Synthetic inorganic ion-exchange materials

The change in selectivities by thermal treatment was studied on crystalline (C-SbA) and amorphous (A-SbA) antimonic(V) acids. The equilibrium distribution coefficients (K_d) of Na⁺ and K⁺ ions in HNO₃ solution showed a maximum on the C-SbA heated at 330 °C. An inverse relationship was noticed between the changes in K_d values and in the lattice constants for the heated C-SbA. A-SbA heated at 20–500°C showed two steps of time dependence of adsorption for Na⁺, while a maximum for K⁺. This behavior can be explained in terms of the transformation from amorphous material to C-SbA.     

Electrochemical properties and structure of ion-exchange membranes upon thermochemical treatment

The effect of temperature-induced morphological changes on the electrochemical and physicochemical properties of the heterogeneous sulfo cation-exchange membrane MK-40 in aqueous, alkaline, and acidic media is subjected to comparative analysis. The deviation between the surface and volume microstructure of swollen membrane samples after their chemical conditioning and thermochemical treatment are visualized by a scanning electron microscope. The porosity and the fraction of the ion-exchange component in membranes subjected to heating in water and aggressive media are observed to increase more noticeably in their surface layer as compared with their volume. The maximum effect thus modified structural characteristics on the transport (conductivity, diffusion permeability, selectivity) and physicochemical (exchange capacity, water content, density, linear sizes) properties is observed for MK-40 membrane samples when heated in a sulfuric acid solution. The effect of thermal destruction of inert polymers (divinylbenzene, caprone) involved in the membrane composition on the transport characteristics is revealed.     

Steady-state and transient electrical properties of ion-exchange membrane systems in asymmetric arrangements

The steady-state and transient electrical properties of ion-exchange membranes placed between two solutions with different values of the electrolyte concentration, have been simulated using the network simulation method. The ionic transport processes are theoretically described on the basis of the Nernst-Planck and Poisson equations. The system under study is constituted by a cation-exchange membrane in which the fixed-charge is homogeneously distributed in space and two diffusion boundary layers on both sides of the membrane, the electric double layers at the interfaces being included. The steady-state voltage-current characteristic and the profiles of the ionic concentrations and the electric potential, are analysed. Also, the choronopotentiometric response of the system has been discussed and the time evolution of the electric energy consumption evaluated. In particular, the influence of the ratio of the bathing concentrations on the permselectivity and the chronopotentiometric response of the ion-exchange membrane systems, has been established.     

Copper electrodeposition into ion-exchange materials

Electrodeposition of copper into spherical granules of ion-exchange materials KU-23 and KU-2 out of acid sulfate solutions is studied by a method of cyclic voltammetry. It is discovered that the discharge of copper ions in an ion-exchange matrix is characterized by a cathodic overvoltage that is higher than the overvoltage of the same process on a graphite substrate by 0.08 V, which is most probably connected with a limited mobility of ions localized at fixed groups [RSO ₃ ^? ]. The cyclic voltammogram exhibits an additional cathodic peak in the potential region corresponding to the reduction of single-charged copper ions that form as a result of their accumulation inside pores of the ion-exchange matrix during anodic dissolution of metal deposited previously. It is fixed microscopically that the process of deposition begins at the graphite substrate/ion-exchanger interface and passes into bulk upon the formation of an electron-conducting layer saturated with copper. Preliminary saturation of the ion-exchanger by copper deposited chemically facilitates uniform electrodeposition of copper over the entire volume of pores of the ion-exchange matrix.     

Characterization of non-linear adsorption properties of dextran-based polyelectrolyte displacers in ion-exchange systems

Experimental studies were carried out on the non-linear adsorption properties of dextran-based polyelectrolytes in anion- and cation-exchange chromatographic systems. By monitoring both the induced salt gradients and sequential breakthrough fronts, parameters were determined for use in a Steric Mass Action (SMA) model of non-linear ion-exchange chromatography. These parameters include: total ion capacity of the columns, characteristic charge, steric factor, equilibrium constant, and maximum adsorptive capacity for each of the polyelectrolytes. In addition the number of functional groups were determined by elemental analysis. The values of the SMA parameters were found to be independent of salt and polyelectrolyte bulk phase compositions. Parameters were also determined for a variety of proteins. Experimental isotherms for the polyelectrolytes and proteins were compared with those simulated by the SMA model. Finally, the implications of polyelectrolyte adsorption properties with respect to their ability to act as efficient displacers in ion-exchange displacement systems are discussed.     

Structural change of ion-exchange membrane surfaces under high electric fields and its effects on membrane properties

Structural change of an ion-exchange membrane under a high electric field was investigated by comparing water dissociation and the FTIR spectra between the virgin membrane and that used at an overlimiting current density. From a series of water dissociation experiments at overlimiting current densities, it was observed that water dissociation in an anion-exchange membrane used at an overlimiting current density was higher than that in a virgin membrane at the same current density. The FTIR study revealed that the tertiary amine groups are formed from the quaternary ammonium groups on the anion-exchange membrane surface where ion depletion occurs under the influence of the applied strong electric field. The occurrence of increased water dissociation is considered to be caused by the protonation and deprotonation of the tertiary amine groups in the anion-exchange membrane. On the other hand, there was no structural change for the cation-exchange membrane under the electric field investigated in this study, which is coincident with the results of water dissociation experiments for the CMX membrane. In addition, we found that membrane resistance, permselectivity, and plateau length of the current-voltage curve were affected by the converted tertiary amine groups depending on the solution pH.     

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.     

Characterization of BSA-fouling of ion-exchange membrane systems using a subtraction technique for lumped data

Electrical impedance spectroscopy (EIS) techniques were used to gain insight into BSA fouling of the Neosepta CMX and AMX ion-exchange membranes (IEMs). EIS characterizations were made at concentrations above 0.1 M KCl because the conductance of the IEMs was higher than that of bulk solutions of concentration below 0.1 M KCl. Spectra, expressed in terms of dispersions of the conductance and capacitance with frequency, provided an enhanced indication of IEM fouling during separation processes. Bulk conductance measurements of the solution alone, membrane immersed in solution and fouled membrane immersed in solution showed good agreement with general theoretical predictions. Strong dispersions in capacitance were observed below 1 kHz for each of these configurations. Differences in the dispersions arising from fouling were identified by subtracting the impedance of the solution from those of unfouled and fouled IEMs in solution. The conductance and capacitance dispersions of fouled IEMs decreased with the accumulation of the BSA fouling layer on the surface.     

Amorphous perfluorinated membrane materials: Structure,properties and application

The structure and properties of glassy amorphous perfluorinated polymers are considered with an emphasis of their use as membrane material. The results of the study of free volume in these polymers and simulation of their nanostructure are discussed. The perfluorinated polymers are featured by unusual thermodynamic properties, so the influence of these properties on the parameters of the membranes based on them is examined. In conclusion, various applications of the membranes based on the perfluorinated polymers (predominantly amorphous Teflon AF) in separation processes are described.     

Liquid ion-exchange membrane electrode for lithium

An electrode selective for lithium relative to other alkali metal ions is described. The sensor is based on n-decanol as both the liquid membrane and exchanger. The electrode exhibits more than 3 decades of linear near-Nernstian response and has selectivity comparable to the LAS 15-25 glass univalent-cation electrode.     

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.     

Composition of ion-exchange materials based on titanium phosphate

Composition and structure of synthetic ion-exchange materials based on titanium phosphate were studied. The materials were synthesized from titanium(IV), phosphorus(V), and silicon(IV) reagents taken in various concentrations, using various modes of the synthesis and treatment of the precursors. The dependence of the ion-exchange properties of the final products on the composition of the precursors was examined.     

Modified lignin with ion-exchange properties

Polyfunctional ion-exchangers were synthesized by heterophase amination of α-oxide derivatives of hydrolyzed lignin with aliphatic di-and polyamines. Optimal conditions for their preparation were determined. Certain physicochemical properties were studied. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 492–495, September–October, 2007.     

Synthesis and characterization of an amphoteric ion-exchange membrane

An amphoteric ion-exchange membrane was prepared by chemical grafting of acrylic acid and dimethyl amino-2-ethyl methacrylate on ozonized polyethylene. The effects of the variation of external pH on the physicochemical properties of this membrane were studied (exchange capacity, electrical resistance, water and electrolyte content, and membrane potential). The determination of the mean activity coefficient of the NaCl in the membrane phase using the Donnan equilibrium equation reveals that this coefficient increases with the NaCl concentration in the external solution. Fundamental electrochemical properties of the amphoteric membrane are discussed on the basis of the variation of the membrane selectivity with the external electrolyte concentrations and the pH. The properties at neutral pH are accounted for by a mutual neutralization of some acidic and basic groups in the membrane phase.     

Adsorption properties and porous structure of new carbon materials

The adsorption properties of the new carbon materials, sibunites, which are mesoporous samples with a developed surface of pores, were studied. The isotherms of the adsorption of benzene vapor were determined to estimate the porous structure of these materials. The principal methods for calculating the parameters of the porous structure of sibunites were analyzed. The application of the BET equation even in the presence of a small number of micropores can distort the results, therefore the most suitable method for estimating the surface of mesopores is one that is based on the Dubinin—Zaverina equation. The estimation of the surface of sibunites using water vapor adsorption is demonstrated.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1377–1380, August, 1993.     

Determination of zinc in plant materials using ion-exchange chromatography

The objective of this investigation was to develop a rapid and accurate method for the determination of zinc in plant materials. An ion-exchange separation technique to eliminate interferences in the Zincon procedure for zinc is described. Comparison with the A.O.A.C. method and evaluation of zinc recovery studies show the proposed method to be satisfactory for the analysis of microgram amounts of zinc in plant materials.     

Streaming potential in a liquid ion-exchange membrane electrode

A streaming potential in a liquid membrane electrode sensitive to nicotinate ion (3-pyridinemonocarboxylate), has been observed during dynamic electrode response measurements carried out by sodium nicotinate step-wise concentration increases. It was possible to separate the streaming potential from the dynamic electrode response and to study it as a function of the flow-rate in the cell and of the nature of the liquid membrane support.A streaming potential was observed with Millipore MF-PH supports (mixed esters of cellulose) but not with Fluoropore (polytetrafluoroethylene bonded to polyethylene net) supports.     

Synthesis and ion-exchange properties of ceric tungstate

Ceric tungstate has been prepared under varying conditions of precipitation. Its properties and ion-exchange behaviour have been studied. Separations of Hg(2+) from Zn(2+), Cd(2+) and Pb(2+) ; Co(2+) from Mn(2+) and Fe(3+) ; and Al(3+) from Cr(3+) and Fe(3+) have been carried out on ceric tungstate columns.     

Chelation ion-exchange properties of salicylic acid-urea-formaldehyde copolymers

Chelation ion-exchange properties of copolymers prepared from salicylic acid, urea and formaldehyde by condensation in presence of acid catalyst were studied for Cu²⁺, Fe³⁺, UO²⁺, Mn²⁺,Zn²⁺ and Co²⁺ ions. A batch equilibration method was adopted to study the selectivity of metal ion uptake. This method involved the measurement of distribution of a given metal between the copolymer sample and a solution containing the metal ions. The study was carried out over a wide pH range and in media of various ionic strengths. The copolymer showed a higher selectivity for UO₂ ²⁺, Cu²⁺ and Fe³⁺ ions than Mn²⁺, Co²⁺ and Zn²⁺ ions.