Perfluorinated sulfonic acids (such as perfluorooctanesulfonic, PFOS, and short-chain analogues) are notorious halogenated pollutants that exhibit severe toxicity, even at minute levels. Limited number of experimental studies addressed their thermal decomposition at elevated temperatures. Such scenarios are particularly relevant to open fires and incineration of materials laden with perfluoroalkyl compounds (PFCs). Herein, we construct a detail kinetic model that illustrates major chemical reactions underpinning initial degradation of 1-butanesulfonic acid (CF₃(CF₂)₃SO₂OH), as a model compound of PFOS, and perfluorinated sulfonic acids in general. Reaction rate parameters were estimated based on an accurate density functional theory (DFT) formalism. The kinetic model incorporates four sets of reactions, namely, unimolecular decomposition channels, hydrofluorination, hydrolysis, and fragmentation of the alkyl chain. Results are discussed considering recent experimental measurements. Temperature-dependent profiles for a large array of perfluoroalkyl acyl fluorides, short perfluorinated cuts, and perfluorinated cyclic compounds, are presented. SO₂ emerges as the main sulfur carrier, with a minor contribution from SO₃. HF addition to double carbon bonds in alkenes, and to carbonyl bonds in aldehydic structures signifies a major sink pathway for hydrogen fluoride. Addition of moisture was shown to expedite the destruction of relatively large perfluoroalkyl acyl fluorides into C₁ species. Construction of this model could aid in a better understanding of the fate and chemical transformation of PFCs under a pyrolytic environment pertinent to waste incineration and fluorine mineralization.

全氟磺酸（例如全氟辛烷磺酸，PFOS和短链类似物）是臭名昭著的卤代污染物，即使在微量条件下也显示出严重的毒性。有限数量的实验研究解决了它们在高温下的热分解。这种情况与明火和充满全氟烷基化合物（PFC）的材料的焚化特别相关。在此，我们构建了一个详细的动力学模型，该模型说明了支撑1-丁烷磺酸（CF ₃（CF ₂）₃ SO ₂）初始降解的主要化学反应OH），作为PFOS的模型化合物，通常使用全氟磺酸。反应速率参数是根据准确的密度泛函理论（DFT）形式主义估算的。动力学模型包括四组反应，即单分子分解通道，氢氟化，水解和烷基链断裂。考虑最近的实验测量结果讨论。给出了各种全氟烷基酰基氟，短的全氟化馏分和全氟化的环状化合物的温度相关曲线。SO ₂成为主要的硫载体，SO _3的贡献很小。HF除了在烯烃中的双碳键和在醛结构中的羰基键外，是氟化氢的主要吸收途径。已证明添加水分可加速将较大的全氟烷基酰基氟破坏成C ₁物种。该模型的构建可以帮助更好地了解与废物焚烧和氟矿化有关的热解环境下PFC的命运和化学转化。