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.     

Effect of anion-exchange membrane surface properties on mechanisms of overlimiting mass transfer

Four effects providing overlimiting current transfer in ion-exchange membrane systems are examined. Two of them are related to water splitting: the appearance of additional current carriers (H+ and OH- ions) and exaltation effect. Two others are due to coupled convection partially destroying the diffusion boundary layer: gravitational convection and electroconvection. Three anion-exchange membranes, which differ in surface morphology and the nature of ion-exchange sites within a surface layer, are examined. The ion transfer across these membranes in NaCl solutions is studied by voltammetry, chronopotentiometry, and pH-metry. By excluding the effects of water splitting and gravitational convection, it is shown that the main mechanism of overlimiting mass transfer in narrow membrane cells at low salt concentrations is electroconvection. The reasons explaining why water splitting suppresses electroconvection are discussed. The scenario of development of potential oscillations with growing current and time is compared with that described theoretically by Rubinstein and Zaltzman.     

The effect of ion-conducting spacers on mass transfer — numerical analysis and concentration field visualization by means of laser interferometry

Mathematical model is developed for the study of mass transfer processes under the laminar stationary flow in the channels of electromembrane system formed by alternating cation- and anion-exchange membranes at whose surfaces the ion-conducting spacers are fixed. The results of calculations are given of velocity and concentration fields, of current density distribution along the channel length for some values of Reynolds number and the values of the applied voltage. The comparison is made between the calculated mass transfer characteristics and the experimental data obtained by means of laser interferometry.     

Hydrodynamic Instabilities Driven by Acid-base Neutralization Reaction in Immiscible System

The hydrodynamic instabilities driven by an acid-base neutralization reaction, in contact along a plane interface, placed in a Hele-Shaw cell under the gravitational field are reported.The system consists of the heavier aqueous tetramethyle-ammonium hydroxide below the lighter layer of organic phase with propionic acid as reacting specie. The effect of chemical composition on hydrodynamic instabilities during interfacial mass transfer accompanied by a neutralization reaction is investigated. Depending on the initial concentration of the reacting species, Marangoni convection in the form of roll cells or trains of waves is observed. Mach-Zehnder interferometer is used to measure the change in base concentration at the time of instability formation. The results show that the instabilities resulted from the convection flow are more efficient to the mechanism of mass transfer and can drastically alter pattern formation in the system.     

Transport of glycine in systems with cation-exchange membranes in hydrochloric acid solutions: Effect of a heterogeneous protonation reaction

The electrical mass transfer of cations in electromembrane systems (EMS) with an MK-40 cation-exchange membrane and glycine in aqueous solutions of hydrochloric acid is studied using the method of a rotating membrane disk. Limiting current densities and limiting steps of the transport of cations in such systems are determined. Shown is the possibility of an increase in the electrical mass transfer of glycine as a consequence of the occurrence of a heterogeneous reaction of protonation of its zwitterions. The effect of the membrane surface state on the kinetic regularities of transport of cations in EMS with glycine in solutions of hydrochloric acid is exposed.     

Onset of natural convection in the electrochemical cell with horizontal electrodes under non-steady-state conditions: A numerical study

The disturbance of mechanical equilibrium of stagnant electrolyte containing three types of ions and the onset of natural convection in the electrochemical cell with plane horizontal electrodes under the non-steady-state conditions are studied theoretically. The Navier-Stokes equations in the Boussinesq approximation, the equations of ionic transfer of electrolyte components, which is caused by diffusion, convection, and migration, and the electroneutrality condition were used as the mathematical model of the process. Using the numerical simulation, the regularities of the onset of natural convection of electrolyte solution with the formation of convective cells are studied. The effect of transport properties of solution on the critical time of onset of convection and on the time before the current starts to increase due to the onset of natural convection, on the sizes and shape of convective cells and the mass-transfer rate is investigated by the example of cathodic deposition of metal at the limiting current.     

Numerical simulation of natural convection of electrolyte solution with three types of ions in the electrochemical cell with vertical electrodes

The mass transfer in the electrolyte solution with three types of ions in the electrochemical cell of square section with vertical electrodes is studied. The mathematical model of the process involves the Navier-Stokes equations in the Boussinesq approximation, the equations of ionic transfer of electrolyte components, which is caused by diffusion, convection, and migration, and the condition of electroneutrality. It is shown that this problem corresponds to a special case of thermosolutal convection with regard for thermodiffusion (the Soret effect), where the cell boundaries are permeable to an impurity and the flux of impurity through the boundary is proportional to the heat flux. Using the numerical simulation, the distributions of concentration of ions, solution density, local and average mass-transfer rates are studied. The approximate analytical equations for the limiting current are obtained for typical electrochemical systems.     

Electronic simulation of the supported liquid membrane in electromembrane extraction systems: Improvement of the extraction by precise periodical reversing of the field polarity

In order to understand the limitations of electromebrane extraction procedure better, a simple equivalent circuit has been proposed for a supported liquid membrane consisting of a resistor and a low leakage capacitor in series. To verify the equivalent circuit, it was subjected to a simulated periodical polarity changing potential and the resulting time variation of the current was compared with that of a real electromembrane extraction system. The results showed a good agreement between the simulated current patterns and those of the real ones. In order to investigate the impact of various limiting factors, the corresponding values of the equivalent circuit were estimated for a real electromembrane extraction system and were attributed to the physical parameters of the extraction system. A dual charge transfer mechanism was proposed for electromembrane extraction by combining general migration equation and fundamental aspects derived from the simulation. Dual mechanism comprises a current dependent contribution of analyte in total current and could support the possibility of an improvement in performance of an electromembrane extraction by application of an asymmetric polarity changing potential. The optimization of frequency and duty cycle of the asymmetric polarity exchanging potential resulted in a higher recovery (2.17 times greater) in comparison with the conventional electromebrane extraction. The simulation also provided more quantitative approaches toward the investigation of the mechanism of extraction and contribution of different limiting factors in electromembrane extraction. Results showed that the buildup of the double layer is the main limiting factor and the Joule heating has lesser impact on the performance of an electromebrane extraction system.     

Effect of intermittent convection movements on voltammogram and current transients

The influence of intermittent convection movements on electrochemical voltammograms is investigated. When the bath temperature rises to 315 K, the voltammograms exhibit irregular plateaus that differ for independent voltammetry scans, even when the setup is maintained under exactly the same conditions. In this paper, we show that such behavior can be caused by convection movements that develop in the electrolytic cell as a consequence of velocity fluctuations, since no bubbles or regular convective patterns are observed at this temperature. Theoretical current-potential curves for the heterogeneous deposition of metals on silicon electrodes is derived from a model consisting of a one-dimensional balance equation that includes diffusion, convection, and reaction through a time-dependent boundary condition. We obtain the current density associated with the adsorption of particles on the surface and, through this expression, we consider the effect of constant convective velocities on voltammograms. Finally, we examine the effect of random convective movements, described by a Monte Carlo algorithm that takes into account the random temporal fluctuations around a null convective current. The model predicts accentuated fluctuations on the current profiles, especially on the current plateaus that correspond to a stationary current regime. The validity of the theoretical model is checked against experimental data.     

Development and application of SBA‐15 assisted electromembrane extraction followed by corona discharge ion mobility spectrometry for the determination of Thiabendazole in fruit juice samples

A new sample preparation method based on SBA‐15 assisted electromembrane extraction coupled with corona discharge ion mobility spectrometer was developed for the determination of Thiabendazole as a model basic pesticide in fruit juice samples. The addition of SBA‐15 in the supported liquid membrane in electromembrane extraction system not only can lead to enhancement of the effective surface area, but also introducing the negatively charged silanol groups into supported liquid membrane might improve migration of positively charged analytes toward the supported liquid membrane and finally into the acceptor solution. To investigate the effect of the presence of SBA‐15 in the supported liquid membrane on the extraction efficiency, a comparative study was carried out between the conventional electromembrane extraction and SBA‐15/electromembrane extraction methods. Under the optimized conditions, SBA‐15/electromembrane extraction method showed higher extraction efficiencies in comparison with conventional electromembrane extraction method. SBA‐15/electromembrane extraction method exhibited a low limit of detection (0.9 ng/mL), high preconcentration factor (167) and high recovery (83%). Finally, the applicability of SBA‐15/electromembrane extraction method was studied by the extraction and determination of Thiabendazole as a model basic pesticide in fruit juice samples.     

Mathematical model for the overlimiting state of an ion-exchange membrane system

A three-layered mathematical model is proposed for describing the overlimiting state in an ion-exchange membrane system. The model’s prominent feature is the allowance for the space-charge region; the water dissociation reaction, which is catalyzed by active ionogenic groups; and the coupled gravitational and electroosmotic convection, which leads to the emergence of dependence of the effective diffusion layer thickness on the electric current density. The model is used for calculating, on the basis of known initial current-voltage curves and dependences of effective transport numbers on the current density, such internal characteristics of the system as the diffusion layer thickness, distribution of concentration of ions, space charge, and electric-field strength at various current densities.     

Improvement of metal recovery by electrodialysis

In every electrolysis process, increasing the efficiency of metal extraction is one way of reducing the loss of metal and so the pollution. For this purpose, electromembrane processes, the most important of which is electrodialysis, can be used on effluents of the electrolysis bath or on solutions undergoing electrodeposition. Electrodialysis is used just after electrodeposition to extract the metal from the effluent. It restores the concentration of the solution to the level of the bath. However, the flow of ions through the membrane pair is accompanied by a certain quantity of water. A model in agreement with the experimental results gives the main parameters involved in the transmembrane transfer and the optimal conditions. In another way, electromembrane processes are used in the solution while electrolysis is running. They give a relative enrichment of one of the metals. The model shows that this relative enrichment is always associated with a decrease in the true concentration. However, the overpotentials are reduced and the quantity of metal deposit increases. This relative enrichment can be obtained either by complexationelectrodialysis, by transport-depletion or by electro-electrodialysis. In each case, the energy consumption is indicated.     

Transfer of Amino Acids through a Membrane/Solution Interface in the Presence of Heterogeneous Chemical Protonation Reaction

A physicochemical model for the transfer of amino acids through the interface between a cation-exchange membrane and an amino acid aqueous solution is proposed. The model allows for a heterogeneous reaction of protonation of the amino acid zwitterion. The model calculations are compared with experimentally determined migration transport numbers for glycine cations in an electromembrane system with an MK-40 membrane. The comparison shows that, owing to the protonation reaction, the glycine flux can increase by ca. 30%.     

Mass transfer in the rotating electrochemical cell with vertical cylindrical electrodes: the effect of rotational rate and cell geometry on the limiting current density

The mass transfer in the rotating electrochemical cell with vertical cylindrical electrodes containing a binary electrolyte is theoretically studied. The Navier-Stokes equations in the rotating system of coordinates, the equations of ionic transfer of electrolyte components, which is caused by diffusion, convection, and migration, and the condition of electroneutrality are used as the mathematic model of the process. The effects of centrifugal force and Coriolis force are studied by using the numerical simulation; the effect of geometry of electrochemical cell on the limiting mass transfer rate is determined.     

Unsteady-state effects in limiting current measurements

In the measurement of limiting currents, unless the approach to the mass transfer limiting conditions by a current ramp or by potential scan is sufficiently slow, the apparent limiting currents obtained are higher than those corresponding to steady state transport.A review of experimental results on limiting currents in free convection at horizontal electrodes indicates that steady state transport may be achieved nearly three times faster by potential scan than by a current ramp. Examination of limiting current data obtained on a rotating disk reveals that this is also the case in laminar forced convection.An unsteady-state diffusion model allows the prediction of the maximum current obtained in fast potential scanning. Criteria are established for estimating the time required for reaching steady-state transport conditions when a current ramp or potential scan is used for the approach to limiting current.     

Role of magnetic forces in electrochemical reactions at microstructures

The effect of an external magnetic field (up to 0.8 T) on the anodic dissolution of microstructures has been investigated systematically. Copper and silver wires (100 microm in diameter) were embedded in epoxy resin and dissolved potentiostatically while a magnetic field was periodically switched on and off. A special feature of the thus prepared structures is that they show a smooth transition from an inlaid disk to a recessed disk electrode. An increase or a decrease of the limiting current density in the presence of B was found depending on the orientation of the magnetic field and the hydrodynamic conditions in the cell (natural or forced convection). The magnetic forces which are responsible for this are the Lorentz force and the gradient force. We propose a model which discusses the interaction of these forces with the natural and the forced convection to explain the experimental results.     

Electromembrane extraction—Three‐phase electrophoresis for future preparative applications

The purpose of this article is to discuss the principle and the future potential for electromembrane extraction (EME). EME was presented in 2006 as a totally new sample preparation technique for ionized target analytes, based on electrokinetic migration across a supported liquid membrane under the influence of an external electrical field. The principle of EME is presented, and typical performance data for EME are discussed. Most work with EME up to date has been performed with low‐molecular weight pharmaceutical substances as model analytes, but the principles of EME should be developed in other directions in the future to fully explore the potential. Recent research in new directions is critically reviewed, with focus on extraction of different types of chemical and biochemical substances, new separation possibilities, new approaches, and challenges related to mass transfer and background current. The intention of this critical review is to give a flavor of EME and to stimulate into more research in the area of EME. Unlike other review articles, the current one is less comprehensive, but put more emphasis on new directions for EME.     

Limiting Current Densities in a System with Cation-Exchange Membrane MK-100 Rotating in a Glycine–HCl Solution

Limiting diffusion current densities in an electromembrane system (EMS) comprising cation-exchange membrane MK-100 and a glycine solution containing hydrochloric acid are studied on a rotating membrane disk. The dependence of the limiting current density at a given rotation rate of the disk on the equilibrium volume concentrations of glycine cations and protons in solution is described by a regression model. The diffusion fluxes of these cations in the EMS are shown to be independent.     

Electric mass transport of sodium chloride through cation-exchange membrane MK-40 in dilute sodium chloride solutions: A rotating membrane disk study

The polarization properties of an electromembrane system consisting of an MK-40 membrane and a dilute sodium chloride solution are investigated with an experimental apparatus, which includes a rotating membrane disk with a horizontally positioned membrane. For the electrochemical systems of MK-40/0.01 M NaCl and MK-40/0.001 M NaCl, effective ion transport numbers and partial current-voltage curves are determined 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. The space-charge distribution in the diffusion layer and in the membrane is calculated for various current densities and rotation rates of the membrane. It is shown that when electric-current densities are greater than the limiting value, ion fluxes of the salt increase as a result of a decrease in the effective thickness of the diffusion layer. This decrease is caused by the development of space charge, electroconvection, water dissociation, and the exaltation effect in the region near the membrane. It has been established that in dilute solutions the limiting current is not purely electrodiffusive in nature.     

Chronopotentiometric Method of Studying Electroosmosis in Systems with Ion-Exchange Membranes and Lysine Solutions

A new method of chronopotentiometric study of electroosmotic water transfer in the electromembrane system containing amino acid solution is elaborated. An electrodiffusion problem, which allows for a convective solvent transfer in the system, is formulated and solved. By comparing calculated and experimental transition times for MK-40 and MF-4SK cationite membranes in lysine monohydrochloride solutions, the electroosmotic permeability of the membranes and transport numbers of water through them are calculated. A considerably higher electroosmotic water transport through MK-40 as compared with MF-4SK is attributed to differences in their nature and structure.