Abstract
Density functional theory results are presented for elementary steps leading to coke growth within a steam cracking unit. The discussed pathway starts from toluene and ultimately, 1-methylnaphthalene is formed. In order to find the rate determining step for coke formation, the pseudo first-order rate coefficients of the various steps are compared taking into account the concentrations of diverse coke precursors. The influence of the polyaromatic environment is studied for a large set of methylated polycyclic aromatic molecules, by means of carbon–hydrogen bond dissociation enthalpy values. Subsequent hydrogen abstraction reactions at the methylated polyaromatics, by a methyl radical, are also examined. The abstraction is found to preferentially occur at the larger systems and is in general faster compared to abstractions at the analogous non-methylated species.