RATE RULE MODELING OF PAH GROWTH

The kinetic modeling of the pyrolysis and combustion of polycyclic aromatic hydrocarbons (PAHs) is crucial to address practical challenges in the current energy transition, such as the evolution of carbonaceous nanoparticles formation that is also interesting for the synthesis of high-value carbon materials [1]. Quantum mechanical calculations are extensively used to develop fundamentallybased kinetic models, however a fully detailed approach is impractical for large PAHs. In this work, we apply a theory-based lumped approach for the definition of reaction classes and rate rules to describe the kinetics of PAHs growth through two relevant reaction classes i.e., the HACA mechanism and the recombination of benzyl-like radicals with propargyl [2]. Based on literature theoretical calculations, our in-house master equation based lumping tool was combined with PSSA to obtain rate constants of global reactions to be implemented in CRECK kinetic model. First, we refined the rate rule definition for the rate constants for 1-ring to 4-ring aromatics. Then, we updated the model with the newly derived rate constants.