Modeling the thermochemistry of nitrogen-containing compounds group additivity.

First-principles based kinetic modeling is essential to gain insight into the governing chemistry of nitrogen-containing compounds over a wide range of technologically important processes, pyrolysis, oxidation and combustion. It also enables the development of predictive, fundamental models key to improving understanding of the influence of nitrogen-containing compounds present as impurities or process additives, considering safety, operability and quality of the product streams. A prerequisite for the generation of detailed fundamental kinetic models is the availability of accurate thermodynamic properties.

Modeling the kinetics of hydrogen abstraction reactions in nitrogen-containing compounds group additivity.

New group additivity values are presented to enable the modeling of a broad range of intermolecular hydrogen abstraction reactions involving nitrogen-containing compounds. From a dataset of 316 reaction rate coefficients calculated at the CBS-QB3 level of theory in the high-pressure limit, 76 group additivity values and 14 resonance corrections have been estimated. The influence of substituents on both the attacked hydrogen and attacking radical, being a carbon or nitrogen atom, has been investigated systematically.