NIST Real Fuels Chemical Kinetic

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• NIST Real Fuels Chemical Kinetic
• Combustion Model Database
• D.R. Burgess, Jr., T.C. Allison, J.A. Manion, and
  W. Tsang
• Physical and Chemical Properties Division
• National Institute of Standards and Technology
• Real Fuels
• Transportation, Aviation fuels gasoline,
  diesel, jet
• Mixtures of n-paraffins, iso-paraffins, olefins,
  naphthenes, aromatics
• Individual component composition Gas(C4-C11),
  Diesel/Jet (C9-C15)
• Model Complexity
• Methane/O2 several dozen species 100 some
  reactions
• Heptane/O2 100s of species 1000s of
  reactions
• Problem
• for small molecules keeping track of data is
  not too difficult

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• Information Overload means
• Time Consuming Bookkeeping Chores just dont
  get done
• Compromised Quality in results
• Data Management is a rate-limiting step in the
  development of robust, validated models

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• State of the Art for Combustion Modeling
• High Performance Tools and Advances
• Advanced Comput. Fluid Dynamics (CFD)
• Quantum Chemical Methods
• Master Equation Analysis
• Automated Mechanism Generation
• Mechanism Reduction Tools
• Understanding details of PAH formation
• etc.

4

• State of the Art for Combustion Modeling
• High Performance Tools and Advances
• Advanced Comput. Fluid Dynamics (CFD)
• Quantum Chemical Methods
• Master Equation Analysis
• Automated Mechanism Generation
• Mechanism Reduction Tools
• Understanding details of PAH formation
• etc.

• Archaic Data Management
• 19th century (computer-wise) paradigms
• Flat text files
• Formats traceable to ANSI Fortran (1977)
• Minimal error checking procedures
• Minimal electronic pedigree documentation
• Ad hoc symbolic species/reactions notation
• etc.

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Miller, J. A. Klippenstein, S. J. J. Phys.
Chem. A. 107, 2680-2692 (2003)
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C2H6 L 8/88C 2H 6 00 00G
200.000 3500.000 1000.000 1 1.07188150E00
2.16852677E-02-1.00256067E-05 2.21412001E-09-1.900
02890E-13 2 -1.14263932E04 1.51156107E01
4.29142492E00-5.50154270E-03 5.99438288E-05
3 -7.08466285E-08 2.68685771E-11-1.15222055E04
2.66682316E00 1.18915940E04 4 C6H8
H6W/94C 6H 8 0 0G 300.000
3000.000 1 0.28481979E02-0.15702948
E-01 0.26771697E-04-0.11780109E-07 0.16573427E-11
2 0.93346445E04-0.12500226E03
0.15850439E01 0.40215142E-01 0.78439543E-05
3 -0.38761325E-07 0.18545207E-10 0.17949613E05
0.19112625E02 4 i-C4H5
H6W/94C 4H 5 0 0G 300.000
3000.000 1 0.10229092E02
0.94850138E-02-0.90406445E-07-0.12596100E-08
0.24781468E-12 2 0.34642812E05-0.28564529E02
-0.19932900E-01 0.38005672E-01-0.27559450E-04
3 0.77835551E-08 0.40209383E-12 0.37496223E05
0.24394241E02 4 HCCHCCH
82489C 4H 3 g 0300.00 4000.00
1000.00 1 0.01075274e03
0.05381153e-01-0.05549638e-05-0.03052266e-08
0.05761740e-12 2 0.06121419e06-0.02973025e03
0.04153882e02 0.01726287e00-0.02389374e-05
3 -0.01018700e-06 0.04340505e-10 0.06338071e06
0.06036507e02 4 c.ccho
11/12/97 c 3h 5o 1 0g 300.000
5000.000 1371.000 1 9.97669730e00
1.15899378e-02-3.93593247e-06 6.08601507e-10-3.522
46874e-14 2 -3.71966345e03-2.42959564e01
2.95202753e00 2.48297051e-02-1.23487153e-05
3 2.49449869e-09-8.44820686e-14-9.23323349e02
1.46236244e01 4 meCy14pd3
bozzelli C 6H 7 0 0g 300.000
5000.000 1352.000 1 1.64509401e01
1.80104599e-02-6.44365088e-06 1.03095614e-09-6.108
14842e-14 2 1.54366624e04-6.72601234e01-9.87
511632e-01 4.83156342e-02-2.09426592e-05 3
6.71221112e-10 1.09340225e-12 2.25173499e04
3.00704019e01 4
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NIST Chemical Kinetic Combustion Model Database

• This unified Web site will provide the combustion
  community with detailed chemical
• kinetic models, along with supporting
  information, used in modeling applications.
• Chemical Kinetic Models used for combustion
  simulations
• Thermochemical Data for fuel components
  reaction intermediates
• Elementary Rate Coefficients for chemical
  reactions relevant to combustion
• The primary focus of the Web site is to provide a
  centralized source of information where
  well-documented, annotated reaction sets can be
  downloaded or uploaded.
• Particular emphasis is given towards promoting
  standards for nomenclature, notation,
  traceability, and communication in the modeling
  community.
• This includes providing systematic classification
  schemes for molecular species and chemical
  reactions.
• NIST not developing models just centralized
  source for data
• Database will NOT warehouse ALL data will
  provide links for some information

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NIST Chemical Kinetic Combustion Model Database

• Current site is working prototype
• Main current tasks are collecting and organizing
  data
• NIST is seeking input and guidance from the
  combustion community with regard to its
  development in order to improve its content and
  capabilities.
• http//kinetics.nist.gov/CKMech
  http//kinetics.nist.gov/realfuels

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One of a Set of Tools under Development in the
Community

• The intent for this site and database is
• To be complementary to other mechanism, modeling,
  and data analysis tools under development
• To target areas not being substantially addressed
  elsewhere such as standards, nomenclature,
  notation, traceability, etc.
• To collect and organize data to be used
  eventually in community wide data evaluation
  process (akin to IUPAC, JPL atmospheric evals,
  but electronic)
• To facilitate collaboration among the community
  with regard to process modeling
• To be integrated into developing infrastructure
  in the chemical sciences

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Related Complementary Efforts

• EVALUATION
• JPL Chemical Kinetics and Photochemical Data for
  Use in Atmospheric Studies
• IUPAC Subcommittee for Gas Kinetic Evaluation
• TOOLS
• PrIMe Process Informatics Model
• CMCS Collaboratory for Multi-Scale Chemical
  Science
• RIOT Range Identification and Optimization Tool
  for Kinetic Modeling (MIT)
• MECHMOD (Leeds)
• DATA
• Burcats Thermochemical Database
• Chemkin Thermochemical Database (Sandia/Reaction
  Design)
• GRI-Mech Combustion Model
• SNL High Temperature Thermodynamics Database
• LLNL Combustion Chemical Kinetic Mechanisms
• Cal Tech Reaction Mechanism Library compilation
• NIST Chemistry Webbook
• NIST Chemical Kinetics Database

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NIST Detailed Chemical Kinetic Combustion Model
Database

• Overview
• Chemical terminology, definitions, etc.
• Links to related effort, etc
• Models
• Archival "flat file" listings of detailed
  chemical kinetic models with brief descriptions
• Dynamical "relational" datasets of detailed
  chemical kinetic models with links to species,
  reaction, and bibliographic information
• Bibliography
• Supporting documentation for models, reactions,
  and species
• Species
• Molecular identifiers such as CASNO, chemical
  names, etc
• Molecular structures and chemical information
  such as structural/chemical formulae, SMILES
  strings, NIChI identifiers, MDL mol files,
  chemical classes, etc.
• Reactions
• Tools to search, manipulate, and compare
  individual reactions or reactions by class for
  specific detailed kinetic models or among models
  or build a model based on recommended values

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Implementation Issues

• Most commonly employed models, thermochemical
  chemical kinetic datasets, and databases are
  FLAT with regard to chemical speciation and
  reaction typing.
• One species
• One reaction
• after another
• Issue Common employed chemical databases are not
  chemical in nature
• Problem Architecture hampers searches based on
  chemical properties
• Need to Identify Species by Chemical
  Functionality (e.g.)
• CH3CH2CH2CH3 (n-Butane) is a normal alkane
• CH2CH-CHCH2 (1,3-Butadiene) is a conjugated
  alkadiene
• CH3CH2CH2CH2O (n-Butoxy) is an alkoxy radical

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Chemical Kinetic Data typically in Flat Format
lacking Descriptive Info

• CH4 H H2 CH3 1.300E04 3.00 33600.
• CH4 O OH CH3 6.923E08 1.56 35500.
• HO2 CO OHCO2 1.500E14 0.0 23600.
• C2H3O OH CH2CO H2O 5.00E12 0.0 0.0
  ! Estimated
• C4H6 O HCO aC3H5 6.00E08 1.45 -860. !
  Fontijn
• CH3 C2H C3H3 H 2.41E13 0.0 0.0
  ! Tsang-Hampson
• C2H5 HCO C2H5CHO 1.81E13 0.0 0.0
  ! Tsang/Hampson 1986
• C4H4 CH3 n-C4H3 CH4 3.98E11 0.0 4972.
  ! 85SCH/CLA
• C4H4 C2H n-C4H3 C2H2 3.90E13 0.0 0.0
  ! 80TAN/GAR
• R4CH3 R72C3H7 C4H10 1.7E13 0.0 0.0
  ! CO 329 KB
• C4H10 R1H H2R20C4H9 5.6E07 2.0
  7700. ! ME 191 CW
• CCC.C H C2H3 C2H5 9.63E32 -5.2 32320.
  ! n51
• CCCC CH4 CCC.C CH3 1.36E14 -0.04
  57100. ! n55
• No standard symbols used for species
• No indicator of reaction type (e.g., bond
  scission, abstraction)
• No links to related reactions
• No links to other possible rate expressions

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Reaction Set in a Dynamic Linked Format
Reaction Datatype e.g., expt, review, est

• Reaction String
• Standardized Symbols for Species
• Links to more information

Links to NIST Chemical Kinetics Database
Reaction Classification -e.g. abstraction, bond
fission -bond broken/formed -reaction sites
Arrhenius parameters
Citation
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http//kinetics.nist.gov/CKMech
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Species by Molecular Formula
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Species Chemical Class
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PAH Classification
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Reaction Set Input Flat Text File
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Reaction Species Set
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Reaction Set in a Dynamic Linked Format
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Species Images w/ Reactions
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All Reactions for a Species
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All Reactions for General Class
C-H abstraction by O centered Radical
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All Reactions for a Specific Type
From a R-CHCH-H Site
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Compare Models
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NIST Chemical Kinetic Combustion Model Database

• This unified Web site will provide the combustion
  community with detailed chemical
• kinetic models, along with supporting
  information, used in modeling applications.
• Chemical Kinetic Models used for combustion
  simulations
• Thermochemical Data for fuel components
  reaction intermediates
• Elementary Rate Coefficients for chemical
  reactions relevant to combustion
• The primary focus of the Web site is to provide a
  centralized source of information where
  well-documented, annotated reaction sets can be
  downloaded or uploaded.
• Particular emphasis is given towards promoting
  standards for nomenclature, notation,
  traceability, and communication in the modeling
  community.
• This includes providing systematic classification
  schemes for molecular species and chemical
  reactions.
• NIST not developing models just centralized
  source for data
• Database will NOT warehouse ALL data will
  provide links for some information

38
NIST Chemical Kinetic Combustion Model Database

• Current site is working prototype
• Main current tasks are collecting and organizing
  data
• NIST is seeking input and guidance from the
  combustion community with regard to its
  development in order to improve its content and
  capabilities.
• http//kinetics.nist.gov/CKMech
  http//kinetics.nist.gov/realfuels