Fundamental Kinetics Database Utilizing Shock Tube Measurements

Transcription

1 Fundamental Kinetics Database Utilizing Shock Tube Measurements Volume 2: Concentration Time-History Measurements D. F. Davidson and R. K. Hanson Mechanical Engineering Department Stanford University, Stanford CA December 28 th, 2006

2 Abstract This volume of the Fundamental Kinetic Database Utilizing Shock Tube Measurements includes a summary of the species concentration time-histories measured and published by the Shock Tube Group in the Mechanical Engineering Department of Stanford University. The cut-off date for inclusion in this volume was December This work has been supported by many government agencies and private companies including: the U.S. Department of Energy, the Army Research Office, the Office of Naval Research, the Air Force Office of Scientific Research, the National Science Foundation, the Gas Research Institute, and the General Motors Research Laboratory. To receive a pdf version of this report please contact Dr. David Davidson at dfd@stanford.edu or it can be downloaded from

3 Table of Contents Abstract...2 Table of Contents...3 Introduction...4 Database Format...6 Small Fuels...8 Methane...8 Ethane...19 Normal Alkanes...25 Propane...25 n-butane...27 n-heptane...29 n-decane...33 Branched Alkanes...35 Iso-Butane...35 Iso-Pentane...39 Iso-Octane...41 Cyclo-Alkanes...47 JP Olefins ,3-Butadiene...49 Aromatics...51 Toluene...51

4 Introduction There is a critical need for standardized experimental data that can be used as targets in the validation and refinement of reaction mechanisms for hydrocarbon fuels. In our laboratory at Stanford University, we are able to provide some of this data in the form of shock tube experiments. The data from shock tube experiments generally takes three forms: ignition delay times, species concentration time-histories and reaction rate measurements. Ignition delay times are a measure of the time from initial shock wave heating to a defined ignition point, often a rapid change in pressure or radical species population. These targets place a constraint on the overall predictive behavior of the reaction mechanism. Does the mechanism predict the time of ignition properly for a particular initial temperature, pressure and mixture composition? These ignition delay times can also be provided in the form of correlation equations which provide similar information in a compact form. Species concentration time-histories are a measure of the concentration of a particular species as a function of time during the entire experiment. These targets place strong constraints on the internal workings of the reaction mechanism. Concentration time-histories for OH, for example, are strongly related to the concentrations of other small radical species including: H-atoms, O-atoms, and HO 2. The production and removal rates of these species have an important role in the reaction progress to ignition. Reaction rate measurements provide the basic rate data that reaction mechanisms are comprised of. Accurate measurements are needed of the rates of critical reactions that important reaction parameters are sensitive to, such as ignition delay times, heat release rates, and product species. These are necessary as it is not yet possible to accurately predict these rates (nor is it likely that they will ever be reliably predicted) without experimental verification. Shock tube data are well suited for comparison with computation models. Shock wave experiments can provide near constant-volume test conditions, generally over the entire time period before ignition, and in many cases for longer times. Shock tube experiments can provide test conditions over a wide range of temperatures, pressure and gas mixtures, typically over temperatures of 600 to 4000 K, pressures from sub-atmospheric to 1000 atm, and fuel concentrations from ppm to percent levels with test times in the 1-10 ms range. Methods have been developed to extend these ranges if need be. The nature of planar shock wave flows as they are formed in conventional shock tubes means that the test gas mixtures are effectively instantaneously compressed and heated, providing very simple initial conditions for modeling. The spatial uniformity of the stationary

5 heated test gas mixture behind reflected shock waves means that only chemistry need be modeled, and fluid mechanical effects such as diffusion, mixing, and fluid movement are not significant in most cases. And finally, the time scales and physical dimensions of shock tube experiments means that the test gas volume can be considered to be adiabatically isolated from its surroundings. The database is comprised of three volumes: Volume 1, ignition delay time measurements; Volume 2, species concentration time-histories; and Volume 3, reaction rate measurements. The formal cut-off point for Volume 2 is December 2005, and work published after this data will be included in later editions. Volume 3 in currently being assembled. A version of the database is available through the PRIME warehouse currently being developed at University of California, Stanford University and NIST.

6 Database Format The data in this volume is limited to species concentration time-histories in oxidative systems. Discrete concentration-time points derived from species timehistories related to ignition time studies are given in Volume 1 and are also included in this volume. Fuel species and data types that are included in this volume are indicated in Table 1. Fuel CH OH CH 3 CO 2 Other hydrogen methane ethane ethylene propane n-butane n-heptane n-decane iso-butane iso-pentane iso-octane JP-10 1,3-butadiene toluene gasoline surrogate CH4 Pressure Pressure Table 1: Fuel species and data types included in database. Shaded areas indicate available data. Each data set includes the literature source of the data, a table describing the range of the data, a short description of the data type, and the data plot. All data in this database have been previously published in refereed journals, conference proceedings or Ph.D. theses. The short description of the data type includes information on the diagnostic used in the measurement, as well as the type of carrier gas (generally argon or nitrogen). The data table includes: the initial reflected shock temperature and pressure, mixture composition, and equivalence ratio. Further information on each species concentration timehistory dataset can be derived from the literature sources of the data. An overview of measurement techniques of species concentration time-histories using laser absorption diagnostics is available in Davidson and Hanson (2001).

7 Laser absorption measurements of species concentration are based on the Beer-Lambert Law: I/I 0 = exp( - k λ P X L) where I/I 0 is the ratio of the transmitted laser power to the incident laser power, k λ is the absorption coefficient (generally in units of [atm -1 cm -1 ]), P is the total pressure in [atm], X is the absorbing species mole fraction [n.d.], and L is the optical path length in [cm] ( the shock tube diameter). The majority of the measurements in the current database were performed in low pressure shock tubes (Stanford 15.2 and 14.3 cm diameter shock tubes). A few measurements were performed in the high pressure Stanford 5 cm diameter shock tube. Experiments where species time-history data is available are shown in bold in the tables and are included in the accompanying files. The numbering of tables in Volume 2 agrees with the numbering of identical tables in Volume 1 and the figure numbers correspond to the table where the data is listed. Older data, including, in particular the methane data of Chang (1995), have been digitized from images in the publications and include only a selection of points from the respective images. D. F. Davidson, R. K. Hanson, Spectroscopic Diagnostics, Chapter 5.2 in Handbook of Shock Waves, Volume 1, G. Ben-Dor, O. Igra, T. Elperin eds. Academic Press, San Diego (2001).

8 Small Fuels Methane Literature Source of Data: E. J. Chang, Shock Tube Experiments for the Development and Validation of Models of Hydrocarbon Combustion, M. Eng. Thesis, (also published as HTGL Report No. T-320), Mechanical Engineering Department, Stanford University, Stanford CA (1995). M. Frenklach, H. Wang, M. Goldenberg,G. P. Smith, D. M. Golden, C. T. Bowman, R. K. Hanson, W. C. Gardiner, V. Lissianski, GRI-Mech An Optimized Detailed Chemical Reaction Mechanism for Methane Combustion, Topical Report GRI-95/0058, Gas Research Institute (1995). Range of Data: Type of Data: Temperature [K] Pressure [atm] Fuel Mole Fraction [%] Oxygen Mole Fraction [%] Equivalence Ratio Methane Table 1: CO 2 species concentration time-history IR laser absorption measurements at μm ( cm -1 ) in argon. Methane Table 2: CH 3 species concentration time-history UV laser absorption measurements at 216 nm in argon. Methane Table 3: OH species concentration time-history UV laser absorption measurements at nm ( cm -1 ) in argon. Formaldehyde pyrolysis data are reported in Chang (1995), but are not included here.

9 Methane Table 1: T 2 P 2 Methane Oxygen φ (E.R.) CO Plateau CO 2 ¼ Plat [K] [atm] [ppm] [ppm] [ppm] [ppm] [μs] Methane Table 2: T 5 P 5 Methane Oxygen φ (E.R.) Peak CH 3 Time [K] [atm] [ppm] [ppm] [ppm] [μs]

10 Methane Table 3: T 5 or T 2 P 5 or P 2 Methane Oxygen φ (E.R.) Max OH ½ Max [K] [atm] [ppm] [ppm] [ppm] [μs]

11 Methane Figure 1. Methane Figure 2.

12 Methane Figure 3.

13 Methane Literature Source of Data: D. Woiki, M. Votsmeier, D. F. Davidson, R. K. Hanson, C. T. Bowman, CH- Radical Concentration Measurements in Fuel-Rich CH 4 /O 2 /Ar and CH 4 /O 2 /NO/Ar Mixtures Behind Shock Waves, Combustion and Flame 113: (1998). Range of Data: Type of Data: Temperature [K] Pressure [atm] Fuel Mole Fraction [ppm] Oxygen Mole Fraction [ppm] Nitric Oxide Mole Fraction [ppm] Equivalence Ratio Methane Table 7: CH species concentration time-history measurements in argon using laser absorption at 431 nm. Data was derived from a digitization of Fig. 2 of Woiki et al. (1998). Methane Table 7: T 5 P 5 Methane Oxygen NO φ (E.R.) CH Peak [K] [atm] [ppm] [ppm] [ppm] [ppm]

14 Methane Figure 7.

15 Methane Literature Source of Data: E. L. Petersen, M. Rohrig, D. F. Davidson, R. K. Hanson, C. T. Bowman, High Pressure Methane Oxidation Behind Reflected Shock Waves, Proceedings of the Combustion Institute 26: (1996). E. L. Petersen, D. F. Davidson, M. Rohrig, R. K. Hanson, C. T. Bowman, A Shock Tube Study of High Pressure Methane Oxidation, Paper 95F-153, Western States Section/The Combustion Institute Fall Meeting, Stanford (1995). E. L. Petersen, D. F. Davidson, M. Rohrig, R. K. Hanson, Shock-Induced Ignition of High-Pressure H 2 -O 2 -Ar and CH 4 -O 2 -Ar Mixtures, AIAA , 31 st AIAA/ASME/SAE/ASEE Joint Propulsion Conference and Exhibit, San Diego (1995). Range of Data: Type of Data: Temperature [K] Pressure [atm] Fuel Mole Fraction [%] Oxygen Mole Fraction [%] Equivalence Ratio Methane Table 8: OH species concentration time-history measurements in argon using laser absorption at nm. Methane Table 8: High pressure ignition delay time data in argon using same definition as found in Methane Table 4 of Volume 1. Methane Table 9: CH 4 species concentration time-history induction time and end time are determined from the interception points (times) of a linear fit through the decaying CH 4 signal and the initial and final signal levels respectively. Methane Table 9: High pressure ignition delay time data using same definition as found in Methane Table 4 of Volume 1.

16 Methane Table 8: OH OH Ignition T 5 P 5 Methane O 2 φ (E.R.) First Rise Peak (Pressure) [K] [atm] [%] [%] [μs] [μs] [μs]

17 Methane Table 9: CH 4 CH 4 Ignition T 5 P 5 Methane O 2 φ (E.R.) Induction End (Pressure) [K] [atm] [%] [%] [μs] [μs] [μs]

18 Methane Figure 8. Methane Figure 9.

19 Ethane Literature Source of Data: E. J. Chang, Shock Tube Experiments for the Development and Validation of Models of Hydrocarbon Combustion, M. Eng. Thesis, (also published as HTGL Report No. T-320), Mechanical Engineering Department, Stanford University, Stanford CA (1995). M. Frenklach, H. Wang, M. Goldenberg,G. P. Smith, D. M. Golden, C. T. Bowman, R. K. Hanson, W. C. Gardiner, V. Lissianski, GRI-Mech An Optimized Detailed Chemical Reaction Mechanism for Methane Combustion, Topical Report GRI-95/0058, Gas Research Institute (1995). Range of Data: Type of Data: Temperature [K] Pressure [atm] Fuel Mole Fraction [ppm] Oxygen Mole Fraction [ppm] Methane Mole Fraction [ppm] Equivalence Ratio Ethane Table 1: CO 2 species concentration time-history IR laser absorption measurements at μm ( cm -1 ) in argon. Low pressure experiments were performed behind incident shock waves. Ethane Table 2: CH 3 species concentration time-history UV laser absorption measurements at 216 nm in argon. Includes mixtures with added methane. Ethane Table 3: OH species concentration time-history UV laser absorption measurements at nm ( cm -1 ) in argon. Ethane Table 1: T2 P2 Ethane Oxygen φ (E.R.) CO Plateau CO 2 ¼ Plat [K] [atm] [ppm] [ppm] [ppm] [ppm] [μs]

20 Ethane Table 2: T 5 P 5 Ethane Methane Oxygen φ (E.R.) Peak CH 3 Time [K] [atm] [ppm] [ppm] [ppm] [ppm] [μs] Ethane Table 3: T 5 P 5 Ethane Oxygen φ (E.R.) Max OH ½ Max [K] [atm] [ppm] [ppm] [ppm] [μs]

21 Ethane Figure 1. Ethane Figure 2.

22 Ethane Figure 3.

23 Ethane Literature Source of Data: M. Rohrig, E. L. Petersen, D. F. Davidson, R. K. Hanson, C. T. Bowman, Measurement of the Rate Coefficient of the Reaction CH+O 2 = Products in the Temperature Range 2200 to 2600 K, International Journal Chemical Kinetics 29: (1997). Range of Data: Type of Data: Temperature [K] Pressure [atm] Fuel Mole Fraction [%] Oxygen Mole Fraction [%] Equivalence Ratio Ethane Table 4: CH species concentration time-history measurements based on laser absorption measurements at 431 nm in argon. CH data was derived from a digitization of Figs. 1 and 5 of Rohrig et al. (1997). Ethane Table 4: T 5 P 5 Ethane Oxygen φ (E.R.) 1 st Plateau Peak CH Peak [K] [atm] [ppm] [ppm] [ppm] [ppm] [μs]

24 Ethane Figure 4a. Ethane Figure 4b.

25 Normal Alkanes Propane Literature Source of Data: D. F. Davidson, J. T. Herbon, D. C. Horning, R. K. Hanson, "OH Concentration Time-histories in n-alkane Oxidation," International Journal of Chemical Kinetics 33: (2001). Range of Data: Type of Data: Temperature [K] Pressure [atm] Fuel Mole Fraction [ppm] Oxygen Mole Fraction [ppm] Equivalence Ratio 1 1 Propane Table 1: OH concentration time-history measurements using laser absorption at nm. T 1 (90%) and T 2 (50%) are the time for the OH mole fraction to reach 90% of the initial plateau level and 50% of the final plateau level respectively. For those conditions where no 1 st plateau is indicated, no distinct plateau existed because of the rapid rise to the final plateau level. Carrier gas is argon. Other unpublished data exist from this study. Propane Table 1: Absorption 1 st 2 nd T 5 P 5 Propane O 2 Coefficient T 1 (90%) Plateau T 2 (50%) Plateau [K] [atm] [ppm] [ppm] [atm -1 cm -1 ]. [μs] [ppm] [μs] [ppm]

26 Propane Figure 1.

27 n-butane Literature Source of Data: D. F. Davidson, J. T. Herbon, D. C. Horning, R. K. Hanson, "OH Concentration Time-histories in n-alkane Oxidation," International Journal of Chemical Kinetics 33: (2001). Range of Data: Type of Data: Temperature [K] Pressure [atm] Fuel Mole Fraction [ppm] Oxygen Mole Fraction [ppm] Equivalence Ratio 1 1 Butane Table 1: OH concentration time-history measurements using laser absorption at nm. T 1 (90%) and T 2 (50%) are the time for the OH mole fraction to reach 90% of the initial plateau level and 50% of the final plateau level respectively. For those conditions where no 1 st plateau is indicated, no distinct plateau existed because of the rapid rise to the final plateau level. Carrier gas is argon. Other unpublished data exist from this study. n-butane Table 1: Absorption 1 st 2 nd T 5 P 5 n-butane O 2 Coefficient T 1 (90%) Plateau T 2 (50%) Plateau [K] [atm] [ppm] [ppm] [atm -1 cm -1 ]. [μs] [ppm] [μs] [ppm]

28 n-butane Figure 1.

29 n-heptane Literature Source of Data: D. F. Davidson, J. T. Herbon, D. C. Horning, R. K. Hanson, "OH Concentration Time-histories in n-alkane Oxidation," International Journal of Chemical Kinetics 33: (2001). Range of Data: Type of Data: Temperature [K] Pressure [atm] Fuel Mole Fraction [ppm] Oxygen Mole Fraction [ppm] Equivalence Ratio 1 1 n-heptane Table 1: OH concentration time-history measurements using laser absorption at nm. T 1 (90%) and T 2 (50%) are the time for the OH mole fraction to reach 90% of the initial plateau level and 50% of the final plateau level respectively. For those conditions where no 1 st plateau is indicated, no distinct plateau existed because of the rapid rise to the final plateau level. Carrier gas is argon. Other unpublished data exist from this study. n-heptane Table 1: Absorption 1 st 2 nd T 5 P 5 n-heptane O 2 Coefficient T 1 (90%) Plateau T 2 (50%) Plateau [K] [atm] [ppm] [ppm] [atm -1 cm -1 ]. [μs] [ppm] [μs] [ppm]

30 n-heptane Figure 1.

31 n-heptane Literature Source of Data: D. F. Davidson, M. A. Oehlschlaeger, R. K. Hanson, "Methyl Concentration Time- Histories during iso-octane and n-heptane Oxidation and Pyrolysis," Proceedings of the Combustion Institute 31: in press (2006). Range of Data: Type of Data: Temperature [K] Pressure [atm] Fuel Mole Fraction [ppm] Oxygen Mole Fraction [%] Equivalence Ratio n-heptane Table 2-1: CH 3 concentration time-history measurements in argon using narrow-linewidth ring-dye laser absorption of the peak of the predissociatively broadened CH 3 absorpti0n feature B 2 A 1 -X 2 A 2 near 216 nm. Measurements at three wavelengths, , and nm, were deconvolved to separate out the CH 3 absorption from that of a time-dependent interference absorption. n-heptane Table 2-1: T 5 P 5 C 7 H 16 O 2 [K] [atm] [ppm] [ppm]

32 n-heptane Figure 2-1.

33 n-decane Literature Source of Data: D. F. Davidson, J. T. Herbon, D. C. Horning, R. K. Hanson, "OH Concentration Time-histories in n-alkane Oxidation," International Journal of Chemical Kinetics 33: (2001). Range of Data: Type of Data: Temperature [K] Pressure [atm] Fuel Mole Fraction [ppm] Oxygen Mole Fraction [ppm] Equivalence Ratio n-decane Table 1: OH concentration time-history measurements using laser absorption at nm. T 1 (90%) and T 2 (50%) are the time for the OH mole fraction to reach 90% of the initial plateau level and 50% of the final plateau level respectively. For those conditions where no 1 st plateau is indicated, no distinct plateau existed because of the rapid rise to the final plateau level. Carrier gas is argon. Other unpublished data exist from this study. n-decane Table 1: n- Absorption 1 st 2 nd T 5 P 5 Decane O 2 Coefficient T 1 (90%) Plateau T 2 (50%) Plateau [K] [atm] [ppm] [ppm] [atm -1 cm -1 ]. [μs] [ppm] [μs] [ppm]

34 n-decane Figure 1.

35 Branched Alkanes Iso-Butane Literature Source of Data: M. A. Oehlschlaeger, D. F. Davidson, J. T. Herbon, R. K. Hanson, "Shock Tube Measurements of Branched Alkane Ignition Times and OH Concentration Timehistories," International Journal of Chemical Kinetics 36: (2004). M. A. Oehlschlaeger, D. F. Davidson, J. T. Herbon, R. K. Hanson, "Shock Tube Measurements of Branched Alkane Ignition Times and OH Concentration Timehistories," AIAA paper , 41 st AIAA Aerospace Sciences Meeting and Exhibit, Reno NV (2003). Range of Data: Type of Data: Temperature [K] Pressure [atm] Fuel Mole Fraction [%] Oxygen Mole Fraction [%] Equivalence Ratio Iso-Butane Table 1: OH concentration time-history measurements in argon using narrow-linewidth ring-dye laser absorption of the R 1 (5) line of the OH A-X (0,0) band at nm. Sat. indicates laser transmission of ~0. Other unpublished data exists from this study.

36 Iso-Butane Table 1: T 5 [K] P 5 [atm] Fuel [%] O 2 [%] φ E.R. First Peak [μs] First Peak [ppm] Minimum [μs] Minimum [ppm] 50% Peak [μs] Peak [ppm] Sat Sat Sat Sat T 5 [K] P 5 [atm] Fuel [%] O 2 [%] Absorption Coefficient [atm -1 cm -1 ]

37 iso-butane Figure 1.

38

39 Iso-Pentane Literature Source of Data: M. A. Oehlschlaeger, D. F. Davidson, J. T. Herbon, R. K. Hanson, "Shock Tube Measurements of Branched Alkane Ignition Times and OH Concentration Timehistories," International Journal of Chemical Kinetics 36: (2004). Range of Data: Type of Data: Temperature [K] Pressure [atm] Fuel Mole Fraction [%] Oxygen Mole Fraction [%] Equivalence Ratio Iso-Pentane Table 1: OH concentration time-history measurements in argon using narrow-linewidth ring-dye laser absorption of the R 1 (5) line of the OH A-X (0,0) band at nm. Sat. indicates laser transmission of ~0. Other unpublished data exists from this study. Iso-Pentane Table 1: T 5 [K] P 5 [atm] Fuel [%] O 2 [%] φ E.R. First Peak [μs] First Peak [ppm] Minimum [μs] Minimum [ppm] 50% Peak [μs] Peak [ppm] Sat Sat T 5 [K] P 5 [atm] Fuel [%] O 2 [%] Absorption Coefficient [atm -1 cm -1 ]

40 iso-pentane Figure 1. 40

41 Iso-Octane Literature Source of Data: D. F. Davidson, M. A. Oehlschlaeger, J. T. Herbon, R. K. Hanson, Shock Tube Measurements of Iso-Octane Ignition Times and OH Concentration Timehistories, Proceedings of the Combustion Institute 29: (2002). Range of Data: Type of Data: Temperature [K] Pressure [atm] Fuel Mole Fraction [%] Oxygen Mole Fraction [%] Equivalence Ratio Iso-Octane Table 1: OH concentration time-history measurements in argon using narrow-linewidth ring-dye laser absorption of the R 1 (5) line of the OH A-X (0,0) band at nm. Sat. indicates laser transmission of ~0. Other unpublished data exist from this study. Iso-Octane Table 1: T 5 [K] P 5 [atm] Fuel [%] O2 [%] φ E.R. First Peak [μs] First Peak [ppm] Minimum [μs] Minimum [ppm] 50% Peak [μs] Peak [ppm]

42 iso-octane Figure 1. 42

43 Iso-Octane Literature Source of Data: D. F. Davidson, M. A. Oehlschlaeger, R. K. Hanson, "Methyl Concentration Time- Histories during iso-octane and n-heptane Oxidation and Pyrolysis," Proceedings of the Combustion Institute 31: in press (2006). Range of Data: Type of Data: Temperature [K] Pressure [atm] Fuel Mole Fraction [ppm] Oxygen Mole Fraction [%] Equivalence Ratio Iso-Octane Table 2-1: CH 3 concentration time-history measurements in argon using narrow-linewidth ring-dye laser absorption of the peak of the predissociatively broadened CH 3 absorpti0n feature B 2 A 1 -X 2 A 2 near 216 nm. Measurements at three wavelengths, , and nm, were deconvolved to separate out the CH 3 absorption from that of a time-dependent interference absorption. Iso-Octane Table 2-1: T 5 P 5 C 8 H 18 O 2 [K] [atm] [ppm] [ppm]

44 iso-octane Figure

45 Iso-Octane Literature Source of Data: D. F. Davidson, B. M. Gauthier, R. K. Hanson, Shock Tube Ignition Measurements of Iso-Octane/Air and Toluene/Air at High Pressures, Proceedings of the Combustion Institute 20: (2005). Range of Data: Type of Data: Temperature [K] Pressure [atm] Fuel Mole Fraction [%] Oxygen Mole Fraction [%] Equivalence Ratio Iso-Octane Table 2-2: Ignition delay time measurement in synthetic air (79% N 2, 21% O 2 ) based on sidewall PZT pressure measurements and confirmed with CH* (at 431 nm) and OH* (at 306nm) emission measurements. Iso-Octane Table 2-2: T 5 P 5 Iso-Octane φ (E.R.) [K] [atm] [%]

46 iso-octane Figure

47 Cyclo-Alkanes JP-10 Literature Source of Data: D. F. Davidson, D. C. Horning, J. T. Herbon, R. K. Hanson, "Shock Tube Measurements of JP-10 Ignition," Proceedings of the Combustion Institute 28: (2000). Range of Data: Type of Data: Temperature [K] Pressure [atm] Fuel Mole Fraction [%] Oxygen Mole Fraction [%] Equivalence Ratio JP-10 Table 1: OH concentration time-history measurements in argon using narrow-linewidth ring-dye laser absorption of the R 12 (7) line of the OH A-X (0,0) band near nm. The absorption coefficient for 1460K example is k λ = [atm -1 cm -1 ]. Other unpublished data exists. JP-10 Table 1: T5 P5 JP-10 O2 φ (E.R.) Time-topeak Peak OH [K] [atm] [%] [%] [μs] [ppm]

48 JP-10 Figure 1. 48

49 Olefins 1,3-Butadiene Literature Source of Data: C. S. Libby, D. F. Davidson, R. K. Hanson, "A Shock Tube Study of the Oxidation of 1,3-Butadiene," AIAA (2004). Range of Data: Type of Data: Temperature [K] Pressure [atm] Fuel Mole Fraction [ppm] Oxygen Mole Fraction [%] Equivalence Ratio ,3-Butadiene Table 1: OH concentration time-history measurements in argon using narrow-linewidth ring-dye laser absorption of the peak of the R 1 (5) line of the OH A-X (0,0) band at nm. 1,3-Butadiene Table 1: 1/8 1/8 1/4 1/4 50% 50% T 5 P 5 C 4 H 6 φ (E.R.) Peak Peak Peak Peak Plateau peak peak Peak Peak [K] [atm] [ppm] [μs] [ppm] [μs] [ppm] [ppm] [μs] [ppm] [μs] [ppm] T 5 P 5 Wavelength Pathlength Absorption Coefficient [K] [atm] [nm] [cm] [atm -1 cm -1 ]

50 1,3-Butadiene Figure 1a. 1,3-Butadiene Figure 1b. 50

51 Aromatics Toluene Literature Source of Data: D. F. Davidson, B. M. Gauthier, R. K. Hanson, Shock Tube Ignition Measurements of Iso-Octane/Air and Toluene/Air at High Pressures, Proceedings of the Combustion Institute 20: (2005). Range of Data: Type of Data: Temperature [K] Pressure [atm] Fuel Mole Fraction [%] Oxygen Mole Fraction [%] Equivalence Ratio Toluene Table 2-1: Ignition delay time data in air using PZT pressure measurements of the time between the arrival of the reflected shock (the center of the reflected shock bifurcation feature) and the distinct ignition pressure rise (the time of the intersection of the linear extrapolation of the pressure rise with the pre-ignition pressure floor). Similar ignition delay times were recovered from CH and OH emission measurements. Toluene Table 2-1: T 5 P 5 Toluene φ (E.R.) [K] [atm] [%]

52 Toluene Figure

53 Toluene Literature Source of Data: V. Vasudevan, D. F. Davidson, R. K. Hanson, "Shock Tube Measurements of Toluene Ignition Times and OH Concentration Time-histories," Proceedings of the Combustion Institute 330: (2005). Range of Data: Type of Data: Temperature [K] Pressure [atm] Fuel Mole Fraction [ppm] Oxygen Mole Fraction [%] Equivalence Ratio Toluene Table 1: OH concentration time-history measurements in argon using narrow-linewidth ring-dye laser absorption of the R 1 (5) line of the OH A-X (0,0) band at nm. n.d. indicates that the plateau was not well defined and sat. indicated a saturated signal with laser transmission ~0. 53

54 Toluene Table 1: First First Ignition T 5 P 5 C 7 H 8 O 2 φ (E.R.) Plateau Plateau Time Peak [K] [atm] [ppm] [%] [μs] [ppm] [μs] [ppm] n.d n.d n.d n.d sat n.d sat n.d sat n.d sat. 54

55 Toluene Figure 1a. Toluene Figure 1b. 55