(569bd) Regression and Application of Kinetic Group Addivity Theory for Nitrogenated Hydrocarbons

Automatic kinetic model generation generates models with hundreds of species and thousands of reactions. The accuracy and availability of kinetic and thermodynamic parameters is key in obtaining a model that approaches reality. Quantum chemical calculations provide highly accurate parameters. However, due to the scale of automatically generated models, this is infeasible for every molecule and certainly for every reaction. To resolve this, fast estimation methods are employed such as kinetic group additivity. Kinetic group additivity is a method that estimates reaction rates based on the differences in structure of a reactive center compared to a reference reaction of the same reaction family. Each atom participating in the reaction is assigned a kinetic group additive value (ΔGAV°) based on the atom and its direct neighbors. ΔGAV° datasets exist in literature for hydrocarbon and oxygenate decomposition via abstraction and β-scission. These datasets are highly useful in describing pyrolysis and oxidation of (oxygenated) hydrocarbons, which is relevant for many industrial processes employing fossil or biomass feedstocks. The dawn of plastic waste as a renewable feedstock in the chemical industry necessitates expansion of these ΔGAV° datasets towards molecules present in these feedstocks. In this work new ΔGAV° datasets for nitrogenated hydrocarbons are regressed as these are a common impurity in plastic pyrolysis oils. A dataset of 384 reactions is calculated to regress ΔGAV°s for hydrogen abstractions by carbon-centered radicals and hydrogen radicals to nitrogenated hydrocarbons. Furthermore, ΔGAV°s are regressed for all possible β-scission reactions in nitrogenated hydrocarbon radicals, using a dataset of 324 reactions. All reaction rates are calculated at the CBS-QB3 level of theory. Preliminary results can be found in figure 1. The accuracy of the regressed ΔGAV°s will be validated with a modelling study on experiments from literature for aliphatic amine pyrolysis where the studied reactions account for the dominant decomposition pathways.