Study of pH correction process of chloride-bicarbonate dilute solutions by electrodialysis with bipolar membranes

The pH of a dilute chloride-hydrocarbonate solution and the concentrations of chloride ions and carbonic acid anions at the outlet of the alkaline and acid chambers of the electrodialysis cell formed by bipolar and anion-exchange membranes were determined. The decrease in the concentration of hydrocarbonate ions in the alkaline chamber with growth of current density was not equal to its increase in the acid chamber. This disbalance was caused by two concurrent processes: the electromigration ion transport through the anion-exchange membrane and the chemical reactions of hydrocarbonate ions with the water dissociation products formed on the bipolar and anion-exchange membranes. A mathematical model was suggested to describe the electrodialysis correction of the pH of a dilute chloride-hydrocarbonate solution. The experimental data on the correction of pH of the chloride-hydrocarbonate solution were well approximated by both the model that takes into account water dissociation on the anion-exchange membrane and the simplified model that neglects water dissociation. The experimental data agreed well with the results of calculations by the model in which the effective anion transport numbers were calculated only from ion concentrations and diffusion coefficients in solution. This reflects the outer diffusion character of the kinetics of ion transport through the anion-exchange membrane, with pH of dilute solutions corrected by electrodialysis.     

Transport of ions of pyrophosphoric acid through chemically different anion-exchange membranes

Characteristics of mass transport of the anions of pyrophosphoric acid are investigated during electrodialysis through MA-40 and MA-41 anion-exchange membranes. It is established that the rate of mass transport for counterions is greater through the MA-41 membrane than the MA-40 membrane, and thus the former can be used for demineralizing solutions with salts of pyrophosphoric acid. Higher selectivity to pyrophosphate ions is found for the MA-40 membrane compared to the MA-41 membrane in the electrodialysis of mixtures of pyrophosphate and hydropyrophosphate ions, and thus the MA-40 membrane can be regarded as promising for the separation of such mixtures.     

Ionic Transport in Electrodialysis of Ammonium Nitrate

During the electrodialysis of ammonium nitrate solution, the fluxes of salt ions pass through the maximum, which is observed near the limiting current, with increasing current density. A decrease in the flux of ammonium ions at the overlimiting current densities is caused by the effect of competitive transport of solution ions and by the formation of weak NH₃ ? H₂O electrolyte due to the alkalization of solution layer adjacent to the cation-exchange membrane in the desalination channel. A decrease in the flux of nitrate ions in the overlimiting current modes is caused by a change in the composition and catalytic activity of the functional groups of anion-exchange membrane towards the dissociation of water molecules due to the effect of ammonium ions.     

On the theory of steady-state electrodiffusion

The problem of the electrical field strength distribution outside the boundary layer under on passing of steady-state current through electrolyte is considered. The solution is obtained as a small-parameter reciprocal-power expansion; however, the expansion of the solution in terms of positive powers of this parameter, by using of the method of splicing of asymptotic solutions, is divergent. For the region under consideration, an expression for the field strength is obtained, which differs from the corresponding expression obtained from the electrical neutrality conditions.     

Contribution of convection,diffusion and migration to electrolyte transport through nanofiltration membranes

Transport mechanisms through nanofiltration membranes are investigated in terms of contribution of convection, diffusion and migration to electrolyte transport. A Donnan steric pore model, based on the application of the extended Nernst-Planck equation and the assumption of a Donnan equilibrium at both membrane-solution interfaces, is used. The study is focused on the transport of symmetrical electrolytes (with symmetric or asymmetric diffusion coefficients). The influence of effective membrane charge density, permeate volume flux, pore radius and effective membrane thickness to porosity ratio on the contribution of the different transport mechanisms is investigated. Convection appears to be the dominant mechanism involved in electrolyte transport at low membrane charge and/or high permeate volume flux and effective membrane thickness to porosity ratio. Transport is mainly governed by diffusion when the membrane is strongly charged, particularly at low permeate volume flux and effective membrane thickness to porosity ratio. Electromigration is likely to be the dominant mechanism involved in electrolyte transport only if the diffusion coefficient of coions is greater than that of counterions.     

Flux decline during cross flow membrane filtration of electrolytic solution in presence of charged nano-colloids: a simple electrokinetic model

An electrokinetic transport based approach for quantification of reversible flux decline due to the concentration polarization of an electrolyte solution in presence of charged colloids is presented. The model envisions the electrolyte transport across a charged cake or gel layer as transport of ions through charged cylindrical capillaries. This model is coupled with the standard theory of concentration polarization during cross flow membrane filtration. The analysis is carried out entirely in terms of generalized, non-dimensional variables. A dimensionless group termed as the scaled gel layer resistance evolves from the analysis, which accounts for the electrical properties of the charged nano-colloids and the electrolyte solution. A parametric study is performed to elucidate the coupled influence of mass transfer, membrane resistance, gel resistance, and electrical properties of the gel-electrolyte polarized layer. The effects of these parameters are examined on the filtration performance through the model equations.     

Application of Ion-Exchange Membranes for Stabilizing Acidity of a Chromium-Plating Electrolyte Based on Chromium(III) Sulfate

The acidity of a chromium-plating electrolyte based on chromic sulfate may be stabilized in a two-chamber electrolyzer with an anion-exchange membrane (AEM). The optimum concentration of sulfuric acid in the anolyte (c _sa) may be selected on the basis of the material balance equation for the catholyte, which allows for the dependence of the transport number of hydronium ions in AEM on c _sa. No considerable accumulation of Cr²⁺ occurs in the catholyte during a prolonged electrolysis. The transport of formate ions through AEM at working values of electrolyte pH is inconsiderable.     

Permeation of electrolyte water-methanol solutions through a Nafion membrane

The volume flux through a cation-exchange membrane (Nafion 117) separating two equal electrolyte water-methanol solutions as a function of the pressure difference was determined under different experimental conditions. The results show that permeation rates through the membrane are strongly dependent on the methanol content of the solutions, thus the value of the flux increases when the methanol percentage increases. The effect of the electrolyte concentration of the solution on the membrane permeability is less important, although its influence becomes significant at low electrolyte concentration and high methanol content on solvent. This behavior is explained in terms of the amount of solvent sorbed by the membrane. Typical flux behaviors observed with pressure difference are linear at low pressures, exhibiting a positive deviation at higher pressure difference values.     

Influence of cations on the proton leakage through anion-exchange membranes

In the recovery of acids from wastewaters or the regeneration of acids and bases from salts by electromembrane processes, the most important phenomenon which limits the current efficiency is the transport of protons through the anion-exchange membrane (AEM). In this work, the proton leakage through an AEM is studied with a system containing hydrochloric acid or sulfuric acid on the cathodic side and the mixture of acid with one homoanionic salt (Li⁺, Na⁺, K⁺, Cr³⁺, NH₄⁺, (CH₃)₄N⁺ and (C₂H₅)₄N⁺) on the anodic side. The proton leakage is quantified from the value of the proton transport number. The results are analyzed assuming that the rate determining step of proton leakage is the interfacial transfer reaction of protons from the aqueous anodic solution to the membrane. The proton leakage is enhanced by the polarizing power of the cation. The transfer of protons into the membrane seems to be catalyzed by the presence of a layer of adsorbed cations on the surface of the membrane. The presence of salt decreases the proton leakage but it is always greater with H₂SO₄ solutions compared to HCl solutions.     

Solution to the electrodiffusion equations: An investigation of their characteristics

For the case of a steady-state current passing through an electrolyte, the solution to the electrodiffusion equations is investigated and obtained by means of a series expansion in powers of the value of the current. If the solution for a zero value of the current is taken as the zeroth approximation, then it is shown that a series in powers of the current, which determines the solution at a nonzero current, is convergent.     

Short communications

The transport of carbonic acid anions through an anion-exchange membrane (AEM) during electrodialysis is studied. At current densities above limiting diffusion values, fluxes of hydrocarbonates and carbonates are lower than those of strong-electrolyte anions. The reason for the decreased fluxes is the recombination of carbonic acid ions with hydrogen ions that form during irreversible dissociation of water molecules at the solution/AEM interface     

Effect of an ion-exchange filler on the deionized water quality in electrodialysis

Desalination channels, containing an inert separator and a monolayer of ionites AV-17 and KU-2 taken in various volume ratios, are studied while maintaining concentrations of all solution components invariant. It is shown that the composition of the ion-exchange filler of the desalination channel affects the rate of transport of salt ions through relevant membranes, pH, and specific resistance of desalinated solution. The behavior of membrane systems in an overlimiting state is explained by using notions about different mechanisms governing the so-called overlimiting current through anion-exchange and cation-exchange membranes     

Preparation of a Chelating Polymeric Membrane and Application to Uphill Transport

Abstract

Modification of an anion-exchange membrane by (1-(2-arsono-phenylazo))-2-hydroxy-3,6-naphthalenedisulfonic acid (thoron) results in a membrane that can chelate metals. The high affinity of the disulfonate for the anion-exchange sites together with molecular adsorption of the aromatic thoron onto the polymers yields a system that is stable in strong acids at or below 1 M. By employing a relatively high pH sample (5-9) in conjunction with an acidic stripping solution (0.2 - 1.0 M HCl), uphill transport of Cu(II) and Zn(II) was accomplished. The transport rate was increased by means (lower chelating capacity and the use of a chelate-forming aid on in the stripping solution) of promoting the volume diffusion mechanism of membrane transport. With a 0.05 mmol per dry gram chelating capacity and a 0.1 M EDTA stripping solution (pH 6.5), an enrichment factor of 16 was observed in a one-hour experiment with a 200 mL sample, 11 cm² membrane, and 5 mL stripping solution. This value compares favorably with those obtained by other uphill transport modes under the same conditions.     

Potential application of anion-exchange membrane for hydrazine fuel cell electrolyte

A platinum electrocatalyst layer was directly bound to a perfluorinated anion-exchange membrane (AEM) by the electroless plating method and used for the characterization of AEM as a polymer electrolyte membrane for a direct hydrazine fuel cell. The crossover amount of hydrazine through AEM was much lower than that through the cation-exchange membrane (CEM) that did not depend on the applied current density. The fuel cell performance was far superior when using AEM than when using CEM.     

Mathematical model of electrodiffusion transfer through three-layer membrane system: Diffusion layer-ion-exchange membrane-diffusion layer

Three-layer combination formed in dialysis systems, which comprises membrane confined between two diffusion layers, can be considered as a single whole (a fragment) included in numerous complicated electrodialysis assemblies. A mathematical model is developed for estimating the electrodiffusion transfer in such a fragment containing four operating salt ions with the allowance for the membrane heterogeneous structure. The method of solving the problem is based on the integrating of the Nernst-Planck transfer differential equations with the corresponding boundary and interfacial conditions.     

Flow of Multicomponent Electrolyte Solutions through Narrow Pores of Nanofiltration Membranes

The slow flow of a multicomponent electrolyte solution in a narrow pore of a nanofiltration membrane is considered. The well-known semiempirical method of subdivision of electrical potential into quasi-equilibrium and streaming parts and the definition of streaming concentrations and pressure are discussed. The usefulness of this tool for solving the electrohydrodynamic equations is shown and justified: the use of a small parameter enables a system of electrohydrodynamic partial differential equations to be reduced to a system of ordinary differential equations for streaming functions. Boundary conditions for streaming functions at both the capillary inlet and outlet are derived. The proposed model is developed for the flow of a multicomponent electrolyte solution with an arbitrary number of ions. This is coupled with (i) the introduction of specific interactions between all ions and the pore wall and (ii) the inclusion of the dissociation of water in both conservation and transport equations. Effective distribution coefficients of ions are introduced that are functions of both the specific interaction potentials and the surface potential of the nanofiltration membrane material. The axial dependency of surface potential is expressed by the use of a charge regulation model from which the discontinuity in electric potential and ion pore concentrations at the pore inlet and outlet can be described.A relation between the frequently used capillary and homogeneous models of nanofiltration membranes is developed. An example of application of the homogeneous model for interpretation of experimental data on nanofiltration separation of electrolyte solutions is presented, which shows a reasonable predictive ability for the homogeneous model.     

Water transport coefficient distribution through the membrane in a polymer electrolyte fuel cell

The net water transport coefficient through the membrane, defined as the ratio of the net water flux from the anode to cathode to the protonic flux, is used as a quantitative measure of water management in a polymer electrolyte fuel cell (PEFC). In this paper we report on experimental measurements of the net water transport coefficient distribution for the first time. This is accomplished by making simultaneous current and species distribution measurements along the flow channel of an instrumented PEFC via a multi-channel potentiostat and two micro gas chromatographs. The net water transport coefficient profile along the flow channels is then determined by a control-volume analysis under various anode and cathode inlet relative humidity (RH) at 80 °C and 2 atm. It is found that the local current density is dominated by the membrane hydration and that the gas RH has a large effect on water transport through the membrane. Very small or negative water transport coefficients are obtained, indicating strong water back diffusion through the 30 μm Gore-Select^® membrane used in this study.     

Simulation of non-stationary electrodiffusion processes in charged membranes by the network approach

Single techniques of network approach have been used to obtain the numerical solution for a boundary value problem involving the Nernst-Planck and Poisson equations system. A network model has been proposed for a particular physical situation, namely, ionic transport in charged membranes including the Donnan equilibrium relations at the membrane/solution interfaces. With this network model and using the electrical circuit simulation program PSPICE, the ionic concentration profiles as well as electric potentials and ionic fluxes have been simulated as a function of time for the ternary systems HClKCl and NaClKCl.     

Protonation and diffusion phenomena in poly(4-vinylpyridine)-based weak anion-exchange membranes

Purification and concentration of mineral acids can be carried through dialysis processes with anion-exchange membranes. Weak anion-exchange membranes are active only for sufficient acid concentrations in their structure, however too high concentrations result in significant proton leakage, i.e. reduction in the transport selectivity. The present paper deals with the kinetics of acid diffusion through two commercial poly(4-vinylpyridine)-based weak anion-exchange membranes which comprises protonation of the exchanging groups. The electrical conductivity and the water content of the membranes were shown to be linear function of the protonation degree of poly(4-vinylpyridine) groups. Kinetics of protonation and diffusion of acids have been investigated using dialysis cells. First diffusion kinetics has been studied in a conventional dialysis cell, by observation of the transient acid transport through the membrane (macroscopic studies). Besides, protonation kinetics was investigated using a miniaturised dialysis cell coupled to confocal Raman microspectrometer. Profiles of non-protonated and protonated sites in the membrane were recorded along time, depending on the membrane grade and the nature of the acid transported. Interpretation of the two sources of data yielded permeability coefficient and diffusion coefficient, whose meaning is discussed. A mechanism for protonation/diffusion in this type of weak anion exchangers in acidic media was proposed.