DTIC ADA514047: Fundamental Kinetics Database Utilizing Shock Tube Measurements. Volume 3. Reaction Rate Measurements

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Fundamental Kinetics Database
Utilizing Shock Tube Measurements

Volume 3: Reaction Rate Measurements

D. F. Davidson and R. K. Hanson

Mechanical Engineering Department
Stanford University, Stanford CA 94305

January 15th, 2009
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Fundamental Kinetics Database Utilizing Shock Tube Measurements W911NF-07-1-0084
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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 2009.

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, and the Gas Research Institute.

To receive a pdf version of this report please contact Dr. David Davidson
at [email protected] or it can be downloaded from http://hanson.stanford.edu/ .

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Table of Contents
Abstract ................................................................................................................. 2 
Table of Contents .................................................................................................. 3 
Introduction ........................................................................................................... 6 
Database Format Example ................................................................................... 8 
Dissociation/Association Reactions ...................................................................... 9 
H + O + Ar = HO + Ar ..................................................................................... 9 
2 2
CH OCO = CH + CO ...................................................................................... 9 
3 3 2
CH -O-CH = CH O + CH ................................................................................ 9 
3 3 3 3
CH + Ar = Products .......................................................................................... 9 
3
C H CH = Products .......................................................................................... 9 
6 5 3
n-C H = Products .......................................................................................... 10 
7 16
iso-C H = Products ....................................................................................... 10 
8 18
CH O + Ar = Products ..................................................................................... 10 
2
C H CH = Products ........................................................................................ 10 
6 5 2
(CH ) -CO-OH = (CH ) CO + OH .................................................................... 11 
3 3 3 3
CO + M = CO + O(3P) + M ............................................................................. 11 
2
C H = 2CH .................................................................................................... 11 
2 6 3
C H = CH + C H .......................................................................................... 11 
3 8 3 2 5
CH O + M = Products ...................................................................................... 11 
2
Iso-C H = CH + i-C H ................................................................................. 12 
4 10 3 3 7
n-C H = Products .......................................................................................... 12 
4 10
HCO + M = H + CO + M .................................................................................. 12 
C H CH NH = NH + C H CH ...................................................................... 12 
6 5 2 2 2 6 5 2
H + O + M = HO + M ..................................................................................... 13 
2 2
CH NH + M = CH NH + M ........................................................................... 13 
3 2 3 2
CH NH + M = CH NH + M ........................................................................... 13 
3 2 3 2
CH + M = CH + H ......................................................................................... 13 
3 2
NO + M = NO + O + M ................................................................................... 14 
2
N O + M = N + O + M ..................................................................................... 14 
2 2
C H = 2CH .................................................................................................... 14 
2 6 3
CH = CH + H ................................................................................................ 14 
4 3
H + O + M = HO + M ..................................................................................... 14 
2 2
HNO + M = OH + NO + M ............................................................................. 15 
3 2
C H + M = C H + H + M .............................................................................. 15 
2 4 2 2 2
C H = 2CH .................................................................................................... 15 
2 6 3
CH +M = CH + H + M ................................................................................... 15 
4 3
NH + M = NH + H + M .................................................................................. 15 
3 2
HNCO + Ar = NH + CO + Ar ............................................................................ 15 
NH + Ar = N + H Ar ......................................................................................... 16 
NCO + M = N + CO + M .................................................................................. 16 
HCN + Ar = H + CN + Ar ................................................................................. 16 
C N + Ar = 2CN + Ar ...................................................................................... 16 
2 2
NH + M = NH + H + M .................................................................................. 16 
3 2
N O + M = N + O + M ..................................................................................... 17 
2 2
3
Bimolecular Reactions ........................................................................................ 18 
2007-2009 ........................................................................................................... 18 
CH3OH + OH = Products ................................................................................ 18 
CH3 + OH = Products ..................................................................................... 18 
CH + N = Products ......................................................................................... 18 
2
CH O + O = Products ..................................................................................... 18 
2 2
2005-2006 ........................................................................................................... 19 
C H CH + H = C H CH + H ......................................................................... 19 
6 5 3 6 5 2 2
C H CH CH + O = C H CH + HO ............................................................. 19 
6 5 3 3 2 6 5 2 2
CH O +OH = HCO + H O ................................................................................ 19 
2 2
C H CH +OH = Products ............................................................................... 19 
6 5 3
CH COCH +OH = CH COCH +H O ............................................................. 20 
3 3 3 2 2
CH +O = Products ........................................................................................ 20 
3 2
2000-2004 ........................................................................................................... 21 
CH OH + HCO = 2CH O ................................................................................. 21 
2 2
NH + CH = NH + CH .................................................................................. 21 
2 4 3 3
H + HCO = H + CO ........................................................................................ 21 
2
HCO + HCO = CH O + CO ............................................................................. 21 
2
H + CH O = H + HCO .................................................................................... 21 
2 2
NH + NO = Products ...................................................................................... 22 
2
NH + NO = Products ..................................................................................... 22 
2 2
NH2 + NO = Products ..................................................................................... 22 
NH + NO = Products ...................................................................................... 22 
2
1995-1999 ........................................................................................................... 23 
NH + NO = Products ...................................................................................... 23 
2
CH + O = Products ......................................................................................... 23 
2
CH + H = CH + H .......................................................................................... 23 
2 2
NO + NO = Products ..................................................................................... 23 
2 2
CH + CH = Products ..................................................................................... 23 
3 3
CH + H = 1CH + H ....................................................................................... 24 
3 2 2
HCN + OH = CN + H O ................................................................................... 24 
2
CN + OH = Products ....................................................................................... 24 
CN + HCN = C N + H ..................................................................................... 24 
2 2
CN + H = HCN + H ......................................................................................... 24 
2
CN + H = HCN + H ......................................................................................... 25 
2
HNCO + OH = Products .................................................................................. 25 
CO + OH = CO + H ........................................................................................ 25 
2
1990-1994 ........................................................................................................... 26 
CN + NO = Products ...................................................................................... 26 
2
NCO + NO = Products ................................................................................... 26 
2
H + O = OH + O ............................................................................................. 26 
2
CO + OH = CO + H ........................................................................................ 26 
2
OH + OH = H O + O ........................................................................................ 26 
2
O + HNCO = Products ..................................................................................... 27 
OH + HNCO = Products .................................................................................. 27 
C(3P) + H = CH + H ........................................................................................ 27 
2
4
C(3P) + O = CO + O ....................................................................................... 27 
2
C(3P) + C O = Products ................................................................................. 27 
3 2
CN + O = CO + N ............................................................................................ 28 
CN + O = NCO + O ........................................................................................ 28 
2
N O + O = Products ........................................................................................ 28 
2
C(3P) + NO = Products .................................................................................... 28 
CH + NO = Products ....................................................................................... 28 
H + HNCO = NH + CO ................................................................................... 29 
2
NH + HNCO = NH + NCO ............................................................................. 29 
2 3
NH + NO = Products ....................................................................................... 29 
NH + O = Products ......................................................................................... 29 
2
NH + O = Products .......................................................................................... 29 
NH + H = NH + H .......................................................................................... 30 
2 2
NH + NH = N H + H ...................................................................................... 30 
2 2 2
NH + NH = NH + NH ................................................................................... 30 
2 2 3
N + NO = O + N ............................................................................................. 30 
2
N + H = NH + H .............................................................................................. 30 
2
O + H = OH + H ............................................................................................. 31 
2
N + CH = H CN + H ....................................................................................... 31 
3 2
H + O = OH + O ............................................................................................. 31 
2
C(3P) + N = CN + N ........................................................................................ 31 
2
CH + N = HCN + N ......................................................................................... 31 
2
1986-1989 ........................................................................................................... 32 
NH + NH = Products ........................................................................................ 32 
H + H O = OH + H ......................................................................................... 32 
2 2
1974-1985 ........................................................................................................... 33 
NCO + H = NH + CO ....................................................................................... 33 
NCO + H = HNCO + H ................................................................................... 33 
2
CN + H O = HCN + OH ................................................................................... 33 
2
C N + O = CN + NCO .................................................................................... 33 
2 2
CN + O = CO + N ............................................................................................ 33 
HCN + O = Products ....................................................................................... 33 
NCO + O = CO + NO ....................................................................................... 34 
HCN + O = NCO + H ....................................................................................... 34 
CN + H = HCN + H ......................................................................................... 34 
2
CN + HCN = C N + H ..................................................................................... 34 
2 2
NH + NO = Products ...................................................................................... 34 
2
NH + NO = Products ....................................................................................... 34 
NO + H = N + OH ............................................................................................ 35 
N O + O = 2NO ............................................................................................... 35 
2
N + O = NO + N ............................................................................................. 35 
2
O + NO = N + O ............................................................................................. 35 
2

5
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 . The production and removal rates of these species have an
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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
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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 3 is January
2009, and work published after this data will be included in later editions.

A version of the database is available through the PRIME warehouse
currently being developed at University of California, Stanford University and
NIST.
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Database Format
In this report temperatures are given in Kelvin and activation energies are given
in calories/mole and using R = 1.987 [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], [cm3/mol/s], or [cm6/mol2/s]. Pressures are quoted in atm
or bar. The publications are listed in approximately reverse chronological order.

8
Dissociation/Association Reactions
H + O + Ar = HO + Ar
2 2
G. A. Pang, D. F. Davidson, R. K. Hanson, “Experimental Study and Modeling of
Shock Tube Ignition Delay Times for Hydrogen-Oxygen-Argon Mixtures at Low
Temperatures,” Proceedings of the Combustion Institute 32 (2009) 181-188.
For 908-1118 K, 3.0-3.8 atm:
k = 1.04x1013 T0.2 [cm3/mol/s];
∞
k = 6.99x1018 T-1.2 [cm6/mol2/s], F = 0.7.
0 cent
This study provides a preliminary measurement of this rate in this temperature
range.
CH OCO = CH + CO
3 3 2
A. Farooq, D. F. Davidson, R. K. Hanson, L. K. Huynh, A. Violi, “An Experimental
and Computational Study of Methyl Ester Decomposition Pathways using Shock
Tubes,” Proceedings of the Combustion Institute 32 (2009) 247-253.
For 1260-1653 K, 1.4-1.7 atm:
k = 1.55x1012 T0.514 exp(-15182/RT) [1/s].
This study provides a confirmation of the reaction rate suggested by L. K. Huynh,
A. Violi, J. Org. Chem. 73 (2008) 94-101.
CH -O-CH = CH O + CH
3 3 3 3
R. D. Cook, D. F. Davidson, R. K. Hanson, “Shock Tube Measurements of
Ignition Delay Times and OH Time-Histories in Dimethyl Ether Oxidation,”
Proceedings of the Combustion Institute 32 (2009) 189-196.
For 680-1750 K, 1.6-6.6 bar:
k = 1.61x1079 T-18.4 exp(116438/RT) [1/s]
This rate was inferred based on this and previous studies.
CH + Ar = Products
3
V. Vasudevan, R. K. Hanson D. M. Golden, C. T. Bowman, D. F. Davidson,
“High-Temperature Shock Tube Measurements of Methyl Radical
Decomposition,” Journal Physical Chemistry A 111 (2007) 4062-4072.
For 2706-3527 K, 0.7-4.2 atm:
k = 3.09x1015 exp (-80871/RT) [cm3/mol/s] for the CH+H channel
2
For 2253-2975 K, 1.1-3.9 atm:
k = 2.24x1015 exp (-82659/RT) [cm3/mol/s] rate for the CH +H channel
2
This study also includes the rate for the CH+H channel.
2
C H CH = Products
6 5 3
M. A. Oehlschlaleger, D. F. Davidson, R. K. Hanson, “Thermal Decomposition of
Toluene: Overall Rate and Branching Ratio,” Proceedings of the Combustion
Institute 31 (2007) 211-219. See also Western States Section/Combustion
Institute Fall 2005 Meeting, October 17-18, 2005, paper 05F-59.
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