Fundamental Kinetics Database Utilizing Shock Tube Measurements

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1 Fundamental Kinetics Database Utilizing Shock Tube Measurements Volume 1: Ignition Delay Time Measurements D. F. Davidson and R. K. Hanson Mechanical Engineering Department Stanford University, Stanford CA November 1 st,

2 Abstract This volume of the Fundamental Kinetic Database Utilizing Shock Tube Measurements includes a summary of the ignition delay time data measured and published by the Shock Tube Group in the Mechanical Engineering Department of Stanford University. The cut-off date for inclusion into this volume was January 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. 2

3 Table of Contents Abstract...2 Table of Contents...3 Introduction...4 Database Format...6 Small Fuels...8 Hydrogen...8 Methane...11 Ethane...25 Ethylene...29 Normal Alkanes...31 Propane...31 n-butane...35 n-heptane...39 n-decane...47 Branched Alkanes...51 Iso-Butane...51 Iso-Pentane...55 Iso-Octane...57 Cyclo-Alkanes...63 JP Olefins ,3-Butadiene...65 Aromatics...67 Toluene...67 Other Fuels...71 Gasoline...71 Gasoline Surrogate

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 4

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 1 is January 2005, and work published after this data will be included in later editions. A version of the database will soon be available through the PRIME warehouse currently being developed at University of California, Stanford University and NIST. 5

6 Database Format The data in this volume is limited to ignition delay times and discrete concentration-time points derived from species time histories. Fuel species and data types that are included in the volume are indicated in Table 1. Low Pressure High Pressure Fuel ignition OH CH CH 3 CO 2 ignition OH CH 4 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 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 table. 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, the ignition delay time and/or discrete species concentration points (such as time and concentration at the profile peak or plateau). Further information on each dataset can be derived from the literature sources of the data. Measurements are separated into two groups: low and high pressure. The low pressure measurements (generally up to 10 atm) were performed in the Stanford 15.2 and 14.3 cm diameter shock tubes; the high pressure 6

7 measurements (generally above 10 atm) were performed in the Stanford 5 cm diameter shock tube. It should be noted that the ignition times described in these table have different definitions depending on the diagnostic used. In general, for the conditions of the experiments described here, the differences in ignition time from different definitions are not significant. However these differences should be reviewed before comparison with other measurements. The discrete species concentration measurements included for some fuels in this volume can be related to ignition delay times by comparison with the modeled concentrations for these fuels. A discussion of ignition delay time data and other technicalities of shock tube work is given in Davidson and Hanson (2004). D. F. Davidson and R. K. Hanson, Interpreting Shock Tube Ignition Data, International Journal of Chemical Kinetics Vol. 36, pp (2004). 7

8 Small Fuels Hydrogen Literature Source of Data: 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). E. L. Petersen, D. F. Davidson, M. Rohrig, R. K. Hanson, High-Pressure Shock- Tube Measurements of Ignition Times in Stoichiometric H 2 -O 2 -Ar Mixtures, Proceedings of the 20 th International Symposium on Shock Waves, pp , Pasadena (1995). Range of Data: Type of Data: Temperature [K] Pressure [atm] Fuel Mole Fraction [%] Oxygen Mole Fraction [%] Equivalence Ratio 1 1 Hydrogen Table 1: Ignition delay time measurement in argon based on {d[oh]/dt} max from laser absorption of OH at 306 nm. Hydrogen Table 1: T 5 P 5 Hydrogen Oxygen φ (E.R.) Ignition Time [K] [atm] [%] [%] [µs]

9 Hydrogen Table 1 (continued): T 5 P 5 Hydrogen Oxygen φ (E.R.) Ignition Time [K] [atm] [%] [%] [µs]

10 Hydrogen Table 1 (continued): T 5 P 5 Hydrogen Oxygen φ (E.R.) Ignition Time [K] [atm] [%] [%] [µs]

11 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. 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]

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

13 Methane (continued) Literature Source of Data: E. L. Petersen, A Shock Tube and Diagnostics For Chemistry Measurements at Elevated Pressures with Application to Methane Ignition, Ph.D. Thesis, (also published as Topical Report No. TSD-111,) Mechanical Engineering Department, Stanford University, Stanford CA (1998), E. L. Petersen, D. F. Davidson, R. K. Hanson, Ignition Delay Times of Ram Accelerator CH 4 /O 2 /Diluent Mixtures, Journal of Propulsion and Power 15: (1999). E. L. Petersen, D. F. Davidson, R. K. Hanson, Kinetics Modeling of Shock- Induced Ignition in Low-Dilution CH 4 /O 2 Mixtures at High Pressures and Intermediate Temperatures, Paper 97S-066, Western States Section/The Combustion Institute Spring Meeting, Sandia (1997), E. L. Petersen, D. F. Davidson, R. K. Hanson, Ram Accelerator Mixture Chemistry: Kinetics Modeling and Ignition Measurements, CPIA Publication #653, JANNAF 33 rd Combustion Subcommittee Meeting, Monterey (1996). E. L. Petersen, D. F. Davidson, R. K. Hanson, Ignition Delay Times of Ram Accelerator Mixtures, AIAA , 32 nd AIAA/ASME/SAE/ASEE Joint Propulsion Conference, Lake Buena Vista (1996). Range of Data: Type of Data: Temperature [K] Pressure [atm] Fuel Mole Fraction [%] Oxygen Mole Fraction [%] Equivalence Ratio Methane Table 4: High pressure ignition delay time data with argon as the bulk carrier gas 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). These ignition delay time values have been corrected to account for blast wave arrival effects at the shock tube sidewall measurement location. Methane Table 4: Ignition delay times based on emission measurements are also reported for visible (Si photo diode) and selected other wavelengths. 13

14 Methane Table 5: Same as Methane Table 4 but with nitrogen as the bulk carrier gas. Methane Table 6: Same as Methane Table 4 but with helium or nitrogen and helium as the bulk carrier gas. Methane Table 4: Ignition Ignition T 5 P 5 Methane Oxygen Argon φ (E.R.) (Pressure) (Emission) [K] [atm] [%] [%] [%] [µs] [µs]

15 Methane Table 4 (continued): Ignition Ignition T 5 P 5 Methane Oxygen Argon φ (E.R.) (Pressure) (Emission) [K] [atm] [%] [%] [%] [µs] [µs] Methane Table 5: Ignition Ignition T 5 P 5 Methane Oxygen N 2 φ (E.R.) (Pressure) (Emission) [K] [atm] [%] [%] [%] [µs] [µs]

16 Methane Table 5 (continued): Ignition Ignition T 5 P 5 Methane Oxygen N 2 φ (E.R.) (Pressure) (Emission) [K] [atm] [%] [%] [%] [µs] [µs] Methane Table 6: Ignition Ignition T 5 P 5 Methane Oxygen He N 2 φ (E.R.) (Pressure) (Emission) [K] [atm] [%] [%] [%] [%] [µs] [µs]

17 Methane Table 6 (continued): Ignition Ignition T 5 P 5 Methane Oxygen He N 2 φ (E.R.) (Pressure) (Emission) [K] [atm] [%] [%] [%] [%] [µs] [µs]

18

19 Methane (continued) 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]

20

21 Methane (continued) 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. 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. 21

22 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] 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]

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

24

25 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]

26 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]

27 Ethane (continued) 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]

28

29 Ethylene Literature Source of Data: D. C. Horning, A Study of the High Temperature Autoignition and Thermal Decomposition of Hydrocarbons, Ph.D. Thesis, (also published as Report No. TSD-135), Mechanical Engineering Department, Stanford University, Stanford CA (2001). Range of Data: Type of Data: Temperature [K] Pressure [atm] Fuel Mole Fraction [%] 1 4 Oxygen Mole Fraction [%] 3 12 Equivalence Ratio 1 1 Ethylene Table 1: Ignition delay time defined as the peak of the CH* emission at 431 nm. Carrier gas is argon. Ethylene Table 1: T 5 P 5 Ethylene O 2 φ (E.R.) Ignition Time [K] [atm] [%] [%] [µs]

30 Ethylene Table 1 (continued): T 5 P 5 Ethylene O 2 φ (E.R.) Ignition Time [K] [atm] [%] [%] [µs]

31 Normal Alkanes Propane Literature Source of Data: D. C. Horning, A Study of the High Temperature Autoignition and Thermal Decomposition of Hydrocarbons, Ph.D. Thesis, (also published as Report No. TSD-135,) Mechanical Engineering Department, Stanford University, Stanford CA (2001). D. C. Horning, D. F. Davidson, R. K. Hanson, "Study of the High-Temperature Autoignition of n-alkane/o2/ar Mixtures," Journal of Propulsion and Power 18: (2002). D. C. Horning, D. F. Davidson, R. K. Hanson, "Ignition Time Correlations for n- Alkane/O2/Ar Mixtures," Paper 5732, pp , Proceedings of the 23 rd International Symposium on Shock Waves, Fort Worth TX (2001). Range of Data: Type of Data: Temperature [K] Pressure [atm] Fuel Mole Fraction [%] 4 4 Oxygen Mole Fraction [%] Equivalence Ratio 1 1 Propane Table 1: Ignition delay time measurements derived from the peak of CH* emission measurements at 431 nm. Carrier gas is argon. Propane Table 1: T5 P5 Propane O2 φ (E.R.) Ignition Time [K] [atm] [%] [%] [µs]

32

33 Propane (continued) 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). D. F. Davidson, J. T. Herbon, D. C. Horning, R. K. Hanson, "OH Concentration Time Histories in n-alkane Oxidation," Paper 01F-49, Western States Section/The Combustion Institute Fall Meeting, Salt Lake City (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 2: 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. Propane Table 2: 2 nd T 5 P 5 Propane O 2 φ (E.R.) T 1 (90%) Plateau T 2 (50%) Plateau [K] [atm] [ppm] [ppm] [µs] [ppm] [µs] [ppm] st

34

35 n-butane Literature Source of Data: D. C. Horning, A Study of the High Temperature Autoignition and Thermal Decomposition of Hydrocarbons, Ph.D. Thesis, (also published as Report No. TSD-135,) Mechanical Engineering Department, Stanford University, Stanford CA (2001). D. C. Horning, D. F. Davidson, R. K. Hanson, "Study of the High-Temperature Autoignition of n-alkane/o2/ar Mixtures," Journal of Propulsion and Power 18: (2002). D. C. Horning, D. F. Davidson, R. K. Hanson, "Ignition Time Correlations for n- Alkane/O2/Ar Mixtures," Paper 5732, pp , Proceedings of the 23 rd International Symposium on Shock Waves, Fort Worth TX (2001). Range of Data: Type of Data: Temperature [K] Pressure [atm] Fuel Mole Fraction [%] 1 1 Oxygen Mole Fraction [%] Equivalence Ratio 1 1 n-butane Table 1: Ignition delay time measurements derived from the peak of CH* emission measurements at 431 nm. Carrier gas is argon. n-butane Table 1: T 5 P5 n-butane O 2 φ (E.R.) Ignition Time [K] [atm] [%] [%] [µs]

36 n-butane Table 1 (continued): T5 P5 n-butane O2 φ (E.R.) Ignition Time [K] [atm] [%] [%] [µs]

37 n-butane (continued) 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). D. F. Davidson, J. T. Herbon, D. C. Horning, R. K. Hanson, "OH Concentration Time Histories in n-alkane Oxidation," Paper 01F-49, Western States Section/The Combustion Institute Fall Meeting, Salt Lake City (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 2: 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. n-butane Table 2: 2 nd T 5 P 5 n-butane O 2 φ (E.R.) T 1 (90%) Plateau T 2 (50%) Plateau [K] [atm] [ppm] [ppm] [µs] [ppm] [µs] [ppm] st

38

39 n-heptane Literature Source of Data: D. C. Horning, A Study of the High Temperature Autoignition and Thermal Decomposition of Hydrocarbons, Ph.D. Thesis, (also published as Report No. TSD-135,) Mechanical Engineering Department, Stanford University, Stanford CA (2001). D. C. Horning, D. F. Davidson, R. K. Hanson, "Study of the High-Temperature Autoignition of n-alkane/o2/ar Mixtures," Journal of Propulsion and Power 18: (2002). D. C. Horning, D. F. Davidson, R. K. Hanson, "Ignition Time Correlations for n- Alkane/O2/Ar Mixtures," Paper 5732, pp , Proceedings of the 23 rd International Symposium on Shock Waves, Fort Worth TX (2001). Range of Data: Type of Data: Temperature [K] Pressure [atm] Fuel Mole Fraction [%] Oxygen Mole Fraction [%] Equivalence Ratio n-heptane Table 1: Ignition delay time measurements derived from the peak of CH* emission measurements at 431 nm. Carrier gas is argon.

40 n-heptane Table 1: T5 P5 n-heptane O2 φ (E.R.) Ignition Time [K] [atm] [%] [%] [µs]

41 n-heptane Table 1 (continued): T5 P5 n-heptane O2 φ (E.R.) Ignition Time [K] [atm] [%] [%] [µs]

42

43 n-heptane (continued) 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). D. F. Davidson, J. T. Herbon, D. C. Horning, R. K. Hanson, "OH Concentration Time Histories in n-alkane Oxidation," Paper 01F-49, Western States Section/The Combustion Institute Fall Meeting, Salt Lake City (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 2: 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. n-heptane Table 2: 2 nd T 5 P 5 n-heptane O 2 φ (E.R.) T 1 (90%) Plateau T 2 (50%) Plateau [K] [atm] [ppm] [ppm] [µs] [ppm] [µs] [ppm] st

44

45 n-heptane (continued) Literature Source of Data: B.M. Gauthier, D.F. Davidson, R.K. Hanson, "Shock Tube Determination of Ignition Delay Times in Full-Blend and Surrogate Fuel Mixtures," Combustion and Flame, in press (2004). 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 3: Ignition delay time data with Nitrogen as the bulk carrier gas 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. n-heptane Table 4: Ignition delay time data with Nitrogen as the bulk carrier gas using the same ignition time definition as n-heptane Table 3. n-heptane Table 3: T5 P5 n-heptane Oxygen φ (E.R.) Ignition Time [K] [atm] [%] [%] [µs]

46 n-heptane Table 4: T5 P5 n-heptane Oxygen φ (E.R.) Ignition Time [K] [atm] [%] [%] [µs]

47 n-decane Literature Source of Data: D. C. Horning, A Study of the High Temperature Autoignition and Thermal Decomposition of Hydrocarbons, Ph.D. Thesis, (also published as Report No. TSD-135,) Mechanical Engineering Department, Stanford University, Stanford CA (2001). D. C. Horning, D. F. Davidson, R. K. Hanson, "Study of the High-Temperature Autoignition of n-alkane/o2/ar Mixtures," Journal of Propulsion and Power 18: (2002). D. C. Horning, D. F. Davidson, R. K. Hanson, "Ignition Time Correlations for n- Alkane/O2/Ar Mixtures," Paper 5732, pp , Proceedings of the 23 rd International Symposium on Shock Waves, Fort Worth TX (2001). Range of Data: Type of Data: Temperature [K] Pressure [atm] Fuel Mole Fraction [%] Oxygen Mole Fraction [%] Equivalence Ratio 1 1 n-decane Table 1: Ignition delay time measurements derived from the peak of CH* emission measurements at 431 nm. Carrier gas is argon. n-decane Table 1: T 5 P 5 n-decane O 2 φ (E.R.) Ignition Time [K] [atm] [%] [%] [µs]

48

49 n-decane (continued) 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). D. F. Davidson, J. T. Herbon, D. C. Horning, R. K. Hanson, "OH Concentration Time Histories in n-alkane Oxidation," Paper 01F-49, Western States Section/The Combustion Institute Fall Meeting, Salt Lake City (2001). Range of Data: Type of Data: Temperature [K] Pressure [atm] Fuel Mole Fraction [ppm] Oxygen Mole Fraction [ppm] Equivalence Ratio n-decane Table 2: 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. n-decane Table 2: 2 nd T 5 P 5 n-decane O 2 φ (E.R.) T 1 (90%) Plateau T 2 (50%) Plateau [K] [atm] [ppm] [ppm] [µs] [ppm] [µs] [ppm] st

50

51 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 Time Histories," 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 Time Histories," 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: Ignition delay time measurement in argon based on the maximum slope of the CH* emission at 431 nm extrapolated to the zero baseline. Iso-Butane Table 2: 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.

52 Iso-Butane Table 1: T 5 [K] P 5 [atm] Fuel [%] O 2 [%] φ E.R. Ign. Time [µs]

53 Iso-Butane Table 2: 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

54

55 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 Time Histories," 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 Time Histories," 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-Pentane Table 1: Ignition delay time measurement in argon based on the maximum slope of the CH* emission at 431 nm extrapolated to the zero baseline. Iso-Pentane Table 2: 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.

56 Iso-Pentane Table 1: T 5 [K] P 5 [atm] Fuel [%] O 2 [%] φ E.R. Ign. Time [µs] 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

57 Iso-Octane 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 Time Histories," International Journal of Chemical Kinetics 36: (2004) D. F. Davidson, M. A. Oehlschlaeger, J. T. Herbon, R. K. Hanson, Shock Tube Measurements of Iso-Octane Ignition Times and OH Concentration Time Histories, Proceedings of the Combustion Institute 29: (2002). M. A. Oehlschlaeger, D. F. Davidson, J. T. Herbon, R. K. Hanson, "Shock Tube Measurements of Branched Alkane Ignition Times and OH Concentration Time Histories," 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-Octane Table 1: Ignition delay time measurement in argon based on the maximum slope of the CH* emission at 431 nm extrapolated to the zero baseline. Iso-Octane Table 2: 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.

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