Degradation of Polyamide Membranes Exposed to Chlorine: An Impedance Spectroscopy Study

Polyamide is the key material in modern membrane desalination; however, its well-known and incompletely understood drawback is its low tolerance to chlorine, the most efficient in-line disinfectant. Here we report a first investigation of the mechanism and kinetics of chlorine attack using electrochemical impedance spectroscopy (EIS) that directly probes changes in ion permeation upon chlorination at different pH values, focusing on its early stages and low chlorine concentrations (15–197 ppm). EIS results partly conform to an established two-stage mechanism that proceeds as N-chlorination followed by either C-chlorination in acidic conditions or amide bond scission in alkaline conditions. However, early time kinetics in acidic conditions shows inconsistencies with this model, explained by possible effects of direct ring chlorination and finite polymer relaxation rates. The findings indicate that (a) N-chlorination reduces membrane polarity and ion permeability, while C-chlorination has an opposite effect; (b) chlorination in acidic conditions must involve other reactions, such as direct ring chlorination, in addition to N-chlorination and Orton rearrangement; and (c) the ultimate chemical transformations (C-chlorination or amide bond scission) result in an irreversible increase in membrane polarity and loss of ion rejection. The results highlight the potential of EIS as a powerful and sensitive tool for studying chemical degradation of ion-selective materials that may assist in developing new chlorine-resistant membranes.