Assessing relative contributions of PAHs to soot mass by reversible heterogeneous nucleation and condensation

Given the recent EURO 6 regulations, which include limits on particle number density (and hence size) for soot emissions from land vehicles, soot models must be capable of accurately predicting soot particle sizes. Previous modeling work has demonstrated the importance of the relative strengths of nucleation and condensation in predicting soot primary particle size. Due to this importance, a fundamental reversible model for nucleation and condensation, called the reversible PAH clustering (RPC) model, was developed in previous work through the use of statistical mechanics and the results from several recent works. In the present work, the RPC model is enhanced to include multiple nucleation (or dimerization) events from 6 different PAH size groups, resulting in 21 unique dimer pairs. In addition, a soot PAH tracking model is developed to track the amount of each PAH size group within soot particles. The addition of this model resulted in reduced computation times and the ability to investigate PAH-PAH reactions within soot particles. The results of the enhanced RPC model demonstrate that smaller PAHs are most important for the nucleation process, while small and large PAHs are important for the condensation process. These results are shown to be due to the relatively lower reversibility of condensation versus the nucleation process. These findings are discussed in light of recent experimental results in the literature and are shown to be well supported. Keywords: reversibility, PAH nucleation, PAH condensation, laminar diffusion flame, soot model