Fundamental Kinetics Database Utilizing Shock Tube Measurements

Transcription

1 Fundamental Kinetics Database Utilizing Shock Tube Measurements Volume 6: Reaction Rate Measurements (January 2009 to January 2014) D. F. Davidson and R. K. Hanson Mechanical Engineering Department Stanford University, Stanford CA May 1 st, 2014

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3 Abstract This volume of the Fundamental Kinetic Database Utilizing Shock Tube Measurements includes a summary of the reaction rates measured and published by the Hanson Shock Tube Group in the Mechanical Engineering Department of Stanford University. The cut-off date for inclusion in 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, and the National Science Foundation. To receive a pdf version of this report please contact Dr. David Davidson at dfd@stanford.edu or it can be downloaded from 3

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5 Table of Contents Abstract... 3 Table of Contents... 5 Introduction... 7 Database Format... 8 Dissociation/Association Reactions H 2 O 2 + M = 2OH + M... 9 CH 3 -O-CH 3 + Ar = CH 3 O + CH 3 + Ar H 2 O 2 + Ar = 2OH + Ar... 9 Butanal = products Tert-butyl-hydroperoxide = products H+O 2 +CO 2 = HO 2 + CO H 2 O 2 +M = 2OH + M TBHP = OH + tert-butoxy n-dodecane = products MMH = CH 3 NH + NH H 2 O 2 + M = 2OH + M C 2 H 4 +M = C 2 H 2 +H 2 + M pentanone = products Methyl formate = products Acetone = CH 3 + CH 3 CO butanone = products Trioxane = 3 CH 2 O Cyclohexene = C 2 H 4 + 1,3-butadiene CH 2 OH = CH 2 O + H CH 3 O = CH 2 O + H Ethylamine = C 2 H 5 + NH Ethylamine = CH 2 NH 2 + CH MMH = CH 3 NH + NH

6 Bimolecular Reactions CH 3 -O-CH 3 + OH = CH 3 OCH 2 + H 2 O OH + HO 2 = H 2 O + O OH + H 2 O 2 = H 2 O + HO OH + n-butanol = products OH + ethylene = products OH + propene = products OH + 1,3-butadiene = products H + O 2 = OH + O H + O 2 = OH + O OH + H 2 O 2 = HO 2 + H 2 O O 2 + H 2 O = OH + HO OH + butene isomers = products OH + large n-alkanes = products OH + CH 3 = CH 2 (s) + H 2 O MMH + NH 2 = CH 3 NNH 2 + NH CH 3 + HO 2 = CH 3 O + OH CH 3 + HO 2 = CH 4 + O OH + CH 4 = CH 3 O + OH OH + n-butanol = products OH + sec-butanol = products OH + iso-butanol = products OH + small methyl esters = products OH + ketones = products H + iso-butanol = products OH + tert-butanol = products OH + H 2 = H 2 O + H OH + HO 2 = H 2 O + O HO 2 + HO 2 = H 2 O 2 + O OH + methanol = products OH + ethanol = products OH + small aldehydes = products OH + ethylamine = products OH + dimethylamine = products NHNH 2 + H = 2NH

7 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 7

8 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 six volumes: Volumes 1 and 2, ignition delay time measurements; Volumes 2 and 5, species concentration timehistories; and Volumes 3 and this Volume 6, reaction rate measurements. The formal cut-off point for Volume 6 is January 2014, and work published after this data will be included in later editions. Database Format In this report temperatures are given in Kelvin and activation energies are given in calories/mole and using R = [mole/calories/k] when a conversion from a published activation energy in Kelvins is needed and 4.18 Joules = 1 calorie when the published activation energy is in Joules. Reaction rate constants are given in units of [1/s], [cm 3 /mol/s], or [cm 6 /mol 2 /s]. Pressures are quoted in atm. The publications are listed approximately in chronological order. 8

9 Dissociation/Association Reactions 2009 H 2 O 2 + M = 2OH + M Z. Hong, A. Farooq, E. A. Barbour, D. F. Davidson, R. K. Hanson, Hydrogen peroxide decomposition rate: a shock tube study using tunable laser absorption near 2.5 m, Journal of Physical Chemistry A113 (2009) Z. Hong, A. Farooq, E. A. Barbour, D. F. Davidson, R. K. Hanson, Hydrogen peroxide decomposition rate: a shock tube study using tunable laser absorption near 2.5 m, Paper 09F65, Western States Section/Combustion Institute Fall 2009 Meeting, October For K, atm: k 0 = exp( K/T) [cc/mol/s] for M=Ar Experiments in N 2, show a collision efficiency of 0.67 CH 3 -O-CH 3 + Ar = CH 3 O + CH 3 + Ar R. D. Cook, D. F. Davidson, R. K. Hanson, High-temperature shock tube measurements of dimethyl ether decomposition and the reaction of dimethyl ether with OH, Journal of Physical Chemistry A113 (2009) R. D. Cook, D. F. Davidson, R. K. Hanson, Rate measurements of DME decomposition and DME + OH at elevated temperatures, Paper 1P08, 6 th U.S. Combustion Meeting, Ann Arbor MI May For K, atm: k infinity = 4.38x10 21 T exp(-42220k/t)) [1/s] k 0 = 7.52x10 15 exp( K/T) [cc/mol/s] F cent = exp(-t/2510) This rate is an RRKM fit to the measured data. The rate of DME+OH was also measured H 2 O 2 + Ar = 2OH + Ar Z. Hong, R. D. Cook, D. F. Davidson, R. K. Hanson, A shock tube study of OH + H 2 O 2 = H 2 O + HO 2 and H 2 O 2 + M = 2OH + M using laser absorption of H 2 O and OH, Journal Physical Chemistry A114 (2010) For K, atm: k = 9.5x10 15 exp( K/T) [cm 3 /mol/s] over this T and P range. This study also includes a measurement of OH+H 2 O = H 2 O+HO 2. 9

10 Butanal = products D. F. Davidson, S. C. Ranganath, K.-Y. Lam, M. Liaw, Z. Hong, R. K. Hanson, Ignition delay time measurements of normal alkanes and simple oxygenates, Journal of Physical Chemistry A114 (2010) For K, atm: k = 3x10 16 exp( /RT) [1/s], Rate expressions for the two decomposition channels (C 2 H 5 +CH 2 CHO and nc 3 H 7 +HCO) were estimated to be equal that given above. Tert-butyl-hydroperoxide = products S. S. Vasu, Z. Hong, D. F. Davidson, R. K. Hanson, D. M. Golden, Shock tube/laser absorption measurements of the reaction rate of OH with ethylene and propene, Journal of Physical Chemistry A114 (2010) For K, atm: k = 8.13x10-12 T 7.83 exp( K/T) [1/s], This expression is derived from a fit of the current and lower T data. Measurements of OH+ethylene and OH+propene were also performed H+O 2 +CO 2 = HO 2 + CO 2 S. S. Vasu, D. F. Davidson, R. K. Hanson, Shock tube study of syngas ignition in rich CO2 mixtures and determination of the rate of H+O 2 +CO 2 =HO 2 +CO 2, Energy and Fuel 25 (2011) For 1300 K, 8 atm: k 0 = 4.2x10 18 T [cm 6 /mol 2 /s], Measurements are in agreement with earlier recommendations from the GRI- Mech v3.0 natural gas mechanism. H 2 O 2 +M = 2OH + M Z. Hong, D. F. Davidson, R. K. Hanson, An improved H 2 /O 2 mechanism based on recent shock tube/laser absorption measurements, Combustion and Flame 158 (2011) For K: This study provides a summary of recent rate constant measurements in the H2/O2 system and a validated detailed reaction mechanism with these rates. TBHP = OH + tert-butoxy G. A. Pang, R. K. Hanson, D. M. Golden, C. T. Bowman, High-temperature measurements of the rate constants for reactions of OH with a series of large 10

11 normal alkanes: n-pentane, n-heptane, and n-nonane, Z. Phys. Chem. 225 (2011) For K, 2 atm: k(tbhp decomposition) = 3.57x10 13 exp( K/T) [1/s] The paper includes a discussion of TBHP (tertbutylhydroperoxide) kinetics. n-dodecane = products M. E. Macdonald, D. F. Davidson, R. K. Hanson, Decomposition measurements of RP-1, RP-2, JP-7, n-dodecane and tetreahydoquinoline in shock tubes, Journal of Propulsion and Power 27 (2011) For K, 5-44 atm: Rate constant data are given in text. Measurements made by fitting the JetSurF 1.0 mechanism to data. MMH = CH 3 NH + NH 2 R. D. Cook, S. H. Pyun, J. Cho, D. F. Davidson, R. K. Hanson, Shock tube measurements of species time-histories in monomethylhydrazine pyrolysis, Combustion and Flame 158 (2011) For K, 2 atm: k = 1.50x10 58 T exp( K/T) [1/s] The rate for the CH3 decomposition channel is given as 0-20% of the NH 2 channel resulting in an overall unimolecular decomposition rate for MMH of k = 1.64x10 58 T exp( K/T) [1/s] This study also includes measurements of MMH+NH H 2 O 2 + M = 2OH + M Z. Hong, D. F. Davidson, K.-Y. Lam, R. K. Hanson, A shock tube study of the rate constants of HO 2 and CH 3 reactions, Combustion and Flame 159 (2012) For K, 3.5 atm: The rate measurements were determined from species time-history measurements of OH, H 2 O and HO 2, and are given in tabular form in the paper along with rate constant for CH 3 +HO 2. C 2 H 4 +M = C 2 H 2 +H 2 + M W. Ren, D. F. Davidson, R. K. Hanson, IR laser absorption diagnostic for C 2 H 4 in shock tube kinetics studies Combustion and Flame 158 (2011) For K, 2-3 atm: 11

12 k = 2.6x10 16 exp( K/T) [cc/mol/s] This study provides ethylene time-histories as well. 3-pentanone = products K.-Y. Lam, W. Ren, Z. Hong, D. F. Davidson, R. K. Hanson, Shock tube measurements of 3-pentanone pyrolysis and oxidation Combustion and Flame 159 (2012) For K, 1.6 atm: k = 4.383x10 49 T -10 exp( K/T) [1/s] This study provides a rate constant for the association reaction C2H4+CO+M =CH 3 CHCO+M Methyl formate = products W. Ren, K.-Y. Lam, S. H. Pyun, A. Farooq, D. F. Davidson, R. K. Hanson, Shock tube/laser absorption studies of the decomposition of methyl formate, Proceedings of the Combustion Institute 34 (2013) For K, atm: k(ch 3 OH+CO) = 1.1x10 13 exp( K/T) [1/s] k(ch 2 O+ CH 2 O) = 2.6x10 12 exp( K/T) [1/s] k(ch 4 +CO 2 ) = 4.4x10 11 exp( K/T) [1/s] This study provides species time-history measurements of all the major O-atom carriers in the MF decomposition system. Acetone = CH 3 + CH 3 CO 2-butanone = products K.-Y. Lam, W. Ren, S. H. Pyun, A. Farooq, D. F. Davidson, R. K. Hanson, Multispecies time-history measurements during high-temperature acetone and 2- butanone pyrolysis, Proceedings of the Combustion Institute 34 (2013) For K, 1.6 atm: k(acetone) = 2.46x10 14 exp(-69300/rt) [1/s] at 1.6 atm k(2-butanone) = 6.08x10 13 exp(-63100/rt) [1/s] at 1.5 atm This study provides a suggested rate constant for methyl ketene decomposition as well. Trioxane = 3 CH 2 O S. Wang, D. F. Davidson, R. K. Hanson, High-temperature laser absorption diagnostics for CH 2 O and CH 3 CHO and their application to shock tube kinetics studies, Combustion and Flame 160 (2013)

13 For K, 2.1 atm: k = 3.58x10 12 exp( K/T) [1/s] at 2.1 atm This study provides species time-history measurements of aldehydes during pyrolysis. Cyclohexene = C 2 H 4 + 1,3-butadiene I. Stranic, D. F. Davidson, R. K. Hanson, Shock tube measurements of the rate constant for the reaction cyclohexene = ethylene + 1,3-butadiene, Chemical Physics Letters 584 (2013) For K, atm: k = 4.84x10 14 exp( K/T) [1/s] The study provides a very accurate determination of the rate constant used in chemical thermometers in shock tube experiments.. CH 2 OH = CH 2 O + H CH 3 O = CH 2 O + H E. E. Dames, D. M. Golden, Master equation modeling of the unimolecular decompositions of hydroxymethyl (CH 2 OH) and methoxy (CH 3 O) radicals to formaldehyde (CH 2 O) + H, Journal of Physical Chemistry A117 (2013) For K, atm: This study provides Troe-format-fitted expressions for the two title reactions Ethylamine = C 2 H 5 + NH 2 Ethylamine = CH 2 NH 2 + CH 3 S. Li, D. F. Davidson, R. K. Hanson, Shock tube study of ethylamine pyrolysis and oxidation, Accepted by Combustion and Flame April S. Li, D. F. Davidson, R. K. Hanson, K. Moshammer, K. Kohse-Höinghaus, Shock tube study of ethylamine pyrolysis and oxidation, Paper 070RK-0075, 8 th U.S. National Combustion Meeting, University of Utah, May 19-22, For K, atm: k(c 2 H 5 +NH 2 ) = 4.49x10 12 exp( /RT) [1/s] k(ch 2 NH 2 +CH 3 ) = 5.58x10 12 exp( /RT) [1/s] The study includes NH 2 and OH species time-history measurements from oxidation and pyrolysis experiments. 13

14 MMH = CH 3 NH + NH 2 S. Li, D. F. Davidson, R. K. Hanson, Shock tube study of the pressure dependence of monomethylhydrazine, Combustion and Flame 161 (2014) For K, atm: Tabulated data for this reaction are given in the paper. This study also includes a rate constant for NHNH 2 + H = 2NH 2. 14

15 Bimolecular Reactions 2009 CH 3 -O-CH 3 + OH = CH 3 OCH 2 + H 2 O R. D. Cook, D. F. Davidson, R. K. Hanson, High-temperature shock tube measurements of dimethyl ether decomposition and the reaction of dimethyl ether with OH, Journal of Physical Chemistry A113 (2009) R. D. Cook, D. F. Davidson, R. K. Hanson, Rate measurements of DME decomposition and DME + OH at elevated temperatures, Paper 1P08, 6 th U.S. Combustion Meeting, Ann Arbor MI May For K, 1.65 atm: k = 6.32x10 6 T 2 exp(328 K/T) [cc/mol/s] This rate from Curran et al. was found to be in excellent agreement with this measurement. The rate of DME+Ar was also measured OH + HO 2 = H 2 O + O 2 Z. Hong, S. S. Vasu, D. F. Davidson, R. K. Hanson, Experimental study of the rate of OH + HO 2 = H 2 O + O 2 at high temperatures using the reverse reaction, Journal Physical Chemistry A114 (2010) For K, 1.7 atm: k = 3.3x10 13 [cm 3 /mol/s] This study provides a non-arrhenius fit to this data and the lower temperature data of Keyser OH + H 2 O 2 = H 2 O + HO 2 Z. Hong, R. D. Cook, D. F. Davidson, R. K. Hanson, A shock tube study of OH + H 2 O 2 = H 2 O + HO 2 and H 2 O 2 + M = 2OH + M using laser absorption of H 2 O and OH, Journal Physical Chemistry A114 (2010) For K, atm: k = 4.6x10 13 exp(-2630 K/T) [cm 3 /mol/s] This study also includes a measurement of H 2 O 2 +M. OH + n-butanol = products S. S. Vasu, D. F. Davidson, R. K. Hanson, D. M. Golden, Measurements of the reaction of OH with n-butanol at high-temperatures, Chemical Physics Letters 497 (2010)

16 For K, 2.25 atm: Data are given in tabular format. Discussion about the individual branching channels is included. OH + ethylene = products OH + propene = products S. S. Vasu, Z. Hong, D. F. Davidson, R. K. Hanson, D. M. Golden, Shock tube/laser absorption measurements of the reaction rate of OH with ethylene and propene, Journal of Physical Chemistry A114 (2010) For K, 2-10 atm: k = 2.23x10 4 T exp(-1115 K/T) [cc/mol/s], +ethylene, K k = 1.94x10 6 T exp(-540 K/T) [cc/mol/s], +propene, K These expressions are TST calculations fit to the current and lower T data. A measurement of TBHP (tertbutylhydroperoxide) = products was also performed. OH + 1,3-butadiene = products S. S. Vasu, J. Zador, D. F. Davidson, R. K. Hanson, D. M. Golden, Hightemperature measurements and a theoretical study of the reaction of OH with 1,3-butadiene, Journal of Physical Chemistry A114 (2010) For K, 2.2 atm: Data is given in tablular format. Theoretical double Arrhenius expressions are given for certain channels as well H + O 2 = OH + O Z. Hong, D. F. Davidson, E. A. Barbour, R. K. Hanson, A new shock tube study of H + O 2 = OH + O reaction rate using tunable diode laser absorption of H 2 O near 2.5 m, Proceedings of the Combustion Institute 33 (2011) For K, 2 atm: k = 1.126x10 14 exp(-7805 K/T) [cm 3 /mol/s] This study provides another rate constant expression over a wider temperature range using the data of Masten et al. (1990). 16

17 H + O 2 = OH + O OH + H 2 O 2 = HO 2 + H 2 O O 2 + H 2 O = OH + HO 2 Z. Hong, D. F. Davidson, R. K. Hanson, An improved H 2 /O 2 mechanism based on recent shock tube/laser absorption measurements, Combustion and Flame 158 (2011) For K: This study provides a summary of recent rate constant measurements in the H2/O2 system and a validated detailed reaction mechanism with these rates. Improved values for H 2 O 2 +M are included as well. OH + butene isomers = products S. S. Vasu, L. K. Huynh, D. F. Davidson, R. K. Hanson, D. M. Golden, Reactoins of OH with butene isomers: measurements of the overall rates and a theoretical study, Journal of Physical Chemistry A115 (2011) For K, 2.2 atm: Data is given in tablular format. Theoretical discussions about the rate constants for 1-butene, trans-2-butene and cis-2-butene are also given. OH + large n-alkanes = products OH + CH 3 = CH 2 (s) + H 2 O G. A. Pang, R. K. Hanson, D. M. Golden, C. T. Bowman, High-temperature measurements of the rate constants for reactions of OH with a series of large normal alkanes: n-pentane, n-heptane, and n-nonane, Z. Phys. Chem. 225 (2011) For K, 2 atm: k(oh+n-pentane) = 1.27x10 14 exp(-2038 K/T) [cc/mol/s] k(oh+n-heptane) = 1.47x10 14 exp(-1804 K/T) [cc/mol/s] k(oh+n-nonane) = 1.91x10 14 exp(-1801 K/T) [cc/mol/s] k(oh+ch 3 ) = 1.65x10 14 [cc/mol/s] The paper includes a discussion of TBHP (tertbutylhydroperoxide) kinetics. MMH + NH 2 = CH 3 NNH 2 + NH 3 R. D. Cook, S. H. Pyun, J. Cho, D. F. Davidson, R. K. Hanson, Shock tube measurements of species time-histories in monomethyl hydrazine pyrolysis, Combustion and Flame 158 (2011) For K, 2 atm: k = 3.70x10 14 exp(-2620 K/T) [1/s] 17

18 The recommended rate constant for the reaction CH 3 NNH + NH 2 = CH 3 NN + NH 3 is higher than the value proposed by Sun et al. This study also include measurements of MMH decomposition CH 3 + HO 2 = CH 3 O + OH CH 3 + HO 2 = CH 4 + O 2 OH + CH 4 = CH 3 O + OH Z. Hong, D. F. Davidson, K.-Y. Lam, R. K. Hanson, A shock tube study of the rate constants of HO 2 and CH 3 reactions, Combustion and Flame 159 (2012) For K, 3.5 atm: k(ch 3 O+OH) = 6.8x10 12 [cc/mol/s] k(ch 4 +O 2 ) = 4.4x10 12 [cc/mol/s] k(oh+ch 4 ) = Given in tabular form in paper The rate measurements were determined from species time-history measurements of OH, H 2 O and HO 2. OH + n-butanol = products G. A. Pang, R. K. Hanson, D. M. Golden, C. T. Bowman, Rate constant measurements for the overall reaction of OH + 1-butanol = products from 900 to 1200 K, Journal of Physical Chemistry A116 (2011) For K, 1-2 atm: k = 1.95x10 14 exp(-2505 K/T) [cc/mol/s] The paper includes a discussion of the high-pressure decomposition rate constants for C 4 H 9 O. OH + sec-butanol = products G. A. Pang, R. K. Hanson, D. M. Golden, C. T. Bowman, Experimental determination of the high-temperature rate constant for the reaction of OH with sec-butanol, Journal of Physical Chemistry A116 (2011) For K, 1 atm: k = 4.2x10 13 exp(-1550 K/T) [cc/mol/s] The paper includes a three-parameter fit using previous lower temperature data covering K. 18

19 OH + iso-butanol = products G. A. Pang, R. K. Hanson, D. M. Golden, C. T. Bowman, High-temperature rate constant determination for the reaction of OH with iso-butanol, Journal of Physical Chemistry A116 (2012) For K, 1 atm: The paper includes a rate for (k overall k beta ) and a recommendation for the overall rate constant. OH + small methyl esters = products K.-Y. Lam, D. F. Davidson, R. K. Hanson, High-temperature measurements of the reactions of OH with small methyl esters: methyl formate, methyl acetate, methyl propanoate, and methyl butanoate, Journal of Physical Chemistry A116 (2012) For K, 1.5 atm: k(oh+methyl formate) = 2.56x10 13 exp(-2026 K/T) [cc/mol/s] k(oh+methyl acetate) = 3.59x10 13 exp(-2438 K/T) [cc/mol/s] k(oh+methyl propanoate) = 6.65x10 13 exp(-2539 K/T) [cc/mol/s] k(oh+methyl butanoate) = 1.13x10 14 exp(-2515 K/T) [cc/mol/s] The paper includes a discussion of the use of the Kwok and Atkinson structureactivity relations to predict these rate constants. OH + ketones = products K.-Y. Lam, D. F. Davidson, R. K. Hanson, High-temperature measurements of the reactions of OH with a series of ketones: acetone, 2-butanone, 3-pentanone, and 2-pentanone, Journal of Physical Chemistry A116 (2013) For K, 1-2 atm: k(oh+acetone) = 3.30x10 13 exp(-2437 K/T) [cc/mol/s] k(oh+2-butanone) = 6.35x10 13 exp(-2270 K/T) [cc/mol/s] k(oh+3-pentanone) = 9.29x10 13 exp(-2361 K/T) [cc/mol/s] k(oh+2-pentanone) = 7.06x10 13 exp(-2020 K/T) [cc/mol/s] The paper also includes a discussion of the use of the Kwok and Atkinson structure-activity relations to predict these rate constants H + iso-butanol = products I. Stranic, S. H. Pyun, D. F. Davidson, R. K. Hanson, Multi-species measurements in 2-butanol and i-butanol pyrolysis, Combustion and Flame 160 (2013) For K, atm: 19

20 The paper provides recommended rate constants for the various channels of the H+isobutanol reactions, which when implemented improved the simulations of the Sarathy et al. (2012) mechanism. OH + tert-butanol = products I. Stranic, G. A. Pang, R. K. Hanson, D. M. Golden, C. T. Bowman, Shock tube measurements of the tert-butanol + OH reaction rate and the tert-c 4 H 8 OH radical β-scission branching ratio using isotopic labeling, Journal of Physical Chemistry A117 (2013) I. Stranic, G. A. Pang, R. K. Hanson, D. M. Golden, C. T. Bowman, Shock tube measurements of the tert-butanol + OH reaction rate and the tert-c 4 H 8 OH radical β-scission branching ratio using isotopic labeling, Paper 0014, 8 th U.S. National Combustion Meeting, University of Utah, May 19-22, For K, 1.1 atm: k = 7.48x10 13 exp(-2501 K/T) [cc/mol/s] The paper includes rates for the different H-atoms abstraction sites using isotopic measurements. OH + H 2 = H 2 O + H K.-Y. Lam, D. F. Davidson, R. K. Hanson, A shock tube study of H 2 + OH = H 2 O + H using OH laser absorption, International Journal of Chemical Kinetics (2013) For K, atm: k = 4.38x10 13 exp(-3518 K/T) [cc/mol/s] This study provides a high accuracy measurement of this reaction rate constant. OH + HO 2 = H 2 O + O 2 HO 2 + HO 2 = H 2 O 2 + O 2 Z. Hong, K.-Y. Lam, R. Sur, S. Wang, D. F. Davidson, R. K. Hanson, On the rate constants of OH + HO2 and HO2 + HO2: a comprehensive study of H2O2 thermal decomposition using multi-species laser absorption, Proceedings of the Combustion Institute (2013) For K, 1.7 atm: k(oh+ho 2 ) = 7.0x10 12 exp(550 K/T) + 4.5x10 14 exp(-5500 K/T) [cm 3 /mol/s] k(ho 2 +HO 2 ) = 1.0x10 14 exp(-5556 K/T) 1.9x10 11 exp(709 K/T) [cm 3 /mol/s] This rate constant for HO 2 +HO 2 is unchanged from Kappel et al (2002). 20

21 2014 OH + methanol = products L. T. Zaczek, K.-Y. Lam, D. F. Davidson, R. K. Hanson, A shock tube study of CH 3 OH + OH = products using OH laser absorption, Accepted by the Proceedings of the Combustion Institute, April For K, atm: k = 5.71x10 4 T 2.62 exp(343 K/T) [cc/mol/s] This three-parameter fit uses the combined data from Hess and Tully (1989, Jimenez et al (2002), Dillion et al. (2004) and the current study. OH + ethanol = products I. Stranic, G. A. Pang, R. K. Hanson, D. M. Golden, C. T. Bowman, Shock tube measurements of the rate constant for the reaction ethanol + OH, Journal of Physical Chemistry A118 (2014) For K, 1.1 atm: k = 5.07x10 5 T 2.31 exp(608 K/T) [cc/mol/s] This measurement used isotopic ethanol to isolate the different H-atom abstraction sites. OH + small aldehydes = products S. Wang, D. F. Davidson, R. K. Hanson, High temperature measurements for the rate constants of C 1 -C 4 aldehydes with OH in a shock tube, Accepted by the Proceedings of the Combustion Institute, April For K, 1-2 atm: k(ch 2 O) = 1.02x10 7 T 1.92 exp(779 K/T) [cc/mol/s] k(ch 3 CHO) = 4.32x10 6 T 2.02 exp(716 K/T) [cc/mol/s] k(c 2 H 5 CHO) = 5.94x10 6 T 1.98 exp(823 K/T) [cc/mol/s] k(nc 3 H 7 CHO) = 5.36x10 6 T 2.06 exp(658 K/T) [cc/mol/s] This study provides the first measurements for the aldehydes acetylaldehyde, propionaldehyde and n-butyraldehyde at high temperatures. OH + ethylamine = products OH + dimethylamine = products S. Li, D. F. Davidson, R. K. Hanson, High-temperature measurements of the reaction of OH with ethylamine and dimethylamine, Submitted to Journal of Physical Chemistry A, November For K, 1.2 atm: k(ethylamine) = 1.10x10 7 T 1.93 exp(1450 K/T) [cc/mol/s] k(dimethylamine) = 2.26x10 4 T 2.69 exp(1797 K/T) [cc/mol/s] 21

22 This study is in good agreement with VTST calculations by Galano and Alverrez- Idaboy (2008). NHNH 2 + H = 2NH 2 S. Li, D. F. Davidson, R. K. Hanson, Shock tube study of the pressure dependence of monomethylhydrazine, Combustion and Flame 161 (2014) For K, atm: k = 1.5x10 14 exp(-755 K/T) [cc/mol/s] This study also includes a rate constant for MMH = CH 3 NH + NH 2. 22

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