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

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10 Citations (Scopus)


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 CnFm 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.

Original languageEnglish
Article number133118
Publication statusPublished - Feb 2022


  • Gas phase
  • GenX
  • Kinetic model
  • Perfluoroalkyl compounds
  • Thermal decomposition

ASJC Scopus subject areas

  • Environmental Engineering
  • General Chemistry
  • Environmental Chemistry
  • Pollution
  • Public Health, Environmental and Occupational Health
  • Health, Toxicology and Mutagenesis


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