Analysis and Validation of Automatically Generated Detailed Combustion Mechanisms of Large Hydrocarbons and Biofuels This project will

have several hierarchal stages meant to incrementally build up the students competence not only in detailed hydrocarbon high and low temperature combustion of large hydrocarbons but also in automatic generation using REACTION[1,2]. It is expected that signicant results can be produced at each stage to warrant a paper (or communication). 1. Comparison: Generated and Non-generated Mechanisms: This rst stage is meant to be a learning phase for the student in detailed combustion mechanisms, both those automatically generated and those generated by hand, emphasizing the low and and high temperature chemistry of saturated hydrocarbons larger than C12. The differences between the n-alkane[3], 2-methylalkane[4] and possibly highly branched hydrocarbons[5] mechanisms generated by REACTION and produced by hand by Westbrook will be analyzed with emphasis on the reaction classes of Curran[6,7] and Blurock[8,9]. The goal will be a short paper substantiating that mechanisms produced by hand can be generated automatically (possibly in time for a Symposium paper). Some new reaction classes may have to be dened and possibly the rates of the old classes will be updated. 2.Base Mechanisms: An essential component of the generated mechanisms is the base mechanism of C2 to C4 molecules. Several mechanisms from the literature will be implemented as base mechanisms (starting with the LLNL mechanisms of Westbrook, to further increase the correspondence between the generated and hand-produced mechanisms. The mechanisms will focus on n-alkanes and branched alkanes. Numerical validation simulations with zero-dimensional ignition and PSR experiments will be performed. A short paper can come out of this illustrating the effect of different base mechanisms on the validation. All the other generators use a single base mechanism of the research group. 3.Submechanisms and Pathways: A generated mechanism is made through the combination of high and low temperature pathways. Each pathway generates a submechanism that is combined to produce a single large mechanism. Combinations of pathways and possibly new pathways will be explored to examine their necessity under different conditions. This will also validate REACTIONs ability to easily produce different types of mechanisms from extensive (full chemistry in the primary and secondary mechanisms) to nonextensive (for example, extensive primary mechanism and non-extensive secondary mechanisms). This ability is also unique to the REACTION generation system. 4.Substituted Hydrocarbons: At this stage the study will break away from dealing with just saturated hydrocarbons. The rst part of this study will be to produce the reaction classes in REACTION needed to generate mechanisms for methy- and ethylesters. Another part of this study could be for unsaturated hydrocarbons (for which most classes exist already) or even aromatics (where some new reaction classes would need to be produced). Exactly which fuels to generate will be determined when this stage is reached. The decision could depend on the time remaining for the students stay. References: 1.Blurock, E.S. (1995) Reaction: system for modeling chemical reactions. J. Chem. Inf. Comp. Sci., 35, 607. 2.Morac, Gladys , Blurock, Edward S. and Mauss, Fabian(2006) 'AUTOMATIC GENERATION OF A DETAILED MECHANISM FOR THE OXIDATION OF n-DECANE', Combustion Science and Technology, 178: 10, 2025-2038 3.Charles K. Westbrook, William J. Pitz, Olivier Herbinet, Henry J. Curran, Emma J. Silke , A comprehensive detailed chemical kinetic reaction mechanism for combustion of n-alkane hydrocarbons from n-octane to nhexadecane, Combustion and Flame 156 (2009) 181199 4.S.M. Sarathy, C.K. Westbrook, M. Mehl, W.J. Pitz, C. Togbe, P. Dagaut, H. Wang, M.A. Oehlschlaeger, U. Niemann, K. Seshadri, P.S. Veloo, C. Ji, F.N. Egolfopoulos, T. Luf Comprehensive chemical kinetic modeling of the oxidation of 2-methylalkanes from C7 to C20, Combustion and Flame (2011) 5.C.K. Westbrook a,*, W.J. Pitz a, M. Mehl a, H.J. Curran b, Detailed chemical kinetic reaction mechanisms for primary reference fuels for diesel cetane number and spark-ignition octane number, Proceedings of the Combustion Institute 33 (2011) 185192 6.Curran, H.J., Gaffuri, P., Pitz, W.J., and Westbrook, C.K. (1998) A comprehensive modeling study of nheptane oxidation. Combust. Flame, 114, 149. 7.Curran, H.J., Gaffuri, P., Pitz, W.J., and Westbrook, C.K. (2002) A comprehensive modeling study of isooctane oxidation. Combust. Flame, 129, 253. 8.Blurock, E.S. (2004a) Detailed mechanism generation 1: generalized reactive properties as reaction class substructures. J. Chem. Inf. Comp. Sci., 44, 1336. 9.Blurock, E.S. (2004b) Detailed mechanism generation 2: aldehydes, ketones and olens. J. Chem. Inf. Comp. Sci., 44, 1348.