Investigating the impacts of thermochemical group additivity values on kinetic model predictions through sensitivity and uncertainty analyses

Abstract The accuracy of species thermochemical properties is important for predicting combustion characteristics by chemical kinetic models due to their impacts on chemical equilibria of elementary reactions and on backward rate coefficients. As they are frequently estimated based on the group additivity method, the underlying group values directly influence the model prediction accuracy. While a number of studies have recently aimed to improve the accuracy of group values, the dependence of kinetic model predictions on the different groups has not yet been investigated in detail before. In the present work, the impact of group thermochemical parameters on ignition prediction is systematically analyzed by means of sensitivity analysis, employing the oxidation of 2-methylhexane (2-MH) as an example. Very high sensitivities are observed at intermediate temperatures for the peroxy group OO/C/H and its adjacent groups in low-temperature intermediate species. Based on uncertainty analysis, optimization potentials are then determined for the group values of enthalpy of formation, standard entropy, and heat capacity, and they are observed to be considerable for certain groups, especially for the enthalpy of formation values of OO/C/H and its adjacent groups. It is also found that the correct and consistent application of optical isomer corrections in the group additivity method is essential for accurate model predictions. The high optimization potentials of a number of groups motivate the extension of an established kinetic model optimization framework as part of this work, calibrating jointly the rate rules and group values against sets of both global model prediction targets and known species thermochemical properties. This methodology is applied to the considered 2-MH model, yielding very good posterior predictions of ignition characteristics. Overall, the results of this study demonstrate that uncertainties in certain group values will strongly propagate into the model prediction, which motivates future research towards a reduction of those uncertainties.

[1]  First‐principles based group additivity values for thermochemical properties of substituted aromatic compounds , 2015 .

[2]  William J. Pitz,et al.  The role of correlations in uncertainty quantification of transportation relevant fuel models , 2017 .

[3]  C. Westbrook,et al.  Multi-fuel surrogate chemical kinetic mechanisms for real world applications. , 2018, Physical chemistry chemical physics : PCCP.

[4]  William H. Green,et al.  Reaction Mechanism Generator: Automatic construction of chemical kinetic mechanisms , 2016, Comput. Phys. Commun..

[5]  F. Egolfopoulos,et al.  Chemical kinetic model uncertainty minimization through laminar flame speed measurements. , 2016, Combustion and flame.

[6]  William H. Green,et al.  An Extended Group Additivity Method for Polycyclic Thermochemistry Estimation: AN EXTENDED GROUP ADDITIVITY METHOD FOR POLYCYCLIC THERMOCHEMISTRY ESTIMATION , 2018 .

[7]  M. H. Back,et al.  The heat of formation of the ethyl radical , 1984 .

[8]  Apurba K. Das,et al.  A comprehensive iso-octane combustion model with improved thermochemistry and chemical kinetics , 2017 .

[9]  S. Benson,et al.  Additivity Rules for the Estimation of Molecular Properties. Thermodynamic Properties , 1958 .

[10]  Michel Waroquier,et al.  Group additive values for the gas phase standard enthalpy of formation of hydrocarbons and hydrocarbon radicals. , 2005, The journal of physical chemistry. A.

[11]  S. M. Sarathy,et al.  Comprehensive chemical kinetic modeling of the oxidation of 2-methylalkanes from C7 to C20 , 2011 .

[12]  B. C. Garrett,et al.  Current status of transition-state theory , 1983 .

[13]  E. S. Domalski,et al.  Estimation of the Thermodynamic Properties of Hydrocarbons at 298.15 K , 1988 .

[14]  C. Westbrook,et al.  A Comprehensive Modeling Study of iso-Octane Oxidation , 2002 .

[15]  William H Green,et al.  Database of small molecule thermochemistry for combustion. , 2012, The journal of physical chemistry. A.

[16]  Alessio Frassoldati,et al.  Optimization of Chemical Kinetics for Methane and Biomass Pyrolysis Products in Moderate or Intense Low-Oxygen Dilution Combustion , 2018, Energy & Fuels.

[17]  H. Pitsch,et al.  Mechanism optimization based on reaction rate rules , 2014 .

[18]  Tamás Turányi,et al.  Effect of the uncertainty of kinetic and thermodynamic data on methane flame simulation results , 2002 .

[19]  S. Klippenstein,et al.  Ab Initio Computations and Active Thermochemical Tables Hand in Hand: Heats of Formation of Core Combustion Species. , 2017, The journal of physical chemistry. A.

[20]  W. Green,et al.  Oxygenate, oxyalkyl and alkoxycarbonyl thermochemistry and rates for hydrogen abstraction from oxygenates , 2003 .

[21]  H. Bockhorn,et al.  Thermochemical Properties, Rotation Barriers, Bond Energies, and Group Additivity for Vinyl, Phenyl, Ethynyl, and Allyl Peroxides , 2004 .

[22]  Tiziano Faravelli,et al.  New reaction classes in the kinetic modeling of low temperature oxidation of n-alkanes , 2015 .

[23]  Hai Wang,et al.  A new approach to response surface development for detailed gas‐phase and surface reaction kinetic model optimization , 2003 .

[24]  Peng Zhang,et al.  Cascaded group-additivity ONIOM: A new method to approach CCSD(T)/CBS energies of large aliphatic hydrocarbons , 2019, Combustion and Flame.

[25]  Branko Ruscic,et al.  Uncertainty quantification in thermochemistry, benchmarking electronic structure computations, and Active Thermochemical Tables , 2014 .

[26]  Michael Fairweather,et al.  Evaluation of models for the low temperature combustion of alkanes through interpretation of pressure-temperature ignition diagrams. , 2006, Physical chemistry chemical physics : PCCP.

[27]  B. Viskolcz,et al.  Application of the Group Additivity Method to Alkyl Radicals: An ab Initio Study , 2000 .

[28]  Michel Waroquier,et al.  First principles based group additive values for the gas phase standard entropy and heat capacity of hydrocarbons and hydrocarbon radicals. , 2008, The journal of physical chemistry. A.

[29]  Lawrence B. Harding,et al.  A quantitative explanation for the apparent anomalous temperature dependence of OH + HO2 = H2O + O2 through multi-scale modeling , 2013 .

[30]  John M. Simmie,et al.  Critical Evaluation of Thermochemical Properties of C 1 -C 4 Species: Updated Group-Contributions to Estimate Thermochemical Properties , 2015 .

[31]  Ming Jia,et al.  Construction and assessment of reduced oxidation mechanisms using global sensitivity analysis and uncertainty analysis , 2019, Proceedings of the Combustion Institute.

[32]  S. M. Sarathy,et al.  Modeling Ignition of a Heptane Isomer: Improved Thermodynamics, Reaction Pathways, Kinetics, and Rate Rule Optimizations for 2-Methylhexane. , 2016, The journal of physical chemistry. A.

[33]  J. F. Griffiths,et al.  A global sensitivity study of cyclohexane oxidation under low temperature fuel-rich conditions using HDMR methods , 2009 .

[34]  Hai Wang,et al.  Critical kinetic uncertainties in modeling hydrogen/carbon monoxide, methane, methanol, formaldehyde, and ethylene combustion , 2018, Combustion and Flame.

[35]  Kuiwen Zhang,et al.  An experimental and kinetic modeling study of n-hexane oxidation , 2015 .

[36]  A. Császár,et al.  From a network of computed reaction enthalpies to atom-based thermochemistry (NEAT). , 2010, Chemistry.

[37]  S. M. Sarathy,et al.  Optimized reaction mechanism rate rules for ignition of normal alkanes , 2016 .

[38]  Eric L. Petersen,et al.  An ignition delay time and chemical kinetic modeling study of the pentane isomers , 2016 .

[39]  C. Westbrook,et al.  A Comprehensive Modeling Study of n-Heptane Oxidation , 1998 .

[40]  Edward R. Ritter,et al.  THERM: THERMODYNAMIC PROPERTY ESTIMATION FOR GAS PHASE RADICALS and MOLECULES , 1991, Proceeding of Data For Discovery.

[41]  M. Frenkel,et al.  New Group-Contribution Approach to Thermochemical Properties of Organic Compounds: Hydrocarbons and Oxygen-Containing Compounds , 2013 .

[42]  H. Curran.  Developing detailed chemical kinetic mechanisms for fuel combustion , 2019, Proceedings of the Combustion Institute.

[43]  F. Battin‐Leclerc,et al.  An updated experimental and kinetic modeling study of n-heptane oxidation , 2016 .

[44]  T. Turányi,et al.  Uncertainty quantification of a newly optimized methanol and formaldehyde combustion mechanism , 2017 .

[45]  S. Benson,et al.  Thermochemical Kinetics: Methods for the Estimation of Thermochemical Data and Rate Parameters , 1976 .

[46]  A. Burcat.  Thermochemical Data for Combustion Calculations , 1984 .

[47]  C. Westbrook,et al.  Chemical kinetic modeling of hydrocarbon combustion , 1984 .

[48]  Stephen J. Klippenstein,et al.  Multiscale Informatics for Low-Temperature Propane Oxidation: Further Complexities in Studies of Complex Reactions. , 2015, The journal of physical chemistry. A.

[49]  T. Turányi.  Sensitivity analysis of complex kinetic systems. Tools and applications , 1990 .

[50]  N. Cohen,et al.  Revised Group Additivity Values for Enthalpies of Formation (at 298 K) of Carbon–Hydrogen and Carbon–Hydrogen–Oxygen Compounds , 1996 .

[51]  F. Battin‐Leclerc.  Detailed chemical kinetic models for the low-temperature combustion of hydrocarbons with application to gasoline and diesel fuel surrogates , 2008 .

[52]  Michael Frenklach,et al.  Transforming data into knowledge—Process Informatics for combustion chemistry , 2007 .

[53]  Tamás Turányi,et al.  Uncertainty of the rate parameters of several important elementary reactions of the H2 and syngas combustion systems , 2015 .

[54]  Cosmin Safta,et al.  Uncertainty quantification of reaction mechanisms accounting for correlations introduced by rate rules and fitted Arrhenius parameters , 2013 .

[55]  Yang Li,et al.  Extensive Theoretical Study of the Thermochemical Properties of Unsaturated Hydrocarbons and Allylic and Super-Allylic Radicals: The Development and Optimization of Group Additivity Values. , 2018, The journal of physical chemistry. A.

[56]  Chiung-Chu Chen,et al.  Structures, intramolecular rotation barriers, and thermochemical properties of methyl ethyl, methyl isopropyl, and methyl tert-butyl ethers and the corresponding radicals , 2003 .

[57]  Thermodynamic Properties of Ketenes: Group Additivity Values from Quantum Chemical Calculations , 2002 .

[58]  Tamás Turányi,et al.  Uncertainty analysis of NO production during methane combustion , 2008 .

[59]  I. Wlokas,et al.  Response surface and group additivity methodology for estimation of thermodynamic properties of organosilanes , 2018, International Journal of Chemical Kinetics.

[60]  S. M. Sarathy,et al.  A comprehensive chemical kinetic combustion model for the four butanol isomers , 2012 .

[61]  H. Pitsch,et al.  Sensitivity analysis, uncertainty quantification, and optimization for thermochemical properties in chemical kinetic combustion models , 2019, Proceedings of the Combustion Institute.

[62]  D. Golden,et al.  Additivity rules for the estimation of thermochemical properties , 1969 .

[63]  Edward R. Ritter,et al.  THERM: a computer code for estimating thermodynamic properties for species important to combustion and reaction modeling , 1991, J. Chem. Inf. Comput. Sci..

[64]  R. Sivaramakrishnan,et al.  Rate constants for OH with selected large alkanes: shock-tube measurements and an improved group scheme. , 2009, The journal of physical chemistry. A.

[65]  Michael Frenklach,et al.  Optimization and analysis of large chemical kinetic mechanisms using the solution mapping method—combustion of methane , 1992 .

[66]  Kyle E. Niemeyer,et al.  Assessing impacts of discrepancies in model parameters on autoignition model performance: A case study using butanol , 2017, 1708.02232.

[67]  Kaizar Amin,et al.  Introduction to Active Thermochemical Tables: Several “Key” Enthalpies of Formation Revisited† , 2004 .

[68]  Anthony M. Dean,et al.  HYDROGEN ATOM BOND INCREMENTS FOR CALCULATION OF THERMODYNAMIC PROPERTIES OF HYDROCARBON RADICAL SPECIES , 1995 .

[69]  Tamás Turányi,et al.  Local and global uncertainty analyses of a methane flame model. , 2005, The journal of physical chemistry. A.

[70]  Hai Wang,et al.  Joint probability distribution of Arrhenius parameters in reaction model optimization and uncertainty minimization , 2019, Proceedings of the Combustion Institute.

[71]  Todd A. Oliver,et al.  Bayesian analysis of syngas chemistry models , 2013 .

[72]  Tamás Varga,et al.  Determination of rate parameters based on both direct and indirect measurements , 2012 .

[73]  Hans-Heinrich Carstensen,et al.  High-pressure rate rules for alkyl + O2 reactions. 1. The dissociation, concerted elimination, and isomerization channels of the alkyl peroxy radical. , 2011, The journal of physical chemistry. A.

[74]  Heinz Pitsch,et al.  Impact of thermochemistry on optimized kinetic model predictions: Auto-ignition of diethyl ether , 2019 .

[75]  David A. Sheen,et al.  The method of uncertainty quantification and minimization using polynomial chaos expansions , 2011 .

[76]  C. Muller,et al.  THERGAS: a computer program for the evaluation of thermochemical data of molecules and free radicals in the gas phase , 1995 .

[77]  Michael Frenklach,et al.  Systematic optimization of a detailed kinetic model using a methane ignition example , 1984 .

[78]  N. Papayannakos,et al.  Group additive values for the gas-phase standard enthalpy of formation, entropy and heat capacity of oxygenates. , 2013, Chemistry.

[79]  Omar M. Knio,et al.  Global sensitivity analysis of n-butanol reaction kinetics using rate rules , 2018, Combustion and Flame.

[80]  H. Curran,et al.  Revisiting the Kinetics and Thermodynamics of the Low-Temperature Oxidation Pathways of Alkanes: A Case Study of the Three Pentane Isomers. , 2015, The journal of physical chemistry. A.

[81]  Alison S. Tomlin,et al.  The role of sensitivity and uncertainty analysis in combustion modelling , 2013 .

[82]  Alison S. Tomlin,et al.  Determining predictive uncertainties and global sensitivities for large parameter systems: A case study for N-butane oxidation , 2015 .

[83]  H. Pitsch,et al.  Optimized chemical mechanism for combustion of gasoline surrogate fuels , 2015 .

[84]  Xin He,et al.  An adaptive distance-based group contribution method for thermodynamic property prediction. , 2016, Physical chemistry chemical physics : PCCP.

[85]  A. Farooq,et al.  Shock tube measurements of the rate constants for seven large alkanes + OH , 2015 .