Electro-osmotic pumping of sodium chloride solutions

Electro-osmotic pumping (EOP) theory and its characteristics (transport numbers, brine concentration, current density, current efficiency, electro-osmotic coefficients, etc.) of Selemion AMV and CMV ion-exchange membranes were studied. The brine concentration increased with increase in current density and feed water concentration. Current efficiency was nearly constant in a wide range of current densities and feed water concentrations. The water flow through the membranes also increased with increasing current density and feed water concentration. The increase in water flow increased the current efficiency significantly. Consequently, water flow through electrodialysis (ED) membranes had a positive effect on ED. Electro-osmotic coefficients decreased with increasing feed water concentration. Osmotic flow in EOP-ED decreased relative to the total flow with increasing current density while the electro-osmotic flow increased relative to the osmotic flow. Osmotic flow significantly contributes to the total water flow in EOP. Selemion AMV and CMV membranes performed well for salt concentration. A simple membrane potential measurement has been demonstrated to function reasonably satisfactorily to predict membrane performance for salt concentration.     

The effect of ferric ions on the conductivity of various types of polymer cation exchange membranes

Recently, rejuvenated interest to fuel cells has posed a number of problems regarding the polymer electrolyte membrane properties and their behaviour in different electrolyte solutions. This work was dedicated to study the conductivity of H⁺-, Fe³⁺- and mixed H⁺/Fe³⁺-forms of cation exchange membranes Neosepta CMS, Nafion 112, 115 and 117 and Selemion HSF under conditions similar to these in the Fe³⁺/Fe²⁺–H₂/H⁺ fuel cell in the range of current densities 0–90 mA/cm². It was found that the conductivities of these membranes in 1.09 M H₂SO₄ solution decrease in the following order: Selemion HSF › Nafion 117 ≈ Nafion 115 ≈ Neosepta CMS › Nafion 112. Conductivities of perfluorinated membranes were discussed in terms of Hsu and Gierke percolation theory [20]. The Fe³⁺-forms of Nafion membranes studied displayed a monotonous decline in the resistance when current increased, which is a manifestation of gradual conversion of the Fe³⁺-form into H⁺-form of these membranes. Unlike the Nafion membranes, the Fe³⁺-forms of Neosepta CMS and Selemion HSF membranes exhibited a sharp jump of resistance at relatively high current densities (more than 70 mA/cm²) that is most probably a result of concentration polarization.     

Water transport study across commercial ion exchange membranes in the vanadium redox flow battery

The water transfer behaviour of Selemion CMV, AMV and DMV membranes (Asahi Glass, Japan) has been studied in the vanadium redox cell, as was the water transfer across Nafion 117 membrane (E.I. Du Pont, USA). The earlier water transport studies of a variety of commercial ion exchange membranes and non-ionic separators in the vanadium redox cell have shown that the net water transport through anion exchange membranes and non-ionic separators in the vanadium redox cell is from the positive half cell (+ve) to the negative half cell (−ve), while for cation exchange membranes the net water transport is in the opposite direction. In the present study, it was found that a significant amount of water is transferred across cation exchange membranes from the −ve vanadium half cell electrolyte to the +ve vanadium half cell electrolyte by the hydration shells of V²⁺ and V³⁺ ions which carry a large amount of water and can easily permeate through cation exchange membranes due to their relatively high charge numbers. The net amount of water of hydration which is transferred across anion exchange membranes from the −ve half cell electrolyte, however, is almost equal to the net amount of water of hydration which is transferred from the +ve half cell electrolyte. Thus, the net amount of water which is transferred across anion exchange membranes is in the same direction as the osmotic water transfer.     

Limiting current density and water dissociation in bipolar membranes

The behaviour of bipolar membranes in NaCl and Na₂SO₄ solutions is discussed. The membranes are characterized in terms of their limiting current densities. Below the limiting current density the electric current is carried by salt ions migrating from the transition region between the anion and the cation exchange layer of the bipolar membrane. In steady state these ions are replaced by salt ions transported from the bulk solutions into the transition region by diffusion and migration due to the fact that the ion-exchange layers are not strictly permselective. When the limiting current density is exceeded, the salt transport from the transition region can no longer be compensated by the transport into the region and a drastic increase in the membrane resistance and enhanced water dissociation is observed. This water dissociation is described as being a combination of the second Wien effect and the protonation and deprotonation of functional groups in the membrane. The limiting current density is calculated from a mass balance that includes all components involved in the transport. The parameters used in the mathematical treatment are the diffusion coefficients of salt ions and water, the ion mobilities in the membrane, the fixed charge densitiy of the membrane, the pK_b values of the functional groups and the solution bulk concentrations.     

The influence of H2SO4 electrolyte concentration on proton transfer resistance of membrane/solution interface

The proton transfer resistance of membrane/solution interface is investigated in this paper by employing H₂SO₄ aqueous solution with different concentration. Two commercial cation exchange membranes, Nafion1135 and PE01 membranes with different ion exchange capacity were selected as test membranes; Proton transfer resistance measurements were made by A.C impedance techniques. The proton transfer resistance of membrane/solution interface increases quickly from 0.059 to 2.22 Ω with the decrease of H₂SO₄ concentration from 2.0 to 0.05 mol/L. The ion exchange capacity of the membrane, or more exactly, the surface charge of the membrane has obviously effect on the membrane/solution resistance due to the formation of electrical double layer (EDL). The effect of electrolyte concentration on membrane/solution interface resistance can be explained by the electrical interactions between ions and charged groups of the membrane: high concentration of ions in the medium can compress the EDL and reduce the electrical interactions between ions and charged groups of the membrane.     

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.     

Transport properties of highly ordered heterogeneous ion-exchange membranes

Model "ordered" heterogeneous ion exchange membranes are made with ion exchange particles heaving ion exchange capacity in the range 3 to 2.5 meq/gr (dry basis) and diameters ranging from 37 to 7 microm and 2 component room-temperature vulcanizing silicon rubber as a polymeric matrix, by applying an electric field normal to the membrane surface during preparation. These membranes were shown to have an improved ionic conductivity compared with "nonordered" membranes based on the same ion exchange content (for instance, at 10% resin content "nonordered" membranes show <10(-5) mS/cm while "ordered" membranes have conductivity of 1 mS/cm). The transport properties of ordered membranes were compared with those of nonordered membranes, through the current-voltage characteristics. Limiting currents measured for the ordered membranes were significantly higher than those of the nonordered membranes with the same resin concentration. In addition, higher limiting currents were observed in ordered membranes as the resin particles became smaller. Energy dispersion spectrometry analyses revealed that the concentration of cation exchange groups on the membrane surface was higher for ordered membrane as compared to that of nonordered membranes. This implies that the local current density for the conducting domains at the surface of the nonordered membranes is higher, leading to higher concentration polarization and, eventually, to lower average limiting current densities. The effect of ordering the particles on the membrane conductivity and transport properties was studied, and the advantages of the ordered membranes are discussed.     

Electrochemistry in supercritical trifluoromethane

The use of trifluoromethane (CHF₃) as a solvent for electrochemical studies in supercritical conditions is analyzed. The dielectric and electrical conductivity of supercritical CHF₃ was measured at 323.15 K at several densities. The solubility and electrical conductivity of tetrabutylammonium hexafluorophosphate (TBAPF₆) and decamethylferrocenium hexafluorophosphate (Fe(Cp*)₂PF₆) in supercritical CHF₃ were measured at 323.15 K as a function of density. It was found that, in spite of the high ion pair formation of the TBAPF₆ in the supercritical solvent, this salt is a suitable supporting electrolyte, having a conductivity much higher than that reported for other electrolytes in low dielectric constant supercritical solvents. The limiting currents measured for decamethylferrocene (Fe(Cp*)₂) and decamethylferrocenium hexafluorophosphate (Fe(Cp*)₂PF₆) at a platinum microdisc in supercritical CHF₃ at several densities and 323.15 K, show the feasibility of using the proposed supercritical system as a model for electrochemical studies in variable density media. The effect of concentration of the supporting electrolyte on the limiting current at the microelectrode is qualitatively discussed in terms of a recent theory which takes into account the ion association of the supporting and electroactive electrolytes.     

Cation exchange membranes as solid solutions

The ion exchange equilibrium between KCl and SrCl₂ solutions and the cation selective membrane CR61 AZL386 has been examined. Equilibrium isotherms are measured for membrane—electrolyte equilibria for two total concentrations of Cl^?in the electrolyte solution and at three different temperatures. The results show that Sr²⁺ is strongly preferred to K⁺ in the membrane. Selectivity increases with temperature in the range 10°C to 40°C. It decreases with increasing total concentration from 0.01 N to 0.03 N. Electrolyte absorption in the membrane was not detected for the experimental conditions used. Contents of water in the membrane is constant for external salt concentrations between 3 x 10^?8N and 3 x 10^?2N. The difference in water content between the pure K form and the pure Sr form is approximately 5%.A thermodynamic treatment of ion exchange is presented. The thermodynamic equilibrium constant for the exchange reaction 2 KR + SrCl₂ = SrR₂+ 2 KCl has been determined by two different integration procedures, R being an ion exchange site in the membrane. The variations of the thermodynamic functions ΔG_mix, ΔH_mix and ΔS_mix are calculated from experimental data for an assumed mixing process of membranes in the pure forms.Activity coefficients for the membrane components are calculated from experimental data. Results are compared to two lattice models. A model with a random distribution of K⁺, Sr²⁺ and a vacant site seems preferred at low concentration of Sr²⁺. At high concentrations, Sr²⁺ and the vacant site associate.     

Heterogeneity of Ion-Exchange Membranes: The Effects of Membrane Heterogeneity on Transport Properties

The heterogeneity of different cation-exchange membranes (Neosepta CMX, Selemion CMV, and HJC heterogeneous membrane) and their effects on transport properties were investigated using chronopotentiometry, membrane conductivity, and current-voltage curves. Modifying the classical Sand equation, a method has been developed to determine the fraction of the conducting region (epsilon) of the ion-exchange membrane. The epsilon values of the CMX, CMV, and HJC membranes were 0.93, 0.95, and 0.75, respectively. Considering the characteristics of each membrane-the CMX and CMV are reinforced homogeneous membranes, while the HJC is a heterogeneous membrane-the epsilon values determined in this study seem to be reasonable. The dependence of membrane conductivities and the limiting current densities on the fraction of conducting region of each membrane have also been studied. Copyright 2001 Academic Press.     

A discussion on ion conductivity at cation exchange membrane/solution interface

By Gouy–Chapman–Stern–Grahame (CGSG) model, the electric double layer at ion exchange membrane/solution interface consists of two parts: the Stern layer and the diffusion layer. The ions in Stern layer are compacted and considered to be immobile. The relation of diffusion layer mean conductivity K with outer Stern layer potential φ₀, the boundary potential φ_δ and the electrolyte concentration C₀ is educed for symmetric electrolyte system. The results show that K is higher than that of the bulk solution and is greatly influenced by φ₀, φ_δ and C₀.The examination of PE01 cation exchange membrane/solution interface resistance R_e measured by ac impedance technique, shows that R_e value decreases quickly as the KCl electrolyte concentration rises. The effect of electrolyte concentration on the resistance of EDL can be explained by the electrical interactions between ions and charged groups of the membrane. Since the membrane/solution interface resistance is much higher than that of bulk solution, therefore, a further analysis based on the theory developed in this study proves that the ion transfer resistance R_e of membrane–solution interface predominantly occurs at Stern layer as a result of static electrical interaction.     

Electric mass transfer of sodium chloride through cation-exchange membrane MK-40: A rotating membrane disk study

An experimental device consisting of a rotating membrane disk with horizontally positioned cation-exchange membrane MK-40 is described. The device’s design makes it possible to simultaneously obtain current-voltage curves (CVC) and dependences of effective transport numbers for ions of electrolyte and water dissociation products on the current density. Partial CVC are calculated and limiting current densities and diffusion layer thickness are determined at various disk rotation rates. At current densities below the limiting value, the disk’s CVC obey regularities of electrodiffusion kinetics. Upon raising the current density further, the salt ion fluxes increase due to a decrease in the effective diffusion layer thickness, which is caused by the emergence in the near-membrane region of a space charge and electroconvection. At high current densities there occur oscillations of the potential jump that are caused by hydrodynamic instability of the near-membrane solution layer.     

Effects of the composition of acid solutions and the presence of organic acids on oxygen electroreduction to hydrogen peroxide in a carbon black gas-diffusion electrode

This paper reports on the effects of the K₂SO₄, H₂SO₄, NaCl, HCl, and tetrabutylammonium bromide concentrations (0.01–0.0002 M) and the presence of formic, acetic, and butyric acids in the electrolyte on the kinetic characteristics of oxygen reduction to H₂O₂ in a carbon black gas-diffusion electrode (GDE) and on the H₂O₂ accumulation kinetics in electrolyte at current densities of 30–100 mA/cm². The introduction of K₂SO₄ and tetrabutylammonium bromide in the electrolyte led to an increase in the transfer coefficient α and a decrease in the coefficients in the Tafel equation. The concentration and the current efficiency of H₂O₂ decreased with the salt to acid concentration ratio. The organic acids reduced the current efficiency of H₂O₂ and increased the electrode polarization. Peracids with a current efficiency of up to 0.27% and concentration of up to 7.5 mM were obtained. Solutions of H₂O₂ with concentrations of 0.6–3.3 M and current efficiencies of 17–75% were obtained at current densities of 30–100 mA/cm² in electrolytes with salt and inorganic acid concentrations of 0.9–40 g/l and in the presence of organic acids.     

Kinetics of silver electrodeposition from thiocarbamide solutions at a regular surface coverage with sulfide ions

Kinetics of silver electrodeposition in the presence of sulfide ions is studied on electrodes renewed by cutting off a thin surface layer, at a controlled time of contact of the “fresh” surface with the electrolyte. Solutions containing 10^?2 M AgNO₃, 0.1 M thiocarbamide, 0.5 M HClO₄, and from 2 × 10^?6 to 1.5 × 10^?5 M Na₂S are studied. It is shown that under the studied conditions, the effect of silver electrodeposition on the surface concentration of sulfide ions is insignificant. As the concentration of sulfide ions in solution and their coverage on the electrode surface θ increase, the cathodic polarization decreases. Tafel curves plotted for θ = const are used in estimating the exchange current i ₀ and the transfer coefficient α. It is shown that α ≈ 0.5 and weakly depends on θ, whereas the exchange current increases with the increase in θ by an approximately linear law from 10^?5 A/cm² at θ ? 0 to 10^?4 A/cm² at θ = 0.43. The obtained data are compared with the results of kinetic studies of silver anodic dissolution in similar solutions.     

Energy-saving seawater electrolysis for hydrogen production

The change in the polarization potentials of anode and cathode due to pH change on electrode surfaces during galvanostatic polarization was examined in 0.5 M NaCl solutions of different pH. On the basis of these results, feeding of the anolyte after oxygen evolution to the cathode compartment for hydrogen production was examined for energy-saving seawater electrolysis. This was assumed to prevent the occurrence of a large pH difference on cathode and anode in electrolysis of neutral solution if sufficient H⁺ is permeated through the membrane. The cell performance was examined using Nafion 115 or Selemion HSF membranes for separation of anode and cathode compartments. The permeation fraction of H⁺ with Nafion 115 was 45–65% in 0.5 M NaCl and was about 90% in 0.25 M Na₂SO₄. These values were smaller than 97% necessary for prevention of the occurrence of pH difference on cathode and anode. The permeation fraction of H⁺ with Selemion HSF became more than 97% during electrolysis of 0.025 M Na₂SO₄, and the cell voltage was kept at low values. These results indicate the effectiveness of our seawater feeding system if the 97% H⁺ permeation fraction through the membrane is attained. Contribution to the Fall Meeting of the European Materials Research Society, Symposium D: 9th International Symposium on Electrochemical/Chemical Reactivity of Metastable, Warsaw, 17th-21st September, 2007.     

Transport properties of vanadium ions in cation exchange membranes:: Determination of diffusion coefficients using a dialysis cell

Diffusion coefficients of vanadium ions in cation exchange membranes are of interest because they allow to calculate the ion exchange across the membrane in an all vanadium redox flow battery which leads to undesired cross contamination and energy losses in the battery system. Diffusion coefficients of V²⁺, V³⁺, VO²⁺ and VO⁺₂ ions in CMS, CMV and CMX cation exchange membranes have been determined by measuring the ion exchange fluxes of these ions with H₃O⁺ ions using a dialysis cell. The experimental data are evaluated on the basis of integrated flux equations which require also ion exchange sorption equilibria obtained already in previous work. The lowest diffusion coefficients are observed in the CMS membrane for all vanadium ions. This membrane turns out to be the most suitable one for being applied in a vanadium battery since it is expected to prevent most effectively cross contamination of vanadium ions.     

Simulation of ion mass transfer processes with allowance for the concentration dependence of diffusion coefficients

The system of equations describing ion transport in a binary electrolyte z _a-z _c with allowance for the linear dependence of the diffusion coefficients on the concentration was analyzed in the framework of the phenomenological Nernst-Planck approach. The expressions are obtained that define concentration profiles of ions and conditions favorable for the limiting current caused by the achievement of the concentration of a saturated solution (in the case of the anodic reaction) and depletion of the near-electrode region in electroactive cations (in the case of the cathodic reaction). The revealed theoretical dependence of the limiting current on the volume concentration of the salt agrees with published experimental data. The voltammetric characteristics of the corresponding systems were calculated. The role of the migrational component of the ion flow is discussed. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 638–642, April, 2006.     

Direct ethanol oxidation fuel cell with anionite membrane and alkaline electrolyte

A number of cathode catalysts were synthesized from nitrogen-containing organic complexes on XC-72R carbon black for an alkaline electrolyte. The catalysts were studied by the rotating disc electrode (RDE) technique. The polyacrilonitrile (PAN), phthalocyanine (Pc), and cobalt tetra(methoxyphenyl)porphyrin (CoTMPP) systems showed the highest activity. The slope of the oxygen polarization curves in the first region in 1 M KOH was 35–40 mV; this corresponds to concentration polarization in an alkaline solution in the O₂-HO₂⁻ system. A cyclic voltammetry study demonstrated that the catalytic systems with the highest corrosion stability were Pc + Co + Fe/XC-72R and CoTMPP/XC-72R pyropolymer. The activity of the catalysts decreased by 20–25% compared with the initial current densities on average. An ethanol-oxygen fuel cell with a Fumasep FAA anionite membrane and nonplatinum catalysts was tested. The maximum power density was 32 mW/cm² at 40°C. The stability test of the fuel cell showed that the materials used for the membrane-electrode assembly allowed more than 100 h of continuous operation with constant working characteristics.     

Numerical Solution of the Problem of the Limiting Current for the Copper Electrodeposition from a Solution of Cupric Sulfate and Sulfuric Acid in Conditions of Natural Convection

Equations for a boundary layer, written in self-similar variables, are integrated numerically to obtain distributions of concentration of ions Cu²⁺, H⁺, and SO₄ ^2–; a hydrodynamic velocity; partial currents of electrolyte components; and the limiting current of copper deposition and determine the Rayleigh number for the system under consideration. The results are compared with an approximate analytical solution obtained earlier.