Thermodynamic driving forces for PAH isomerization and growth during thermal treatment of polluted soils

For a limiting case of thermodynamic equilibrium, the importance of two classes of thermal chemical reactions that modify the structure and bioactivity of polycyclic aromatic hydrocarbons (PAH) was assessed computationally. These reactions are molecular weight (MW) growth by acetylene addition, and intramolecular rearrangement (isomerization). Temperatures (300-1100 degrees C), and the chemical environment (C(2)H(2)/H(2) molar ratios) were selected for relevancy to thermal treatment of PAH-contaminated soils under oxygen-free conditions. Molecular mechanics methods [MM3(92)] were used to compute thermochemical properties for calculation of equilibrium constants, i.e., heats of formation, standard entropies, and heat capacities for 30 PAH with empirical formulae C(14)H(10), C(16)H(10), C(18)H(10), C(18)H(12), C(20)H(10), and C(20)H(12). Included were 11 PAH containing only six-membered rings and 19 PAH containing both five- and six-membered rings. For each of these PAH the calculations predict that with increasing temperature, isomerization increases the "complexity" of the PAH mixture, i.e., the relative abundance of each PAH isomer in the mixture other than the most stable isomer, increases. Isomerization also partially transforms non-mutagens to mutagens, e.g., pyrene and benzo[e]pyrene to fluoranthene and benzo[a]pyrene, respectively, and partially converts cyclopenta[c, d]pyrene (CPEP) and chrysene, both human cell mutagens, to one and three additional human cell mutagens, respectively. Acetylene addition transforms the non-mutagens phenanthrene and pyrene to the mutagens triphenylene and CPEP, respectively. Some of the predicted PAH have been observed elsewhere among the products of aromatics pyrolysis. This study elucidates PAH reactivity for comparison with measurements, and identifies PAH reactions to be monitored and avoided in soil thermal decontamination and other waste remediation processes.