CH₃) or ethanol (CH₃-CH₂-OH) added to the fuel stream, have been examined both computationally and experimentally. Computationally, the local rectangular refinement method, which incorporates Newton's method, is used to solve the fully coupled nonlinear conservation equations on solution-adaptive grids for each flame in two spatial dimensions. The numerical model includes C6 chemical kinetic mechanisms with up to 59 species, detailed transport, and an optically thin radiation submodel. Experimentally, thermocouples are used to measure gas temperatures, and mass spectrometry is used to determine concentrations of over 35 species along the flame centerline. Computational results are examined throughout each flame, and validation of the model occurs through comparison with centerline measurements. Very good agreement is observed for temperature, major species, and several minor species. As the level of additive is increased, temperatures, some major species (CO₂, C₂H₂), flame lengths, and residence times are essentially unchanged. However, peak centerline concentrations of benzene (C₆H₆) increase, and this increase is largest when dimethyl ether is the additive. Computational and experimental results support the hypothesis that the dominant pathway to C₆H₆ formation begins with the oxygenates decomposing into methyl radical (CH₃), which combines with C2 species to form propargyl (C₃H₃), which reacts with itself to form C₆H₆.     

Numerical study on effect of CO2 addition in flame structure and NOx formation of CH4‐air counterflow diffusion flames

Numerical study with detailed chemistry has been conducted to investigate the effect of CO₂ addition on flame structure and NO_x formation in CH₄–air counterflow diffusion flame. Radiation effect is found to be dominant especially at low strain rates. The addition of CO₂ makes radiation effect more remarkable even at high‐strain rates. It is, as a result, seen that flame structure is determined by the competition between the radiation and strain rate effects. The important role of CO₂ addition is addressed to thermal and chemical reaction effects, which can be precisely specified through the introduction of an imaginary species. Thermal effect contributes to the changes in flame structure and NO formation mainly, but the effect of chemical reaction cannot be neglected. It is noted that flame structure is changed considerably due to the addition of CO₂, in such a manner, that the path of methane oxidation prefers to take CH₄→CH₃→C₂H₆→C₂H₅ instead of CH₄→CH₃→CH₂→CH. Copyright © 2001 John Wiley & Sons, Ltd.