A reaction mechanism having molecular growth up to benzene for hydrocarbon fuels with up to four carbon-atoms was extended to include the formation and growth of polycyclic aromatic hydrocarbons (PAHs) up to coronene (C24H12). The new mechanism was tested for ethylene premixed flames at low (20 torr) and atmospheric pressures by comparing experimentally observed species concentrations with those of the computed ones for small chemical species and PAHs. As compared to several existing mechanisms in the literature, the newly developed mechanism showed an appreciable improvement in the predicted profiles of PAHs. The new mechanism was also used to simulate PAH formation in counterflow diffusion flames of ethylene to study the effects of mixing propane and benzene in the fuel stream. In the ethylene-propane flames, existing experimental results showed a synergistic effect in PAH concentrations, i.e. PAH concentrations first increased and then decreased with increasing propane mixing. This PAH behavior was successfully captured by the new mechanism. The synergistic effect was predicted to be more pronounced for larger PAH molecules as compared to the smaller ones, which is in agreement with experimental observations. In the experimental study in which the fuel stream of ethylene-propane flames was doped with benzene, a synergistic effect was mitigated for benzene, but was observed for large PAHs. This effect was also predicted in the computed PAH profiles for these flames. To explain these responses of PAHs in the flames of mixture fuels, a pathway analysis has been conducted, which show that several resonantly stabilized species as well as C4H4 and H atom contribute to the enhanced synergistic behaviors of larger PAHs as compared to the small ones in the flames of mixture fuels. (c) 2013 The Combustion Institute. Published by Elsevier Inc. All rights reserved.