Ultra-short chain fluorocarboxylates exhibit wide ranging reactivity with hydrated electrons

Recent reports demonstrate that technologies generating hydrated electrons (e_aq^-; e.g., UV-sulfite) are a promising strategy for destruction of per- and polyfluoroalkyl substances, but fundamental rate constants are lacking. This work examines the kinetics and mechanisms of e_aq^- reactions with ultra-short chain (C2-C4) fluorocarboxylates using experimental and theoretical approaches. Laser flash photolysis (LFP) was used to measure bimolecular rate constants (k₂; M^-1 s^-1) for e_aq^- reactions with thirteen per-, and for the first time, polyfluorinated carboxylate structures. The measured k₂ values varied widely from 5.26 × 10⁶ to 1.30 × 10⁸ M^-1s^-1, a large range considering the minor structural changes among the target compounds. Molecular descriptors calculated using density functional theory did not reveal correlation between k₂ values and individual descriptors when considering the whole dataset, however, semiquantitative correlation manifests when grouping by similar possible initial reduction event such as electron attachment at the α-carbon versus β- or γ-carbons along the backbone. From this, it is postulated that fluorocarboxylate reduction by e_aq^- occurs via divergent mechanisms with the possibility of non-degradative pathways being prominent. These mechanistic insights provide rationale for contradictory trends between LFP-derived k₂ values and apparent degradation rates recently reported in UV-sulfite constant irradiation treatment experiments.