Thermodynamics of Mobile Ion in Ion Exchange Membranes: Water-Swollen-Membrane Reference State and Quasi-Regular Solution Model.

Thermodynamics of mobile ions in swollen ion exchange membranes (IEM) are essential for understanding their permselectivity. The theoretical modeling of the ion activity coefficient and the ion partitioning of the IEM is challenging. Based on a water-swollen membrane reference state and a quasi-regular solution model, we successfully correlated the ion activity coefficient in various IEMs. For all the studied 59 systems, the correlation coefficient r and determination coefficient R² are 0.973 and 0.947, respectively. As expected, the water activity in the IEM and the ion partitioning between the IEM and the external salt solution are represented. In the new theory framework, the standard chemical potential of the counterion is different from that of the aqueous solution. Moreover, the ion activity coefficient in the IEM reaches unity for the infinite dilution external salt concentration for all systems. Our quasi-regular solution model only considered the short-range interactions between the co-ions and the "effective free counterion", but it showed excellent correlation ability with the activity coefficient data of extensive systems. A power-law relation between the effective concentration of the free counterion and the apparent concentration of the free counterion was suggested. This indicates that the long-range electrostatic interactions in the swollen IEM are negligible due to abundant counterion condensation shielding the charge of the polymer chain.