Kinetic Description of the Membrane-Solution Interface for Ion-Selective Electrodes.

The theoretical models for ISEs almost exclusively assume thermodynamic equilibrium at the membrane/solution-phase boundary. In this report, we present a new, congruent model which combines first-order reaction kinetics of ion-exchange at the phase boundary and diffusional mass transport in the adjoining phases in the continuity equation. The influence of the rate constant in the new kinetic model has significant impact on the predicted transients corresponding to instantaneous change in the sample solution composition. The simulated transients generated with the new model coincide with the transients recorded in common potentiometric experiments, e.g., with transients recorded upon step change in the primary or interfering ion concentrations. The simulated transients also align well with previously published transients representing special cases of potentiometry (e.g., super-Nernstian response, non-Nernstian responses in the presence of highly interfering ions). The implementation of the kinetic model for simulating the transients in the water layer test also resulted in a better agreement with the experiments compared to the previous models.