LIMITING CURRENT-DENSITY AND WATER DISSOCIATION IN BIPOLAR MEMBRANES

The behaviour of bipolar membranes in NaCl and Na2SO4 solutions is dis cussed. The membranes are characterized in terms of their limiting cur rent densities. Below the limiting current density the electric curren t is carried by salt ions migrating from the transition region between the anion and the cation exchange layer of the bipolar membrane. In s teady state these ions are replaced by salt ions transported from the bulk solutions into the transition region by diffusion and migration d ue to the fact that the ion-exchange layers are not strictly permselec tive. When the limiting current density is exceeded, the salt transpor t from the transition region can no longer be compensated by the trans port into the region and a drastic increase in the membrane resistance and enhanced water dissociation is observed. This water dissociation is described as being a combination of the second Wien effect and the protonation and deprotonation of functional groups in the membrane. Th e limiting current density is calculated from a mass balance that incl udes all components involved in the transport. The parameters used in the mathematical treatment are the diffusion coefficients of salt ions and water, the ion mobilities in the membrane, the fixed charge densi tiy of the membrane, the pK(b) values of the functional groups and the solution bulk concentrations.