Investigation of ion-selective electrodes with neutral ionophores and ionic sites by EIS. I. Theory

Models of an ion selective electrode involving an ionophore and mobile sites in a membrane are proposed. The first model, called the phase boundary potential model, supposed thermodynamic equilibrium; it allows the concentrations of the various species to be calculated. Then, a kinetic model, which takes into account the ionic transfer at the membrane|solution interfaces, was derived. The impedance of the membrane was calculated. It shows that a membrane with nernstian behavior shows only one capacitive loop in the impedance diagram, which is related to the conductivity and dielectric properties of the material of the membrane. Non-nernstian behavior is related to slow ionic transfer at the membrane|solution interfaces or/and transport limitation of the species in the membrane. Finite rate constants of the ionic transfer lead to a capacitive loop in the middle frequency range, whereas finite rate transport leads to a diffusional impedance in the low frequency range.