Osmotic and Gibbs–Donnan equilibrium for ions and neutral solutes

Abstract

The general set of equations for the equilibrium of two solutions with a mixture of non-permeating and permeating ions and neutral solutes at each side of a permselective membrane is formulated using the principles of electroneutrality and mass conservation law for each solution, and equilibrium conditions: equality of electrochemical potentials at both sides of the membrane for each permeating solution component. There is at least one permeating neutral chemical species (solvent) in the system. The theory is in general valid for non-ideal solutions. The generalized Gibbs–Donnan (G–D) equilibrium coefficients depend on activities/fractions of all species at one side of the membrane, and charges of ions and partial molar volumes of all species. The equilibrium osmotic pressure across the membrane is also provided by the theory and can be calculated using the ratio of activities (or equivalently the G–D factor) of any permeating neutral solute (including solvent) or the ratios of activities (or equivalently the G–D factors) of any two permeating ions.