Reverse Current Pulse Method To Restore Uniform Concentration Profiles in Ion-Selective Membranes. 1. Galvanostatic Pulse Methods with Decreased Cycle Time

The applications of ion-selective electrodes (ISEs) have been broadened through the introduction of galvanostatic current pulse methods in potentiometric analysis. An important requirement in these applications is the restoration of the uniform equilibrium concentration profiles in the ISE membrane between each measurement. The simplest restoration method is zero current relaxation, in which the membrane relaxes under open-circuit conditions in a diffusion-controlled process. This paper presents a novel restoration method using a reverse current pulse. An analytic model for this restoration method is derived to predict the concentration profiles inside ISE membranes following galvanostatic current pulses. This model allows the calculation of the voltage transients as the membrane voltage relaxes back towards its zero-current equilibrium value. The predicted concentration profiles and voltage transients are confirmed using spectroelectrochemical microscopy (SpECM). The reverse current restoration method described in this paper reduces the voltage drift and voltage error by 10 to 100 times compared to the zero current restoration method. Therefore, this new method provides faster and more reproducible voltage measurements in most chronopotentiometric ISE applications, such as improving the detection limit and determining concentrations and diffusion coefficients of membrane species. One limitation of the reverse current restoration method is that it cannot be used in a few applications that require background electrolyte loaded membranes without excess of lipophilic cation exchanger

Limitations of Current Polarization for Lowering the Detection Limit of Potentiometric Polymeric Membrane Sensors

Ion fluxes across polymeric ion-selective membranes are a decisive parameter dictating the lower detection limit of potentiometric ion sensors. An applied current was earlier proposed to counteract such fluxes and reduce the detection limit to ultratrace levels. So far, however, the method has not been used in practical situations since the correct current amplitude requires prior knowledge of the sample composition. This paper explores the use of the stir effect to evaluate the optimal current by theory and experiments. It is shown that the traditionally used steady-state model assuming a uniform distribution of ion exchanger in the membrane, fixed with time, violates the electroneutrality condition. A modified steady-state model is introduced that allows for a concentration tilt of the ion exchanger and predicts that a stir effect can indeed be utilized to find the optimal current. Ideally, by choosingthe optimal current and very long measurement times, the thermodynamic detection limit might be obtained. However, in practice the stir effect declines at low concentrations and the conditions are far from steady state. Therefore, the improvement of the lower detection limit achievable by galvanostatic control is only about 1 order of magnitude. A numerical finite-difference approximation is shown to trace the experimental potential responses of silver-selective electrodes well and to reproduce the stireffect adequately, even for different conditioning protocols. The stir effect is successfully used to improve the detection limit of electrodes with ill-optimized inner solutions; however, significant improvements beyond what is commonly feasible by chemical optimization does not seem to be easily achievable. The results indicate that with conventional membranes the possibility of improving the detection limit by current polarization is much more limited than assumed so far