Transfer of Sodium Ion across Interface between Na+-Selective Electrode Membrane and Aqueous Electrolyte Solution: Can We Use Nernst Equation If Current Flows through Electrode?

Electrochemical impedance and chronopotentiometric measurements with Na+-selective solvent polymeric (PVC) membranes containing a neutral ionophore and a cation exchanger revealed low-frequency resistance, which is ascribed to Na+ ion transfer across the interface between the membrane and aqueous solution. The attribution is based on the observed regular dependence of this resistance on the concentration of Na+ in solutions. The respective values of the exchange current densities were found to be significantly larger than the currents flowing through ion-selective electrodes (ISEs) during an analysis in non-zero-current mode. This fact suggests that the interfacial electrochemical equilibrium is not violated by the current flow and implies that the Nernst equation can be applied to interpret the data obtained in non-zero-current mode, e.g., constant potential coulometry.

Voltammetric Ion Sensing with Ionophore-Based Ion-Selective Electrodes Containing Internal Aqueous Solution, Improving Lifetime of Sensors.

The possibility of voltammetric ion sensing is demonstrated, for the first time, for ion-selective electrodes (ISEs) containing an internal aqueous solution. ISEs selective to calcium, lithium and potassium ions are used as model systems. The internal solution of the ISEs contains a chloride salt of the respective cation and a ferrocenemethanol or ferrocyanide/ferricyanide redox couple. A platinum wire is used as the internal reference electrode. It is shown, theoretically and experimentally, that the dependence of oxidation and reduction peak potentials on the sample composition obeys the Nernst law, while the peak currents virtually do not depend on the sample composition. Thus, the electrode behavior is similar to that reported by Bakker's group for solid contact ISEs with ultra-thin membranes (200-300 nm). It is shown that the use of classical ISEs with relatively thick membranes (100-300 µm) and internal aqueous solution allows for the sensor lifetime of about one month. It is also shown that use of a suitable background electrolyte allows for improvement of the detection limits in voltammetric measurements with ISEs.

Constant Potential Coulometric Measurements with Ca2+-Selective Electrode: Analysis Using Calibration Plot vs. Analysis Using the Charge Curve Fitting.

The possibility of analysis using charge curve fitting in constant potential coulometric mode instead of using a calibration plot is explored, for the first time. The results are compared with the analysis based on the use of a calibration plot. A Ca2+ ion-selective electrode, with and without an electronic capacitor in series, is used as a model system in pure solutions of CaCl2. Both techniques delivered good results (error within 2%) when the final and the initial concentration values differed by not more than three times. Larger differences result in 10-25% error. The presence of an electronic capacitor in the measurement circuit and in series with the electrode, allows for significantly faster response.

The Origin of the Non-Constancy of the Bulk Resistance of Ion-Selective Electrode Membranes within the Nernstian Response Range.

The dependence of the bulk resistance of membranes of ionophore-based ion-selective electrodes (ISEs) on the composition of mixed electrolyte solutions, within the range of the Nernstian potentiometric response, is studied by chronopotentiometric and impedance measurements. In parallel to the resistance, water uptake by the membranes is also studied gravimetrically. The similarity of the respective curves is registered and explained in terms of heterogeneity of the membranes due to the presence of dispersed aqueous phase (water droplets). It is concluded that the electrochemical equilibrium is established between aqueous solution and the continuous organic phase, while the resistance refers to the membrane as whole, and water droplets hamper the charge transfer across the membranes. In this way, it is explained why the membrane bulk resistance is not constant within the range of the Nernstian potentiometric response of ISEs.

Electrochemical Properties of Nitrate-Selective Electrodes: The Dependence of Resistance on the Solution Concentration.

The electrochemical properties of ion-exchanger-based solvent polymeric ion-selective electrodes (ISEs)—bulk and interfacial resistance, capacitance, and polarization under a galvanostatic current step—are studied, with a nitrate ISE based on tetradecylammonium nitrate (TDANO3) as a model system. The study is performed by chronopotentiometric and impedance measurements, and focuses on the dependence of the aforementioned properties on the concentration of NO3− anions in solution. The impacts from the bulk and the interfacial charge transfer to the overall membrane resistance are revealed. It is shown that the bulk resistance of the membranes decreases over an increase of NO3− concentration within the range of a Nernstian potentiometric response of the ISE. This fact, also reported earlier for K⁺- and Ca2+-selective ISEs, is not in line with current views of the mechanism of the ISE response, or of the role of ion exchange in particular. The origin of this effect is unclear. Estimates are made for the concentration of ionized species (NO3− and TDA⁺) and, respectively, for the TDANO3 association constant, as well as for the species diffusion coefficients in the membrane.

Tuned galvanostatic polarization of solid-state lead-selective electrodes for lowering of the detection limit.

Lowering of the detection limit of solid-state lead-selective electrodes was achieved by using the tuned galvanostatic polarization method. A Nernstian response was obtained down to nanomolar concentrations (low detection limit 10(-9) mol dm(-3)Pb(2+)). Good repeatability of the calibration curves was achieved by using a well established measuring procedure. Relatively high cathodic current densities were applied to the solid-state membrane in order to shorten the measurement time. Successful determination of lead in a synthetic sample (pPb(2+)=7.97±0.08) was achieved by introducing an analytical protocol and favourably compared to inductively coupled plasma mass spectrometry (pPb=7.93). By applying this method, a significant improvement in the detection limit of solid-state lead-selective electrodes was attained.

Obtaining Nernstian response of a Ca(2+)-selective electrode in a broad concentration range by tuned galvanostatic polarization.

Linear Nernstian response is obtained for a neutral ionophore-based Ca(2+)-selective electrode down to 10(-10) M CaCl2 by means of galvanostatic polarization. The densities of the applied cathodic current were tuned for particular concentrations of Ca2+. The procedure included recording the potential at zero current, followed by measurements when current is passed through the electrode, and then again at zero current. The respective chronopotentiometric curves included negative ohmic drop immediately after turning the current on, the polarization domain, and positive ohmic drop when the current was turned off, followed with the relaxation domain. The potentials immediately after the positive ohmic drops were used as analytical signals. These potentials make a straight line with Nernstian slope when currents are tuned (optimized) for each particular concentration. An iteration procedure is proposed which allows for simultaneous optimization of the current density and accessing analyte concentration in the sample.

Potentiometric estimation of the stability constants of ion-lonophore complexes in ion-selective membranes by the sandwich membrane method: theory, advantages, and limitations.

Segmented sandwich membrane method of studying stoichiometry and stability constants of ion-ionophore complexes in ion-selective membranes is considered in detail. The experimental data (reported earlier in Russian) concerning complexes of various ions with valinomycin, with H+-selective neutral ionophore hexabutyltriamidophosphate, and with anion-binding neutral ionophore p-hexyl trifluoroacetylbenzoate is presented in a compact form. Advantages of titration technique in the sandwich membrane method (the presence of an internal criterion of reliability, and the possibility of direct determination of complex stoichiometry coefficients) are specially addressed. Biases of the estimates of the constants caused by ion-pair formation in real membranes and by diffusion potential are analyzed by means of computer simulations. The possibility of revealing two coexisting complexes with different compositions is also discussed.

Selectivity of lithium electrodes: correlation with ion-lonophore complex stability constants and with interfacial exchange current densities.

Lithium-selective electrodes with solvent polymeric membranes based on two different dicyclohexylamide neutral ionophores are studied systematically. The selectivity of lithium response is studied by means of the ordinary potentiometric experiments. Stability constants of lithium, sodium, and potassium ions with the neutral ionophores are measured by means of the segmented sandwich membrane method. Charge transfer through the membrane bulk and across the membrane/solution interface is studied by means of electrochemical impedance spectroscopy. Well-resolved Faradaic impedance semicircles are obtained, allowing calculation of exchange current densities for lithium, sodium, and potassium. It is clearly demonstrated that the potentiometric selectivity coefficients correlate well with thermodynamic equilibrium parameters. The correlation with exchange current densities also exists, although it is low, and seems rather qualitative than quantitative. The results are treated in favor of equilibrium at the membrane/solution interface. It is also concluded (tentatively) that the kinetic description is equivalent to the equilibrium one, giving evidence that ion-ionophore complexes form directly at the interface.