Mechanism optimization based on reaction rate rules

Accurate chemistry models form the backbone of detailed computational fluid dynamics (CFD) tools used for simulating complex combustion devices. Combustion chemistry is often very complex and chemical mechanisms generally involve more than one hundred species and one thousand reactions. In the derivation of these large chemical mechanisms, typically a large number of reactions appears, for which rate data are not available from experiment or theory. Rate data for these reactions are then often assigned using so-called reaction classes. This method categorizes all possible fuel-specific reactions as classes of reactions with prescribed rules for the rate constants. This ensures consistency in the chemical mechanism. In rate parameter optimizations found in the published literature, rate constants of single elementary reactions are usually systematically optimized to achieve good agreement between model performance and experimental measurements. However, it is not kinetically reasonable to modify the rate parameters of single reactions, because this will violate consistency of rate parameters of kinetically similar reactions. In this work, the rate rules, that determine the rates for reaction classes are calibrated instead of the rates of single elementary reactions leading to a chemically more consistent model optimization. This is demonstrated by optimizing an n-pentane combustion mechanism. The rate rules are studied with respect to reaction classes, abstracting species, broken C–H bonds, and ring strain energy barriers. Furthermore, the uncertainties of the rate rules and model predictions are minimized and the pressure dependence of reaction classes dominating low temperature oxidation is optimized.