Electric field enhanced water dissociation at the bipolar membrane junction from ac impedance spectra measurements

Abstract Preliminary experimental results of the ac impedance spectra of a bipolar ion-exchange membrane are reported and interpreted on the basis of a previous theoretical model based on the Nernst–Planck/Poisson equations. It is shown that the experiments can provide valuable electrochemical information about the bipolar junction structure and the electric-field enhanced water dissociation phenomenon that occurs at this junction, although the high number of unknown parameters involved makes it difficult to obtain accurate values for the parameters characteristic of this phenomenon.

Bipolar membranes under forward and reverse bias conditions. Theory vs. experiment

Abstract Bipolar membranes are layered structures composed of one cation-and one anion-exchange membrane joined together in series. The current—voltage curves of two recently developed bipolar membranes have been analysed theoretically and experimentally under both forward and reverse bias conditions. The experimental trends observed are high conductivity under forward bias conditions and high impedance first, and then electric field enhanced (EFE) water dissociation for high enough applied voltages, under reverse bias conditions. The forward bias measurements can contribute to a better knowledge of some of the transport parameters entering also in the reverse biased membrane. Comparison of…

Effects of pH on ion transport in weak amphoteric membranes

Abstract We have studied theoretically the effect of pH on the ion transport through amphoteric polymer membranes composed of weak polyelectrolytes where the charged groups are randomly distributed along the axial direction of the membrane. This system serves as a simplified model for the pH controlled ion transport and drug delivery through membranes of biological interest. The theoretical approach employed is based on the Nernst-Planck equations. The complete system of electrical charges formed by: (i) the pH dependent, amphoretic membrane fixed charge, and (ii) the four mobile charges (the salt ions and the hydrogen and hydroxide ions) have been taken into account without any additional …

A pH-tunable nanofluidic diode: electrochemical rectification in a reconstituted single ion channel.

We report pH-dependent electrochemical rectification in a protein ion channel (the bacterial porin OmpF) reconstituted on a planar phospholipid membrane. The measurements performed at single-channel level show that the electric current is controlled by the protein fixed charge and it can be tuned by adjusting the local pH. Under highly asymmetric pH conditions, the channel behaves like a liquid diode. Unlike other nanofluidic devices that display also asymmetric conductance, here the microscopic charge distribution of the system can be explored by using the available high-resolution (2.4 A) channel crystallographic structure. Continuum electrostatics calculations confirm the hypothesized bi…

pH and supporting electrolyte concentration effects on the passive transport of cationic and anionic drugs through fixed charge membranes

Abstract The effects of pH and supporting electrolyte concentration on the passive transport of an ionized (cationic or anionic) drug through a thick fixed charge membrane have been theoretically studied. This system constitutes a simplified model for the pH controlled ion transport and drug delivery through membranes of biological and pharmaceutical interest. Calculations were carried out for different values of the membrane fixed charge, supporting electrolyte and drug concentrations covering a broad range of the conditions usually found in experiments. The theoretical approach employed is based on the Nernst–Planck flux equations, and all of the species present in the system (the neutral…

Activity coefficients and Donnan coion exclusion in charged membranes with weak-acid fixed charge groups

Abstract We have studied theoretically the effects that the dissociation equilibrium of weak-acid fixed charge groups (e.g. carboxyl groups) exerts on the mean activity coefficients in charged membranes using a Donnan formalism. The model calculations indicate that unless carbon dioxide is excluded from the external aqueous solution, the pH of the membrane solution can be low enough to affect significantly the effective fixed charge concentration and the coion exclusion when the membrane fixed charge concentration is high compared with the external solution salt concentration. Although this problem was already pointed out in previous studies, the possibility that the pH and salt concentrati…

Effects of water dielectric saturation on the space–charge junction of a fixed-charge bipolar membrane

Abstract The dielectric saturation at the space–charge junction of a fixed-charge bipolar membrane is studied using the theoretical approach by Booth for the water dielectric constant and the Poisson equation for the electrical double layer at the junction. The numerical solution gives the electric field and dielectric constant profiles through the junction as well as the junction thickness as a function of the voltage drop. The water dielectric constant decreases substantially for the large electric fields that may occur at the narrow bipolar junction.

Passive Transport of Ionic Drugs through Membranes with pH-Dependent Fixed Charges

We have studied both theoretically and experimentally the passive transport of ionic drugs through membranes with pH-dependent fixed charge. The system considered constitutes a simplified model for pH-controlled drug delivery through membranes of biochemical and pharmaceutical interest. The theoretical approach employed is based on the Nernst-Planck flux equations and all of the species present in the system (the neutral or ionic drug and the hydrogen and hydroxide ions) have been taken into account together with a Langmuir-type isotherm for the adsorption of the ionic drug onto the membrane surface. The membrane permeabilities of cationic, anionic, and neutral drugs through porous membrane…

Electric field-assisted proton transfer and water dissociation at the junction of a fixed-charge bipolar membrane

Abstract Electric field-enhanced (EFE) water dissociation can occur at the interfacial space charge junction of both biological and synthetic fixed-charge bipolar membranes. This dissociation has so far been analysed on an electrochemical basis using modified second Wien effect and absolute rate theories. We propose a statistical thermodynamics model to describe the cooperative orientation of the water molecules by the electric field at the bipolar junction. The approach is simple and retains some of the essential aspects of the phenomenon. In particular, the EFE water dissociation can now be rationalised on the basis of a field-assisted proton transfer mechanism involving the membrane fixe…

Modeling of the Salt Permeability in Fixed Charge Multilayer Membranes

A Simple Model for Ac Impedance Spectra in Bipolar Membranes

A new model accounting for the ac impedance spectra of synthetic ion-exchange bipolar membranes is presented. The theoretical approach is based on the Nernst−Planck and Poisson equations and applies some of the concepts used in the semiconductor pn junctions to the case of a bipolar membrane. The results presented are the current−voltage curves and the impedance spectra at electric currents above the limiting current. It is shown that the model is able to identify the main contributions to the bipolar membrane impedance and gives valuable information about the bipolar junction structure and its influence on the characteristic parameters involved in the field-enhanced water dissociation phen…

Ion selectivity and water dissociation in polymer bipolar membranes studied by membrane potential and current–voltage measurements

Abstract A polymer bipolar ion-exchange membrane consists of a layered structure involving one cation and one anion ion-exchange layer joined together in series. In this study, the ionic selectivity and water dissociation rate of six commercial bipolar membranes was evaluated from the measurements of the membrane potential in a concentration cell and the current–voltage curve in a four-point measuring cell. Bipolar membrane technology requires polymer membranes presenting high ion selectivities and water dissociation rates, and in this paper we have addressed the basic physico-chemical phenomena involved, both theoretically and experimentally. We have shown that the effects of the bipolar j…

Model calculations of ion transport against its concentration gradient when the driving force is a pH difference across a charged membrane

Model calculations of the steady-state ion transport against its external concentration gradient when the driving force of this transport is a pH difference across a charged membrane are presented. We have solved numerically the exact Nernst-Planck equations without any additional simplifying approximation, such as the Goldman constant field assumption within the membrane. The validity of this assumption for a broad range of pH values, and salt and membrane fixed charge concentrations was analyzed critically. The membrane characteristics studied are the ionic fluxes and the membrane potential. Special attention is paid to the physical mechanism which leads to the ion transport against the c…