Partition energy in polyamide membranes and its link to ion-ion selectivity

Abstract

Understanding the mechanisms of molecular transport in polyamide membranes is imperative to improve their solute-specific selectivity. We explored the partitioning behaviors of water and salts in polyamide membranes to elucidate the role of ion-membrane interactions in the transport. Quartz crystal microbalance (QCM) was employed to quantify the mass uptake at different temperatures and determine partition energies (E_k) for water and salts under two different pH values. Zeta potential and permeability tests were conducted to support the ion-membrane affinity trends observed with QCM and link these trends to ion-ion selectivity. Our results demonstrate a high affinity of water to the polyamide membrane (E_k < 0), with a significant swelling effect attributed to dipole interactions and hydrogen bonding. Ion partitioning revealed distinct differences between monovalent and divalent cations, as well as between kosmotropic and chaotropic anions. Specifically, divalent cations (Ca²⁺ and Mg²⁺) exhibited considerably lower partition energies (-0.99 and 0.29 kcal mol^-1, respectively) and more efficient charge neutralization, indicating stronger interactions with the membrane compared to monovalent cations (∼2.2 kcal mol^-1). The partition energies of the chaotropic iodide and kosmotropic sulphate anions were substantially different (-5.5 and 4.0 kcal mol^-1, respectively), likely due to the different tendency of these anions to shed their hydration shell and stick to the polymer. Last, our permeability tests indicate the potential existence of an intrinsic tradeoff between ion partitioning and intrapore diffusion, presumably due to the opposite effects that ion-membrane interactions have on these transport steps. Overall, our work underscores the role of ion-specific interactions in membrane transport and selectivity.