On the discrepancy between nominal and effective charge density of polyamide reverse osmosis membranes

Quantitative and reliable information on the ionization of functional groups in polyamide (PA) active layers of thin film composite membranes is of vital importance for understanding and modeling of ion transport. Independent measurements using Ag⁺ ion-probing with RBS, XPS, or ICP-MS, indicate a nominal charge density in the order of 0.5 M. Conversely, model fitting to salt rejection experiments suggests an effective membrane charge at least three orders of magnitude lower for brackish water (BWRO) and seawater (SWRO) membranes. In this study we show that the original interpretation of the ion-probe experiments is inconsistent with the principles of ion partitioning used in ion transport models. We provide an alternative interpretation of ion-probe experiments in the literature, explaining the results through binding of silver ions to the carboxylic groups. By using this interpretation, the discrepancy between nominal and effective charge can be resolved: the Ag measured in the ion-probe experiments is mostly bound to the membrane (-COOAg, not –COO⁻/Ag⁺), while the membrane is virtually uncharged. Consequently, the ion-probe experiments can quantify the concentration of functional groups, but not theirpK_a. We propose that confinement affecting membrane ionization, should be explicitly included in ion-transport modeling.