Transfer of electrolyte ions and water dissociation in anion-exchange membranes under intense current conditions

Polarization characteristics of electromembrane systems (EMS) based on the Russian commercial heterogeneous membranes MA-40 and MA-41, the anion-exchange heterogeneous membrane AMH (Mega, Czech Republic), and the modified membrane MA-40M are studied by the method of rotating membrane disk in dilute sodium chloride solutions. The effective transport numbers of ions are found; the partial voltammetric characteristics (VAC) with respect to chloride and hydroxyl ions are measured; the limiting current densities are calculated as a function of the membrane disk rotation rate. In terms of the theory of the overlimiting state of EMS, based on experimental VAC and the dependences of the effective transport numbers on the current density, the following internal parameters of systems under study are calculated: the space charge and electric field strength distribution over the diffusion layer and the membrane. It is shown that water dissociation can be virtually completely eliminated by substituting chemically stable quaternary ammonium groups inert with respect to water dissociation in the surface layer of a heterogeneous anion-exchange membrane MA-40 for the active ternary and secondary functional amino groups. The maximum electric field strength values at the membrane/solution interface, which were found in the framework of the theory of over-limiting state, turned out to be close for all anion-exchange membranes studied, namely, (7?C9) × 10⁶ V/cm. This suggests that it is the nature of ionogenic groups in the surface layer rather than the field effect that plays the decisive role in the membrane ability to accelerate the water dissociation reaction. It is proved experimentally that in highly intense current modes of the electrodialysis process, the thermal hydrolysis of quaternary ammonium bases occurs in strongly basic MA-41 and AMH membranes by the Hofmann reaction to form ternary amino groups catalytically active in water dissociation reaction. Based on the concept on the catalytic mechanism of water dissociation, the fraction of ternary amino groups formed by thermal hydrolysis in the surface layer (the space charge region) of monopolar anion-exchange membranes MA-41 and AMH is assessed quantitatively as 0.7 and 6.5%, respectively.     

Ion transfer across ion-exchange membranes with homogeneous and heterogeneous surfaces

A homogeneous (AMX) and two heterogeneous (MA-40, MA-41) anion-exchange membranes, as well as a heterogeneous cation-exchange membrane (MK-40), are studied by electronic scanning microscopy, voltammetry, and chronopotentiometry. The presence of conducting and nonconducting regions on the surfaces of heterogeneous membranes is established by means of element analysis. The fraction of conducting regions is found by an image treatment. The surface of the AMX membrane was partially coated with microspots of a paint to make it heterogeneous (AMXheter). Voltammetric and chronopotentiometric measurements for AMX, AMXheter, and MA-41 membranes in NaCl solutions are carried out and the pH changes in the solution layers adjoining to these membranes are recorded. Analysis of obtained results shows that the concentration polarization of studied membranes characterized by the potential drop and the rate of water dissociation at the interface is mainly governed by the properties of their surfaces. It is found that the local limiting current density through conducting regions of a heterogeneous membrane is several times higher than the average limiting current through a homogeneous membrane.     

The dissociation rate of water molecules in systems with cation- and anion-exchange membranes

Within the framework of the mathematical model of Nernst-Planck-Poisson, an attempt is undertaken to theoretically describe the electrodiffusion of ions in the system diffusion layer/monopolar ionexchange membrane, which is accompanied by dissociation of water molecules. The formulas for estimating the current density transferred through a monopolar membrane by hydrogen or hydroxyl ions formed in dissociation of water in the space-charge region are derived. The rate constants and other parameters of dissociation of water molecules in the space-charge region of monopolar membranes under conditions of stabilization of the diffusion layer thickness are calculated. Their comparative analysis with the similar characteristics of bipolar membranes is carried out. For the phosphoric-acid heterogeneous membrane MK-41 in which the polarization conditions in the current density range under study are not so severe and the reaction layer is not being depleted as in the bipolar membrane MB-3 (contains the same phosphoric-acid groups), it is shown that only single-charged phosphoric-acid groups are involved in the water dissociation reaction. For MK-41, the calculated constants of the heterolytic reaction of water molecule dissociation are lower than for the heterogeneous membrane MA-40 containing ternary and quaternary amino groups. It is confirmed that the nature of ionogenic groups in membranes is a factor that determines the rate of water dissociation in systems with ion-exchange membranes.     

Mass transfer mechanism and chemical stability of strongly basic anion-exchange membranes under overlimiting current conditions

The dynamics of changes in overall and partial voltammetric characteristics with respect to chloride and hydroxide ions is studied by the method of rotating membrane disk (RMD) under the conditions of stabilized diffusion layer thickness for the original strongly basic MA-41P and homogeneous AMX membranes and also for the modified heterogeneous MA-41P-M membrane at high current densities. For unmodified anion-exchange membranes at currents exceeding the limiting value, the hydrolysis of fixed ammonium bases produces secondary and ternary amino groups which are catalytically active in the reaction of water molecule dissociation. The hydrolysis of amino groups in the membrane surface layer is the mechanism of degradation of electrochemical characteristics of strongly basic membranes. This results in the increase of transport numbers with respect to hydroxide ions and weakening of mass transfer with respect to salt ions. For the surface-modified heterogeneous anion-exchange membranes, no degradation of electrochemical characteristics is observed. The characteristics of the surface-modified MA-41P-M membrane remain stable: after long-term operation of the energized membrane, the partial currents with respect to hydroxide ions are close to zero and the mass transfer with respect to salt ions is considerably intensified. The dependences of the thickness of the hydrolyzed layer of a strongly basic anion-exchange membrane on the time of its exposure to solutions of high pH are determined. An original method is developed for determination of the hydrolyzed layer thickness for strongly-basic anion-exchange membranes, which is based on the copper ability to form stable complex compounds with weakly basic amino groups of anion-exchange membranes.     

Influence of the nature of membrane ionogenic groups on water dissociation and electrolyte ion transport: A rotating membrane disk study

Polarization properties of electromembrane systems (EMS) consisting of a heterogeneous membrane, either the MK-41 phosphonic acid membrane or the MK-40 sulfonic acid membrane, and dilute sodium chloride solutions are investigated with the rotating membrane disk method. For the MK-41/0.01 M NaCl and MK-41/0.001 M NaCl EMS, effective ion transport numbers and partial current-voltage curves (CVC) are measured for sodium and hydrogen ions, and limiting-current densities and the diffusion-layer thickness are calculated as functions of the rotation rate of the membrane disk. With the theory of the overlimiting state of EMS, internal parameters of the systems under investigation—the diffusion-layer thickness, the space-charge distribution, and electric-field strengths in the diffusion layer and in the membrane—are calculated from experimentally obtained CVC and the dependence of effective transport numbers on current density. The catalytic influence of ionogenic groups on the dissociation rate of water is analyzed quantitatively. Partial CVC for H⁺ ions are calculated for the space-charge region in MK-40 and MK-41 membranes. Analogous CVC for bipolar membranes containing sulfonic acid and phosphonic acid groups are compared. The dissociation mechanism of water is the same in all EMS and is independent of the membrane type and the nature of the functional groups.     

Effect of chemical modification of ion-exchange membrane MA-40 on its electrochemical characteristics

Transport characteristics of commercial heterogeneous anion-exchange membranes MA-40 and MA-41 are studied, together with those of membrane MA-40M fabricated by treating the MA-40 surfaces with a strong polyelectrolyte complex. It is demonstrated that, after modification, the electrical conductivity of MA-40M in an NaOH solution increases. At overlimiting currents, the water dissociation rate on this membrane decreases as compared with the initial membrane. At the same time, no noticeable change in the rate of transport of counter-ions (ions Cl^-) through the membrane at a fixed potential drop is discovered at under-and overlimiting currents. The MA-40M membrane behavior is explained by the conversion of secondary and tertiary functional ammonium groups in the near-surface membrane layers approximately 80 μm thick into quaternary groups during the treatment by the polyelectrolyte.     

Electroosmotic transport of water and aprotic solvent in heterogeneous membranes

Electrosmotic water transport in MK-40, MA-40, and MA-41 electrodialysis membranes before and after their treatment by aprotic solvent solution and electroosmotic permeability of a MK-40/MA-40 membrane couple in water and N,N-dimethyl acetamide were studied for the first time. It is found that N,N-dimethyl acetamide produces practically no effect on the properties of the studied ion-exchange materials and its transport number through the MK-40/MA-40 membrane couple is independent both of the initial lithium chloride concentration in a desalting cell of the concentrator electrodyalizer and its volume fraction in the solution. The initial concentration of lithium chloride in the desalting cell does not affect the transport numbers of water in the studied membrane couple either. However, these depend on the volume fraction of the organic component in the solution and this dependence features an extremum. A method for estimation of electroosmotic permeability of the membrane couple in aqueous-organic solutions of electrolytes is suggested.     

Electric mass transport through homogeneous and surface-modified heterogeneous ion-exchange membranes at a rotating membrane disk

Polarization characteristics of the homogeneous MF-4SK perfluorinated sulfonated cation-exchange membrane and the heterogeneous MK-40 sulfonic acid membrane with its surface modified by a homogeneous film of Nafion are studied at a rotating membrane disk in 0.1 and 0.001 M sodium chloride solutions. Partial current-voltage curves (CVC) are obtained for sodium and hydrogen ions, and limiting current densities in the electromembrane systems (EMS) under study are calculated as a function of the rotation rate of the membrane disk. Contribution from different mechanisms (electrodiffusion, electroconvection, dissociation of water, and the effect of the limiting-current exaltation) to the total ion flow is estimated experimentally and theoretically under conditions that the diffusion layer in the EMS has stabilized in thickness. It is established that surface modification of the heterogeneous MK-40 membrane with a 7 μm layer of a modifying agent almost completely eliminates the dissociation of water molecules, and the properties of the heterogeneous MK-40 membrane approximate those of the homogeneous Nafion membrane. From IR spectra and potentiometric titration curves of the MK-40 and MF-4SK membranes, it is shown that the acidity of the sulfonate groups in these membranes is nearly identical, but a difference in the dissociation rate of water at these membranes is determined by a different character of charge-density distribution and potential near the membrane-solution interphase boundary. By means of the theory of the overlimiting state in EMS, the internal parameters of the systems under investigation are calculated: distribution of space-charge density and electric-field potential in the diffusion layer and in the membrane. Partial CVC are calculated for H⁺ ions for the space-charge region in the phase of the MF-4SK and MK-40/Nafion ion-exchange membranes. Partial CVC with similar characteristics are compared for the heterogeneous monopolar MK-40 and the bipolar MB-2 membranes, which contain sulfonate groups. It is concluded that the membrane surface layer, where the space charge is localized, plays a dominant role in speeding up the dissociation of water in EMS.     

Interaction of Organic Surfactants with Heterogeneous Ion-Exchange Membranes

The effect of organic surfactants (1,4-butynediol, benzoic and disulfonaphthalene acids) on electrochemical properties of heterogeneous ion-exchange membranes MK-40 and MA-40 is studied. The surfactants effect the membrane properties both under equilibrium conditions and, especially, in the electric field, suggesting that they are involved in both the exchange sorption and the electrotransport. The mechanism of their effect on the anionite membrane is considered. It is shown that bipolar boundaries can arise in the membrane, promoting water dissociation and transport of hydrogen and hydroxyl ions in the field direction.     

The effect of aprotic solvent on the selectivity of ion-exchange membranes

The effect of N,N-dimethylacetamide on the selectivity of heterogeneous (MK-40, MA-40, and MA-41) and homogeneous (MF-4SK) ion-exchange membranes is studied for the first time. Concentration dependences of electrical conductivity and diffusion permeability of the membranes were measured experimentally over wide lithium chloride concentrations; on their basis, electrodiffusion coefficients of the co- and counterions were calculated. The interrelation between the electrodiffusion coefficients and the specific moisture capacity of the heterogeneous and homogeneous membranes (which affect their selectivity) is revealed. The calculated electrodiffusion coefficients were used in the calculations of the electromigration transport numbers of counterions in the initial membranes and those processed in mixed solvent. It is shown that the heterogeneous membrane selectivity either increased under the action of the aprotic solvent to polymer material (MA-40, MA-41) or remained practically unchanged (MK-40); the selectivity of homogeneous perfluorinated membranes (e.g., MF-4SK) decreased, thus approaching that of the studied heterogeneous anion-exchange membranes.     

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.     

The effect of silver ions and nanoparticles on the properties of ion-exchange materials

The effect of silver ions and nanoparticles on the electrochemical properties of KU-2-8 sulfocationite, MF-4SK homogeneous sulfocationite membrane, and MA-40 heterogeneous anion-exchange membrane is studied. Using scanning electron microscopy, the particle distribution throughout the cationexchanger thickness is studied. The method of IR spectroscopy is used for studying the interaction of silver nanoparticles and ions and also of Cu²⁺ and Ni²⁺ ions with secondary and tertiary amino groups. It is shown that the mobilities of sodium and silver ions are close in sulfocationites, which suggests that silver ions are quickly washed out of such materials. In the anion-exchange membrane, silver ions are bound into complexes with ionogenic groups and induce an increase in the water dissociate rate in the membrane. The reduction of silver ions contained in cation-exchangers in a molar fraction of 80% with sodium borohydride affords a conducting metal silver film on their surfaces. The introduction of silver nanoparticles into the MA-40 anionexchange membrane is accompanied by the increase in both the limiting electrodiffusion current and the water dissociation rate in the membrane, which is apparently due to the partial oxidation of metal silver particles to afford silver oxide in the near-surface membrane layer. The latter oxide exhibits weak catalytic activity with respect to water dissociation reaction in the membrane, which results in an insignificant increase in the effective transport numbers of hydroxide ions through the membrane.     

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.     

Effect of the chemical nature of the ionogenic groups of ion-exchange membranes on the size of the electroconvective instability region in high-current modes

The size of the electroconvective instability region on the membrane-solution boundary at currents exceeding the limiting diffusion current was measured by laser interferometry. The influence of the chemical nature of the ionogenic groups of ion-exchange membranes on the development of electroconvective instability was studied. The thickness of the electroconvection region decreased as the catalytic activity of the ionogenic groups of commercial and pilot membrane samples with respect to the heterolytic water dissociation increased. The maximum size of the electroconvective instability region and the minimum currents at which it was recorded for the anion-exchange membranes under study were determined for the highly basic modified anion-exchange membrane MA-41M with an almost completely suppressed water dissociation function. A correlation was found between the size of the convective instability region and the characteristic points on the current-voltage curves.     

Rate of Generation of Ions H<Superscript>+</Superscript> and OH<Superscript>−</Superscript> at the Ion-Exchange Membrane/Dilute Solution Interface as a Function of the Current Density

Partial currents of water dissociation products through cation- and anion-exchange membranes that form thin desalination channels in electrodialyzers are measured. The investigations are performed in a broad interval of flow rates during desalination of dilute sodium chloride solutions at overlimiting currents. A water dissociation theory, which was developed for bipolar membranes, and a mass transfer theory that allows for the space charge formation at overlimiting currents are used to derive an expression, according to which the rate of generation of the H⁺ and OH^? ions is defined by the ratio of the current density to its critical value at which water starts undergoing discernible dissociation.     

Transport properties of anion-exchange membranes: Effect of the formation of complexes

Electroconductivity and diffusion permeability of heterogeneous anion-exchange membranes MA-40 and MA-41 are studied in solutions containing copper, nickel, and zinc cations. The composition of species present in the contacting solution is calculated on the basis of conditions of equilibrium and material balance with allowance made for the tendency of these cations to form complexes. It is shown that the reason for the electroconductivity of MA-40 increasing in dilute solutions of transition metal chlorides is the complexing between these cations and functional groups and the resultant increase in the overall positive charge of the polymer matrix. The complexing with ions of copper and zinc in the electromembrane phase reduces the mobility of chloride ions, thus lowering the membranes’ electroconductivity with increasing concentration of equilibrium solutions. The membranes are characterized using a method of determination of the transport properties and structure of the membranes. The method is applied for the first time to the complexing co-ions, with allowance made for variations in their charge and composition.     

Effect of an aprotic solvent on the properties and structure of ion-exchange membranes

The effect of the aprotic solvent dimethylacetamide on the equilibrium and transport properties of heterogeneous (MK-40, MA-40, and MA-41) and homogeneous (MF-4SK) ion-exchange membranes is investigated. On the basis of concentration dependences of the conductivity and diffusion permeability of membranes, model calculations of transport-structural parameters that reflect the structural and kinetic characteristics of conducting phases of the swollen polymer are performed. The effect of the aprotic solvent on the flow of current through the structural fragments of the ion-exchange material is estimated. The causes of changes that are induced in the properties of the membranes by the aprotic solvent are ascertained.     

Effect of concentration polarization on electrodialytic concentrating of dilute NaCl and NH4NO3 solutions

Electrodialytic concentrating of dilute sodium chloride and ammonium nitrate solutions is studied in a wide range of current densities. Using the model of limiting electrodialytic concentrating, based on the experimental data, the transport characteristics of MK-40/MA-40 membrane pair in the above electrolytes and the hydration numbers of these electrolytes were determined. It is found that a degree of concentration polarization has an effect on the main parameters of limiting electrodialytic concentrating: the current efficiency, the water transfer number across the test membrane pair, and the concentration of solution in the concentrating compartment. These parameters determine the effectiveness of concentrating. It is found that the electrodialytic concentrating is most effective at the limiting current due to the lowest electroosmotic permeability of membrane pair and the highest current efficiency.     

Sodium chloride concentration by electrodialysis with hybrid organic-inorganic ion-exchange membranes: An investigation of the process

This study examines how conditions for modifying homogeneous MF-4SK and heterogeneous MK-40 membranes with tetraethoxysilane affect membrane properties. The microstructure of the bulk membrane and its surface, both before and after exposure to the modifying agent, is examined by scanning electron microscopy, spark spectrophotometry, and standard contact porosimetry. The process of sodium chloride concentration by electrodialysis with hybrid organic-inorganic membranes in cells with noncirculating concentration compartments is investigated, and a mathematical model of the concentration process by electrodialysis is used to determine transport properties: current efficiency, diffusion and osmotic permeabilities, and the salt hydration number. For highly hydrophilic membranes, it is shown that water transport occurs both in ion hydration shells and also as free water. It is established that after modified membranes undergo additional heat treatment, the transport of free water ceases, and the water transport number decreases. This is in accord with an increase in the salt content of the concentrate during concentration by electrodialysis.     

Electrical conductivity of cation-and anion-exchange membranes in ampholyte solutions

Several laws governing ampholyte transport through ion-exchange membranes are established by a comparative analysis of the concentration dependence of electrical conductivity for homogeneous (CMX, AMX) and heterogeneous (MK-40, MA-41) membranes in NaCl, LysHCl, and NaH₂PO₄ solutions. The increase in the electrical conductivity of membranes in ampholyte solutions as the solutions become more dilute is explained by the increased fraction of divalent ions of the amino acid (cation-exchange membrane) or from phosphoric acid (anion-exchange membrane) in the membrane as a result of Donnan exclusion of hydrolysis products (hydroxide ions or protons, respectively).