Chemical bonding in potential PFAS products from the thermal degradation of energetic devices, a DFT analysis

This work investigates stability and chemical bonding in possible per- and polyfluoroalkyl substances (PFAS) generated through the disposal of munitions in controlled detonations and open burns. Density functional theory (DFT) calculations were used to determine bond dissociation enthalpies (BDEs), activation energies, and other chemical properties. Calculated parameters were used to determine the functional groups most likely to be present based on the level of fluorination and the position of fluorines. In compounds that form C-O bonds, the presence of α-fluorines significantly strengthens the C-O bond by ∼4-18 kcal/mol. The results of this study indicate that fluoroalkyl alcohols are a very likely product of the disposal of munitions. This work was designed to expedite the analytical process of confirming that PFAS are created from current disposal methods of energetic devices by providing insight as to of what types of compounds should be expected. The PFAS generated in such reactions are expected to contain some functional groups (i.e., nitro and nitrite) that have not been known to exist as a result of the environmental degradation of industrially relevant PFAS, therefore, they may have been overlooked before. These initial results imply that PFAS with nitro functionalities may be formed in these conditions considering the abundance of NO₂ radicals expected to be present as well as the strength of the C-N bond that can form (∼40-50 kcal/mol) whereas with nitroso functionalities are not expected to be found since the bonds formed are much weaker (∼25-35 kcal/mol), and nitrosoalkanes are known to decompose under mild conditions. Although these results are promising, analytical work is needed to assess the conclusions of this study in real systems.