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.     

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.     

Correction of pH of diluted solutions of electrolytes by electrodialysis with bipolar membranes

The current efficiencies of the water dissociation water and the voltage-current characteristics of the bipolar (asymmetric bipolar) membranes were measured in a two-chamber electrochemical cell. The cell was formed of an MB-3 bipolar membrane or an asymmetric bipolar membrane, which is an MA-40 heterogeneous membrane with a thin surface layer in the form of a cation-selective homogeneous film and MA-40 and MA-41 heterogeneous monopolar membranes. The dissociation of water on MA-40 in 0.01 M sodium chloride decreased the current efficiency of the acid and alkali both in the channel with a bipolar membrane and in the channel with an asymmetric bipolar membrane. The effective ion transport numbers across MA-40 and MA-41 at different pH values were determined. The water dissociation rate on MA-40 decreased at pH > 9.5. A kinetic model of the electrodialysis of a dilute solution of sodium chloride in a two-chamber unit cell with a bipolar and anionite membranes was suggested.     

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.     

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.     

Electrodialysis of Binary Electrolyte Mixtures with Membranes Modified by Organic Species

The modification of anion-exchange membranes MA-40 by lauric acid and sodium polystyrenesulfonate is studied. By measuring the wetting angle and using IR spectroscopy, the mechanism of sorption of the modifiers by the membranes is established. The membrane modification is accompanied by hydrophobization of a surface layer and the formation of strong bonds between functional groups of membranes and modifiers. The concentration dependence of the ion separation coefficients in electrodialysis of binary electrolyte mixtures with modified and nonmodified membranes is studied. The selectivity of modified membranes to less-hydrated ions increases and the smaller the solution concentration, the larger the ions.     

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.     

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.     

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).     

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.     

Colorimetric detection of iron ions (III) based on the highly sensitive plasmonic response of the N-acetyl-l-cysteine-stabilized silver nanoparticles

We report here a facile colorimetric sensor based on the N-acetyl-l-cysteine (NALC)-stabilized Ag nanoparticles (NALC–Ag NPs) for detection of Fe³⁺ ions in aqueous solution. The Ag NPs with an average diameter of 6.55 ± 1.0 nm are successfully synthesized through a simple method using sodium borohydride as reducing agent and N-acetyl-l-cysteine as protecting ligand. The synthesized silver nanoparticles show a strong surface plasmon resonance (SPR) around 400 nm and the SPR intensity decreases with the increasing of Fe³⁺ concentration in aqueous solution. Based on the linear relationship between SPR intensity and concentration of Fe³⁺ ions, the as-synthesized water-soluble silver nanoparticles can be used for the sensitive and selective detection of Fe³⁺ ions in water with a linear range from 80 nM to 80 μM and a detection limit of 80 nM. On the basis of the experimental results, a new detection mechanism of oxidation–reduction reaction between Ag NPs and Fe³⁺ ions is proposed, which is different from previously reported mechanisms. Moreover, the NALC–Ag NPs could be applied to the detection of Fe³⁺ ions in real environmental water samples.     

Photo-induced formation of silver nanoparticles and polymerization of acrylamide derivatives

The effect of silver ions and silver nanoparticles on the rate of polymerization of acrylamide and N-isopropylacylamide was investigated. Composites of silver particles of diameter around 30 nm and polyacrylamide were prepared by the photochemical method in the absence of any photosensitizer. The particles formed were characterized by UV–visible spectrophotometry, XRD, and TEM. It was shown that the presence of metal ions such as Ag⁺, Co²⁺, and Ni²⁺ in the acrylamide monomer is essential for photoinduced polymerization.     

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.     

Reductive sorption of molecular oxygen from water on silver-KU-23 sulfo-cation exchanger nanocomposites in different ionic forms

New silver-containing nanocomposites different in their dispersity of metal were synthesized on the basis of strongly and weakly basic anion-exchange resins. The chemical activity of the nanocomposites with respect to oxygen dissolved in water was investigated. It was shown that silver nanoparticles in samples based on strongly basic anion exchangers and weakly basic anion exchangers in the NO₃⁻ salt form are not oxidized by oxygen; for weakly basic matrices in the free amine form, this process occurs to only a small extent. The resistance to oxygen is explained by inhibition of processes of formation of silver oxides. Nanocomposites based on strongly basic anion-exchange resins are recommended for testing as to catalytic activity.     

Mechanism of silver nucleation upon the radiation-induced reduction of its ions in polyphosphate-containing aqueous solutions

Long-lived (hours to days) silver clusters, Ag ₄ ²⁺ , Ag ₄ ⁺ , Ag ₈ ²⁺ , etc., are formed upon the radiation-induced reduction of Ag⁺ ions in aqueous solutions containing sodium polyphosphate. The efficiency of the cluster formation decreases and the stability of the clusters increase with a rise in the concentration of the polymeric stabilizer. In the course of the aggregation of clusters, their sizes increase, quasi-metallic particles emerge, and the process terminates with the formation of silver nanoparticles. The mechanism of silver nucleation upon the radiation-induced reduction of silver ions in aqueous solutions is discussed.     

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.     

Coupled convection of solution near the surface of ion-exchange membranes in intensive current regimes

Mechanisms responsible for the overlimiting ion transfer in membranes systems are discussed. The overlimiting transfer is shown to be due largely to the action of four effects coupled with the concentration polarization of the system. Two of these are connected with the water dissociation near the membrane/solution interface: the emergence of additional charge carriers (ions H⁺ or OH^?) in the depleted solution layer and the exaltation of transfer of salt counterions. The latter effect is connected with the perturbation of electric field caused by the water dissociation products. The other two effects are two versions of coupled convection, which leads to partial destruction of the depleted diffusion layer. These include gravitational convection and electroconvection. The former is caused by the emergence of the solution’s density gradient. The latter develops via a mechanism of electroosmotic slip. In this work, methods of voltammetry and chronopotentiometry and pH measurements are used to study the transfer of ions through homogeneous membranes Nafion-117 and AMX as a function of the concentration of sodium chloride solutions in the underlimiting and overlimiting current regimes. In a 0.1 M NaCl solution, gravitational convection makes a considerable contribution to the transfer of salt ions near the membrane surface in intensive current regimes. The influence of this effect on the electrochemical behavior of membrane systems weakens with the solution dilution and with increasing relative transfer of the H⁺ and OH^? ions that are generated at the membrane/solution interface. In conditions where gravitational convection is suppressed and the water dissociation near the membrane/solution interface is not great, the major contribution to the overlimiting growth of current is made by electroconvection. Topics for discussion in the paper include the mutual influence of effects on one another, in particular, the effect the rate of generation of the H⁺ and OH^? ions exerts on the gravitational convection and electroconvection and the reasons for the different behavior of cation-and anion-exchange membranes in intensive current regimes.     

Chemical activity of silver nanoparticles in anion-exchange matrices with respect to molecular oxygen dissolved in water

New silver-containing nanocomposites different in their dispersity of metal were synthesized on the basis of strongly and weakly basic anion-exchange resins. The chemical activity of the nanocomposites with respect to oxygen dissolved in water was investigated. It was shown that silver nanoparticles in samples based on strongly basic anion exchangers and weakly basic anion exchangers in the NO ₃ ^? salt form are not oxidized by oxygen; for weakly basic matrices in the free amine form, this process occurs to only a small extent. The resistance to oxygen is explained by inhibition of processes of formation of silver oxides. Nanocomposites based on strongly basic anion-exchange resins are recommended for testing as to catalytic activity.     

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.     

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.