Experimental and kinetic modeling of methyl octanoate oxidation in an opposed-flow diffusion flame and a jet-stirred reactor

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Proceedings of the Combustion Institute 33 (2011) 1037–1043

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Experimental and kinetic modeling of methyl octanoate oxidation in an opposed-flow diffusion flame and a jet-stirred reactor G. Dayma a,b,*, S.M. Sarathy c, C. Togbe´ a, C. Yeung c, M.J. Thomson c, P. Dagaut c a

CNRS, 1C, Ave de la recherche scientifique – 45071 Orle´ans cedex 2, France University of Orle´ans, Faculte´ des Sciences – 45067 Orle´ans cedex 2, France c Department of Mechanical and Industrial Engineering, University of Toronto, Toronto, ON, Canada b

Available online 21 August 2010

Abstract New experimental results, consisting of concentration profiles of stable species as a function of temperature, were obtained for the oxidation of methyl octanoate in a jet-stirred reactor (JSR) at 0.101 MPa, 0.5 < u < 2 and 800 < T (K) < 1350. In addition, new experimental data, consisting of concentration profiles of stable species as a function of distance from fuel port, generated in an opposed-flow diffusion flame at 0.101 MPa are presented. A detailed chemical kinetic model was developed to study the oxidation of methyl octanoate (CAS 111-11-5), a model compound for biodiesel fuels, under the present conditions. The kinetic model consists of 383 chemical species and 2781 chemical reactions (most of them reversible). Experimentally, the oxidation of methyl octanoate in the JSR at atmospheric pressure does not show low temperature and negative temperature coefficient behavior, whereas hot ignition occurs at about 800 K. The present modeling results are in reasonably good agreement with the experimental data, describing the intermediate species measured in the jet-stirred reactor and in opposed-flow diffusion flame experiments. Ó 2010 The Combustion Institute. Published by Elsevier Inc. All rights reserved. Keywords: Methyl octanoate; Opposed-flow diffusion flame; Jet-stirred reactor; Kinetic modeling; Biodiesel

1. Introduction Diesel engines will continue to be used in the future because of their high efficiency; however more sustainable and environment-friendly fuels

*

Corresponding author at: CNRS, 1C, Ave de la recherche scientifique – 45071 Orle´ans cedex 2, France. Fax: +33 238696004. E-mail address: [email protected] (G. Dayma).

are needed to reduce carbon dioxide emissions. Fuels derived from biomass (i.e., biofuels) are already blended in variable quantities with petroleum-derived diesel fuel [1–3]. Reduced emissions of carbon oxides and polyaromatic hydrocarbons (PAH) have been reported, showing the usefulness of biodiesel [3,5]. The so-called “biodiesel” is a mixture of mono-alkyl esters obtained by transesterification, with methanol, of long carbon-chain fatty acids obtained from renewable lipid feedstock (i.e., mostly oleaginous plants) [4]. Biodiesel fuels are complex mixtures of ca. C14–C22 esters

1540-7489/$ - see front matter Ó 2010 The Combustion Institute. Published by Elsevier Inc. All rights reserved. doi:10.1016/j.proci.2010.05.024

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with varying degrees of unsaturation. Therefore, surrogate model fuels are used for simulating their kinetics of oxidation. Previous kinetic studies showed a strong similitude between the oxidation of n-hexadecane and that of RME [6,7], allowing its use as a chemical surrogate; however, recently long-chain methyl esters were proposed as biodiesel model fuels [7–9]. As part of continuing efforts to improve the knowledge of renewable fuels oxidation, we present new experimental and modeling results for the oxidation of methyl octanoate (MO), a potential biodiesel surrogate, in a JSR and an opposedflow diffusion flame at 0.101 MPa and a wide range of initial conditions. 2. Experimental 2.1. Jet-stirred reactor We used the JSR experimental set-up described earlier [8,10]. It consisted of a 4 cm diameter (39 cm3) fused-silica sphere (wall catalytic reactions minimized), equipped with 4 nozzles of 1 mm I.D. for the admission of the gases, which achieve the stirring. A nitrogen flow of 50 L/h was used to dilute the fuel. As before [8,11–13], all the gases were preheated to minimize temperature gradients. High purity oxygen (99.995% pure) was used. The fuel (>99% pure, Sigma–Aldrich) was sonically degassed before use and a HPLC pump (Shimadzu LC10-AD-VP and DGU-20-A3) was used to deliver the fuel to an atomizer-vaporizer assembly maintained at 200 °C. Good thermal homogeneity along the vertical axis of the reactor was observed for each experiment by thermocouple (0.1 mm Pt– Pt/Rh 10% located inside a thin-wall silica tube) measurements (gradients of ca. 1 K/cm). The accuracy of these measurements is estimated at +/ 5K. The reacting mixtures were sampled using a fusedsilica sonic probe. The samples were taken at steady temperature and residence time (70 ms) and analyzed by gas chromatography (ca. 4–6 kPa) and Fourier transform infrared spectroscopy (20 kPa) [14]. These analytical equipments allowed measuring the concentrations of MO, oxygen, hydrogen, ethanal, propanal, methane, ethane, ethylene, acetylene, C3–7 1-alkene, 1,3-butadiene, CH2O, CO, CO2, and unsaturated methyl esters from methyl propenoate to methyl 6-heptenoate. A good repeatability of the measurements and a good carbon balance (ca. 100 ± 10%) were obtained in this series of experiments. 2.2. Opposed-flow diffusion flame A detailed explanation of the experimental opposed-flow diffusion flame and corresponding sampling set-up has been described by Sarathy et al. [15]. A fuel mixture of 98.2% N2 and 1.8%

fuel (99% pure MO) is fed through the bottom port at a mass flux of 0.0142 g/cm2 -sec, while an oxidizer mixture of 42.25% O2 and 57.75% N2 is fed through the top port at a mass flux of 0.0137 g/cm2-sec. At these plug flow conditions, the Reynold’s Number is in the laminar flow regime (i.e. Re < 400), the flame is on the fuel side of the stagnation plane, and the fuel side strain rate is approximately 33 s 1. An ultrasonic atomizer sprays the liquid fuel into a stream of N2 gas. The temperatures of the gases exiting the top and bottom burner ports were 420 and 400 K, respectively. Analytical techniques used to measure the species in the sample included: non-dispersive infrared detection (NDIR) for CO and CO2; gas chromatography/flame ionization detection (GC/ FID) with an HP-Al/S PLOT column for C1 to C5 hydrocarbons; and GC/FID equipped with a methanizer (i.e., Ni catalyst) and Poraplot-U column for oxygenated hydrocarbons such as acetaldehyde/ethenol, formaldehyde, and ketene. The precision of species measurements is estimated to be ±15%. Temperature measurements were obtained using a 254 lm diameter wire R-type thermocouple (Pt–Pt/Rh 13%). The measured temperatures were corrected for radiation losses [16]. This apparatus was unable to accurately measure temperatures on the oxidizer-rich side of the flame (i.e., 10.5 mm above the fuel port). 3. Modeling The opposed-flow diffusion flame computations were performed using the OPPDIF code [17]. The JSR kinetic modeling was performed using the Chemkin II computer package [18,19]. The reaction mechanism used here has a strong hierarchical structure. It is based on the oxidation mechanism proposed earlier for a variety of hydrocarbons [20] and extended to the modeling of the oxidation of methyl esters and ethanol blended fuels [8,21]. It is available from the authors ([email protected]) and as supporting information. The rate constants for reverse reactions were computed from the corresponding forward rate constants and the appropriate equilibrium constants, Kc = kforward/kreverse, calculated from thermochemistry [8,21,22]. Since no cool flame was detected in JSR experiments, the proposed kinetic scheme only includes high temperature chemistry. In the following, we will only discuss rate constants that have changed compared to our previous works [8,14]. Rate constants for unimolecular initiations by C–H bond rupture (788. MHP6D4D + OH = H2O + NC4 H5 + MP2D, 789. MHP6D4D + H = H2 + NC4 H5 + MP2D, 790. MO = MO8J + H, 791. MO = MO7J + H, 792. MO = MO6J + H, 793. MO = MO5J + H, 794. MO = MO4J + H, 795. MO = MO3J + H) were kept from our previous studies,

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whereas those for C–C bond ruptures have been reevaluated and taken from [23] for reaction 796, MO2J + H = MO, from [24] for reactions 797: MO = OMMJ + H, 798: MO = MHP7J + CH3, 799: MO = MHX6J + C2H5, 800: MO = MPE5J + NC3H7, and 801: MO = MB4J + PC4H9, from acetone oxidation by [25] for reaction 802, MO = MP3J + C5H11-1, dimethyl carbonate by [26] for reaction 803, MO = ME2J + C6H13-1, and dimethyl ether from [27] for reaction 804, MO = CH3OCO + C7H15-1. As explained previously, fuel consumption was not sensitive to these reactions in our previous experimental conditions (1.01 MPa), but at the present atmospheric pressure conditions unimolecular reactions have increased sensitivity. H-abstractions by radicals were not modified, except those with peroxy radicals that were removed. b-scissions by Csp3–Csp3 bond breaking (reactions 909–916, 918, and 919, i.e. 909: MO + MO2J = MO4J + MO, 910: MO + MO2J = MO3J + MO, 911: MO + MO2J = OMMJ + MO, 912: MO8J = C2H4 + MHX 6J, 913: MO7J = C3H6 + MPE5J, 914: MO6J = C4H8-1 + MB4J, 915: MO6J = CH3 + MHP6D, 916: MO5J = C5H10-1 + MP3J, 918: MO4J = C6H12 1 + ME2J, 919: MO4J = NC3H7 + MPE4D) were taken from [28] with an activation energy decreased by 3 kcal mol 1 for the formation of methyl ethanoyl radical (ME2J, reaction 915). Moreover, the rate constant for the C–O bond rupture yielding methoxy (920: MO3J = C7H141 + CH3OCO) has been updated and taken from [29]. b-scissions by C–H bond breaking were not modified. As specified in our previous work dealing with methyl heptanoate oxidation [14], rate constants for H-transfer through 5-, 6- and 7-membered ring transition states (934: MO3J = H + MO3D, 935: MO3J = H + MO2D, 936: MO2J = H + MO2D, 937: MO8J = MO5J, 938: MO8J = MO4J, 939: MO8J = MO3J, 940: MO7J = > MO4J, 941: MO7J = >MO3J, 942: MO6J = > MO3J, 943: MO4J = >MO7J, 944: MO4J = OMMJ, 945: MO3J = >MO7J, 946: MO3J = > MO6J, 947: MO3J = OMMJ, 948: MO2J = MO7J) have been reevaluated to be consistent with the rate constants determined by Tsang et al. [30] for octyl radicals. Moreover, the activation energy of the H-transfer when carbon “M” is involved has been increased by 5 kcal mol 1 because of the presence of the acyloxy group in the cycle of the transition state. Rate constants for oxidation reactions yielding methyl octenoates were not changed. Finally, the C0–C3 sub-mechanism has been updated thanks to recently widely validated detailed kinetic mechanism proposed by [31]. The transport property database was mostly from [32]. Additional transport parameters were determined for stable C2–C10 saturated and unsaturated methyl esters and their corresponding radicals. We assumed that the transport properties are similar for saturated and unsaturated methyl

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esters of the same chain length. For methyl ester radical species, the transport properties of their stable counterpart were used. The methods used for calculating transport properties are given in [33]. 4. Results and discussion 4.1. Jet-stirred reactor Figures 1, 2 and 3 present a comparison between the experimental and modeling results. The model gives an overall good representation of the data. For the three equivalence ratios, the reactivity of MO is well predicted over the temperature range. The low temperature region was investigated at u = 1 and no reactivity was observed, as expected, i.e. no cool flame nor negative temperature coefficient was observed under these experimental conditions due to the high dilution of the mixture, the short residence time, and the atmospheric pressure. For the lean and the stoichiometric mixtures, the consumption of the intermediates is too fast after 1100 K. This phenomenon can particularly be seen on the hydrogen profiles and may be related to an over production of small radicals. For u = 2, at high temperature, the formation of H2 and C2H2 is under-predicted by this model. The variation of the mole fractions of 1-olefins (from C2H4 to 1C7H14) along temperature is well predicted. Ethane, methane and hydrogen concentration profiles are also well predicted. At high temperature, the modeling is in good agreement with the data for CO, CO2, and H2O. Reaction path analyses, (Fig. 4), were performed to determine the most important pathways for the consumption of MO at T = 1050 K, u = 1, s = 70 ms and 0.101 MPa. Under these conditions, half of the fuel is consumed, mostly by H-abstractions by H and OH to produce MO2J (20%), MO7J, MO6J, MO5J, MO4J, and MO3J (all 11%), MO8J (5%) and MOMJ (5%). Due to its enhanced stability, MO2J is the most abundant among the primary radicals. This radical mainly decomposes by b-scission (reaction 922: MO2J = C5H11-1 + MP2D, 84%) to give 1-pentyl and methyl propenoate, which is a minor product species. The MO2J also isomerizes (reaction 950: MO2J = MO5J, 12%) and yields MO5J by a 1–4 H-atom transfer. MO8J isomerizes into MO4J (reaction 938: 54%) by a 1–5 H-atom transfer or gives ethylene and MHX6J by b-scission (reaction 912: 45%). MHX6J then mainly produces methyl propenoate and propyl after 1–5 isomerization into MHX6J and b-scission. MO7J also isomerizes into MO4J (reaction 940: 54%) by a 1–4 H-atom transfer or decomposes by b-scission (reaction 913: 54%) and yields propene and MPE5J. MPE5J mainly produces methyl propenoate and ethyl after 1–4 isomerization into MPE2J followed by a b-scission. MO6J reacts by b-scission to give

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Fig. 1. Methyl octanoate oxidation in a JSR at 0.101 MPa, s = 70 ms and u = 0.6. The initial mole fractions were: methyl octanoate, 0.1%; O2, 2.08%; N2, 97.81%. Experimental data (symbols) are compared to calculations (lines with small symbols).

Fig. 2. Methyl octanoate oxidation in a JSR at 0.101 MPa, s = 70 ms and u = 1. The initial mole fractions were: methyl octanoate, 0.1%; O2, 1.25%; N2, 98.65%.

methyl radicals and methyl 6-heptenoate (reaction 915: 25%) and 1-butene and MB4J (reaction 914: 75%). MB4J then decomposes by b-scission and yields ethylene and ME2J, which isomerizes into

MEMJ that decomposes into formaldehyde and CH3CO. MO5J gives 1-pentene and MP3J (reaction 916: 49%) and methyl 5-hexenoate and ethyl (reaction 917: MO5J = C2H5 + MHX5D,

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Fig. 3. Methyl octanoate oxidation in a JSR at 0.101 MPa, s = 70 ms and u = 2. The initial mole fractions were: methyl octanoate, 0.1%; O2, 0.625%; N2, 99.275%.

O O

-C2H5

O

O O

O

O O

O

+

O O

-C2H4

-nC3H7

O O

CH2O + CH3CO

O

-nC3H7

O

-C3H6

O

1-C4H8 O

O

O

-C2H4

O

O

O

+

O

+H, +OH

O

+H, +OH O

O

O

-H2, -H2O O

O

+

+H, +OH

-H2, -H2O

O

-CO

O O

+H, +OH O

O

O

1-C5H10

-H2, -H2O

O

-CH3

CH2O +

O

-H2, -H2O

O

-C2H4

O

O

O O

O

C2H4 + 1-C5H11

O

-CH3OCO

O

-C2H5

C2H4 + 1-C4H8

O O

O

O

+

O

O

O

+

C2H4 + CH3OCO

O

C2H4 + C2H5 C2H4 + nC3H7

Fig. 4. Flow rate analysis for methyl octanoate oxidation in a JSR at T = 1050 K, u = 1, s = 70 ms and 0.101 MPa (the thickness of the arrows is proportional to the importance of the reaction path). The products enframed were quantified.

49%). MO4J is produced by H-abstractions from the fuel (61%) but also from the isomerization of MO7J (24%) and MO8J (15%). The MO4J radical decomposes to either 1-hexene and ME2J (reaction

918: 81%) or propyl and methyl 4-pentenoate (reaction 919: 19%). Reaction 918 is favored because of the stability of ME2J. MO3J decomposes by b-scissions, mainly into 1-butyl and

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methyl 3-butenoate (reaction 921: MO3J = PC4H9 + MB3D, 67%) but also into 1-heptene and CH3OCO (reaction 920: 28%) because the activation energy of the Csp3–Csp3 bond b-scission is lower than that of the Csp3–Csp2 one. Finally, MOMJ completely decomposes by b-scission to produce formaldehyde and C7H15CO, which in turn gives 1-heptyl radicals by CO removal. 1-Heptyl radicals yield 1-olefines from ethylene to 1-pentene and smaller alkyl radicals after isomerizations and b-scissions. 4.2. Opposed-flow diffusion flame The measured species in the opposed-flow diffusion flame included MO (MO), carbon monoxide (CO), carbon dioxide (CO2), formaldehyde (CH2O), methane (CH4), acetylene (C2H2), ethylene (C2H4), ethane (C2H6), ketene (CH2CO), propane (C3H8), propene (C3H6), propyne (pC3H4), 1-butene (1-C4H8), 1,3-butadiene (1,3-C4H6), 1-pentene (1-C5H10), 1-hexene (1-C6H12), and 1-heptene (C7H14). The isomers ethanal (i.e., acetaldehyde) of C2H4O, (CH3CHO) and ethenol (C2H3OH), have the same retention time on the GC column, so we assume that the C2H4O measured in the GC is the combined concentration of acetaldehyde and ethenol in the flame. Figure 5 displays the measured and predicted species and temperature profiles obtained in the opposed-flow diffusion flame. The model well reproduces the experimentally measured tempera-

ture, the reactivity of MO, and the production of CO and CO2. The model well reproduces the shape of the minor product species profiles and the height and position of their maximum measured concentrations. The model’s quantitative prediction is considered good if the predicted maximum mole fraction is within a factor 1.5 of the measured maximum mole fraction. The model performs well in predicting the maximum concentrations of CH4, C2H2, C2H4, C3H4, 1,3-C4H6, 1C4H8, C7H14, and CH2CO. The model moderately (i.e., 1.5–2 times) underpredicts the maximum concentration of C2H6 and moderately overpredicts the concentration of CH2O, C3H6, C5H10, and C6H12. There is a large underprediction of C2H4O by the model. The overprediction of CH2O may be due to experimental error resulting in analyte loss through polymerization in the sampling lines [34]. Appreciable levels (i.e., hundreds of ppm) of unsaturated esters, such as methyl 2propenoate, methyl 3-butenoate, etc., are predicted by the model, but were not detected in the opposed-flow diffusion flame despite having the necessary analytical systems in place. It is hypothesized that errors in the flame experiments result in these species decomposing upon contact with hot surfaces in the high pressure side of the sampling line. Further investigation is required to test this hypothesis. A reaction path analysis was performed to determine the most important pathways for the consumption of MO at 1052 K. This is the temperature at which approximately 50% of the fuel

1800

TEMPERATURE (K)

1600 1400 1200 1000 800 600 Measured Corrected Predicted

400 200 0 0

5 10 15 20 DISTANCE FROM FUEL PORT (mm)

Fig. 5. Experimental (solid symbols) and computed (lines with symbols) profiles obtained from the oxidation of methyl octanoate in an atmospheric opposed-flow flame (1.8% MO, 42% O2).

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is consumed. Approximately 96% of the fuel is consumed via H-atom abstraction by H atoms (65%), OH radicals (3%), and CH3 radicals (25%). Abstraction is favoured for H atoms bonded to the a-carbon (20%) and the other secondary carbon atoms in the alkyl chain (13% each). 7% of the fuel is consumed by various unimolecular decomposition reactions leading to an ester radical and an alkyl radical. The reaction pathways in the non-premixed flame are similar to those in the premixed reactor. Therefore the diagram in Figure 4 describes the opposed-flow diffusion flame reaction pathways well. The primary difference is that CH3 radicals play a greater role in abstraction reactions within the flame where combustion is non-premixed, while OH radicals are predominant in the jet-stirred reactor where fuel and oxidizer are premixed. Once the intermediate esters are formed, they decompose via identical routes in both experimental configurations and lead to the same product species. 5. Conclusion New experimental results were obtained for the oxidation of methyl octanoate in a JSR and in an opposed-flow diffusion flame at 0.101 MPa. They consisted of concentration profiles of stable species (e.g., reactants, intermediates, and final products) obtained after probe sampling and chemical analysis. The proposed high temperature kinetic model represents the data fairly well. It was used to delineate the main routes of oxidation of the fuel. Further model validations are needed for ignition, low temperature and high pressure conditions. Appendix A. Supplementary data Supplementary data associated with this article can be found, in the online version, at doi:10.1016/j.proci.2010.05.024. References [1] X. Montagne, Sae Tech. Paper (1996) 962065. [2] M.S. Graboski, R.L. McCormick, Prog. Energy Combust. Sci. 24 (2) (1998) 125–164. [3] T.W. Ryan, D. Mehta, T.J. Callahan, in: P. Duret, X. Montagne (Eds.), Which Fuels for Low CO2 Engines?, Technip, Paris, France, 2004, pp. 59–67. [4] L. Ryan, F. Convery, S. Ferreira, Energy Policy 34 (17) (2006) 3184–3194. [5] C. Ilkilic, Energy Sources Part A-Recovery Util. Environ. Eff. 31 (6) (2009) 480–491. [6] P. Dagaut, S. Gail, M. Sahasrabudhe, Proc. Combust. Inst. 31 (2) (2007) 2955–2961.

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