Optimization of Reaction Models With Solution Mapping

Optimization of Reaction Models with Solution Mapping 

Michael Frenklach, Andrew Packard and Ryan Feeley 

Usually, chemical reaction models are composed from individual reactions steps, ether elementary or global. Each reaction step has a prescribed rate law, which is characterized by a set of parameters. The parameter values are collected from literature, evaluated using theoretical machinery, estimated by empirical rules, or simply guessed. The predictive power of a reaction model is thus determined by two factors, the authenticity of the reaction steps and the correctness of the rate parameters. For the purpose of the present discussion, we assume that the complete set of reaction steps (i.e., the reaction mechanism) is known and our focus is entirely on the identification of the correct parameter values. It is pertinent to mention, though, that the process of reaching conclusions on the authenticity of the reaction mechanism is often based on and is coupled to the parameter identification. The assumption of the known mechanism should not be viewed as a simplification of the problem but rather a pedagogical device for presenting the material. 

The objective of this chapter is to introduce the reader to determination of best-fit parameter values of a chemical kinetics model given a set of experimental measurements and, more generally, to development 

Comprehensive Chemical Kinetics, Volume 42, 243-291 Copyright 2007 Elsevier B.V. All rights reserved. ISSN 0069-8040/doi 10.1016/S0069-8040(07)42006-4 

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Optimization of reaction models with solution mapping... 

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