Experimental and Chemical Kinetic Modeling Study of 3-Pentanone Oxidation

Abstract

Shock tube ignition delay times have been measured for 3-pentanone at a reflected shock pressure of 1 atm (±2%), in the temperature range 1250-1850 K, at equivalence ratios of 0.5-2.0 for O(2) mixtures in argon with fuel concentrations varying from 0.875 to 1.3125%. Laminar flame speeds have also been measured at an initial pressure of 1 atm over an equivalence ratio range. Complementary to previous studies [Pichon S., Black, G., Chaumeix, N., Yahyaoui, M., Simmie, J. M., Curran, H. J., Donohue, R. Combust. Flame, 2009, 156, 494-504; Serinyel, Z.; Black, G.; Curran, H. J.; Simmie, J. M. Combustion Sci. Tech., 2010, 182, 574-587], laminar flame speeds of 2-butanone have also been measured, and relative reactivities of these ketones have been compared and discussed. A chemical kinetic submechanism describing the oxidation of 3-pentanone has been developed and detailed in this paper; rate constants for unimolecular fuel decomposition reactions have been treated for falloff in pressure with nine-parameter fits using the Troe Formulism. Both compounds treated in this work may be used as fuel tracers, thus further ignition delay time measurements have been carried out by adding 3-pentanone to n-heptane in order to test the effect of the blend on ignition delay timing. It was found that the autoignition characteristics of n-heptane remained unaffected in the presence of 15% 3-pentanone in the fuel, consistent with results obtained using acetone and 2-butanone [Pichon S., Black, G., Chaumeix, N., Yahyaoui, M., Simmie, J. M., Curran, H. J., Donohue, R. Combust. Flame, 2009, 156, 494-504; Serinyel, Z.; Black, G.; Curran, H. J.; Simmie, J. M. Combustion Sci. Tech., 2010, 182, 574-587].

An experimental and kinetic modeling study of the pyrolysis and oxidation of n-C3C5 aldehydes in shock tubes

“…The presence of the H-C=O groups leads to the formation of resonantly stabilized radicals and the reactivity of the H-atoms in the β site is slightly enhanced with respect to secondary H-atoms in alkanes. This fact is also evident observing the enthalpy of formation in Table 3 and it is further supported by the kinetic study of 3-pentanone oxidation by Serinyel et al [73]. Rate constants for abstractions from the remaining secondary and primary H-atoms were adopted according to their values used for n-alkanes [77].…”

Shock tube measurements of 3-pentanone pyrolysis and oxidation

“…CO 2 laser absorption of C 2 H 4 C 2 H 4 was measured using CO 2 laser absorption at 10.532 lm. This diagnostic takes advantage of the strong overlap of the P (14) line of the CO 2 laser transition with the strong Q-branch of the m 7 ethylene band. It is capable of detecting 100 ppm levels of C 2 H 4 over a path length of 15 cm at 1200 K and 3 atm.…”

“…More accurate species mole fraction time-histories are obtained by accounting for this effect rather than assuming a constant coefficient evaluated at the initial temperature. To determine these approximate time-varying absorption coefficients, the temperature and pressure profiles were calculated using the Serinyel et al mechanism of NUI Galway [14] under either constant energy (U) and volume (V) constraints or constant enthalpy (H) and pressure (P) constraints (using CHEMKIN PRO [26]). The species mole fraction time-histories were then inferred from the measured absorption data using known values of the absorption coefficients evaluated at the simulated T and P.…”

“…The test mixtures were 0.1-1% 3-pentanone in balance argon. In the present study, the CHEMKIN PRO package [26] was used to simulate all species time-histories under the standard constant energy and volume assumption (constant U, V), and the Serinyel et al mechanism of NUI Galway [14] was chosen as the base mechanism. To the best of our knowledge, the Serinyel et al mechanism is the only available detailed mechanism in the literature that is suitable for high temperature 3-pentanone combustion.…”

“…From their experiments, they concluded that 3-pentanone has much faster ignition delay times than found for acetone, n-pentane, methyl butanoate and butanal. Similarly, Serinyel et al [14] performed shock tube ignition delay time measurements in the temperature range 1250-1850 K, pressures near 1 atm., and equivalence ratios of 0.5-2.0 for mixtures of 0.875-1.31% 3-pentanone in O 2 /argon. They also conducted laminar flame speed measurements in a spherical bomb for mixtures of 3-pentanone in air with various equivalence ratios at an initial temperature of $305 K and an initial pressure of 1 atm.…”