Thermal decomposition of heptafluoropropylene-oxide-dimer acid (GenX)

Incineration appears as a viable strategy in the disposal of the notorious perfluoroalkyl substances (PFASs) in a process that typically leads to fluorine mineralization. Central in the design of such operation is to comprehend the underlying chemical mechanisms that dictate thermal fragmentation of PFASs into smaller perfluorinated cuts and HF. Among notable short-chain PFASs entities is the heptafluoropropylene-oxide-dimer acid (HFPO-DA, C₅F₁₁C(O)OH), commercially known as GenX synthesized as a possible replacement of other PFASs compounds. However, reaction pathways that underpin the degradation of GenX at temperatures relevant to its decomposition in incinerators (i.e., cement kilns), remain unknown. Herein, we map out all plausible initial reactions that govern the thermal decomposition of GenX. Simultaneous elimination of HF and CO₂ appears as the kinetically most favored channel with an accessible activation enthalpy of ∼62.0 kcal/mol. Fission of the ether linkage in the 1,1,1,2,2,3,3-heptafluoro-3-[(1-fluoroethenyl)oxy] propane molecule (that forms after HF/CO₂ elimination) affords a wide array of C_nF_m cuts, most notably CF₂ at elevated temperatures. Constructed kinetic model plots temperature-dependent profiles of important species. It is predicted that GenX to commence decomposition around 700 K at a residence time of 2.0 s, a value that is generally applied in incinerators. Findings from the study call to further investigate interactions between the predicted major fluorine carriers (HF and CF₂) and other constituents encountered in relevant incineration mediums, most notably, calcium hydroxides and polymeric materials.